Clay Containing Polymeric NanoComposites, Volume 1, L.A. Utracki

Clay-Containing
Polymeric
Nanocomposites
Volume 1
L.A. Utracki
Clay-Containing
Polymeric
Nanocomposites
Volume 1
L.A. Utracki
C. Vasile
Rapra Technology Limited
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First Published in 2004 by
Rapra Technology Limited

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©2004, Rapra Technology Limited
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ISBN: 1-85957-437-8
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Preamble
Preamble
L.A. Utracki
During the last few years terms like nanomaterials, nanocomposites and
nanosystems have become fashionable. It seems that anything with ‘nano’ attached
to it has nearly a magical effect – not so much on performance as on expectations.
There is an extensive worldwide effort to introduce nanotechnology for the
production of materials with specific functional characteristics, e.g.,
semiconducting, electromagnetic, optical, etc. New magneto-resistance materials
with nanometre-scale spin-flip mean free path of electrons have been
commercialised. The National Science Foundation (NSF) has solicited
collaborative research proposals in the area of nanoscale science and engineering,
including: nanoscale biosystems; nanoscale structures; novel phenomena and
control; nanoscale devices and system architecture; nanosystems-specific software;
nanoscale processes; multi-phenomena modelling and simulation at the nanoscale
level; studies on societal implications of nanoscale science and engineering, etc.
Nanostructures are of interest to many technologies. The potential of precise
control of impurities and defects in a crystal and the ability to integrate perfect
inorganic and organic nanostructures may lead to a new generation of advanced
materials. To electronics, they offer quantum devices (resonant tunnelling
transistors; single electron transistors; cellular automata based on quantum dots)
and new processor architectures. To catalysis, they form the templates for catalytic
activity, zeolite pores, etc. In biology, nanostructures are components of the
mitochondrion, the chloroplast, and the ribosome.
The advances in the synthesis and fabrication of isolated nanostructures range
from colloidal synthesis of nanocrystals to the growth of epitaxial quantum dots.
The techniques of molecular biology have made a wide range of biological
nanostructures readily available through cloning and overexpression in bacterial
production systems. Furthermore, work has begun on the use of self-assembly
techniques to prepare complex and designed spatial arrangements of
nanostructures. Techniques derived from microlithography in microelectronics
(viz. photo, X-ray, and e-beam lithography) offer the potential to economically
generate new types of 3D-structures. In short, there is a great potential for the
wide use of nanotechnology for functional materials and devices.
The central theme of this book is the use of nanotechnology for the
development of new structural polymeric systems, the polymeric nanocomposites
(PNCs), and particularly the clay-containing polymeric nanocomposites (CPNCs).
These mass produced materials are dispersions of inorganic, nanoscale platelets
in a polymeric matrix. Economics preclude the use of most of the manufacturing
methods developed for ceramic and metallic nanocomposites. The key to the
success of the CPNC industry is to provide new materials significantly
outperforming the old ones at a marginal incremental cost increase per unit
volume. Considering that at present the nanoclay is a natural mineral with well-
i
Clay-Containing Polymeric Nanocomposites
recognised variability of composition, the secondary concerns focus on the

consistency of performance, not only at the batch-to-batch level, but also on a
long-term basis.
Nanostructures are intermediate in size between molecular and micron-size
systems, such as blends and composites. There is no doubt that structures with
architecture controlled on the molecular level may lead to refined properties or
even new sets of performance characteristics. Chemists have known this for
centuries, viz. more recent developments in nanosize structures such as fullerenes,
buckytubes, dendrimers and complex block copolymers. The unexpected
behaviour of adsorbed monolayers of organic molecules on a high-energy crystal
surface was discovered many decades ago. In the meantime the advances of
microscopy reached atomic-scale, providing images of crystalline unit cells and
bioactive macromolecules. Thus, it is legitimate to ask what, if anything, is so
different about the nanomaterials that warrants the distinction.
It is known that within the nanometre scale such properties as the melting
temperature, the remanence of a magnet, and the band gap of a semiconductor
depend upon the size of the component crystals. Furthermore, it has been shown
that the mechanical properties of metallic alloys hyperbolically increase with the
reduction of domain size.
It is customary to define nanocomposites in terms of the size of the dispersed
particles and the specific behaviour they engender. Thus, at least one dimension
of these particles must be less than 10 nm. Since these particles are usually
crystalline, the size and high surface energy leads to high surface area to volume
ratio and strong orientational forces that may lead to high packing densities and
quantum behaviour (explored as electronic, magnetic or optic elements in
microelectronics technology). In the most popular nanofiller in the CPNC industry,
montmorillonite, over 40% of atoms rest on the surface – the clay lamellae should
be treated either as giant inorganic molecules or at least as hybrids occupying the
grey zone between molecules and particles. This is not mere semantics, but has
profound consequences as far as the fundamentals of CPNC are concerned, viz.
miscibility or flow behaviour.
This book summarises the pertinent developments in the area of the science
and technology of clay-reinforced polymeric nanocomposites. There are several
reasons for using clays, viz. availability, cost, and aspect ratio. The theory and
experiments show that to maximise the benefits of nanotechnology the clay must
be fully decomposed into individual crystalline lamellae (exfoliated) and these
must be uniformly dispersed in a given matrix material. Furthermore, considering
the large aspect ratio of clay platelets, their orientation must be controlled – for
some applications perfect alignment is desirable, whereas in others isotropicity
of reinforcement is essential. For example, aligning clay lamellae perpendicular
to the flux direction may increase barrier properties by a factor of 100, whereas
orienting them in the flux direction will hardly change the barrier properties
over those of the matrix. Considering that the relaxation time of standard clay
platelets (aspect ratio of 200 to 300) is of the order of one hour and that their
dimensions are of the nanometre scale, the dispersion and orientation of clay
during polymer processing is challenging.
The main difficulties for CPNC technology rest in the hygroscopic character
of clay and strong solid-solid interactions. It is a relatively simple task to disperse
clay platelets or lamellae (i.e., to exfoliate them) in water or in water-soluble,
ii
Preamble
polar monomers or oligomers (e.g., amino acids or glycols). However, preparation

of CPNC in a hydrophobic, non-polar high molecular weight polymer, e.g., a
polyolefin or polystyrene, is difficult. The most sensible way to approach the
problem is to consider the process of preparation of CPNCs as blending two
highly immiscible ingredients, i.e., from the perspective of polymer blending and
compatibilisation. As in polymer blends here also one is obliged to ensure good
interaction between the two antagonistic components: hygroscopic clay and
hydrophobic polymer.
The clay of preference is montmorillonite (MMT) with micron-sized particles
formed by stacks of three-layer sandwiches: a layer of Mg and Al oxides inbetween
the silicate layers. These sandwiches of 0.96 nm thickness and an average diameter
of about 100 to 500 nm are the desired reinforcing entities for CPNC. The chemical
constitution of the MMT unit cell offers three types of reactive sites: anions on
the silicate surface, hydroxyl (–OH) groups, and (few) cations on the narrow
edges. Historically, compatibilisation of clay involved forming an ionic bond
between the clay surface and organophilic onium cations, especially quaternary
ammonium ones. The advantage of this is that the chemical reaction not only
changes the hydrophilic clay character into hydrophobic, but also it causes the
clay particles to expand, i.e., to intercalate as a first step to the total dispersion of
the clay platelets, i.e., to exfoliation. The disadvantage is that this chemical
equilibrium process is diffusion controlled hence it may require an excess of
intercalatant and it may take a long time to complete!
‘Compatibilisation’ with at least partial utilisation of the –OH groups has
been carried out using their ability to react with epoxy or acid anhydride groups.
However, since the –OH groups are mostly located on the peripheries of clay
particles, there are few of them readily accessible and the reaction does not
necessarily lead to intercalation/exfoliation. Since the solid-solid interactions are
100 times stronger than liquid-liquid ones, it is imperative that there is good
miscibility between the pre-intercalated clay and the polymeric matrix – if not,
even the initially exfoliated clay platelets may reassemble during processing.
The most reasonable strategy is to prepare exfoliated CPNC using multiple
steps, for example:
1. Swelling sodium montmorillonite in warm water which causes the interlayer
spacing to expand from the initially dry state of 0.96 to about 1.3 nm.
2. Intercalation with cations suitable for the envisaged CPNC organophilic
molecules, onium or Lewis-base types that increase the interlayer spacing to
about 3 to 4 nm and will improve miscibility between the clay and the matrix.
3. Reactive compatibilisation of the organoclay/matrix polymer system, which
results in stable exfoliation of the clay platelets (interlayer spacing larger
than 8.8 nm). This step may not be necessary for highly polar polymers, such
as water-soluble polymers (e.g., polyvinyl pyrrolidone or polyvinyl alcohol),
or even for polyamides, but it is crucial for polyolefins or styrenics.
4. Melt compounding the pre-intercalated clay with matrix polymer. An
alternative strategy is to disperse the product of step (2) in a monomer and
polymerise it. This method has been particularly successful when the
intercalatant used in step (2) can be incorporated into the macromolecular
chain, thus forming what has became known as ‘hairy clay platelets’ with
over one thousand macromolecules end-tethered to the clay surface.
iii
To provide condensed information on the essential elements of CPNC technology,

the book is divided into parts:
Part 1. Introduction – presents a general overview of nanocomposites with
polymeric as well as non-polymeric matrices.
Part 2. Basic elements of PNC technology – focuses on the general methods and
principles of polymeric nanocomposites. It starts with a brief description of PNC
comprising non-clay nanoparticles (e.g., carbon nanotubes, polyhedral oligomeric
silsesquioxanes (POSS), etc.), and then focuses on the clay-containing polymeric
nanocomposites. The individual elements of CPNC technology are discussed,
namely the general characteristics of clays, methods of purification, and the diverse
methods used for intercalation and exfoliation.
Part 3. Fundamental aspects – discusses the pertinent aspects of the
thermodynamics, thermal stability, rheology, crystallisation and mechanical
behaviour.
Part 4. Technology of CPNC – reviews the evolution of CPNC technology for
specific polymeric matrices, primarily using the patent literature. Thus, CPNCs
with individual polymer matrices are reviewed, starting in historical order with
polyamide (PA), polyolefin (PO) and other thermoplastics, then epoxies,
polyurethanes and other thermosets.
Part 5. Performance – discusses selected properties of CPNCs, viz. mechanical,
flame retardancy, and barrier.
Part 6. Closing remarks – summarises the information.
Part 7. Appendices – provides explanations of abbreviations, symbols, and
concepts used in the book.
Part 8. References – contains well over 1,000 references to open and patent
literature up to the beginning of 2004.
Polymeric nanotechnology is in statu nascendi. In consequence, there is a bit
of confusion and uncertainty about its value and the most suitable applications.
Hopefully, this book will help answer some of these questions and in a small way
accelerate wider introduction of this technology.
In 1953, after getting a chemical engineering degree and spending the
obligatory six-month stage as plant engineer, I started graduate studies in the
field of phase equilibria and flow of polymer solutions. To emphasise the
objectiveness of scientific writings it is expected to use the impersonal form.
However, after 50 years in the profession I wish to revert to a more personal
style, dedicating this latest creation (and, as Hermann Mark used to say, the
dearest) to Czeslawa, my Wife, Friend and Supporter of nearly as many years.
Curiously, this book was not planned, but rather it evolved in response to
questions, comments and stories told to me by my colleagues from the Americas,
Asia and Europe. There are too many people to whom I owe my thanks to list
them all, but I wish to express my thanks to a very special trio: to Robert Simha
who has been my mentor and brilliant star to follow for all these 40-odd years of
my post-doc’ing with him, to Osami Kamigaito for introducing me to the
fascinating world of clay-containing polymeric nanocomposites, and to my
colleague and friend of many years, Jørgen Lyngaae-Jørgensen.
Leszek Utracki
Montreal, March 2004
iv
Contents
Contents Volume 1
Preamble .................................................................................................... i
Part 1 Introduction
1.1 General ............................................................................................... 1
1.2 NCs with Ceramic or Metallic Matrix .............................................. 2
1.2.1 Metallic Nanoparticles in Amorphous Matrix ................................ 2
1.2.2 Magnetic Oxides in Silica Nanocomposites .................................... 2
1.2.3 Optoelectronics ............................................................................... 3
1.2.4 Summary on Non-Polymeric NC .................................................... 3
1.3 NCs with Polymeric Matrix .............................................................. 3
1.3.1 PNC Definitions .............................................................................. 6
1.3.2 Methods of Characterisation of CPNCs .......................................... 8
1.3.2.1 X-Ray Diffraction (XRD) .................................................. 8
1.3.2.2 Small Angle Neutron Scattering (SANS) .......................... 11
1.3.2.3 Transmission and Atomic Force Electron Microscopy
(TEM and AFM) ............................................................. 14
1.3.2.4 Fourier Transform Infrared Spectroscopy (FTIR) ............ 15
1.3.2.5 Nuclear Magnetic Resonance Spectroscopy (NMR) ........ 16
1.3.2.6 Other Methods ................................................................ 17
1.3.3 Determination of PNC Properties ................................................. 18
1.3.4 PNC Types and Methods of their Preparation .............................. 18
1.3.5 PNCs of Commercial Interest ........................................................ 18
1.3.6 Journals and Research Groups ...................................................... 29
1.3.7 Historical Perspective .................................................................... 30
Part 2 Basic Elements of Polymeric Nanocomposite Technology

2.1 Nanoparticles of Interest to PNC Technology ................................. 35
2.1.1 General .......................................................................................... 35
2.1.2 Layered Nanoparticles .................................................................. 35
2.1.3 Fibrillar Nanoparticles .................................................................. 38
2.1.3.1 Carbon Nanotubes (CNTs) ............................................. 38
2.1.3.1.1 Origin, Characteristics and Structure .................. 38
2.1.3.1.2 Computation of Potential CNT Properties .......... 41
2.1.3.1.3 Non-Polymeric Applications of CNTs ................. 44
2.1.3.1.4 Sources ................................................................. 46
2.1.3.1.5 PNC with CNTs for Electrical Conductivity ....... 46
2.1.3.1.6 Graphite .............................................................. 47
v
2.1.3.1.7 PNC with CNTs – Thermoset Matrix ................. 48
2.1.3.1.8 PNC with CNTs – Thermoplastic Matrix ............ 50
2.1.3.2 Rod-Like CdSe Nanocrystals ........................................... 54
2.1.3.3 Imogolite ......................................................................... 54
2.1.3.4 Vanadium Pentoxide, V2O5 ............................................. 54
2.1.3.5 Inorganic Nanotubes ....................................................... 55
2.1.4 Other Nanoparticles ...................................................................... 56
2.1.4.1 Spherical or Nearly-Spherical Particles ............................ 56
2.1.4.2 Sol-Gel Hybrids ............................................................... 56
2.1.4.3 Polyhedral Oligomeric Silsesquioxanes (POSS) ............... 58
2.1.4.3.1 Origin and Structure ............................................ 58
2.1.4.3.2 Properties ............................................................. 60
2.1.4.3.3 Sources ................................................................. 66
2.1.4.3.4 Applications ......................................................... 67
2.2 Clays ............................................................................................... 73
2.2.1 General Characteristics ................................................................. 73
2.2.2 Crystalline Clays ........................................................................... 74
2.2.2.1 Kaolins ............................................................................ 74
2.2.2.2 Serpentines ...................................................................... 74
2.2.2.3 Illite Group (Micas) ......................................................... 74
2.2.2.4 Chlorites and Vermiculites .............................................. 76
2.2.2.5 Other Clays ..................................................................... 76
2.2.2.5.1 Glauconite ........................................................... 76
2.2.2.5.2 Sepiolite, Palygorskite and Attapulgite ................ 76
2.2.2.5.3 Mixed-Layer Clay Minerals ................................. 76
2.2.2.6 Smectites or Phyllosilicates .............................................. 76
2.2.2.6.1 Bentonite ............................................................. 79
2.2.2.6.2 Montmorillonite (MMT) ..................................... 80
2.2.3 Purification of Clay ....................................................................... 84
2.2.4 Reactions of Clays with Organic Substances ................................. 85
2.2.4.1 Clay in Aqueous Medium ................................................ 90
2.2.4.1.1 General ................................................................ 90
2.2.4.1.2 Reactions with Edge Cations ............................... 91
2.2.4.1.3 Reactions with –OH Groups ............................... 91
2.2.4.1.4 Reaction with the Silicilic Surface Anions ........... 91
2.2.4.1.5 Stabilisation by Polyelectrolytes .......................... 92
2.2.4.2 Clay Dispersion in Polar Organic Liquids ....................... 93
2.2.4.3 Absorption of Organic Molecules by Organoclay ........... 93
2.3 Intercalation of Clay ....................................................................... 97
2.3.1 Introduction .................................................................................. 97
2.3.2 Intercalation by Solvents and Solutions ....................................... 100
2.3.3 Intercalation by Organic Cations ................................................ 102
2.3.4 Intercalation by Organic Liquids ................................................. 124
2.3.5 Intercalation by Monomers, Oligomers or Polymers ................... 126
vi
Contents
2.3.5.1 Intercalation of Purified Clay by Hydrophobic
Compounds ................................................................... 126
2.3.5.2 Intercalation of Purified Clay by Hydrophilic
Compounds ................................................................... 127
2.3.6 Two-Step Intercalation ................................................................ 135
2.3.6.1 Intercalation by Silylation ............................................. 136
2.3.6.2 Intercalation Utilising Epoxy Compounds .................... 138
2.3.6.3 Intercalation Utilising Organic Anions .......................... 139
2.3.6.4 Intercalation Utilising Macrocyclic Oligomers
(Cyclomers) ................................................................... 139
2.3.7 Intercalation by Inorganic Intercalants ........................................ 140
2.3.8 Melt Intercalation ....................................................................... 142
2.3.8.1 Quiescent (or Static) Melt Intercalation ........................ 143
2.3.8.2 Dynamic Melt Intercalation .......................................... 149
2.3.8.2.1 Melt Mixing ...................................................... 149
2.3.8.2.2 Mixing Equipment ............................................. 150
2.3.8.2.3 Mixing in an Extensional Flow Field ................. 158
2.3.8.2.4 Melt Intercalation in a PA Matrix ..................... 160
2.3.8.2.5 Melt Intercalation in PEG Matrix ..................... 165
2.3.8.2.6 Melt Intercalation in PO Matrix ....................... 165
2.3.9 Temperature and Pressure Effects on Interlamellar Spacing ........ 183
2.3.10 Layered Nanofillers, other than Montmorillonite ....................... 185
2.3.10.1 Kaolinite ........................................................................ 186
2.3.10.2 Micas and Synthetic Micas ............................................ 189
2.3.11 Summary of the Intercalation Methods ....................................... 198
2.4 Exfoliation of Clays ...................................................................... 201
2.4.1 Principles ..................................................................................... 202
2.4.2 Polymerisation in the Presence of Organoclay ............................. 204
2.4.2.1 Monomer Intercalation – PA-6 Nanocomposites .......... 204
2.4.2.2 Monomer Modification – Acrylic-Based
Nanocomposites ............................................................ 206
2.4.2.3 Non-Reactive Intercalated Clays ................................... 209
2.4.2.4 Co-Vulcanisation ........................................................... 210
2.4.2.5 Common Solvent Method – Polyimide Based
Nanocomposites ............................................................ 210
2.4.2.6 Other Methods – Epoxy-Based Nanocomposites .......... 218
2.4.2.7 Other Methods – PU-Based Nanocomposites ................ 224
2.4.2.7.1 Metal Particles ................................................... 224
2.4.2.7.2 Silica .................................................................. 225
2.4.2.7.3 Cadmium Sulfide Particles (CdS) ....................... 225
2.4.2.7.4 Organoclays ....................................................... 225
2.4.3 Melt Exfoliation .......................................................................... 232
2.4.3.1 PA-Based CPNCs ........................................................... 233
2.4.3.2 PO-Based CPNCs .......................................................... 237
vii
2.4.3.3 PCL-Based CPNCs ........................................................ 242
2.4.3.4 Other Systems ............................................................... 245
2.4.4 Functional CPNC ........................................................................ 245
2.4.4.1 Liquid Crystal/Clay Composite (LCC) .......................... 245
2.4.4.2 Biodegradable CPNC with Polylactic Acid (PLA) ......... 246
2.4.4.3 Poly(N-Vinyl Carbazole)/MMT .................................... 252
2.4.4.4 Polydiacetylene .............................................................. 254
2.4.4.5 Clay-Functional Organic Molecules .............................. 254
2.4.4.6 Super-Absorbent CPNC ................................................ 255
2.4.4.7 Emulsion Polymerisation of CPNC ............................... 255
Part 3 Fundamental Aspects

3.1 Thermodynamics ............................................................................ 257
3.1.1 Glass Transition in Thin Films .................................................... 257
3.1.2 Nanothermodynamics ................................................................. 260
3.1.3 Vaia’s Lattice Model for Organoclay Intercalation by
Molten Polymer ........................................................................... 263
3.1.3.1 Introduction .................................................................. 263
3.1.3.2 Entropic Contributions ................................................. 264
3.1.3.3 Interactions ................................................................... 266
3.1.3.4 Consequences of the Model ........................................... 267
3.1.3.5 Model Prediction versus Static Intercalation Results ..... 270
3.1.4 Computations of Polymeric Brushes ............................................ 271
3.1.5 Balazs Self-Consistent Field Approach ........................................ 272
3.1.5.1 Numerical Simulation ................................................... 273
3.1.5.2 Analytical Self-Consistent-Field Theory for
Compatibilised Systems ................................................. 278
3.1.5.3 Phase Behaviour ............................................................ 280
3.1.5.4 Contribution and Potential of the SCF Method ............ 285
3.1.6 Scaling Theory for Telechelic Polymer/Clay Systems ................... 287
3.1.7 Solid Surface Effects on Molecular Mobility ............................... 291
3.1.7.1 Surface Energy of Solids ................................................ 291
3.1.7.2 Polymer Adsorption on Solid Particles .......................... 293
3.1.7.3 Nanoscale Rheology ...................................................... 294
3.1.7.4 Molecular Modelling of Nanoconfined Molecules
(Intercalation) ................................................................ 298
3.1.8 Kinetics of Polymer Intercalation ................................................ 302
3.1.8.1 Macromolecular Diffusion ............................................ 302
3.1.8.2 Stationary Intercalation ................................................. 304
3.1.8.3 Simulation of Melt Intercalation Kinetics ...................... 306
3.1.9 Pressure-Volume-Temperature Dependence for CPNC ................ 309
3.1.9.1 Equations of State (eos) ................................................. 309
viii
Contents
3.1.9.2 Simha-Somcynsky (S-S) Equation of State ..................... 310
3.1.9.3 Extension of S-S eos to Binary Miscible Systems ........... 315
3.1.9.4 Extension of S-S eos to Suspensions .............................. 317
3.1.9.5 Extension of S-S eos to Nanocomposites ....................... 318
3.1.9.5.1 Diluted, Exfoliated CPNC
– Simplified Approach ....................................... 319
3.1.9.5.2 Dilute, Exfoliated CPNC
– Gradient Mobility Approach .......................... 324
3.1.9.5.3 Intercalated CPNC – Concentration Gradient ... 327
3.1.9.5.4 PVT – Concluding Notes ................................... 331
3.2 Thermal Stability ........................................................................... 333
3.2.1 Thermal Stability During Processing ........................................... 333
3.2.2 Flame Retardancy and High Temperature Stability ..................... 339
3.2.3 Photo-Oxidative Stability ............................................................ 340
3.3 Rheology ....................................................................................... 341
3.3.1 Introduction ................................................................................ 341
3.3.2 Multi-Phase Flow Behaviour – An Overview .............................. 342
3.3.3 Rheology and Microrheology of Disc Suspensions ...................... 344
3.3.4 Similarity Between CPNC and Liquid Crystal Flow .................... 347
3.3.5 End-Tethered versus Non-Tethered CPNC .................................. 350
3.3.6 Fourier-Transform Rheology of CPNC ....................................... 356
3.3.7 Rheology of CPNC with PA Matrix ............................................ 356
3.3.7.1 Effects of Moisture ........................................................ 360
3.3.7.2 Strain Effects ................................................................. 363
3.3.7.3 Dynamic Flow Curves ................................................... 363
3.3.7.4 Apparent Yield Stress .................................................... 368
3.3.7.5 Zero-Shear Viscosity and the Clay Aspect Ratio ........... 369
3.3.7.6 Flow-Induced Orientation ............................................. 370
3.3.7.7 Steady-State Flow Curves – Shear History Effects ......... 372
3.3.7.8 Fourier Transform Analysis of CPNC ........................... 376
3.3.8 Rheology of CPNC with PO Matrix ........................................... 376
3.3.9 Foaming of CPNC ....................................................................... 384
3.3.10 Rheology of CPNC with PS and Styrenics Matrix ...................... 387
3.3.11 Rheology of CPNC with Other Polymer Matrix Types ............... 390
3.3.12 Rheology of CPNC – A Summary ............................................... 392
3.4 Nucleation and Crystallisation ...................................................... 395
3.4.1 Introduction ................................................................................ 395
3.4.2 Fundamentals of Crystallisation .................................................. 396
3.4.3 Effects of Clay on Crystallisation of PA-6 Matrix ....................... 399
3.4.4 Clay Effect on Crystallisation of Other Polyamides .................... 408
3.4.5 Crystallisation of PO Matrix ....................................................... 409
ix
3.4.6 Crystallisation of PEST Matrix ................................................... 414
3.4.7 Crystallisation of Syndiotactic PS Matrix .................................... 416
3.5 Mechanical Behaviour ................................................................... 417
3.5.1 Micromechanics of CPNC ........................................................... 417
3.5.2 Prediction of Tensile Strength ...................................................... 426
3.5.3 Fatigue Resistance of CPNC ........................................................ 428
Contents Volume 2
Part 4 Technology of Clay-Containing Polymeric

Nanocomposites
4.1 Thermoplastic CPNC .................................................................... 435
4.1.1 Polyamides (PA) .......................................................................... 435
4.1.1.1 PA-Type Nanocomposites from Toyota ......................... 436
4.1.1.2 PA-Type Nanocomposites from AlliedSignal Inc. .......... 441
4.1.1.3 AMCOL Technology for PA .......................................... 445
4.1.1.4 Other Technologies for the Production of CPNC
with PA Matrix ............................................................. 452
4.1.1.5 Mechanical Exfoliation of PA-Type CPNC ................... 462
4.1.1.6 PA-6/Kaolinite Nanocomposites .................................... 469
4.1.2 Polyolefins (PO) .......................................................................... 470
4.1.2.1 Toyota Patents on PO-Based CPNC .............................. 472
4.1.2.2 Dow Patents on CPNC Technology for PO ................... 476
4.1.2.3 Sekisui Chemical Patent on PO-Based CPNC ................ 481
4.1.2.4 Diverse Technologies for the Preparation of
CPNC with PO-Matrix ................................................. 483
4.1.3 General Methods of CPNC Preparation ...................................... 498
4.1.3.1 Hudson’s Clay Grafting Method ................................... 499
4.1.3.2 Hasegawa et al. Method with Functionalised
Compatibilisers ............................................................. 500
4.1.3.3 CPNC with Amino-Aryl Lactam Clays ......................... 503
4.1.3.4 Ishida’s Method ............................................................. 503
4.1.3.5 Edge Reactions of Clay Platelets ................................... 505
4.1.4 Vinyl Polymers and Copolymers ................................................. 506
4.1.4.1 Polymerisation in the Presence of Clay .......................... 507
4.1.4.1.1 Bulk Polymerisation by the Free Radical
and Coordination Methods ............................... 508
4.1.4.1.2 Emulsion and Suspension Methods ................... 516
4.1.4.1.3 Solution Polymerisation Methods ...................... 526
4.1.4.2 Other CPNC Prepared by Solution Method .................. 530
x
Contents
4.1.4.3 Vinyl-Type CPNC Prepared by Melt Compounding ...... 533
4.1.4.4 Vinyl Polymer Matrix – A Summary ............................. 542
4.1.5 CPNC in Water-Soluble Polymeric Matrix .................................. 543
4.1.6 Thermoplastic Polyesters (PEST) ................................................. 553
4.1.7 Polycarbonate (PC) ..................................................................... 565
4.1.8 Liquid Crystal Polymers (LCP) .................................................... 567
4.1.9 Fluoropolymers ........................................................................... 569
4.1.10 CPNC with High Temperature Polymers .................................... 573
4.1.11 Electroconductive CPNC ............................................................. 576
4.2 Thermoset CPNC .......................................................................... 579
4.2.1 Epoxy Resins ............................................................................... 579
4.2.2 Unsaturated Polyester Resin ........................................................ 588
4.2.3 Polyurethanes .............................................................................. 590
4.2.4 Other CPNC with Thermoset Matrix ......................................... 599
4.3 Elastomeric CPNC ........................................................................ 601
Part 5 Performance
5.1 Mechanical Properties ................................................................... 611
5.2 Flame Retardancy of CPNC .......................................................... 611
5.3 Permeability Control ..................................................................... 618
Part 6 Closing Remarks

6.1 Summary ....................................................................................... 625
6.2 The Future .................................................................................... 627
6.2.1 Composition ................................................................................ 627
6.2.2 Method of Preparation ................................................................ 628
6.2.3 Characterisation and Testing ....................................................... 629
Part 7 Appendices
7.1 General and Chemical Abbreviations ............................................ 631
7.2 International Abbreviations for Polymers ...................................... 640
7.3 Abbreviations for Organic Cations Used as Clay Intercalants ....... 646
7.4 Notations ...................................................................................... 649
7.4.1 Notation Roman Letters ............................................................. 649
7.4.2 Notation – Greek Letters ............................................................. 652
7.4.3 Subscripts .................................................................................... 655
7.4.4 Superscripts ................................................................................. 655
7.4.5 Mathematical Symbols ................................................................ 655
xi
7.5 Dictionary ..................................................................................... 656
Dictionary References .......................................................................... 692
7.6 Companies Active in Organoclay, and/or CPNC Technology ....... 694
Part 8 References
References ..................................................................................... 697
Part 9 Index
Index .................................................................................................... 765
xii
Introduction
Part 1
Introduction
Introduction
1
Introduction
1.1 General
Nanocomposites (NCs) are materials that comprise a dispersion of nanometre-
size particles in a matrix. The matrix may be single or multicomponent. It may
contain additional materials that add other functionalities to the system (e.g.,
reinforcement, conductivity, toughness, etc.). The matrix may be either metallic,
ceramic or polymeric - only the latter type is of interest at present.
Depending on the matrix nature, NCs may be assigned into one of the three
categories:
• Polymeric (PNC),
• Ceramic (CNC),
• Metallic (MNC).
The nanoparticles are classified as:
1. Lamellar,
2. Fibrillar,
3. Tubular,
4. Spherical, and
5. Others.
For the enhancement of mechanical and barrier properties anisometric particles,
especially lamellae are preferred. However, for rigidity and strength fibrillar are
preferred, while for functional NCs (e.g., optical, electrical conductivity) spherical
or other particles have also been used.
Since the aspect ratio of exfoliated, mineral MMT is p = 50 to 2000, the specific
surface is in the order of 750 to 800 m2/g. The reinforcing effect of nanoparticles is
related to the aspect ratio (p) (ratio of the length or thickness to that of the diameter)
and to the particle-matrix interactions. Independent of the actual dimensions, for
p > 500 the reinforcing effects are the same as those of an infinitely large particle.
Furthermore, the anisometric particles start overlapping when the volume fraction
exceeds the ‘maximum packing volume fraction (φm)’ [Utracki, 1995]:
for discs: 1/φm = 1.55 + 0.0598p
for rods: 1/φm = 1.38 + 0.0376p1.4 (1)
For example, Equation 1 predicts that for discs with an aspect ratio of
p = 500 the overlapping volume fraction is φm = 0.00032 (for rods φm = 0.00004).
The overlapping generates a 3D network that in melts is responsible for the yield
stress and in solid state for significant reinforcing effects. Hence a small amount
of anisometric particles leads to large effects.
1
Because of the small size, the nanoparticles are invisible to the naked eye;
hence, they may be used to engender reinforced, but transparent composites
(polymeric or ceramic). On a molecular level, the surface energy of clay particles
is high. As a result, adsorbed molecules have a tendency to be strongly bonded in
the layer adjacent to the clay surface [Horn and Israelachvili, 1998]. This results
in a solid-like behaviour of the 5 to 6 nm thick surface layer and progressive
reduction of viscosity with distance to bulk liquid viscosity at about 100 to
120 nm.
In the absence of antagonistic interactions (such as hydrophilic nanoparticles
in a hydrophobic matrix) the clay/organic liquid system may not require interface
modification. PNCs can be used as a matrix for traditional multiphase systems
(viz. blends, composites or foams), replacing neat polymers.
1.2 NCs with Ceramic or Metallic Matrix

Despotakis [2001] published a review of nanotechnology, where he discussed
the importance of the technology to diverse applications, types and sources of
nanoparticles and commercial developments.
1.2.1 Metallic Nanoparticles in Amorphous Matrix

Iron, cobalt and nickel nanoparticles are obtained either by thermal reduction
under hydrogen of silica-based matrices containing 0.1-20 wt% of metal cations
or by ionic implantation. Their morphologies and properties (electric or magnetic)
depend on the processing conditions.
In the case of hydrogen reduction, two kinds of matrices have been used,
dense sodalime silicate glasses and porous silica gels. In the first case, reduction
is controlled by diffusion of hydrogen inside the glass and yields a broad size
distribution. In the second case, much smaller size distributions occur with particles
exhibiting either a super-paramagnetic or -ferromagnetic behaviour according to
the reduction temperature. Differences are observed between nickel on one part
and iron and cobalt on the other. The last two have a greater tendency to form
silicates and are more sensitive to re-oxidation.
In the case of ionic implantation, the implanted element appears to be both in
metallic and ionised states. The metallic fraction gives rise to nanoparticles with
a super-paramagnetic behaviour. The ratio of metal:oxide depends on the
implantation parameters (dose and energy). Due to the small implantation depth,
further thermal treatments can easily lead to total reduction or to a re-oxidation.
1.2.2 Magnetic Oxides in Silica Nanocomposites

In the area of thin layer magneto-optical recording, apart from metallic multilayer
devices, barium hexaferrite and yttrium garnet are good candidates. An alternative
is to disperse particles inside a transparent matrix. Preliminary studies have been
performed on the system of iron oxide/silica with 20 wt% Fe2O3.
Iron containing gels were prepared from Fe(NO3)3, tetraethyl orthosilicate
(TEOS), ethanol, HNO3, H2O and formamide. After gelation and drying, the
magnetic properties were measured. Below 700 °C, paramagnetic behaviour was
observed, while at higher temperature, ferromagnetic γ-Fe2O3 particles were
formed. Near 1000 °C a new phase, closely related to ε-Fe2O3, was observed
with a coercive field of ca. 7000 Oe.
2
Introduction
1.2.3 Optoelectronics
Semiconductors with carrier lifetime of the order of one picosecond (ps) are necessary
for ultrafast optoelectronic applications. NC semiconductors of GaAs grown by
molecular-beam-epitaxy at low temperatures (LT-GaAs) show a unique combination
of electronic and optoelectronic properties. Implantation of GaAs can result in
properties that are similar to those of LT-GaAs: sub-ps carrier lifetime, high resistivity,
and high electron mobility. Carrier lifetimes as short as 30 fs were determined for the
samples annealed at 500 °C. The short carrier lifetime in high energy ion implanted
GaAs seems to be controlled by the nanoscale morphology, i.e., by the carrier capture/
recombination at the intrinsic point and/or by extended defects.
Another nanocomposite optoelectronic material system comprises Cu-diffused
InP crystals. These contain nanometre-size metallic precipitates that radically
modify the dynamics of photoconductivity and photoluminescence decay.
Furthermore, they significantly reduce the electron and hole trapping time. Spectral
photoresponse measurements evidenced the presence of a well-exposed Urbach-
tail in the sub-band gap radiation absorption, whereas a Z-scan type experiment
has shown an enhancement in both the intensity dependent IR absorption and
the nonlinear refractive index.
1.2.4 Summary on Non-Polymeric NC

The principles of reinforcement and the strategies discussed for the polymer based
NC are valid for the other matrices. Non-polymeric NC systems studied are
listed in Table 1.
1.3 NCs with Polymeric Matrix

In consequence of the outlined fundamentals, PNCs normally require 1-3 vol% of
nanoparticles. They behave as a single phase and single component material. PNCs
exhibit transparency, low density, reduced flammability, low permeability and enhanced
mechanical properties. Furthermore, they may be easily modified by additives and
used replacing neat polymers in polymer blends, traditional composites or foams.
There are several methods of classification of polymeric nanocomposites. For
example, one may consider how many dimensions of the dispersed particles are
in the nanometre range:
1. One dimension. The nanoparticles are in the form of sheets of one to a few
nanometres thick to hundreds to thousands of nanometres long and wide,
hence they can be named as polymer-layered crystal nanocomposites
[Pinnavaia and Lan, 2000a]. These systems are of principal industrial interest
and the main object of this publication. There are a wide variety of both
synthetic and natural crystalline materials that can be used.
2. Two dimensions. These nanoparticles are elongated, viz. fibres, nanotubes or
whiskers, e.g., carbon nanotubes [Ebbesen, 1997] or cellulose whiskers [Favier
et al., 1997, Chazeau et al., 1999]. The polymeric nanocomposites containing
single-walled or multi-walled carbon nanotubes (CNTs) have been extensively
studied. At low loading, they show low density, high mechanical properties,
and electrical conductivity.
3. Three dimensions. These are mainly iso-dimensional spherical particles, for
example, obtained by the sol¯gel methods [Reynaud et al., 1999], and by
polymerisation promoted directly from their surface [von Werne and Patten, 1999].
3
Table 1 NCs with either a ceramic or metallic matrix

Matrix Nano-particles Properties
Silica, SiO2 NiFe2O4 spinel Magnetic properties
Silica, SiO2 Fe By electro deposition
Fe Zn Reaction milled
α-Fe R2Fe14B Magnetic properties
ZrO2 Al2O3 Pore structure stability

Al2O3 ZrO2 Pore structure stability
Metal particles Gold shells Blocking properties
Fe-oxides Cr-oxides Magnetic properties
Al2O3 SiC Creep, strength, toughening
Di-alkyl amine Exfoliated MoS2 High electrical conductivity
Al2O3-ZrO2 SiC Microstructure and performance
(electrical conductivity, refractoriness,
wear and impact resistance) depend
on the calcinating temperature
SiO2 ZnO Sol-gel method
Alumina, Al2O3 SiC Improved abrasion resistance
Fe/Cr Cr2O3 Magnetic properties
Al2O3 SiC or Y2O3 (5 Sintering
vol%)
SiC BNx SiC grain boundary, oxidation
resistance and mechanical properties
control by BNx nanotubes
γ-Al2O3 Amorphous SiO2 Reaction sintering

coated
Al2O3 ZrO2 Room temperature electrostatic self
assembly
Matrix (e.g., Carbon nitride Preparation for use in lubricants,
anodic alumina) nanofibres and catalyst supports, gas storage, and
nanospheres, C3N4 drug delivery
Alumina, Al2O3 C Structure and superplasticity
Pb-zirconate- PbS Piezoelectric and pyro-electric
titanate behaviour
γ-Fe2O3 Ag Negative magnetization
Si3N4 20 vol% SiC Strength, structure, properties
4
Introduction
Table 1 Continued...
Matrix Nano-particles Properties
Al2O3 Ni or Ni-Co Pressureless sintering, processing,
properties
CoPt Ag For high density recording media
Metal matrix Nanosize Structure-related mechanical
C-fibres performance
Al Cu Jet vapour deposition
Al2O3ZrO2 BaTiO3 Bio-applications for bone grafting
The materials are either structural or functional. In this book the focus is on the
former. To this date, it is primarily the structural nanocomposites based on layered
silicates, i.e., clays (CPNC), which have been commercially produced. Clays are easily
available and their intercalation methods have been known since the 1930s [Theng,
1974]. Owing to the nanometre-size particles, CPNC show markedly improved
mechanical, thermal, optical, and physicochemical properties when compared with
neat polymers or their composites [Kojima et al., 1993a]. The improvements include
moduli, strength, heat resistance, barrier properties, flammability, etc.
Nanometre-scale structures are frequently found in biological materials with
impressive performance [Mark, 1996]. For example, bone has a structure of 4 nm
thick hydroxyapatite crystals dispersed within a collagen matrix. In the desire to
synthesise analogues to biological systems several methods for constructing
synthetic composites with a degree of nanometre-scale organisation have been
tried. Thus, elongated ceramic particles have been precipitated within polymer
matrices by drawing the polymer during the precipitation reaction, silica and
CdS have been precipitated in liquid crystal polymer (LCP) [Kovar and Lusignea,
1988; Nelson and Samulski, 1995], metals have been electrodeposited inside the
pores of commercial nanopore membranes [Martin, 1996], and polymers have
been grown within the cavities of layered inorganic structures and zeolites [Okada
and Usuki, 1995; Frisch and Mark, 1996]. Furthermore, an organic-inorganic
nanocomposite was formed by dissolving the inorganic polymer (LiMo3Se3)n in
a conventional monomer acting as the solvent, then polymerising the matrix in
situ [Golden et al., 1996].
The above mentioned methods are well suited for the preparation of a
particular composition, but they are not versatile enough to offer good control
over nanometre-scale architecture and composition in all resins. Several strategies
have been developed for constructing ordered nanocomposites with well-defined,
tunable nanoarchitecture and the ability to be used in a wide variety of polymers:
1. Addition of nanoparticles, especially anisometric ones, viz. nanofibres,

nanotubes or nanoplatelets. Owing to the expanding industrial interest, the
present text will focus on this type of PNC, in particular the ones with the
clay platelets.
2. Copolymerisation or grafting polymeric chains with monomers having bulky
groups, viz. the polyhedral oligomeric silsesquioxanes (POSS) [Lichtenhan
5
et al., 1995; Lichtenhan, 1996; Haddad and Lichtenhan, 1996; Lichtenhan

and Schwab, 2001; Le´sniak, 2001].
3. Preparation of ordered nanoscale structures using the LCP technology [Gin
et al., 1998].
4. Sol-gel methods [Mauritz et al., 1995; Wen and Wilkes, 1996; Deng et al.,
1998].
5. Hydrothermal method [Quian et al., 2000].
6. Others.
Polymer nanocomposites are emerging as a new class of industrially important
materials. At loading levels of 2-3-vol%, they offer similar performance to
conventional polymeric composites with 30-50 wt% of reinforcing material. Note
that high filler loading in the latter materials causes an undesirable increase of
density; hence heavy parts, decreased melt flow, and increased brittleness.
Furthermore, the classical composites are opaque with often a poor surface finish
– these problems are absent in PNCs.
The clay-containing PNC, a CPNC, offers several advantages over the matrix
polymer or classical composites. The main improvements are in: modulus, impact
strength, heat resistance, dimensional stability, barrier properties (for gases and
liquids), flame retardance, optical properties, ion conductivity, thermal stability,
etc. Since these advantages are achieved at low clay loading the density is virtually
unaffected and the CPNC may be used to replace the neat polymer in blends,
composites or foams. Synergistic effects in these applications have been reported.
Current consumption of PNC is only a few kilotons per annum, projected to
increase by 2009 to 500 kton/y. The cost differential between the neat matrix
and its PNC is about 10 to 15%. CPNC’s main market is in the transport
industries, with growing demand for packaging, appliances, building and
construction, electrical and electronic, horticulture, power tools, etc.
Several reviews on nanoparticles, clays and polymeric nanocomposites are
available, viz. on the chemistry of clays [van Olphen, 1977; Wittingham and
Jacobson, 1982; Newman, 1987], a short one on clay-containing PNC [Giannelis,
1998], on flammability [Gilman et al., 1998; Gilman et al., 1998], a large and
well written one [Alexandre and Dubois, 2000], on clay-containing PNC [Ruban
et al., 2000], on synthetic clays and resulting PNC [Carrado, 2000], on
nanoparticles [Shipway et al., 2000; Ajayan et al., 2003], and more recent ones
on CPNC [Utracki and Kamal, 2002; Okamoto, 2003], etc. Several edited
proceedings of nanocomposite symposia are also available, viz. [Utracki and Cole,
2002; Krishnamoorti and Vaia, 2002; Hahn, 2002; Komarneni, 2002; Laine,
2001; Lyon, 2001; Nakatani, 2001; Benedek et al., 2001; Komarneni et al., 1997;
Komarneni et al, 2000; Pinnavaia and Beall, 2000], etc.
1.3.1 PNC Definitions

Clay-containing polymeric nanocomposite (CPNC): a polymer or copolymer
having dispersed exfoliated individual platelets obtained from an intercalated
layered material.
Compatibilisation: Process of modification of the interfacial properties in
CPNC, resulting in formation of the interphase, formation and stabilisation of
the desired morphology.
6
Introduction
Exfoliated layered material: individual platelets (of an intercalated layered

material) dispersed in a carrier material or a matrix polymer with the distance
between them > 8.8 nm. The platelets can be oriented, forming short stacks or
tactoids or they can be randomly dispersed in the medium.
Exfoliation: converting intercalate into exfoliate.
Intercalant: material sorbed between platelets (of the layered material) that
binds with their surfaces to form an intercalate. Often the intercalant is an onium
salt, viz. C18H37-NH3+Cl-, that bonds ionically with platelet anion. Intercalation
may involve organic or inorganic salts, monomers, polymers, etc.
Intercalated material: layered material with organic or inorganic molecules
inserted between platelets, thus increasing the interlayer spacing between them
to at least 1.5 nm.
Intercalating carrier: a carrier comprising water with or without an organic
solvent used to form an intercalating composition capable of achieving
intercalation of the layered material.
Intercalating composition: a composition comprising an intercalant, an
intercalating carrier for the intercalant polymer and layered material.
Intercalation: forming an intercalate.
Layered material: synthetic or mineral inorganic compound, such as smectite
clay, formed of adjacent layers with a thickness, for each layer, of 0.3-1 nm.
Interlayer spacing: also known as d-spacing, d001 or basal spacing is the mineral
thickness (in MMT = 0.96 nm) and the galley thickness, i.e., the thickness of the
repeating layers as seen by XRD.
Interlayer thickness = d-spacing less the mineral layer thickness.
Li-MMT: lithium montmorillonite.
Miscibility: polymer system, homogeneous down to the molecular level,
associated with the negative value of the free energy and heat of mixing, ΔGm ≈
ΔHm ≤ 0, and ∂2ΔGm/∂φ2>0. Operationally, it is a thermodynamically stable CPNC,
where the clay platelets are well dispersed into a homogeneous polymeric matrix.
MMT: montmorillonite.
Na-MMT: sodium montmorillonite.
H-MMT: protonated MMT, etc.
Matrix polymer: thermoplastic, thermoset, or elastomeric polymer in which
the intercalate or exfoliate is dispersed to form a clay-based polymeric
nanocomposite (CPNC).
Nanocomposite (NC): a matrix material (metallic, ceramic or polymeric in
nature) having dispersed particles, with at least one dimension that does not
exceed 10 nm.
Platelets: individual layers of the layered material.
Polymeric nanocomposite (PNC): a polymer or copolymer having dispersed
in it nanosized particles, viz. platelets, fibres, spheroids, etc.
Short stack or tactoid: intercalated or exfoliated clay platelets aligned parallel
to each other.
Spacing: Two measures of spacing are used: interlayer spacing, (also known
as d-spacing, d001 or basal spacing) and interlamellar spacing. The former
7
comprises the latter plus the platelet thickness. For example for MMT: d001 =
interlamellar spacing + 0.96 (nm).
1.3.2 Methods of Characterisation of CPNCs
1.3.2.1 X-Ray Diffraction (XRD)

The key to CPNC performance is the extent of intercalation and exfoliation, XRD
is the principal method that has been used to examine this. One example of the
wide angle X-ray scattering data obtained for polystyrene (PS)/clay systems
[Tanoue et al., 2003] is shown in Figure 1 as the scattering intensity versus 2θ,
where θ is the angle of diffraction. Within the range of 2θ ≤ 10° the XRD spectrum
of PS is featureless. Incorporation of 4.8 wt% of intercalated organoclay shows
a distinct peak and a shoulder. Their positions and shapes provide information
on the structure of the diffracting species, the organoclay. The presence of multiple
peaks in XRD spectra is quite common - it often originates from different
organoclay structures and its incomplete change during incorporation in a
polymeric matrix [Polzsgay et al., 2004].
The instruments that measure X-ray scattering are divided into the more
common wide angle and newer small-angle X-ray scattering machines, WAXS
and SAXS, respectively. It is common to consider the scattering angle 2θ = 2° as
a boundary between these two, but newer WAXS instruments frequently are
able to provide reliable scattering profile down to 2θ = 1°. The interlayer spacing,
d001, is commonly determined from the XRD spectrum as arbitrary intensity
versus 2θ. The spacing is then calculated from Bragg’s law:
d00n = nλ/(2sinθ) (2)
where n is an integer, θ is the angle of incidence (or reflection) of the X-ray beam,
and λ is the X-ray wavelength – most X-ray machines use Cu-Kα1 radiation with
λ = 0.1540562 nm. For the principal reflection, n = 1, the dependence given by
Equation 2 is shown in Figure 2. It is worth noting that, within the range of
interest for CPNC (2θ = 1-12°), there is a straight-line relation between d001 and
1/(2θ):
1/2θ = –0.00012773 + 0.11331d001
or: d001 = 0.0011273 + 8.8253/2θ; R = 1.0000 (3)
where R is the correlation coefficient.
The peak position and the interlayer spacing related to it is one part of the
information provided by XRD measurements. The intensity of the diffraction
peak and its dependence on the concentration of scattering particles yields another.
Cullity and Stock [2001] in their monograph on X-ray diffraction derived the
following relation for the intensity (I) of the diffraction peak of α-substance
mixed with β-substance:
Iα = Kφα/[φα(μα - μβ) + μβ] (4)
where φα is the volume fraction of the diffracting substance α, and μ is the mass
absorption coefficient. Depending on the relative magnitude of μα and μβ within
the full range of concentration Equation 4 predicts additivity, as well as positive
or negative deviation from it. However, within the limited range of clay
concentrations used in CPNC, the relation may be simplified to read:
8
Introduction
Figure 1 XRD of PS and PS with 4.8 wt% of Cloisite® 10A (clay treated with
dimethyl benzyl hydrogenated tallow ammonium chloride (2MBHTA)) [Tanoue et
al. 2003].
Figure 2 Bragg’s law dependencies for Cu-Kα1 radiation with λ = 0.1540562 nm.
The straight line is given by Equation 3; correlation coefficient R = 1.0000.
Iα = K´wα Ineat α (5)

where wα is the weight fraction of substance α.
It has been frequently observed that during exfoliation (especially during the
mechanical exfoliation of intercalated clay in a PO matrix) the position of the
XRD peak remains at the same angular position 2θ, but it broadens and its
9
intensity decreases. Parallel with these changes there is an enhancement of the

CPNC performance. It can be postulated that in this case the exfoliation process
involves breakage of intercalated stacks and/or peeling of individual platelets or
short stacks. On this basis Ishida and co-workers [2000] used XRD to calculate
the degree of exfoliation XE:
XE = 100 × [1 – A/A0] (6)
where A and A0 are the area under the XRD peak for the PNC and for the
mixture with intercalated clay, respectively. Replacing in Equation 6 the intensity
ratio of Equation 5 by the area under the peak ratio, is motivated by an additional
assumption that during the progressive dispersion process many stacks slightly
change the interlayer spacing hence the observed broadened peak is an envelope
over a family of peaks having similar interlayer spacings.
However, there are several possible sources for the XRD peak broadening in
a CPNC – one being the assumed above existence of a variety of clay stacks with
a range of similar d001 spacing. Another mechanism of peak broadening is based
on the imperfections in the crystalline lattice of m-layers of clay platelets forming
a stack t = (m – 1) × d001 thick. Another mechanism of peak broadening is based
on the imperfections in the crystalline lattice of m-layers of clay platelets forming
a stack t = (m – 1) × d001 thick and scattering the X-rays at angles θ1 and θ2.
Because of the small angle difference between θ1 and θ2 the destructive interference
of reflected beams is incomplete [Cullity and Stock, 2001]. Calculation leads to
the following formula credited to Scherrer:
t = kλ/(B1/2cosθ) ; k ≅ 0.9 (7)
where θ ≅ (θ1 + θ2)/2 is the angle of X-ray beam incidence corresponding to the
peak position, λ is the X-ray wavelength, and B1/2 ≅ θ1 - θ2 is peak width (in
radians) at half peak height (Imax/2). From Equation 7 the number of clay platelets
per average stack with the interlayer spacing d001 is:
m = 1 + t/d001 (8)
Note that in this interpretation the peak broadening is caused by crystalline defects
in individual platelets within the stack having about constant interlayer spacing,
and not by overlapping peaks that correspond to stacks with different interlayer
spacing.
The development of technology often requires more precise information on
the interlayer spacing than that provided by WAXS. With growing frequency
SAXS and small angle neutron scattering (SANS) are being used within the effective
scattering angle down to 2θ = 0.05 or the characteristic diffracting distance of
about 180 nm.
Thus, for example, Bafna et al. [2003] used SAXS and WAXS to study the
effects of addition of maleated polyethylene (PE-MA) on PE/MMT structural
parameters. By performing scattering experiments on specimens oriented in three
orthogonal directions, the authors managed to determine not only the interlayer
spacing, but three-dimensional (3D) orientations of six structural features, viz.
size of tactoids (ca. 120 nm), organoclay (d002 ≅ 2.4 to 3.1 nm), spacing in
undispersed clay (d002 ≅ 1.3 nm), clay (110) and (020) planes, thickness of PE
crystalline lamellae (d001 ≅ 19 to 26 nm), and polymer unit cell (110) and (200)
planes.
10
Introduction
1.3.2.2 Small Angle Neutron Scattering (SANS)

Small-angle neutron scattering (SANS) may also be used to determine d001 spacing
in PNC. The method is more sensitive, permitting the range of measurements to
be extended to small angles, thus to large spacings. Furthermore, it is readily
adapted to different specimens and provides additional structural information
not available from XRD.
As far as nanocomposites are concerned, SANS was initially used to study
structure and interparticle interactions in aqueous dispersions of MMT, hectorite
and kaolinite [Ramsay and Lindner, 1993; Brown et al., 1998]. Measurements
were carried out on a water dispersion of MMT under static conditions and
shear flow in a Couette-type cell. At concentration w = 5 to 65 g/L and low ionic
strength, the suspensions were thixotropic. The self-organised structures were more
extensive when the MMT particles were more anisotropic. Here, under no-flow
condition, SANS detected preferential platelet alignment at distances larger than
d001 = 10.3 nm. Under low shear stress, MMT platelets showed preferential
alignment in the direction of flow. This orientation occurred over a large range
of deformation rates, giving rise to anisotropic scattering; furthermore, spatial
correlations persisted. At shear rates exceeding 104 s-1 the ordered platelet
structure was destroyed and only preferential alignment was observed. Shear
alignment was also observed in dispersions of kaolinite. As before, particle
alignment increases with flow rate.
More recently, SANS has been used to study the structural aspects of clay
dispersions in water-soluble polymers. Jinnai and co-workers [1996] investigated
a four-component clay-polymer-salt-water system, consisting of polyvinyl methyl
1/ 2
ether (PVME; Mn = 18 kg/mol, radius of gyration rg2 ≅ 5 nm), Na-vermiculite
[Si6.13Mg5.44Al1.65Fe0.50Ti0.13Ca0.13Cr0.01K0.01O20(OH)4Na1.29], n-butyl-ammonium
chloride, and heavy water. A single vermiculite crystal was placed in the cell and
the concentration of PVME changed. It has been known [Walker, 1960] that
depending on the temperature the system has two structures, separated by Tc = 14 °C:
below Tc vermiculite shows uniform swelling (gel phase) with d001 of about 12 nm
while above this temperature the gel structure degenerates into local tactoids
with d001 of about 2 nm (tactoid phase).
The neutron diffraction experiments were carried out at the Japan Atomic
Energy Research Institute using the SANS-J instrument. The study showed that
addition of PVME had no effect on the phase transition temperature between the
tactoid and gel phases. Furthermore, in the tactoid phase the spacing of 1.94 nm
indicated absence of polymer diffusion into the interlamellar galleries. However,
in the gel phase the clay plates were found to be better aligned and more regularly
spaced than in the system without the polymer. The diffraction pattern from the
polymer-containing sample was sharper. It showed pronounced first-order and
strong second-order diffraction peaks, which is rare for an aqueous sample. In
the gel phase, d001 decreased with polymer content, from 12 to 8 nm.
The conformation and location of the polymer chains in these mixtures were
not unequivocally determined. In the gel phase PVME macromolecules can fit in
the d001 = 12 nm interlayer space. They are either: (A) adsorbed onto the surface
of a single plate, in a flattened configuration, (B) in the supernatant fluid
surrounding the gel, or (C) they form bridges between two adjacent clay platelets.
1/ 2
In the tactoid phase it is not possible for a polymer with rg2 ≅ 5 nm to exist as
free chains inside the tactoids.
11
Similar results were obtained when PVME was replaced by polyethylene glycol
1/ 2
(PEG; Mn = 18 kg/mol, radius of gyration rg2 ≅ 5 nm) [Hatharasinghe, 1998].
Thus, the new system consisted of n-butyl ammonium vermiculite, PEG, n-butyl
ammonium chloride, and heavy water. In analogy to the system with PVME,
here also as PEG volume fraction increased from 0 to 0.04 the d001 spacing
(obtained by SANS) decreased from 12 to 6.5 nm (see Figure 3). However, the
addition of polymer had no effect on the phase transition temperature between
the tactoid and gel phases of the clay system, Tc = 13 ± 1 °C. As for the other
system, the PEG presence in the gel phase made the clay plates more parallel and
more regularly spaced.
The d001 spacing versus PEG volume fraction, φ, was fitted to the hyperbolic
relation with three empirical parameters ai:
d001 = a0 + a1/(a2 + φ) (9)
The least squares fit to PEG data yielded the following parameter values:
ao = 3.896 ± 1.793; a1 = 0.1363 ± 0.0995; and a2 = 0.0163 ± 0.0091 with the
standard deviation σ = 0.571 and the correlation coefficient squared, r2 = 0.9983. In
Figure 3 the data from the previously studied system with PVME are also shown.
The dependence is similar, indicating that the two chemically different polymers
bring about a similar contraction of the gel phase.
It is noteworthy that the authors generalised their d001 vs. φ data using an
exponential, instead of hyperbolic dependence:
d001 = a0 + a1 exp{-a2φ} (10)
Figure 3 Interlayer spacing of n-butyl ammonium vermiculite vs. volume fraction

of the added water-soluble polymer: circles - PEG, squares - PVME. The solid line
was calculated by the least-squares fit of PEG data to Equation 9.
[Data: Jinnai et al., 1996; Hatharasinghe et al., 1998].
12
Introduction
The least squares fit to PEG data yielded the following parameter values:
ao = 6.123 ± 0.743; a1 = 6.148 ± 0.737; and a2 = 74.825 ± 24.304 with the standard
deviation σ = 0.513 and the correlation coefficient squared, r2 = 0.9986. Thus, Equations
9 and 10 seem to provide similarly good descriptions for the observed phenomenon.
However, they give quite different limiting values for infinite dilution of clay platelets
at φ → 0, viz. d001 = 12.26 and 80.97 nm, respectively. As can be judged from the data
in Figure 3, the limiting value predicted by Equation 10 is not acceptable.
The explanation for the mechanism responsible for this reduction of
interlamellar spacing should be consistent with the structure of macromolecules
in suspension as well as with the rapid phase transition from gel to tactoid. In
aqueous medium, n-butyl ammonium vermiculite is expected to form hydrogen
bonds with surrounding water. In the absence of polymer, the interlamellar spacing
is about 11 to 12 nm. Since water monolayer thickness is about 0.28 nm, the
large interlamellar spacing most likely originates from the electrostatic repulsion
of butyl ammonium chloride ions associated head-to-tail with butyl ammonium
vermiculite salt. Addition of a polymer seems to cause progressive extraction of
the ionic species from the interlamellar species. It has been assumed that, because
a large number of solvent molecules must be desorbed to accommodate a single
polymer molecule, the translational entropy so gained by the system provides a
strong driving force for polymeric adsorption. However, this assumption may
not be correct in the aqueous media, where the hydrogen bonding of water
molecules is energetically preferred.
SANS has been used by Carrado and co-workers [1996] to monitor the
structural changes in synthetic hectorite upon hydrothermal crystallisation in
the presence of polyvinyl alcohol (PVAl). It was found that the PVAl coats the
small initially formed silicate particles, hindering their further growth. However,
upon removal of the polymer no change has been observed in the extended
inorganic network. Similarly, Muzny and co-workers [1996] monitored the
dispersion of synthetic hectorite in a polymer matrix. The organically modified
clay platelets were dispersed in polyacrylamide (PAA). The studies showed that a
homogeneous dispersion was achievable only with a large excess (equivalent to
five times the cationic exchange capacity (CEC) of the silicate or higher) of the
organic cationic intercalant.
Krishnamoorti and Giannelis [1997] studied the linear viscoelastic behaviour
of end-tethered poly-ε-caprolactone (PCL) with MMT intercalated with ω-amino
dodecyl acid (ADA). The dynamic shear moduli, storage (G´) and loss (G´´),
were determined at small amplitude on either freshly loaded specimens, or
pre-sheared at large amplitude. The large-amplitude oscillatory shear significantly
reduced the linear viscoelastic response, decreasing the low frequency value of
G´´ by one and G´ by two decades. Such a sharp decrease of the signal means that
in the sheared specimens the polymeric matrix controls the CPNC flow behaviour;
hence the MMT platelets are oriented. The alignment was confirmed by SANS.
Similar effects have been reported in several rheological studies (see Section 3.2)
as well as for injection moulded CPNCs [Kojima et al., 1994; 1995].
Ho and co-workers [2001] studied SANS of clay suspensions in non-aqueous
media. The stated aim was to understand and optimise the potential processing
conditions for clay dispersed in a polymeric matrix. As a model system the authors
used Na-MMT (Cloisite ® Na + ) and MMT intercalated with 2-methyl
2-hydrogenated tallow ammonium chloride (MMT-2M2HT; Cloisite® 15A or
C15A) from Southern Clay Products (SCP). Prior to experiments, Na-MMT was
13
fractionated and from Cloisite® 15A excess of the intercalant was extracted with
hot ethanol. The purified samples were dried in a vacuum oven at room
temperature for 3 days. The clays were then dispersed in chloroform, benzene,
toluene, p-xylene, cyclohexane and octane.
Both as-received and purified samples were studied. The scattering profiles
and dispersion behaviour in organic solvents of the as-received and purified C15A
were significantly different, confirming that the organic modifier was present in
excess. However, in both cases the clay platelets were fully exfoliated in chloroform
while they were only swollen in benzene, toluene and p-xylene. The scattering
profiles indicated that the swollen tactoids of purified clay were thinner, and
therefore more numerous. Neither the purified nor the as-received clay showed
any temperature effect on scattering. According to atomic force microscopy (AFM)
the average diameter of C15A platelets was in the range of 0.4-1.0 μm, giving the
aspect ratio: p = 400 to 1000.
The SANS experiments at the wave vector q ≡ (4π/λ) sin(θ/2) = 0.004 to 0.517 Å-1
(θ is the scattering angle) were carried out at the National Institute of Standards
and Technology (NIST). The measurements were conducted using either dry clay
powders or dispersions of C15A in deuterated organic solvents, with Na-MMT in
a solution of deuterated/protonated water (D2O/H2O). For well-dispersed, individual
thin circular disks, theory predicts that isotropic, total coherent scattered intensity
depends mainly on the platelet thickness, diameter, orientation, concentration, and
the scattering contrast between the solvent and the clay. The presence of the intercalant
as well as formation of stacks could also be accounted for.
In agreement with the WAXS data the interlayer spacing of purified C15A was
determined by SANS as d001 = 2.43 nm. The d001 spacing in dry Na-MMT was found
to be d001 = 0.99 nm. Both SANS and WAXS data indicated that at a concentration of
ca. 0.5 to 4 wt% in deionised water, Na-MMT platelets were fully exfoliated. The
scattering intensity varied with 1/qn, with n ≅ 2.2. This value is consistent with
calculations assuming total exfoliation of platelets, which are 1 nm thick and
have diameter of about 600 nm. For C15A in an organic solvent the thickness of
the tallow layer depended on the solvent, increasing with the solvent solubility
parameter from 1.61 nm (for toluene or xylene) to 1.86 nm (for chloroform).
Correspondingly, the calculated average number of platelets in the stack varied
from 3 to 1, hence in chloroform the organoclay was fully exfoliated.
1.3.2.3 Transmission and Atomic Force Electron Microscopy (TEM and AFM)
At limiting low scattering angle, 2θ ≅ 2°, the XRD/WAXS scattering intensity and
resolution decrease, i.e., the method is not useful for spacing: d > 8.8 nm. Within
this range TEM may be used to determine the extent of intercalation/exfoliation.
However, TEM also offers a direct method for confirming the XRD data
(micrograph in Figure 4(a)) and with growing frequency it is being used at low
magnification (micrograph in Figure 4(b)) to check on the uniformity (or lack) of
clay stack dispersion in polymeric matrix. The low magnifications are also useful
to check the purity of clay, e.g., the presence of non-layered particles such as
quartz.
Dennis and co-workers [2000; 2001] proposed a method for quantification
of TEM images. Micrographs with magnification of 130,500 were cover with a
mask in which twelve squares of 1 × 1 inch (2.5 cm × 2.5 cm) were cut out. The
degree of dispersion was expressed as the number of clay platelets per square
inch. This dispersion measure was found to correlate well with the tensile modulus.
14
Introduction
(a)
(b)
Figure 4 TEM of intercalated organoclay in PS matrix: (a) magnification 150k, (b)

4.1k [Tanoue et al., 2003a].
Atomic force microscopy (AFM) has been used mainly in a tapping mode at
the cantilever’s frequency of 300 kHz and amplitude of 50-100 nm. The difference
between the clay modulus and that of a polymer results in good image resolution.
Starting in 1990, high resolution TEM (HRTEM) became the preferred tool
for the determination of structure, in particular of crystalline nanoparticles, viz.
carbon (CNT) or boron nitride nanotubes (BN-NT). The magnification in
HRTEM is x106 or better, with resolution of 0.1 nm (JEOL 4000EX, 400 kV,
Cs = 1 mm, focus spread = 8 nm, divergence angle = 0.7 mrad) [Gavillet, 2001].
1.3.2.4 Fourier Transform Infrared Spectroscopy (FTIR)

Since 1964 FTIR has been used to study the hydration of bentonite, and the
formation of an electrical double layer between the platelets. Significant differences
in the silicate stretching region, νSi-O = 1150 to 950 cm-1, are related to water
(H2O or D2O) and hydrated cation (Na+, K+,Ca+2, etc.) content, which in turn is
related to the interlayer spacing between the clay platelets [Shrewring et al., 1995].
Yan and co-workers [1996] have shown that in hydrated MMT νSi-O exponentially
decreases with the clay-to-water ratio, all the way to exfoliation. Oxidation or
reduction of the metallic ions within the octahedral clay layers introduces changes
to CEC clay hydration and swellability, hence the FTIR spectrum [Yan and Stucki,
1999].
The use of FTIR for characterisation of CPNCs is more recent. Initially, it has
been used in studies of the polymer matrix morphology, e.g., conformation and
crystallisation behaviour of sPS [Wu et al., 2001] or α- to γ-crystalline form
transition of PA-6 [Wu et al., 2002]. However, the Si-O stretching vibration has
been found to be very sensitive to long range interactions caused either by imposed
15
stress [Loo and Gleason, 2003], or expansion of the interlayer spacing [Cole,
2003]. The advantage of the spectroscopic methods, FTIR and Raman, is that
along with XRD they are applicable to the intercalated system, and stretch to
exfoliated CPNC that do not scatter X-rays.
To examine the interactions between the clay platelets, the intercalating agent
and polymer, FTIR provides important information. By comparing the
experimental and calculated spectra the type and intensity of interactions can be
identified [Aranda and Ruiz-Hitzky, 1999]. The method has also been used to
analyse the thermal decomposition of ammonium intercalants during the melt
compounding method of CPNC preparation [Tanoue et al., 2003]. More details
are provided in Section 3.2.
1.3.2.5 Nuclear Magnetic Resonance Spectroscopy (NMR)

Solid-state 1H, 13C, 15N and 29Si magic angle spinning (MAS) NMR spectroscopy
at frequencies 100.40, 30.41 and 79.30 MHz, respectively has been used. The
tensile modulus (E) was found [Usuki et al., 1995] to be proportional to the chemical
shift (Cs; in respect to tetramethyl silane) of 15N in ammonium-clay complex with
the slope: dE/d(Cs) = 0.1097 (GPa/ppm). The chemical shifts provide information
about the degree of clay hydration, the interactions engendered by intercalation
and the structure of clay-organic matrix complexes.
NMR has also been used to determine PEG chain dynamics within the interlayer
spacing of synthetic mica/MMT [Schmidt-Rohr and Spiess, 1994]. According to
Aranda and Ruiz-Hitzky [1992] the intercalation of MMT by PEG increased the
interlayer spacing by Δd001 = 0.8 nm. Thus, the polymer conformation within these
interlamellar galleries may be either a 0.8 nm diameter helix, or two chains in a
planar zigzag conformation. The former was deemed to be more probable.
Measurements of the 1H NMR line widths and relaxation times across a large
temperature range were used to determine the effect of bulk thermal transitions
[Kwiatkowski and Whittaker, 2001]. The 13C cross-polarity/magic angle spinning
NMR spectra of PEG within the nanocomposite showed that the type of motion
being experienced by these chains is the helical jump motion of the α-transition,
thus the same as within the crystalline phase of neat PEG. The short proton spin-
lattice relaxation time in the rotating frame, 1H T1ρ, measured across a wide
range of temperatures by 1H NMR provided additional evidence that these chains
undergo helical jump motion. Measurements of 1H NMR spectra across a wide
temperature range have confirmed that large amplitude motion of the PEG chains
within the montmorillonite nanocomposite persist below the Tg of neat PEG.
There was no observed change in the rates of relaxation at the transition
temperatures expected for neat PEG.
Solid-state NMR, both proton and 13C, was used to study CPNC with PA-6 as
matrix [VanderHart et al., 2001]. The nanocomposites with 5 wt% organoclay
were generated either by blending or by in situ polymerisation. The systems
contained mineral MMT having non-stoichiometric amounts of Mg2+ and Fe3+
ions substituted into the octahedral, central layer of the clay platelet. The presence
of Fe3+ ion contaminants in the MMT induced paramagnetic properties. The
paramagnetic contribution to the proton longitudinal relaxation time (T1H) is a
function of the field and Fe3+ concentration in the clay. These paramagnetic
properties can be used to determine the hard-to-get information on CPNCs, viz.
the degree of dispersion, the stability of intercalant, etc. Evidently, NMR can also
16
Introduction
provide information on the preponderance of α- and γ-crystalline phases of PA-6

in CPNCs. The α-crystallites are characteristic of the neat PA-6, while γ-crystallites
are formed in the presence of clay platelets.
The Fe3+ induced paramagnetism of MMT and the resulting spin-diffusion-
moderated reduction in longitudinal proton relaxation time, T1H, may be used to
rank the degree of clay dispersion in CPNCs, and to investigate morphological
stratification of the PA-6 α- and γ-crystallites with respect to the clay surface. It
was found that variations in T1H correlate well with TEM measurements of the
clay dispersion. The chemical stability of dimethyl dihydrogenated tallow
ammonium ion (2M2HTA) used as MMT intercalant was also investigated.
During the organoclay compounding with PA-6 at 240 °C most of the intercalant
decomposed, releasing a free amine with one methyl and two hydrogenated tallow
substituents. According to the authors, the combination of temperature and shear
stress in blending caused decomposition. However, judging by T1H, the CPNCs
with the best dispersion of clay also had the most extensively degraded intercalant.
The polarity of PA-6 macromolecules well compensated for the loss of the
2M2HTA intercalant.
Solid state NMR has also been used to quantitatively determine the degree of
clay dispersion in PS/MMT nanocomposites [Bourbigot et al., 2003]. A new
method, similar to the one described above, was developed. In both, paramagnetic
Fe3+ within the octahedral layer of MMT has been used. The results correlate
with XRD and TEM data. The new method is significantly faster than TEM, but
with the difference that the information pertains to the bulk of the specimen, not
to its surface. Evidently, both these methods are applicable only to clays containing
paramagnetic Fe3+.
1.3.2.6 Other Methods

MAS-NMR is particularly valuable for the reactive systems, i.e., those PNC that
are prepared by dispersing intercalated clay into a monomer, which is then
polymerised. Direct evidence that the reaction involves Si atoms has been reported
[Sellinger et al., 1998; Komori et al., 1999a,b].
Diverse calorimetric methods have also been used. For example, a differential
scanning calorimetry (DSC)/dynamic thermal analysis (DTA) method was used
to characterise the layered material, e.g., to study clay hydration [Lagaly et al.,
1975]. Thermogravimetric analysis (TGA) has been used for examining interlayer
packing density [Vaia et al., 1994]. Chromatography was used to determine the
heat of reaction involved in the formation of intercalate complex [Bruno et al.,
1999].
The cone calorimeter is an indispensable tool for flammability studies. The
measurements are conducted according to ASTM E 1354-92 at an incident flux
of 50 kW/m2 using a cone shaped heater. Exhaust flow is set at 24 L/s and the
spark continues until the sample ignites. All samples should be run in duplicate
and the average value reported. The results are reproducible to within about
10% [Gilman et al, 1999; Gilman et al., 2000a,b; Zhu et al., 2001a,b].
Electrophoretic mobility provides an important insight into the surface charge
of clay particles. As expected, large changes have been reported as a function of
pH. This information is crucial for the optimisation of the intercalation process
[Wilson et al., 1999].
17
Copper sulfide
1.3.3 Determination of PNC Properties

Standard test methods have been used to determine PNC properties. CPNC usually
contains low clay concentration, which results in increased melt viscosity,
significant improvement of barrier properties, reduction of flammability, improved
optical properties and increased rigidity.
Thermodynamic and flow properties and the diverse effects of nanoparticles
on the nucleation and crystallinity of polymeric matrices are discussed later in
this book. For example, it has been reported that the impact strength of crystalline
polymer is reduced by incorporation of nanoparticles. For example, addition of
2.2 wt% of organoclay to PA-6 reduced the impact strength by a factor of 4.3.
However, recent data suggest that the problem is related to the influence of clay
on the crystallisation kinetics. By proper selection of process variables, the same
impact strength of PNC as of the matrix resin was obtained [Graff, 1999]. The
fundamentals of the mechanical behaviour, details on the measurements of the
mechanical and barrier properties of CPNCs, as well as on the flame retardancy
are included in later sections of this book.
1.3.4 PNC Types and Methods of their Preparation

As shown in Table 2, during recent years many different polymers have been
used as a matrix for CPNC with a diversity of nanoparticles and for a variety of
applications, from enhancement of mechanical performance, reduction of
permeability, good flame retardancy, improved optical properties, engendering
magnetic, electric or light-transmitting performance, biocompatibility,
thermochromic effects, etc.
1.3.5 PNCs of Commercial Interest

As shown in Table 3, the commercially important PNCs all contain exfoliated
clays, in particular montmorillonite (MMT). The dimensions of the latter particles
are typically: thickness 0.96 nm, with width and length from ca. 50 to about
1500 nm.
Several large plastics producing companies have heavily invested in the
development and production of CPNC (Toyota Central Research and
Development Laboratories (Toyota – for short), Unitika, Ube, AlliedSignal-
Honeywell, RTP Co., Basell, GM, Showa Denko, Bayer, BASF, Solutia, Dow
Plastics, Magna International, Mitsubishi, Eastman, etc.). At least one company
(Nanocor) is totally dedicated to the manufacture of organoclays and polymer
concentrates for use in CPNC. Ube Industries, RTP Co. and Bayer have started
production of the experimental PA-based PNCs with clay nanoparticles for
moulding or film blowing. GE Plastics has developed conductive grades of PC
and PPE/PA experimental alloy with carbon nanotubes. Additional information
is included in Table 4.
After 2.5 years of development, recently, General Motors Corporation (GMC)
announced that in collaboration with Basell Polyolefins (50-50 BASF-Shell joint
venture created in 1990 by merging Elenac, Basell and Targor), Southern Clay
Products, and Blackhawk Automotive Plastics Inc., it has developed thermoplastic
olefin nanocomposite (or TPO-based CPNC) for step-assist use in 2002 GMC
Safari and Chevrolet Astro vans. The key to success is the exfoliation of MMT
achieved during polymerisation.
18
Table 2 Examples of PNCs with functional properties
Polymer Nanoparticles Process and/or key characteristics References
Polyacrylic acid Copper sulfide Optical properties of films [Gotoh et al. 2001]
Poly(2-oxazoline) Au-nanoparticles Polymerisation on functionalised Au [Jordan et al., 2001]
PS, polymethyl methacrylate Lyophilized smectic clays Free radical emulsion or solution [Hoffman et al.,
(PMMA), styrene-acrylonitrile polymerisation 2000a,b]
copolymer (SAN)
PVAl Amorphous Fe2O3 nanoparticles Uniformly dispersed super paramagnetic [Kumar et al., 2000]
nanoparticles
Polyaniline (PANI) TiO2 Polymerisation in the presence of [Su and Kuramoto,

nanoparticles 2000]
Poly(styrene-b- Organo-platinum or organo-silver The bound organo-metal was reduced by [Brown et al., 2000]
acrylic acid) spherical nanoclusters hydrogen
Polyacrylonitrile or CdS Synthesis under gamma radiation [Qiao et al., 2000

polyacrylamide a,b,c,d]
Polyimine NiO For magnetic properties [Castro et al., 2000]
A polymer α-RuCl3 [Wang et al., 2000]
Polyacrylamide Ni Synthesis under gamma radiation [Liu et al., 2000]
Polyvinyl acetate (PVAc) PbS Synthesis under gamma radiation [Qiao et al., 2000]
Polyethylene (PE) Au or Ag nanoparticles Optical anisotropy [Dirix et al, 1999a,b]
19
Introduction
20
PCL Tetraethoxysilane Chemical synthesis of a biocompatible [Tian et al., 1999]

silica-aliphatic polyester hybrid
Hydroxyethyl methacrylate Tetraethoxysilane In situ acid-catalysed sol-gel in free radical [Hajii et al., 1999]
(HEMA) polymerisation
Poly(amido-amine) dendrimer Complexing and immobilisation of SAXS and SANS indicate CuS at periphery [Beck Tan et al.,
dendrimer particles with (CuS)15 of dendrimer molecules. 1999]
PVAl Carbon nanotubes Thermomechanical and electrical properties [Shaffer and Windle,
1999a,b]
PVC Cellulose whiskers Mechanical performance [Dubief et al., 1999]
Poly(ethylene glycol-b-lactide) Core-shell MeO-PEG/PLA- Stable core-shell type spherical, stable [Kim et al., 1999]
with a methoxy group at PEG- methacryloyl latex particles nanoparticles with a number-averaged
end and methacryloyl group at diameter of about 30 nm
PLA
Polymer solution Fe Nanocomposites by reduction of Fe2+ [Yu et al., 1999]
PET Intercalated clay Polycondensation [Frisk and Laurent,

1999]
Aromatic PA Aromatic PA fibers Polymer blending [Akita and

Kobayashi, 1999]
Poly(4-vinylpyridine) (P4VP) MMT from Milos Protonation by acidity of MMT [Fournaris et al.,
(neutral, salt and quaternised 1999]
forms)
7 10 [Biswas et al., 1999]
Poly-N-vinylcarbazole Colloidal nanometer size manganese DC conductivities improved 10 to 10
polypyrrole or polyaniline dioxide (MnO2) fold
(PANI)
PANI Iron oxide nanoparticles Cast film preparation of conductive NC [Tang et al., 1999]
Styrene-maleic anhydride TiO2 Covalently bonded, stable 3D [Wang et al., 1999]

copolymer (SMA) nanocomposites.
Poly(styrene-co-acrylic acid) Nano particles of ZnS Simultaneous polymerisation and [Cheng et al., 1999]
precipitation
Polydimethyl siloxane (PDMS) Zirconia Sol-gel method [Dirè et al., 1998]
A polymer Mn-Zn ferrites Room temperature synthesis [Mathur et al., 1999]
Poly(maleic monoester) Fe2O3 Thin films [Lee and Kang, 1998]
Polycarbonate-co-poly(p-ethyl CdS Enzyme-catalysed synthesis [Wang et al., 1999]

phenol)
Poly(itaconic acid-co-acrylic Cu2+- complex and Cu [Huang et al., 1998]
acid)
Polydiacetylene Cadmium sulfide Nonlinear optical properties [Schwerzel et al., 1998]
Polystyrene sulfonate, Layered double hydroxide, Surface and interphase properties [Wilson et al., 1999]
polyvinyl sulfonate Mg6Al2(OH)16CO3 × 4H2O
Polyacrylamide Ag Synthesis of nanocomposites at RT [Zhu et al., 1998]
21
Introduction
22
Epoxy Dispersed clay with alkylammonium Improved tensile strength and modulus at [Massam et al., 1998]
ions T < Tg
Polypyrrole or polythiophene V2O5 Interleaved nanocomposites for lithium [Goward et al., 1998]
batteries
PEG Mo 2 S Intercalation [Gonzales et al.,
1998a,b]
Latex Cellulose whiskers, 5 × 300 nm Strong effects of processing on NC [Favier et al., 1997]
performance
Carboxylated-PS Emulsion ultrasonication followed by Stable nanoparticles [Mei et al., 1997]
polymerisation
Thiol-containing polymers CdS Enzymatic synthesis [Premachandran et al.,
1997]
PP PP was blended with smectite X-ray diffraction and IR spectroscopy [Kurokawa et al.,
studies performed 1997]
A polymer NbSe2 Superconducting polymers [Tsai, 1997]
A polymer LiMoO3 Encapsulative precipitation [Wang et al., 1997]
Polyacrylamide Ag Synthesis under gamma radiation synthesis [Zhu et al., 1997]

Polydiacetylene Ag Optical properties [Zhou et al., 1996]
PMMA or PS Au Radical polymerisation [Gonsalves et al.,

1996]
Perfluoro sulfonate Ionomer SiO2-TiO2 nanoparticles Sol-gel process [Shao et al., 1996]
PEG V2O5 intercalative nanocomposites Synthesis, structure, and reactions have [Liu et al., 1996]
been studied
Polymer electrolyte Xerogel V2O5 Synthesis, characterisation, and transport [Kloster et al., 1996]
properties
PANI V2O5 Redox polymerisation of aniline in V2O5 [Wu et al., 1996]

Xerogel
Polypyrrole SnO2 Polymerisation in the presence of [Maeda and Armes,

nanoparticles 1995]
PEG TiS2 [Lemmon and Lerner,

1995]
Polypyrrole γ-Fe2O3 particles Electrical and magnetic characterisations [Jarjayes et al., 1995]
Polyethers MoS2 Preparation and characterisation [Lemmon and Lerner,

1994]
A polymer Ag, 20 to 50 nm diameter At 0.1 to 2 wt% long-term antimicrobial [Aymonier et al.,

effect 2002]
PVC CaCO3, 15 to 40 nm diameter Ca(OH)2 + CO2 in rotating bed reactor + [Chen et al., 2002]
surface treatment
23
Introduction
24
Table 3 Examples of commercially important PNCs
Matrix Major players Nanoparticles Properties Applications
Polyamide, esp. Toyota, AlliedSignal, Exfoliated silicates, Compared to PA: similar Automotive (e.g., truck
PA-6 Ube, Nanocor, Unitica, e.g., 1-3 vol% Na- density, transparency, mirror housing, engine
Showa Denko, Bayer, montmorillonite. 70 °C higher HDT, 70% higher covers), tool housing, garden
BASF, and Solutia- Exfoliation is crucial tensile modulus, 130% higher equipment,
Dow. Ube CPNC is flexural modulus, 50% lower telecommunication,
commercially available; oxygen permeability, 70% lower aerospace, speciality
RTP offers to supply flammability, etc. application, barrier film for
PNC on demand food packaging, etc.
Polyolefins, esp. Basell, GM, Southern Exfoliated smectite ≤5- Low density (0.91 g/ml) with Automotive: body panels,
polypropylene (PP) Clay Products Inc., wt%. Compatibilizer stiffness equivalent to door panels, interior trim,
and copolymers Toyota, Ford, Dow is needed; e.g., Toyota composites with 35 wt% talc, instrument panels, pillars,
Plastics, and Magna uses maleic anhydride dimensional stability, low-T consoles, etc.
International modified PP impact strength, ductility to –
35 °C, high heat ageing, 75%

lower flammability, excellent
surface finish
Polystyrene and Toyota Surface-treated clay High strength, tensile modulus Aerospace, automotive
blends with particles; 4.8 wt% increased by 37% (over PS),
poly(styrene-co- 43% smaller thermal expansion
vinyl methyl
oxazoline)
Polyethylene Eastman, Bayer, BASF, Solution-expanded Transparency, low permeability, Food packaging, esp. as
terephthalate (PET) Tetra-Laval clay particles present high strength and stiffness, low central layer in co-formed
during the density beer, juice and soft drink
polycondensation bottles
Matrix Major players Nanoparticles Properties Applications
Ethylene-vinyl Nanocor, Mitsubishi Exfoliated smectite NC to be the central layer in Packaging films, for moisture
alcohol copolymer clay particles; loading multilayer, co-formed products and oxygen sensitive foods
(EVAl) ≤5-wt% and electronics
Polyoxymethylene Showa Denko, Bayer Montmorillonite (?) Low warpage, low shrink, high Automotive under-hood
or acetal (POM) surface quality, HDT increased applications, electronics, etc.
by 45 °C, 40% higher modulus
Polyolefins (PO) Toyota, Mitsui, Showa Polypropylene Low density, high rigidity and Automotive
Denko, Mitsubishi columnar crystals strength
25
Introduction
Table 4 Examples of companies active in the nanotechnology field

Company Comments
Advanced Diamond-like nanocomposites as a protective wear resistant
Refractory thin film for commutator bars in DC motors.
Technologies, Inc.,
Buffalo, NY
AlliedSignal Corp. Toughened PA nanocomposites for films, injection and
(now Honeywell) blow moulding. Compared with PA, the nanocomposites
have 50-80% higher stiffness and up to 70 °C higher HDT
with ca. 1% increase of density. The nanocomposites retain
PA toughness, clarity, hot-fill heat resistance, and oil/grease
resistance. PA-6 with 2 or 4 wt% organoclay has three or
six-fold reduction of O2 transmission rate (OTR).
Applied Sciences Manufacturer of vapour-grown carbon nanotube made by
pyrolysis of coal. Pyrograf-III comes in 100- and 200-nm
diameter and has potential as an electrically conductive
additive and modifier of plastics' coefficient of thermal
expansion. The nano-tubes enhance electrical conductivity
over a broad resistivity range and boost mechanical
properties – at 0.5% loading the volume resistivity is ca.
104 ohm-cm.
Argonide Manufactures alumina ceramic nanowhiskers by electro-
explosion of metal wire. The NanoCeram whiskers (2 nm
diameter, ca. 100 nm length) are used as reinforcements
and thermally conductive additives.
Basell In collaboration with General Motors and Southern Clay
Products developed nanoclay/TPO compound for
automotive step assist vans of 2002. The step is moulded by
Blackhawk Automotive Plastics.
Bayer AG Producer of PA-6 nanocomposites for transparent barrier
film packaging Durethan LPDU 601-1 and LPDU 601-2,
which offer different degrees of barrier improvement (LPDU
is data link layer Protocol Data Unit delivered through a
network.
Carbolex Carbon nanotube sales for research and industry.
Clariant CPNC with PP matrix for packaging applications. Supplier
Masterbatches of of Nanomer masterbatches (with PO matrix) for use in
Milford, Delaware making nanocomposite plastics.
Crenova Manufacturer of electrically conductive PA-12 with carbon
(Vestamid) nanotubes.
Dow Plastics Developing in-reactor compounding of nano-PP by using
nanoclays as the catalyst support for in situ polymerisation
of PP. The focus is on highly loaded (up to 10% clay)
systems for semi-structural automotive uses.
26
Introduction
Company Comments
Eastman Chemical Jointly with Nanocor developing nanocomposites of PET

via the in-reactor approach. Its initial focus is on rigid
containers, coinjected with the nanocomposite barrier layer
in the middle.
GE Plastics Manufacturer of electrically conductive PPE/PA blends with

CNT for automotive painted parts.
Hybrid Plastics Pioneered the development of polyhedral oligomeric

silsesquioxanes (POSS) for plastics. The technology bridges
the property space between hydrocarbon-based plastics and
ceramics. It imparts new or improved properties to
materials through the controlled reinforcement of polymer
chains at the molecular level.
Hyperion Catalysis Producer of carbon nanofibers, viz. Graphite Fibril™

nanotubes. Its hollow carbon nanotubes 10 nm in OD
diameter are 10 to 100 microns long, for at least a 1000:1
aspect ratio and are primarily used to provide high
conductivity at 0.5 wt% loading. Hyperion supplies
masterbatches containing 15-20% fibrils in, e.g., PA-6, -12
and -66, PBT, PC, PEEK, PEI, PPS, and PS, PP, PET, and
EVA.
IBM R&D activities on nanocomposites in applications such as

polymer light emitting diodes.
Kabelwerk Eupen EVAc/organoclay compositions for wire & cable

(Belgium) applications. Drastic reduction of heat release at 3 to 5
wt% clay loading.
Nanocor; Formed to capitalise on the patented technology for

subsidiary of the chemically modified clays into plastic resins, improving
AMCOL strength, heat stability and barrier properties. Supplier of
International Corp organoclay and its concentrates PA-6, MDX6 and PP.
Licensed by Toyota Central R&D Labs to use their
technology.
Nanomaterials Precision manufacturer of powders and devices.

Research
Corporation
NexTech Manufacturer of innovative ceramic products (nano

Materials, Ltd. powders) to meet the needs of the chemical,
electrochemical, electronics and consumer markets.
Physical Sciences Research contract from the National Science Foundation to

Inc. develop an advanced carbon nanotube membrane for direct
methanol fuel cells.
27
Company Comments
Polymeric Supply Thermoset CPNC with unsaturated polyester for marine

and transport applications.
RTP Co. Manufacture organoclay-reinforced PA-6 and PP, as well as

polyether ether ketone (PEEK) (and other polymers) with
carbon nanotubes for static-dissipative bodies, e.g., in
semiconductor applications.
Shenzhen Chengyin Focused on the R&D of nanostructured titanium dioxide in

Technology Co., anti-ultraviolet, antibacteria, antistatic and photocatalysis.
Ltd.
Showa Denko Commercial production of PA-66 and POM

nanocomposites by melt compounding with organoclay for
improved flame retardancy and rigidity. The FR grades:
Systemer FE 30600 and 30602 provide UL 94V-0 and V-2
performance, respectively, at 0.4 mm thickness. Their flex
moduli are 30-80% higher, and HDT 30 to 80°C higher,
than those of neat PA.
Southern Clay Manufacturer of clay and clay products, e.g., intercalated

Products, Inc, clays for use in CPNC.
(SCP) Gonzales,
TX
Toyota Central Hold the first patents on nanocomposites. Licenses for the
R&D Laboratories, technology of PA-6 nanocomposites given first to Ube
Nagakute International and Nanocor. Other licensees for this as well
as PP-based CPNC technology followed. Toyota succeeded
in producing CPNC by melt compounding in a twin-screw
extruder.
Ube International Manufactures the nylon-clay hybrids (NCH), of PA-6, PA-

66, PA-12, and PA-6/66 for extrusion and injection
moulding. Compared to neat PA-6, NCH has 68% higher
tensile modulus and 126% higher flexural modulus. At 2
wt% clay the oxygen permeability is reduced by a factor of
two.
Unitika Co. PA-6 nanocomposites for injection moulding (e.g., Nylon

M2350) produced using a proprietary reactive exfoliation
technology.
Yantai Haili Ind. Ultrahigh molecular weight polyethylene

& Commerce of (UHMWPE)/organoclay for earthquake-resistant pipes.
China
28
Introduction
A TPO with 2.5 wt% clay is as stiff as PP with 10 times the amount of talc. The
PNC is much lighter; the weight savings can reach 20%, depending on the part
and the material that is being replaced by the TPO nanocomposite. The
nanocomposites are stiffer, less brittle at low temperatures, more durable and
more recyclable than currently used materials. Parts made of nanocomposites
cost about as much as conventional TPO, but it takes less material to manufacture
them. GMC expects the price to improve as the volume of CPNC used by the
transport industry will increase. However, for use in body panels the TPO CPNC
requires additional research.
1.3.6 Journals and Research Groups

During the last few years there has been an explosion of scientific journals related
to nanotechnology:
1. Carbon Nanotubes: Synthesis, Structure, Properties and Applications, Eds.,
M.S. Dresselhaus, G. Dresselhaus and P. Avouris, Applied Physics Series,
Springer, Berlin; 2001.
2. Fullerenes, Nanotubes and Carbon Nanostructures, Marcel Dekker, Inc., New
York, 2002.
3. International Journal of Nanoscience, World Scientific, Singapore, 2002.
4. Journal of Nanoparticle Research, Kluwer Academic, Dordrecht, 1999.
5. Journal of Vacuum Science & Technology. B, Microelectronics and Nanometer
Structures Processing, Measurement and Phenomena, Published for the
American Vacuum Society by the American Institute of Physics, 1991.
6. Lab on a Chip, Royal Society of Chemistry, Cambridge, UK, 2001.
7. Materials Science & Engineering. C, Biomimetic and Supramolecular Systems,
Elsevier, Amsterdam, 1999.
8. Microscale Thermophysical Engineering, Taylor & Francis, London, 1997.
9. Nano Letters, American Chemical Society, 2001
10. Nanostructured Materials, Pergamon Press, c1992-c1999; absorbed by Acta
Materialia.
11. Nanotechnology, Pergamon Press, 1990.
12. Physica E. Low-Dimensional Systems & Nanostructures, North-Holland,
Amsterdam, 1997.
13. Virtual Journal of Nanoscale Science & Technology [electronic], American
Institute of Physics, 2000.
While there is no monograph on PNC, there are several volumes of proceedings
published [Komarneni, 1996; Komarneni et al., 2000]. Several industrial consortia
have been established for the sole purpose of advancing R&D on PNC, viz. Dow-
Magna International, Toyota-Ube-Mitsui-Mitsubishi, Basell-GM-Southern Clay, etc.
In Canada and the USA, there are also research consortia on CPNC at, e.g., the
National Research Council Canada (NRCC), the National Institute for Science and
Technology (NIST) and Edison Polymer Innovation Corporation (EPIC). NRCC
activities focus on CPNC development, NIST concentrates on the inflammability of
CPNCs. To the EPIC consortium five Ohio-based universities have submitted project
proposals on development of PNC for thermoplastics, coatings, elastomers, advanced
composites, and for core technology (rheological behaviour, nanoparticle/polymer
29
interface, and particle surface chemistry) where fundamental issues will be investigated
that apply to all of the application technologies. Activities focus on coatings,
electro-optical behaviour, barrier properties, elastomers, synthesis and processing,
advanced composites and core technologies. NSF announced the Nanoscale Science
and Engineering (NSE) program for the USA universities with US$74 million budget
for FY 2001. The number of international conferences on PNC is growing
exponentially – in 2001 there were at least six major conferences in Europe and
North America. Guided by the evident industrial interests, this monograph will focus
on the PNCs developed as structural materials comprising exfoliated clay particles.
1.3.7 Historical Perspective

Intercalation of clays started in the 1930s. For hydrophilic applications in paper
coating, H2O + Na4P2O7 + compounds with -OH groups (e.g., PEG) were used at
high stresses [Maloney, 1939]. Dry smectite galley spacing of Δd001 = 0.35 nm,
increased upon swelling with 3 molecular layers of H2O to 1.2-1.4 nm. In the
early 1950s, for hydrophobic applications clay started to be intercalated with
quaternary alkonium chlorides. For example, fatty quatenary alkonium chlorides
were used, viz. methyl and/or benzyl hydrogenated tallow ammonium chloride
(containing 2.0% C14, 0.5% C15, 29.0% C16, 1.5% C17, 66.0% C18 and 1.0%
C 20 alkyl groups). The organoclays, commercialised by NL Industries as
Bentone™, were found useful for thickening lubricating greases, oil-based muds,
packer fluids and paint-varnish-lacquer removers [Hauser, 1950; Jordan, 1950].
Soon, the process was described in the textbooks [Grim, 1968].
The first use of an organoclay in polymers was to reinforce elastomers [Carter
et al., 1950]. The patent describes MMT intercalation using diverse onium
compounds, viz. ammonium, phosphonium, arsonium, stannonium, etc. The
organoclay was combined with elastomeric latex, and then processed by standard
methods. In 1961, Blumstein reported polymerisation of vinyl monomers (e.g.,
methylmethacrylate) in the presence of intercalated MMT. In 1963 Nahin and
Backlund patented low density polyethylene (LDPE)-organoclay 1:1 compositions.
In the organoclay the amount of onium salt (e.g., hexamethylene diamine) varied
from 4 to 16 wt%. The aim was to produce rigid, γ-ray crosslinkable compound.
The patent describes methods of intercalation, hot mill blending, moulding and
irradiation. Nanocomposites with PVC and PS were also discussed. In the latter
case, the authors stress the difference in behaviour of PS melts compounded with
organoclay and polymerised in its presence.
In 1976 Fujiwara and Sakamoto (from Unitika) filed a patent application for
the use of ammonium-salt intercalated clays in a hydrophobic matrix. In particular,
the organoclay was added to monomer prior to its polymerisation into a polyamide
– this led to the first CPNC. A few years later, Toyota obtained the first US patent
for the polymerisation of several vinyl monomers, e.g., styrene, in the presence of
clay [Kamigaito et al., 1984]. The composition contained 85 wt% of clay, hence
exfoliation was impossible, but in the presence of styrene the interlayer spacing of
MMT expanded from d001 = 1.25 to 1.5 nm. Upon addition of dichloro-dimethyl
silane rapid polymerisation resulted in good mechanical performance. In the
following years attention shifted to dispersion of small quantities of MMT in
PA-6 – the work resulted in several US patents [Okada et al., 1988; Kawasumi et
al., 1989]. The process consisted of caprolactam polymerisation in the presence
of organoclay.
30
Introduction
The melt exfoliation process for PA-based PNCs was developed in the early
1990s at AlliedSignal [Maxfield et al., 1995, 1996; Christiani and Maxfield,
1998]. The later patents describe a three step process:
1. Treating a suspension of clay with peptising Na6P6O18 in aqueous solution
at 50-90 °C with organosilanes, organotitanates or organozirconates that
increase the interlayer spacing to at least d001 = 5 nm.
2. Saturation of the dried clay with precursor monomer then polymerising it.
3. Compounding the modified clay with matrix polymer until the desired level
of exfoliation is reached.
The complexes of organosilanes, organotitanates and/or organozirconates (with
or without onium salt) showed prolonged thermal stability at temperatures above
300 °C.
Owing to the high hydrophobicity and non-polar nature of polyolefins, preparation
of PO-based CPNC is more difficult; hence historically it followed that of PA-based
ones. The first patents from Toyota were for elastomers reinforced with clay and carbon
black (CB) [Usuki et al., 1989]. To prepare a PP-based CPNC Kawasumi and
co-workers [1997] intercalated NaMMT using an oligomeric PO with polar telechelic
hydroxyl groups. Next, a general method for the preparation of PNC with diverse
polymers was disclosed [Usuki et al., 1999]. The process involves three steps:
(i) Intercalation of clay with an onium ion rendering it compatible with a ‘guest
molecule’.
(ii) Contacting the organoclay with the ‘main guest molecule’ at T ≤ 250 °C.
(iii) Transferring the modified clay to a reactor for PO polymerisation (preferred)
or blending with a synthetic resin.
Since the guest molecule and the polymer added in the 3rd step may not be the
same, it is possible to form CPNC with a miscible blend as matrix. The patent
listed vinyl-based polymers, thermosetting resins and rubbers (e.g., PE, PP, PS,
polyisobutylene (PIB), acrylics, thermoplastic polyurethane (TPU), styrene-
butadiene-styrene terpolymer (SBS), liquid butadiene rubber (BR), polybutadiene
(PB), etc.) as the matrix. For example, maleated-PP (PP-MA) with high acid value
hence low MW) was used as the ‘guest molecule’ that resulted in good exfoliation
[Kato et al., 1997].
In a patent from Dow, PO-based CPNC was prepared by Nichols and Chou
[1999]:
(i) Intercalation with an organic, polymeric or inorganic intercalant (e.g., Si(OC2H5)4,
Si(OCH3)4, Ge(OC3H7)4, Ge(OC2H5)4) that resulted in Δd001 = 0.5-60 nm.
(ii) After drying at 50-80 °C or calcination at 450-550 °C, the intercalated material
was dispersed in a monomer or melt-blended until at least 80 wt% of the layers
were exfoliated (aspect ratio p = 10-2000). The claims mention LDPE and
linear low density PE (LLDPE) copolymers with density ρ = 850-920 kg/m3 and
a melt index (MI) = 0.1-10 g/min.
Another method for the preparation of PO-type PNCs followed similar steps
[Hudson, 1999]:
(i) MMT was functionalised in H2O/EtOH with aminosilane, e.g., amino
ethyl-dimethyl ethoxysilane;
31
(ii) Carboxylated or maleated PO was grafted to the functionalised MMT by

amine-carboxyl bond; and
(iii) 0.1-50 wt% of the modified particles was dispersed in PE or PP.
The key is the physical bonding through co-crystallisation between the grafted
PO and the main PO resin.
One of the drawbacks of the ammonium salt intercalated NC is the low
temperature stability. To solve the problem, Ellsworth [1999] used 10-80 phr
organophosphonium R1P+(R2)3 cations (where R1 is a C8-C24 alkyl or arylalkyl
group and each R2 is an aryl, arylalkyl, or a C1-C6 alkyl group) with a melt
processable fluoroplastic. The dispersion was carried out by melt blending in a
twin-screw extruder (TSE). The resulting interlayer spacing was d001 ≥ 3.5 nm.
While organoclays intercalated with conventional, quaternary ammonium cations
are stable only up to about 250 °C, the one intercalated with tributyl-hexadecyl-
phosphonium bromide (3BHDP) was reported stable to about 370 °C, making it
possible to prepare CPNC with high temperature engineering or speciality polymers.
Another method for PNC preparation uses bentonite intercalated with primary
C12- or C16-ammonium chloride and treated with an epoxy [Ishida et al., 2000].
The authors consider the method applicable to any matrix polymer. The key
factor has been the addition of 2 wt% epoxy (e.g., Epon 825; see Figure 5). In
the first step of the process, MMT was treated with C12- or C16-ammonium
chloride, filtered then dried overnight at 100 °C. The modified clay and epoxy
were added to molten polymer and melt mixed for 10 to 120 min.
The epoxy was capable of swelling the ammonium-treated clay, allowing
virtually any monomer or polymer to interdiffuse. Intercalated or exfoliated
composites have been prepared with 24 different polymers, using a clay loading
of 10 wt%. Comparing the XRD spectra of samples containing epoxy with those
for samples without epoxy led to the conclusion that there was an increased
dispersion of clay in the former systems. Several factors affect the efficiency of
nanocomposite formation as well as its structure. Therefore, while intercalation
and/or exfoliation are not complete for all the polymers tested, lower clay loading,
longer mixing time, and higher swelling agent concentrations might have resulted
in a better exfoliation. Table 5 shows that for several polymers (with 10 wt%
clay (MMT-ADA) and 2 wt% epoxy (Epon 825)) mixing for 30 min resulted in
a partial nanocomposite structure.
Figure 5 Chemical composition of Epon-series of epoxy resins from Shell. Epon

828 contains three species: 88% with n = 0, 10% with n = 1 and 2% with n = 2
(hence an average <n> = 0.14). In Epon 825 n = 0; in Epon 826 <n> = 0.07; in
Epon 1001 <n> = 2.3 and in Epon 1004 <n> = 4.8. Similar resins are available
from other manufacturers, e.g., Dow (DER-series) or Ciba (Araldite-series).
32
Introduction
Table 5 Results of CPNC formation after melt mixing a polymer for

30 min with 10 wt% of MMT-ADA and 2 wt% epoxy
[Ishida et al., 2000]
Polymer Exfoliated MW Result
(%) (kg/mol)
Polyethyl methacrylate (PEMA) 50 515 exfoliated
Polyisobutylene 39 500 exfoliated
Poly(1-butadiene) 23 420 exfoliated
Polyisoprene 26 410 exfoliated
Polybutyl methacrylate (PBMA) 66 337 intercalated
Chloroprene (CR) 81 188 exfoliated
Poly(1-butene) 26 185 exfoliated
SAN 85 185 intercalated
Polyoxadecyl methacrylate 0 170 intercalated

(PODMA)
PE 68 125 intercalated
PMMA 50 120 exfoliated
PVAc 70 60 exfoliated
PS 54 45 exfoliated
PC 64 29 exfoliated
PCL 54 15 exfoliated
PEG 82 10 intercalated
PVAl 80 2 exfoliated
Polytetrafluoroethylene (PTFE) 89 unknown exfoliated
PP 77 unknown intercalated
PA-12 99 unknown exfoliated
PVC 100 unknown exfoliated
POM 70 unknown exfoliated
33
In principle, owing to the polarity of thermosetting monomers or pre-polymers,

the exfoliation of clays in these resins is simpler. The low molecular weight
monomeric components may diffuse more easily to the interlayer galleries.
For example, Pinnavaia and co-workers [Pinnavaia and Lan, 1998; Wang and
Pinnavaia, 1998] prepared epoxy nanocomposites with layered silicilic acid
(magadiite). The CPNC showed great improvement in tensile modulus and
strength. Using alkylammonium, dimethyl di-octadecyl amine (MMT-2M2ODA)
the clay layers were found spaced at about 8 nm. In another study Wang and
Pinnavaia [1998b] used MMT intercalated with protonated octadecylamine
(MMT-ODA) and PEG, then crosslinked it with diisocyanate. Thus prepared
elastomeric polyurethane nanocomposites had the clay dispersed in the form of
tactoids. Detailed discussion on these systems may be found in Part 4.2.
34
Introduction
Part 2
Basic Elements of Polymeric

Nanocomposite Technology
Nanoparticles of Interest to PNC Technology
2.1
Nanoparticles of Interest to
PNC Technology
2.1.1 General
Nanoparticles used in polymeric nanocomposites have been divided into three
categories defined in terms of the number of dimensions of their nanometre size,
viz. one dimension (platelets), two dimensions (fibres and whiskers), and three
dimensions (nearly spherical particles). Layered nanoparticles that can be
exfoliated into a dispersion of individual platelets are of main interest. Out of
these, in industry the mineral or synthetic clays have a dominant position, hence
these will be discussed in greater detail.
2.1.2 Layered Nanoparticles

The layered materials of interest to CPNC technology have an average platelet
thickness from 0.7 to about 2.5 nm. A partial listing is given in Table 6. The average
Table 6 Layered nanoparticles for use in CPNC

Smectite clays Montmorillonite, Bentonite, Nontronite, Beidellite,
Volkonskoite, Hectorite, Saponite, Stevensite, Sauconite,
Sobockite, Svinfordite
Other clays Vermiculite; Illite, Ledikite, Attapulgite, Magadiite, Kenyaite,

Mica
Synthetic MgO(SiO2)s(Al2O3)a(AB)b(H2O)x (where AB is an ion pair, e.g.,

clays NaF); synthetic Magadiite; Lucentite and Somasif (from Co-
Op); Laponite (Mg4Li2Si8O20OH2F2+2, from SCP);
Fluorohectorite (Corning)
Layered 2n- Mg6 Al3.4 (OH)18.8 (CO3)1.7 H2O

hydroxides Zn6 Al2 (OH)16 CO3 nH2O
Chlorides FeCl3, FeOCl
Chalcogenides TiS2, MoS2, MoS3, (PbS)1.18(TiS2)2
Cyanides Ni(CN)2
Oxides H2Si2O5, V6O13, HTiNbO5, Cr0.5V0.5S2, W0.2V2.8O7, Cr3O8,

MoO3(OH)2, VOPO4-2H2O, CaPO4CH3-H2O, MnHAsO4-H2O,
Ag6Mo10O33, etc.
Others Graphite, oxidised graphite, nanotalc, etc.
Smectite clays Synthetic clays Hydroxides Chlorides 35

Chalcogenides Cyanides Oxides
interparticle spacing between layers of the layered material or fibrils of the fibrillar
material may depend on concentration – the higher the loading the smaller the spacing.
Since PNCs are mainly used as structural materials, the preferred layered
materials are phyllosilicate clays of the 2:1 type, more precisely smectites, and in
particular montmorillonite (MMT). The layer surface has 0.25 to 0.9 negative
charges per unit cell and a commensurate number of exchangeable cations in the
interlamellar galleries. The amount of this high aspect ratio nanomaterial that
needs to be added to a polymeric matrix to engender CPNC with improved
performance can be as little as 5 ppm. The aim is to totally exfoliate the platelets,
but frequently doublets and short stacks (tactoids) may also be present.
Considering the importance of MMT a more detailed description of its structure
and properties is given below.
While MMT is abundant and inexpensive its main drawback is that it is a
mineral with variable composition, which is impossible to totally purify. Variability
of CPNC has frequently been blamed on structural (particle size distribution and
aspect ratio) as well as chemical (surface reactivity) variability. Consequently,
there is a growing interest in synthetic or at least semi-synthetic layered materials
with well-controlled physical and chemical properties. While experiments with
these model systems are essential for development of a basic knowledge of
intercalation and exfoliation, the hope is that the technology can be developed to
produce synthetic layered materials on a large-scale for the manufacture of CPNC
with consistent performance characteristics.
To prepare functional PNCs other layered materials (than MMT) as well as
non-layered materials have been used, e.g., metallic particles, metal oxides, metal
sulfides, etc. The structure and size of these particles depends on the method of
preparation, which in turn is dictated by the principal application of these
materials. There is a growing interest in synthetic layered nanofillers (see Table 7).
Hectorite has a significantly smaller aspect ratio (p) than MMT, viz. p < 100, but
their synthetic homologues have even smaller diameter flakes, viz. p = 10 to 30.
By contrast with hectorite, synthetic fluoromica (FM) can be prepared with high
aspect ratio, e.g., p < 2,000 [Yano et al., 1993]. Their advantages/disadvantages
are summarised in Table 8.
A simple method for producing synthetic fluoromica (FM) at a relatively low
temperature was described by Tateyama et al. [1993]. Accordingly, a powdery
mixture of 10 to 35 wt% of an alkali silicofluoride (e.g., Na2SiF6) as the main
component (optionally with an alkali fluoride) and natural talc is heated for
about one hour at 700 to 900 °C. The resulting material has the general formula:
αMFxβ(aMgF2xbMgO)xγSiO2 where M is an alkali metal (Li, Na, K), and
0.1 ≤ α ≤ 2: 2 ≤ β ≤ 3; 3 ≤ γ ≤ 4; a + b = 1 are coefficients. For example,
swellable FM may have the composition: talc/LiF/Na2SiF6 = 80:10:10; or
talc/Na 2 SiF 6 /Al 2 O 3 = 70:20:10. The heating temperature greatly affects
swellability and the interlayer spacing. For example, the fluoromica produced
at 700-750 °C shows the XRD peak at d001 = 0.91 nm, while that produced at
780-900 °C has the XRD peak at d001 = 1.61 nm.
A one-step method for the preparation of synthetic grafted smectite clays has
been described [Carrado et al., 2001]. By contrast with the older methods that start
with a mineral precursor, e.g., talc, to produce Li-hectorite (CEC ≅ 0.8 meq/g), the
new process involves sol-gel hydrothermal transformation of an organotetraethoxy
silane (TEOS) or organotrialkoxy silane, viz. phenyltriethoxy silane (PTES). Aqueous
slurries of LiF, magnesium hydroxide, and the silane are refluxed for 2-5 days.
36
Table 7 Synthetic clays

Company Synthetic clay Clay type
Laporte Industries, Ltd., Laponite LRD or RD was SYnL-1;
Luton UK/Southern Clay developed by Laporte more than hectorite;
Products Inc., 30 years ago, and has been 25 x 10 nm
P.O. Box 44, Gonzales, manufactured at the Widnes site
TX 78629 - (888) since 1985
Fax (210) 672-7206;
http://www.laponite.com/
NL Industries; Baroid Barasym SMM-100, composition SYn-1;
Division, (%): SiO2: 49.7 Al2O3: 38.2, muscovite-type;
idp@baroid.com TiO2: 0.023, Fe2O3: 0.02, MgO: mica-montmorill-
0.014, Na2O: 0.26, K2O: <0.01, onite
Li2O; 0.25, F: 0.76, P2O5: 0.001, CEC = 0.7 meq/g
S: 0.10;
Süd Chemie AG Optigel SH, composition (%): SYnH-1;
Rheologicals (United SiO2: 57-61 MgO: 25-29 Li2O Hectorite density:
Catalysts Inc.) Postfach 20 0.5-0.9, Na2O: 2.5-3.5, 2.5 g/cm3;
2240 8 Munich 2, moisture: 12%
Germany
Telex: 23 821, 05 23 872
Co-Op Ltd. Somasif™ ME100 fluoromica Montmorillonite-
23-3, Ichiban-Cho (FM) or fluorohectorite (FH), type;
Chiyoda-Ku, Tokyo 102- also intercalated grades available CEC = 0.7–0.8
8383, Japan Contact: Mr. Lucentite™ SWN is lithium meq/g; dry
T. Kunimochi Tel: +81 3 magnesium sodium silicate; d001 = 0.95 nm;
3296-8839 intercalated Lucentite™ SAN is pH = 9–10
Fax +81 3 3219-1460 SWN intercalated with Na-Smectite;
E-mail: Quaternium-18, and Lucentite™ pH = 10-11
kunimo-t@unicoop.co.jp SPN is SWN intercalated with
PEG-25-diethyl-ammonium
chloride; other grades are
available
Kunimine Industries Co., Sumecton® Na-Saponite;
Ltd. 1-10-5, Iwamoto-cho, CEC = 0.712
Chiyoda-ku, Tokyo 101 meq/g
Tel: +81 3 3866-7251
Fax: +81 3 3866-2256
Topy Co., Ltd. Li-taeniolite CEC = 2.6 meq/g
5-9, Yonban-cho,
Chiyoda-ku, Tokyo 102-
8448, Japan
Corning, Inc. Lithium fluorohectorite,
Li1.12[Mg4.88Li1.12]Si8F4
37
Table 8 Relative merits of mineral versus synthetic clay

Clay Advantages Disadvantages
Mineral Well-known technology; Variability of composition; Difficult

Availability; Price: US$ removal of amorphous clays; Poor
1,600/ton in 2001 reproducibility of PNC performance;
Crystallographic defects that prevent
total exfoliation
Synthetic* Control of composition Developing technology; Limited

and shape; High aspect sourcing; Price: US$ 2,300/ton in
ratio: p ≤ 15,000; 2001
Reproducibility of PNC
performance
Note: The term "synthetic" may be a misnomer, as most of these clays are based
on mineral precursors, viz. talc, which may also suffer from some disadvantages
listed for the mineral clays. Consumers beware!
The organic content in the resulting PTES-hectorite was ca. 20-25 wt%. As
evidenced by FTIR (peak at 1430 cm-1) the organics comprise phenyl groups
attached to Si via direct Si-C bonds. Furthermore, 29Si NMR peaks at -79 and
-66 ppm evidenced the presence of RSi(OMg)(OSi)2 and RSi(OMg)(OSi)(OH)
species, respectively. XRD of the synthetic hectorite (FH) showed the interlayer
spacing, d001 = 1.3 and 1.39 nm for, respectively, PTES- and TEOS-based clays.
The organoclays were found to be stable up to at least 400 °C.
2.1.3 Fibrillar Nanoparticles

The diameter (d) of the fibres of interest is d = 1 to ≤ 20 nm, and the average
length, l = 30 to about ≤ 200 nm. Useful fibrillar materials are: carbon nanotubes,
imogolite, vanadium oxide, inorganic nanotubes, cellulose whiskers, etc.
2.1.3.1 Carbon Nanotubes (CNTs)
2.1.3.1.1 Origin, Characteristics and Structure

Iijima from the NEC discovered carbon nanotubes (CNTs) in 1991. These are
hollow tubular structures with wall thickness of 0.07 nm, and interlayer spacing
of 0.34 nm. CNTs are classified as either single- or multi-wall nanotubes (SWNT
or MWNT, respectively). While a SWNT consists of only a single cylinder, a
MWNT consists of 2 to ≤ 30 concentric tubes.
A SWNT has an average diameter of 1.2-1.4 nm, and density (ρ) = 1.33 to
1.40 g/ml. These are hollow graphene tubes with a wall thickness of 0.07 nm,
readily aggregating into ropes or bundles with an interlayer spacing of 0.34 nm.
The C-C bond length is aC-C = 0.14 nm, hence shorter than that in diamond,
indicating greater strength. The theoretical and experimental range of values of
SWNT tensile modulus is E = 1 to 1.5 TPa (that of diamond is 1.2 TPa), tensile
strength is 11 to 63 GPa (10¯100 times higher than the strongest steel at a fraction
38
of the weight). The electrical resistivity is about 10-4 W-cm, thermal conductivity
ca. 2 kW/m/K, thermal stability in vacuum up to 2800 °C, maximum current
density = 1013 A/m2 (electric-current-carrying capacity 1000 times higher than
copper wires) [Tans et al., 1997].
A MWNT has inner diameter (ID) = 1.2 to 5 and outside diameter (OD) = 10 to
over 50 nm. MWNT are described as 2 to 10 μm long, but the limit to how long
they may grow is unknown. A MWNT looks like a rope made of bundles of
concentric single-wall CNTs. In a bundle each tube is very thin, and the coupling
between them is weak. As a result, even if one nanotube breaks, it has almost no
effect on the others – the crack is blocked, and the fracture stops. Practically, one
may expect MWNT to have the strength of 130 GPa, i.e., nearly 100 times that
of steel at 6-fold lower density [Ijima et al., 1996; Treacy et al., 1996; Yakobson
et al., 1996; 1997]. CNT are 200 times stronger than carbon fibres (CF) and
their diameter is more than 1,000 times smaller.
There are a few books on CNTs [e.g., Saito et al., 1998, Harris, 1999 and
Dresselhaus et al., 2001] and some reviews, viz. Ajayan, 1997, Dai, 1999, Sánchez-
Portal et al., 1999, Nalwa, 2000, Fisher and Brinson, 2001, Dai and Mau, 2001,
Iijima, 2002, Burstein, 2003, and Mamalis et al., 2004. Less information is
available on the use of CNTs in polymer nanocomposites, e.g., Lahr and Sandler,
2000, Thostenson, et al., 2001, Maruyama and Alam, 2002 and Wang et al.,
2003a. There are several journals dedicated to nanoscience and technology, and
since 2002 a specialised journal has been published: Fullerenes, Nanotubes, and
Carbon Nanostructures.
If the buckyball is designated C60 then the zero-length ‘carbon nanoball’ is
C70 and the carbon nanotube (see Figure 6) might be C1,000,000. From the physics
point of view a CNT is a unidirectional single crystal, with a unit cell of about
1.7 nm that keeps on propagating and repeating. The properties of nanotubes
depend on the atomic arrangement, the tube diameter and length. CNTs are
linear fullerenes that, by definition, contain only hexagonal and pentagonal faces,
satisfying the Euler’s theorem. As in a buckyball, the defectless enclosed nanotube
must have 12 pentagons [Dresselhaus et al., 1996; Chico et al., 1996].
CNTs can be described in terms of the tube chirality, defined by the chiral
vector and the chiral angle as shown in Figure 7. A CNT can be visualised as a
strip cut and rolled from an infinitely large hexagonal sheet of graphite. The
cutting can be done at diverse angles and the strip can have a range of widths.
r
These can be expressed by the chiral angle (θ) and the chiral vector ( C n ). Its unit
vectors a1 and a2 are also shown [Thostenson et al., 2001]. In terms of chirality,
armchair (n, m) = (n, n) and zigzag configurations (n, m) = (n, 0) are distinguished.
Tubes with the chiral vector (n, m) = (5, 5), (10, 10), (9, 0) and (10, 5) are
known. Depending on chirality, CNT conductivity can be metallic or
semiconducting.
Figure 6 Carbon nanotube with one end closed.
39
Figure 7 A CNT as a strip cut and rolled from a large sheetr of graphite at chiral
angle, θ, and different width, expressed by the chiral vector, C n , composed of unit
r r
vectors a1 and a2 with their magnitude expressed by the integers (n, m). The latter
are the number of steps along the zigzag carbon bonds of the hexagonal lattice.
Reproduced from Thostensen et al., copyright 2001, with permission from Elsevier.
Iijima and Ichlhashi [1993] discovered SWNTs two years after reporting on
MWNTs. Since then, several methods for the preparation of SWNT or MWNT
have been developed. These include: (1) arc-discharge, (2) laser ablation, (3) gas-
phase catalytic growth from carbon monoxide, and (4) chemical vapour deposition
(CVD) from hydrocarbons. For use in composites, large quantities of CNT are
required making the first two methods too expensive. Furthermore, the CNTs
are contaminated by catalyst particles, amorphous carbon, and non-tubular
fullerenes, thus costly purification is required. The two latter gas-phase processes
(3) and (4) are more suitable for large-scale production and tend to yield CNTs
with fewer impurities [Huang et al., 1998].
Sarangi et al. [2001] have prepared CNTs starting either with diamond-like
carbon (DLC), with PE, or with CH4 + H2 gases as precursors. Microwave at
2.45 GHz with RF bias of -600 V was used. The samples were annealed under vacuum
at 1000 °C. Long MWNT were obtained from DLC (ID = 1.8, OD = 3-50 nm).
Starting with PE, short MWNT were obtained growing from metal particles.
The laboratory production rate at the National Tsing Hua University is ca. 5 g
every 40 min. The CVD method gives great purity MWNTs with high aspect
ratio [Tai, 2002]. Tangled CNTs with outer diameter of ca. 10-50 nm, can be
produced in large quantity and low cost, but with less control over the aspect
ratio and structure.
A new and simple method for CNT production was published recently [Pan
and Bao, 2002]. A common laboratory ethanol burner was used with a flame of
about 25 mm in diameter in the middle and 80 mm in height with 15 mm wick.
The metal substrate was austenitic stainless steel (SS) 20 x 10 x 10 mm with
mechanically polished down-facing surface that was pre-etched in HNO3. The
SS block was inserted into the central core of the flame where the temperature
was 610 to 780 °C. The flame was not controlled. After ca. 20 min a thick CNT
film was formed. High density, vertically aligned tubes were observed. These
40
grew uniformly (by the root-growth mechanism) from nickel oxide or iron oxide
particles on the stainless steel substrate. The MWNTs were 20 to 80 nm in diameter
and 60 to 100 μm in length.
Another publication suggests that CNT may be quite preponderant – they have
been found in the exhaust gases of most (if not all) trucks or cars with high mileage
that use either diesel oil or gasoline [Lee et al., 2002a]. The authors collected
samples from silencers of unleaded gasoline cars with mileage from 1600 to 120,500.
Samples were dispersed in acetone for TEM. All showed the presence of
interconnected spherical-like carbon particles, ca. 20-40 nm. However, high
resolution TEM revealed the presence of hollow polyhedral, multilayered (2 to 6)
structures with d-spacing of 0.34 nm. The structure was similar to that generated
in the carbon-arc discharge nanotube process (at 2500-3000 °C).
Windle and his collaborators studied aqueous suspensions of CNTs [Shaffer
and Windle, 1999a]. Stable suspensions were engendered by either acid-oxidation
and/or by bromination. The process reduced the tube length by a factor of about
two and formed oxygen-containing groups. Plots of suspension viscosity versus
CNT concentration indicated the presence of an asymptote at about 3 to 4 vol%
(depending on the CNT average length). The authors fitted the dispersion data
to the Schltz-Blaschke equation, derived for polymer solutions. Thus an analogy
was proposed between entangled polymer macromolecules in solution and
entangled CNTs in aqueous suspension. At concentrations exceeding the
asymptotic value (the maximum packing volume fraction, φm), e.g., at 5 vol%,
the dispersion formed a viscoelastic gel. The data could be fitted to a relation
describing suspension viscosity, e.g., to that derived by Simha [1952], provided
that the intrinsic viscosity [η] and φm, which depend on the CNT size and aspect
ratio, are treated as adjustable.
A more thorough rheological study of these suspensions was published by
Kinloch et al. [2002]. The experimental value of strain for the linear viscoelastic
response was reported to be 1%. The steady shear flow was highly shear thinning.
In another publication from this laboratory, Shaffer and Windle [1999b] used
aqueous suspension for the fabrication of CNT nanocomposites with PVAl as
the matrix. PNCs with up to 50 wt% loading were prepared. The percolation
threshold for the electrical conductivity was found to be at a CNT loading of
5 to 10 wt%, indicating that CNT do not behave as rigid rods, but are coiled
with a rather low value of the average aspect ratio.
Song et al. [2003] reported that dispersion of MWNT (diameter, d ≅ 25 nm
and length, l ≅ 735 nm) in aqueous medium engendered a liquid crystalline (LC)
behaviour. The transition from isotropic to nematic LC took place at CNT
concentration φ > 0.043.
2.1.3.1.2 Computation of Potential CNT Properties

To explore the possibilities of CNTs the theoretical computation of properties of
individual SWNTs, their aligned crystalline bundles and interactions with polymeric
matrix have been carried out. These lead to sometimes surprising results that require
experimental confirmation.
Structural properties of a CNT crystal were computed by Tersoff and Ruoff
[1994]. The calculations used a valence force model for computing atomic
interactions within each tube, and the Lennard-Jones 6-12 potential to calculate
interactions between tubes in the bundle. The computations were carried out for
41
bundles of CNTs of uniform diameter, ranging from d = 1 to 6 nm. A local

maximum on the elastic modulus (M) versus d was found for dmax ≅ 1.5 nm.
Similarly, the cohesive energy, Ea, versus d was found to go through a local
maximum. The computed value of the equivalent bulk modulus in the radial
direction, Mmax ≅ 0.3 eV/Å3 = 0.69 TPa, is comparable to the tensile modulus in
the axial direction, E = 1 to 1.5 TPa. The computations also indicated that while
the small diameter tubes, d < 2 nm, are perfectly cylindrical, those with larger
diameters are flattened against each other by van der Waals forces.
Using molecular dynamics (MD) Yakobson et al. [1996] studied deformation
of CNTs under load in axial compression, bending and torsion. Depending on the
stress, the nanotubes reversibly transformed into different morphologies, with each
shape change associated with an abrupt release of energy and a singularity in the
stress-strain curve. The authors also noted that the MD computations resulted in
behaviour predicted by the classical continuum shell model with properly chosen
parameters (tensile modulus, E = 5.5 TPa, Poisson ratio, ν = 0.19, and SWNT wall
thickness h = 0.066 nm). The model accurately predicted the SWNT behaviour
beyond the linear response. The simulations showed that CNTs sustain large
deformations without signs of brittleness, plasticity, or atomic rearrangements.
Lordi et al. [1999] studied the distribution of pentagons on CNT tips. Five
pentagons are located at the tube end. From high-resolution TEM and computer-
image simulation, the authors identified the pentagon distribution, which, as it
was shown, controls the oxidation.
However, the applicability of the continuum model to CNT deformation is
not universal [Harik, 2001]. The author derived two non-dimensional parameters
that control SWNT buckling:
1. The SWNT aspect ratio, pCNT ≡ dCNT/LCNT <<1;
2. The axial strain, ε11 = (LCNT - LCNTo)/LCNT <<1.
Furthermore, it has been shown that the properties of a small diameter CNT
with d ≅ 2a1 (a1 is the width of the hexagonal C-C cell) may be calculated using
a beam model. The latter model was advanced by Odegard et al. [2002]. The
authors linked the computational chemistry with solid mechanics by substituting
discrete molecular structures with equivalent-continuum models. The method
equates the molecular potential energy of a SWNT with the strain energy of a
representative truss in the continuum model. The model was used to determine
the effective thickness and bending rigidity of a graphene sheet forming the CNT.
The computations gave significantly higher values for the wall thickness than
that used by Yakobson et al. [1996] (h = 0.066 nm) or measured as the interlayer
spacing between graphene sheets (h = 0.34 nm) – for extensional modes of
deformation h = 0.69 and for shear h = 0.57 nm were found. Similarly, the
computed flexural modulus was higher (E = 1.22 eV) than that calculated from
Robertson et al. [1992] data (E = 0.85 eV).
In these calculations, a uniform hexagonal structure of long SWNTs was
assumed, while the synthetic CNTs do contain defects. Furthermore, the defects
may be beneficial for the CNT-matrix interactions. For these reasons, there is a
certain dichotomy between the computed and measured parameters. The great
benefit of the computations is to show the general functional dependencies between
an idealised structure and performance. While the absolute values of the computed
parameters may not be achievable, the tendency is real, which is important for
the practitioners.
42
Computations involving PNCs with CNTs dispersed in a matrix are scarce.

For example, Lordi and Yao [2000] investigated the molecular mechanics in
nanotube-based PNCs using a force-field molecular-model. The binding energies
and frictional forces between CNTs and polymeric matrices were found to play a
minor role in determining the interfacial strength. The key factor was the helical
conformation of polymeric macromolecules around the nanotube.
Odegard et al. [2001] proposed a method for computing the reinforcing effects
of SWNTs in a PNC. The main premise has been that the size of macromolecules and
nanotubes is similar, thus the basic assumptions of continuum mechanics (that the
densities of mass, momentum and energy do not depend on the length scale) are not
valid. In PNC containing SWNTs the polymer/nanotube interactions depend on the
local atomic structure. Consequently, the bulk mechanical properties of the PNC
cannot be determined through traditional approaches based on continuum. The
adopted approach involved determining: (1) a representative volume element (RVE)
of the molecular structure of the nanotube and adjacent polymer chains by using
MD simulations, and then (2) an equivalent-continuum model of the RVE.
Accordingly, first the vibrational potential energy was computed as a sum of the
energies associated with bond stretching, angle variation and torsion, as well as that
associated with the energy of the non-bonded interactions (van der Waals and
electrostatic effects). These energy contributions were summed over the total number
of bonds in the RVE. MD simulations lead to an equilibrium molecular structure of
a SWNT surrounded by macromolecules. The next stage, the equivalent-continuum
modelling of the RVE, consisted of two main steps: development of an equivalent
truss model and formulation of the equivalent-continuum model. The constitutive
properties of a PE/SWNT system were computed, but the results were not presented.
It is worth noting that the authors ‘concluded’ that for the computation of Young’s
modulus the SWNT wall thickness h = 0.28 nm should be used.
Several reports in the literature, based on direct HRTEM or on Raman spectra,
indicate slippage between the concentric shells of MWNT, between SWNT in a
bundle, and between CNT and the polymeric matrix. Evidently, slippage takes
place at higher strains hence it affects the tensile strength of PNC but not the
initial modulus. The basic question is whether covalent bonding of the matrix
polymer to CNTs may improve the situation. Here the serious danger is that the
change of CNT structure may significantly reduce the mechanical properties of
the tube itself.
Frankland et al. [2002] attempted to simulate the effect of covalent bonding
between (10,10) SWNT and either a crystalline or amorphous PE matrix. This
system was used as a model for the initially non-bonded interface. The simulations
indicated that grafting the matrix to SWNT could have a large influence on shear
properties. The effects of grafting on modulus were not reported.
Bulk properties of CNT/polyimide and CNT/PE systems were also computed
for various CNT composite geometries using the tree-step approach, already
described [Odegard, 2003]. The bulk mechanical properties for various CNT
lengths, volume fractions, orientation, and CNT/polymer interfacial characteristics
were computed. The results indicated that modification of SWNT provides better
adhesion to the polymeric matrix, but might result in poorer overall mechanical
performance than that of non–modified ones, where only van der Waals
interactions between CNT and the matrix are considered.
Frankland et al. [2003] computed the mechanical properties of SWNT
dispersed in an amorphous PE matrix .The main goal of this work was to compare
43
the behaviour of PNC containing continuous and short nanotubes. In both cases
mechanical loading in the axial and transverse direction to the SWNT was applied.
The system with continuous SWNT was highly anisotropic, with greatly increased
modulus in the draw direction. The system with short SWNT did not show
increased modulus relative to the polymer. The MD stress–strain curves were
simulated assuming uniform strain on the entire model.
2.1.3.1.3 Non-Polymeric Applications of CNTs

CNTs have a broad range of electrical, thermal, and structural properties that
depend on the nanotube diameter, length, and chirality, or twist. They come in
insulating, semiconducting and conducting form. The use of CNTs is being
intensely explored in a wide variety of applications, e.g.:
• One of the first applications of CNTs has been in scientific instruments to probe
or move atoms, e.g., for the fabrication of sharp, strong and functionalised AFM
probe tips. Thanks to CNTs the resolution of AFM has been greatly improved.
• Another application of CNTs is as conductive molecular wires. CNTs have
been used for electrostatic charge dissipation (this topic is part of the
discussion on polymeric nanocomposites with CNTs; see Section 2.3.1.5).
• CNTs have been used in vacuum-tube field emission devices (FEDs). For
example, lamps with CNT are twice as bright as traditional, are more energy-
efficient and last ten times longer. Flat panel FEDs are being developed for
computers and TV-sets.
• Since the electrical conductivity of CNTs varies in the presence of diverse
chemical gases, their application as chemical sensors is being explored.
• There are CNT structures that cause the tubes to bend when exposed to
voltage. This opens wide the field of applications as nanoscale actuators,
tweezers, switches as well as mechanical binary memory (on-off) devices.
• A nanotube-based random access memory (RAM) device with a memory
density around 1 GB/mm2 and an operation frequency around 100 GHz has
been reported [Rueckes et al., 2000]. It is expected that CNTs will find
application in smaller and faster computing machines.
• In addition to their high aspect ratio and electronic capabilities, carbon
nanotubes can also function as durable bearings and springs. Induced filling
of the nanotubes further extends the diversity of CNT applications.
• The outstanding thermal conductivity suggests application as heat sinks for
microelectronics, e.g., eliminating the annoying fans in laptops.
• Potential applications of CNTs in structural materials include nanocomposites
for lightweight vehicles for space, air and ground, extra strong fibres and
technical textiles for superstrong bulletproof vests and ropes. SWNTs with
the ability to collapse under compression and then to recover are ideal for
heavy-duty shock absorbers.
• CNTs have also been used for: hydrogen storage, radar-absorbing coatings,
to extend battery lifetime, etc.
The main problem with the use of CNTs is the difficulty in manufacturing them
in pure, reproducible form (hence the high cost, e.g., of purified SWNT ca. US$500
to 1,500/g – see Table 9). The tubes are ‘sticky’ and tend to aggregate, thus when
used as actuators or tweezers they are sluggish, and in mechanical memory devices
44
Table 9 Sources of CNTs (as of December 2002)

Supplier Products Size (nm); Purity Price per g
Bucky USA Fullerenes, SWNT and (not given) US$1,000
MWNT US$100
CarboLex (Sigma SWNT Sample purity: US$60 to
Aldrich) 50-70 vol% 100
CNI, Carbon SWNT by a laser-oven Purified to remove US$750
Nanotechnologies, process catalyst
Inc.
Carbon Solutions SWNT Acid-purified US$500
Guangzhou, China SWNT and MWNT by d = 1.1; purity 50% US$100 to
CVD (10 kg/day) d = 10-40; purity 150 US$10
95% to 20
Hyperion MWNT (bulk quantities) Masterbatches with
15 to 20% CNT
INP Toulouse MWNT by catalytic Purity: >95%; Not
France CVD (bulk quantities) OD = 10-20 provided
Materials and 10-40% carbon arc d = 0.7 to 1.2; US$50 to
Electrochemical formed SWNT in soot, L = 2,000 to 80
Research (MER) and carbon-coated metal 20,000
particles.
Nanocarblab (NCL) Arc-grown SWNT with d = 1.2-1.4; On request
40-90% purity (bulk L = 1,000 to 5,000
quantities)
Nanocs Nanophase carbon OD = 10-50; At
materials: MWNT ~95% L = 1,000 to manufactur-
pure; SWNT; 50,000 (or longer) ing cost.
functionalized CNT, etc.
NanoLab CVD grown MWNT OD = 20-50; US$600
and arrays L = <1,000 20,000 US$300
> 95% pure
Nanocyl S.A., Catalytic CVD grown d = 1; L = 10,000
Belgium nanotubes ID = 6; OD = 25;
SWNT > 60% pure L = 50,000 €500
MWNT > 96% pure €250
Pyrograf® Products, Catalytic CVD grown d = 60-150; "low cost"
Inc. MWNT L = 30,000-100,000
Rosseter Holdings Mainly MWNT (bulk 30-50% purity US$20 to
Ltd. quantities) 25
Sun Nanotech MWNT from China OD = 10-30; US$1.5 to
(purity >80%) L = 1,000-10,000 2.0
45
they are slow. Furthermore, there are serious difficulties in developing interactions
at the nanotube/matrix interface. Thus, the use of CNTs is limited to high value
added applications and niche markets, for example, in electronics and space.
2.1.3.1.4 Sources
As shown in Table 9, numerous organisations on three continents offer CNTs.
Depending on purity, method of synthesis and geographical location, the price
varies from US$1.5 to 1,500 per gram. There is rapid progress in the preparative
methods, which results in increasing purity of the ‘as received’ CNTs. If the
presence of residual catalyst is not detrimental to the desired performance of
nanocomposites, purification may not be necessary and the cost immediately
drops by a factor ranging from 2 to 20 (for MWNT and SWNT, respectively).
Nanocyl offers functionalised CNTs for an additional €50/g. The functionalities
include: -H, -OH, -Cl, -CO, -COOH, -NH2, -SH, -SCH3, etc.
Hyperion Catalysis commercialised unpurified CNTs at US$44/kg (15-20%
purity). These are also available in masterbatches with PC, PBT, PET, PS and
PEEK. GE Co. has developed a polyphenylene ether (PPE)/PA alloy (Noryl
GTX-990EP) with ca. 2-wt% of CNT for electrostatic painting [Scobbo, 1998;
Scobbo et al., 1998]. The alloy has low density (1080 kg/m3), HDT 158 °C,
notched Izod impact strength 600 J/m2, flexural modulus of about 2.4 GMPa,
tensile strength 60 MPa, elongation at break 22%, bulk resistivity of ca. 30 Ωm
and MI = 4.8. The alloy is being used for automotive mirror housings, door
handles, gas tank caps, fuel lines and plastic fenders. The technology is being
adapted to acrylonitrile-butadiene-styrene terpolymer (ABS), PC, thermoplastic
polyester (PEST) and PA automotive compounds.
Toray Industries has developed a catalytic CVD method of producing dual-
wall carbon nanotubes (DWNT), which when commercially produced in 2004
will be available at US10¢/g. According to the Mitsubishi Research Institute, by
2020 the market for fullerenes and CNT will expand to US$3.6 billion. The
projected value of nanostructured materials in 2005 and 2010 is US$96 and
208 billion, respectively [Despotakis, 2003].
2.1.3.1.5 PNC with CNTs for Electrical Conductivity

The earliest use of CNTs in polymeric nanocomposites was for engendering
functional properties, e.g., a semi-conducting, non-linear, light-sensitive current
injection (light-sensitive electrical conductivity) [Romero et al., 1996]; for
molecular optoelectronics consisting of CNT dispersed poly(m-phenylene-
vinylene-co-2,5-di-octoxy-p-phenylene-vinylene) (PmPV) with the electrical
conductivity increased by up to eight orders of magnitude [Curran et al., 1998];
carbon nanotubes helically wrapped by poly(phenyl acetylene) chains for reduced
photodegradation [Tang and Xu, 1999]; polymerisation of pyrrole onto CNT
for enhanced electrical, thermal and magnetic properties [Fan et al., 1999].
MWNTs were dispersed in polyphenylene vinylene (PPV) by spin coating for
high quantum photovoltaic efficiency (ca. twice as large as that of indium-tin-
oxide) [Ago et al., 1999]. A novl PNC of an electroluminescent, conjugated PmPV
and MWNTs was prepared by sonication of the two constituents in toluene
[McCarthy et al., 2000]. As observed under TEM, the polymer crystallised on
the CNT, coating it uniformly and growing out in the form of tree branches.
MWNTs have the ends normally closed, which requires structural defects, viz.
dislocations, sp3-hybridised carbon, or the presence of either pentagons or
46
heptagons. Defects may also occur along the tube body. These nucleate the
crystalline growth of the semiconjugated PmPV.
Sandler et al. [1999] reported that a CNT loading of 0.1 vol% in epoxy
resulted in an increase in electrical conductivity of four orders of magnitude (to
0.01 S/m). A nonionic surfactant has been used to investigate the effects of the
degree of CNT dispersion on conductivity [Gong et al., 2000].
PNCs of MWNTs (d = 80-90 nm) with polypyrrole (PPY) have been prepared
using in situ polymerisation [Chang et al., 2000]. The PNCs were characterised
using SEM, TEM, XRD, Raman scattering, thermogravimetric analysis (TGA),
conductivity, and magnetic susceptibility measuring devices. The PPY adhered to
the CNT exterior, without chemically bonding. The process affected polaron
density and the orientation of PPY macromolecules. The magnetisation of the
composite was found to be the sum of the magnetisations of the components.
The semiconductor-like conductivity of the PNC was larger than that of PPY.
The thermal stability resembled that of PPY.
CNT modification, their conversion into carbides: SiC, WC, etc., coating with
metals or organic electrically conductive polymers has been carried out for a
decade. Recently, one-dimensional PPY/CNT nanocomposites were produced by
electrochemical deposition of PPY onto CNT in well-aligned large arrays [Chen
et al., 2001a]. The coating thickness was controlled by the film-formation charge.
Uniform thickness from 10 to 93 nm was obtained, changing the morphology
from coated individual tubes to filling the gap between all CNT in an array,
forming uniform conductive material.
Unpurified SWNTs with a broad distribution of diameters (dav ≅ 1.1 nm) and
lengths was dispersed in Epon 862 to increase its thermal conductivity [Biercuk et
al., 2002]. At 1 wt% loading the PNC showed a 70% increase in thermal conductivity
at 40 K, rising to 125% at room temperature. The percolation threshold for electrical
conductivity was between 0.1 and 0.2 wt% of the SWNT loading. These results
suggest that the thermal and electrical properties of SWNT-epoxy nanocomposites
may be improved without the need to purify or chemically functionalise the nanotubes.
2.1.3.1.6 Graphite
When electrical conductivity is desired, CNT can be replaced with exfoliated
graphite. Chen et al. [2001b] applied this strategy. The authors used natural
flake graphite with diameters ranging from 50 to 1000 μm. The graphite was
first expanded by treating it with a mixture of concentrated sulfuric acid and
nitric acid for about 16 h. After washing and drying at 100 °C the material was
heat treated at 1050 °C for 15 s, thereby expanding graphite particles in the
c-axis (or orthogonal) direction by a factor of about 350 (compared to the original
graphite). The expanded graphite was mixed with styrene (St) and methyl
methacrylate (MMA) mixture (St/MMA = 70/30), in the presence of benzoyl
peroxide, then heated at 150 °C for 30 min and cooled to room temperature
(RT). A black solid was crushed, rolled on a twin-roll mixer for 5 min, and
moulded into 4 mm thick rectangular plates.
TEM showed that the graphite was dispersed in the form of exfoliated sheets
forming 10-40 nm thick stacks. The transition from electrical insulator to
semiconductor occurred when the expanded graphite content was 1.8 wt% while
at 3.0 wt% loading the electrical conductivity increased from 10-14 to 10-2 S/cm
hence by 12-decades. This enhancement may be attributed to the high aspect
ratio (p), of the dispersed graphite – from the percolation threshold concentration
47
its value, p ≅ 99, was calculated. To preserve the high value of p, hence the
electrical conductivity, extensive roll-milling should be avoided. Addition of up
to 5 wt% of exfoliated graphite linearly increased the tensile strength from 24 to
29 MPa and reduced the notched Izod impact strength from 29 to 19 J/m.
Similarly, Xiao et al. [2001] prepared PNC based on exfoliated graphite with
PS as matrix. Benzoyl peroxide was dissolved in styrene then exfoliated graphite
was added to the reaction vessel. The reaction mixture was stirred for 4 h at
85 °C then for 2 h at 150 °C. Increasing the amount of exfoliated graphite caused
the molecular weight (MW) and molecular weight distribution (MWD) of PS to
increase. The glass transition temperature (Tg) increased to ca. 124 °C. As a
control, the same compositions were prepared by compounding dry blends at
170 °C in a two-roll mill. The in situ prepared PNCs had a higher thermal stability
than either PS or PS/exfoliated graphite prepared by melt blending. The volume
resistivity versus exfoliated graphite content is shown in Figure 8. It is noteworthy
that incorporation of 5 wt% exfoliated graphite into PS, reduced the volume
resistivity by about 3 or 17 decades, respectively for the PNC prepared by melt
blending or by polymerisation. The difference in conductivities originates in the
structural differences between these two types of PNC.
2.1.3.1.7 PNC with CNTs – Thermoset Matrix

The more recent applications of CNT are for enhancement of mechanical
performance. For the optimum effect CNTs should be dispersed within a polymeric
matrix and bonded to it. Furthermore, since the enhancement is related to the
effective aspect ratio, the process must minimise the CNT attrition. The nanotubes
are dispersed by mechanical means or by ultrasonication (1) in a monomer(s),
which is then polymerised, or (2) in a polymer solution.
Figure 8 Reduction of volume resistivity of PS as a function of incorporation of

exfoliated graphite. The upper dependence is for melt compounded PNC, whereas
the lower one is for nanocomposites prepared by polymerisation of styrene in the
presence of graphite [Xiao et al., 2001].
48
The former, reactive approach is preferred for PNC with thermoset matrix.
Most of the early work has been done on epoxy systems. For example, Schadler
et al. [1998] dispersed 5 wt% of MWNT in Epon 828, and then cured it with
triethylene tetraamine. In standard tension and compression tests only relatively
small increases of moduli were found, viz. tension increased from 3.10 (for neat
epoxy) to 3.71 GPa, while compression rose from 3.63 to 4.50 GPa. The Raman
peak position that indicates strain in the C-C bond under load, significantly shifted
under compression, but not under tension. Lourie and Wagner [1998a,b,c; 1999]
reported similar results for SWNT/epoxy PNC. These results indicate a basic
problem with load transfer in tension, particularly severe for PNCs containing
MWNT. Only the outermost layer of each MWNT may be bonded to the matrix.
The interactions between individual layers in MWNT are relatively weak, a van
der Waals-type, and the shear strength between layers is small, similar to that in
graphite (σ12 ≈ 0.48 MPa), confirmed by pullout experiments in AFM [Yu et al.,
2000a]. These authors measured the tensile strengths of MWNT using a
‘nanostressing stage’. The outermost layer showed a Young’s modulus of E = 270
to 950 GPa, and a tensile strength of 11 to 63 GPa. As the straining continued,
the outer layer broke first via the ‘sword-in-sheath’ failure.
Another reason for the relatively low enhancement of epoxy properties by
incorporation of CNT is the tendency of nanotubes to aggregate into bundles. A
nearly constant value of the Raman peak in tension was related to tube sliding
within the nanotube bundles and, hence poor interfacial load transfer between
nanotubes and the matrix [Ajayan et al., 2000]. It is the low modulus of the bundles
that controls the PNC performance, and not the axial modulus of individual tubes.
To enhance the reinforcing effects the authors suggested three methods:
1. Breaking the bundles into individual tube fragments and randomly dispersing
them in the matrix;
2. Radiation or chemical crosslinking of the tubes within bundles to increase
the bundle rigidity and eliminate the inner tube slippage; and
3. Obtaining strong carbon CNT/matrix interfacial interactions.
Cooper et al. [2001] dispersed SWNTs or MWNTs in epoxy and studied the
micromechanical properties using Raman spectroscopy. SWNTs have been
deformed in a diamond anvil pressure cell. Upon hydrostatic compression the
disordered-related peak at wavenumber 2640 cm-1 up-shifted at an initial rate of
23 cm-1/GPa. However, the band downshifted upon application of a tensile stress.
These Raman peak displacements provided evidence of the stress transfer from
the matrix to CNT, thus reinforcement effects. The authors calculated the effective
modulus of SWNT and MWNT dispersed in epoxy as > 1 TPa and about 0.3 TPa,
respectively.
Raman spectroscopy combined with mechanical testing was used to probe
the alignment of CNT in PNC [Wood et al., 2001]. SWNT (0.1 wt%) was
dispersed in a UV curable urethane acrylate oligomer by ultrasonication, mixed
with the curing agent and then sheared to induce flow orientation. The UV cured
films (~150 μm thick) were evaluated, recording the Raman spectral shifts with
strain in the longitudinal and transverse direction. The shifts obtained, in parallel
and perpendicular to the flow direction, were significantly different. The adhesion
between CNT and the polymer exceeded the shear yield strength of the matrix.
Purified MWNTs were dispersed by sonication in a 1,2-dichloroethane solution
of epoxy, polyethersulfone (PES) and 4,4-diaminodiphenylsulfone at 84 °C [Qiao
49
et al., 2002]. Then, the solvent was evaporated and the film crosslinked. The range
of MWNT loadings explored was from 0 to 40 wt%. The bending strength increased
by ca. 136% to ca. 42 MPa. The volume resistivity decreased by six orders of
magnitude from 8.59 × 105 to 0.1415 MΩcm. For the purified MWNT the
percolation threshold of electrical conductivity was high, ca. 20 wt%, indicating
that the CNT were isolated from each other by a layer of polymer.
2.1.3.1.8 PNC with CNTs – Thermoplastic Matrix

As in the case of the thermoset matrices, here there are also two main routes to
formation: (1) by dispersing CNT in a polymer solution, and then evaporating
the solvent, or (2) dispersing CNT in monomer(s) and then polymerising it (them).
However, for thermoplastics a third method, melt compounding has also been
tried. Evidently, the melt compounding method would be preferred in an industrial
environment, thus it is being explored with growing frequency.
1. The Solution Method

Whereas the reactive approach is preferred for thermoset matrices, the solution
method has been favoured for thermoplastics. The method involves preparation
of a polymer solution and mixing it with a dispersion of CNT in the same solvent.
For example, Jin et al. [1998] first ground MWNT, then dispersed it in chloroform,
and sonicated. The suspension was then added to a chloroform solution of
polyhydroxyamino ether (PHAE; a thermoplastic reaction product of an amine
with diglycidyl ether and epoxy; BLOX from Dow). To align the nanotubes, cast
films (with up to 50 wt% CNT) were stretched at T = 95 to 100 °C up to 500%.
The alignment was confirmed by XRD.
Shaffer and Windle [1999b] dispersed CNT in aqueous PVAl solutions
(MW = 85-146 kg/mol), with CNT. Stirring at 480 rpm was required to prevent
aggregation, and then the adsorbed polymer sterically stabilised the system. The
films were cast under controlled water evaporation conditions. The tensile elastic
modulus and damping versus CNT concentration and temperature were examined.
The data could be fitted to the theoretical expression if E = 150 MPa was assumed
for the MWNT modulus and the effective length of 35 nm. A threshold for the
electrical conductivity was obtained at about 20 vol%.
Unpurified SWNTs (d = 5 to 20 nm, l ≈ 1 μm for >70%), produced by the arc
discharge method were used in another study. The CNT and PMMA were mixed
together in toluene in an ultrasonic bath for 24 h. Films (about 200 nm thick)
were obtained by spin casting [Stéphan et al., 2000]. The Raman spectra suggested
that PMMA intercalated into CNT bundles. At low concentration, the quantity
of intercalated PMMA may lead to a destruction of bundles, causing a uniform
dispersion of CNT in the solution. The films were prepared for use in multilayer
diodes.
PS (MW = 48 or 280 kg/mol) was dissolved in toluene, and MWNT was
dispersed in it using high energy ultrasonication for 0.5 to 120 min [Qian et al.,
2000]. Next, the PS solution and MWNT suspension were mixed in an ultrasonic
bath for 30 min. The mixture was cast producing uniform, ca. 0.4 mm thick film
for tensile tests. The optimum sonication time increased with the nanotube length,
viz. 30 and 60 min for 15 and 50 μm long tubes (d = 33.6 nm), respectively. A
homogeneous dispersion was obtained without attrition. Tensile tests of the films
showed that addition of 1 wt% MWNT increases the modulus by 36-42% and
50
stress at break by 25%, indicating significant load transfer across the nanotube-
matrix interface. The observed enhancement of stiffness was found to be in good
numerical agreement with the values calculated from the relation [Hill et al., 2002]:
⎡ 3 1+ 2pK1φ 5 1+ 2K2φ ⎤
Ec /E p = ⎢ x + x ⎥
⎣ 8 1− K1φ 8 1 − K2 φ ⎦
(11)
p ≡ l f /d f ; K1 ≡
(E /E ) − 1 :
f p
K2 ≡
(E /E ) − 1
f p
(E /E ) + 2p
f p (E /E ) + 2
f p
where E is tensile modulus of a composite, polymer or fibre (subscript c, p or f,

respectively), p is the fibre aspect ratio and φ is the fibre volume fraction (calculated
as 0.00487). The modulus of MWNTs depends on diameter; here Ep = 450 GPa
was used. Substituting these parameters into Equation 11 yields the PNC modulus
(1 wt% of MWNT) for p = 446 or 1167 as Ec/Ep = 1.48 or 1.62, respectively.
These values are 10% higher than the experimental data of 1.36 and 1.42,
respectively. As in conventional fibre composites, the crack propagation shows
MWNT pull-out, as well as crack bridging by the nanotubes.
Hill et al. [2002] produced SWNTs and MWNTs using the arc discharge and
CVD methods, respectively. Dispersing into HNO 3, refluxing for 48 h,
centrifuging, washing and drying under vacuum purified the CNTs. Purified
samples were refluxed in thionyl chloride and then treated with poly(styrene-co-
p-(4-(4´-vinylphenyl)-3-oxabutanol)). The functionalised CNTs were soluble in
organic solvents (e.g., toluene, THF, or chloroform), making it possible to
intimately mix them with PS. A transparent cast film ca. 50 μm thick, was prepared
with 5 vol% CNT. Its transparency indicated that miscibility of functionalised
CNT with PS resulted in homogeneous dispersion.
A similar approach was used by [Mitchel et al., 2002], who dissolved anionic
PS in toluene at room temperature, and then added appropriate quantities of
either pristine SWNT or its functionalised version. The latter contained 4-(10-
hydroxy decyl) benzoate groups attached to 1 in 66 carbon atoms. The solutions
were dried at room temperature, and then annealed at 180 °C under vacuum and
tested. Nonlinear viscoelastic dynamic melt flow behaviour was absent for PNCs
containing 0.5 wt% of non-functionalised SWNT, but present for PNCs containing
0.35 wt% of the functionalised CNT. Furthermore, the functionalised PNC had
the percolation threshold at 1 vol% SWNT, while that for the pristine SWNT-
based composites was twice this amount. Functionalisation resulted in better
dispersion and significant enhancement of performance.
Poly(p-phenylene benzobisoxazole) (PBO) has been synthesised in the presence
of 0, 5 and 10 wt% SWNT (diameter of ca. 0.95 nm) [Kumar et al., 2002]. The
reaction was conducted in polyphosphoric acid (PPA) at 100, 160 and 190 °C
for 36 h, and then the product was spun into fibres using dry-jet wet spinning.
Dried fibres were heat-treated at 40 MPa tension in N2 at 400 °C for 2 min. No
CNT aggregates were observed under a polarised microscope. The tensile
properties of the PBO fibre containing 10 wt% SWNT indicated that the modulus
increased by 21%, strain at break by 40%, and the tensile strength by 61%. The
compressive strength was also higher by 43%. The PBO/SWNT systems
51
demonstrated less thermal shrinkage and less creep under stress. The morphology
of these fibres suggests a co-alignment of the SWNT and PBO fibrillae within the
oriented composite fibre.
2. The Reactive Method

Jia et al. [1999] reported on the reactive preparation of PNC with MWNT dispersed
in a PMMA matrix. Two CNTs were used: (1) as prepared (purity > 98%), and (2)
the former CNT ground in a ball mill for 20 min, boiled for 0.5 h in concentrated
HNO3 then washed and dried. TEM of the latter sample showed significant
fragmentation of the original CNTs. The CNTs were dispersed in methyl
methacrylate (MMA), the free radical initiator (2,2´-azobisisobutyronitrile (AIBN))
was added and the reaction was conducted at T = 358 to 363 K. For the untreated
CNT the required amount of AIBN was three times greater than what was needed
to polymerise MMA alone. The performance of the resulting PNC was poor. For
the ball milled CNT there was no need for extra initiator and reasonable
enhancement of performance was obtained (at 5% CNT tensile strength increased
30%, toughness 11%, hardness 42% and HDT by 39 °C (compared to PMMA)).
The authors postulated that about 24% of the untreated CNTs were attacked by
free-radicals that open their π-bonds. A C-C bonding may be generated between
the nanotube and the matrix. When the π-bonds are at the curved points of the
nanotube, the free radical attack may result in breaking the CNTs, which become
shorter and with opened ends.
The emulsion polymerisation method was used for the preparation of PNC
with polyaniline (PANI) as a matrix in which 0.2 to 10 wt% of CNT was dispersed
[Deng et al., 2002]. TEM and XRD showed a network made of nanotubes and
PANI fibres. However, according to FTIR there was no direct interaction between
these two components. The conductivity and thermal properties depended on
CNT content, viz. PANI conductivity increased 25-fold by incorporation of
10 wt% CNT.
3. The Melt Compounding Method

Considering the high cost of CNT and the need to work with small quantities of
material, the early publications revealed quite unorthodox melt processing methods
[Haggenmueller et al., 2000]. The authors prepared SWNT/PMMA nanocomposites
with enhanced mechanical and electrical properties by engendering high CNT
alignment. First, PMMA was dissolved in DMF and combined with the SWNT
dispersion in this solvent (DMF was used for purification of the CNT). The cast
film was subsequently folded and broken into pieces, then hot pressed at 180 °C.
The procedure was repeated 30 times. The final dispersions (containing 1 to 8 wt%
of SWNT) were melt spun to draw down ratio: DR = 20 to 3600. The elastic
modulus and yield strength of the PNC fibres increased with CNT content and
DR. Raman spectroscopy indicated that the nanotubes were well aligned. The
electrical conductivity increased with CNT content, e.g., for 1.3 to 6.6 wt% SWNT,
from 0.118 to 11.5 S/m in the flow direction and from 0.078 to 7.0 S/m in the
perpendicular direction.
Lozano and Barrera [2001] used an internal mixer for dispersing 2 to 60 wt%
of CNT in PP. The CNT was MWNT-type prepared by CVD using large diameter
catalyst particles, which resulted in large nanotubes, having diameter of ca. 80 to
200 nm and length of 30 to 100 μm. Melt compounding eliminated CNT
52
agglomerates yielding isotropic, non-porous PNC. Incorporation of the nanofiller

increased the rate of crystallisation as well as the total crystallinity (from 49 for
PP to 69 for PP with 60 wt% CNT). The tensile yield strength reached maximum
at 5 wt% loading – for higher CNT content the strength was reduced below the
neat PP value. By contrast, the dynamic tensile modulus at room temperature
increased from ca. 5 (for PP) to ca. 18 GPa (for PP with 60 wt% CNT), i.e., by
350%. The authors associated the lack of reinforcement by the CNT with the
increased brittleness of the PP, caused by its inability to further crystallise on
deformation, ‘a property brought on by the molecular restrictions caused by the
fiber dispersion’.
High purity MWNT (purity >95%, diameter 20 to 30 nm, length 20 to
100 μm) was uniformly dispersed in PP, ABS, PS or HIPS in an internal mixer
[Andrews et al., 2002]. The samples from the mixer were crushed, and then
compression moulded into films containing v = 0.5 to 5 vol% of CNT. The
percolation threshold for surface resistivity varied with the matrix; for PP, PS
and ABS it was 0.05, 0.2 and about 9 vol%, respectively. The mechanical
properties showed small improvements. Addition of 12.5 vol% of MWNT to PP
resulted in a doubling of the modulus and a decrease of tensile strength by a
factor of 1.7. For PS systems the modulus increased with 25 vol% loading from
1.9 to 4.5 GPa, along with a linear increase of the glass transition temperature:
Tg (°C) = 96 + 0.48v (vol%). For the other two systems there was little change in
the mechanical properties. The observed failure (nanotubes pull-out) suggested
that surface treatment might improve interfacial bonding and increase tensile
strength.
Pötschke et al. [2002] used a commercial PC compound from Hyperion, with
15 wt% of MWNT (d = 10 to 15 nm; L = 1 to 10 μm). The masterbatch was
prepared by melt compounding in a Buss Kneader. The authors diluted it with PC
in a short TSE (L/D = 10) at 240 °C, to obtain concentrations of 0.5, 1, 2 and
5 wt%. The percolation threshold for electrical conductivity was somewhere
between 1 and 2 wt% – the volume resistivity decreased from 1014 to about
102 Ωcm. The dynamic melt flow of compression moulded PNC was studied at
260 °C and the frequency range from 0.1 to 100 rad/s. Nonlinear viscoelastic
behaviour was evident for a MWNT loading above 1 wt%, coinciding with the
electrical percolation threshold. The increase of melt viscosity with nanotube
composition was higher than that reported for either nanofibres with larger
diameters or for carbon black. This difference is caused by the high aspect ratio
of the MWNT, p > 67.
Melt dispersion of SWNTs and MWNTs in PC has also been described [Sennett
et al., 2003]. The MWNT prepared by CVD had d = 20 to 50 nm and L ≅ 20 μm;
hence a respectable aspect ratio of about 1000. A conical micro-TSE was used at
250 to 266 °C, 80 rpm under N2, and the compounding time was varied from
1 to 120 min. To induce orientation, the extrudate was spun at a fibre draw
speed of 10 to 70 m/min. Good dispersion was obtained even at short residence
time (1 to 5 min), but longer mixing further improved the dispersion. Similarly,
the CNT orientation improved as the fibre draw rate increased, but to obtain
good alignment draw rates > 70 m/min were required. SWNT were found to be
more difficult to disperse than MWNT. The use of lower molecular weight resin
was reported to facilitate the dispersion. Unfortunately, this short and interesting
note does not contain any data on the electrical conductivity or mechanical
performance.
53
2.1.3.2 Rod-Like CdSe Nanocrystals

These nanocrystals show size- and shape-dependent optical and electrical
properties. Quantum rods of CdSe were prepared by pyrolysis of dimethyl
cadmium and selenium tributyl phosphine solution in phosphonic acid. The rods
had 3.0 to 6.5 nm diameter and were 7.5 to 40 nm long. As expected, the band
gap shifted to lower energies with increase of both the diameter and the length of
these crystals [Li et al., 2001a].
2.1.3.3 Imogolite
Imogolite (from imogo = volcanic ash in Japanese) is weathered pumice, discovered
in Murakasami, Japan and described in 1962 by Yoshinaga and Aomine. This
para-crystalline phyllosilicate has a composition written either as: Al2SiO3×(OH)4;
SiAl2O5 · 2.5 H2O or Al2O3×SiO2×nH2O, with molecular weight per crystalline
unit cell of 4754. However, while the nominal Si:Al ratio is 2, the measured one
varies from 1.05:1 to 1.15:1. Imogolite occurs as tubes of several micrometers in
length, having inside diameters of 1.0 and outside diameters of 2.0 – 2.52 nm;
occasionally the tubes may branch out. The nanotubes have good rheological,
adsorptive, and surface properties due to their unique structure and functional
groups on the surface. For example, the tubes may form raft-like structures with
honeycomb-shaped cross-section [Kajiwara et al., 1986; Donkai et al., 1993].
Imogolite may also be synthesised at T = 25-100 °C from a dilute solution of
AlCl3 and Na4SiO4 via precipitation reactions. The imogolite structure has Si in
tetrahedral coordination and Al in octahedral coordination. Imogolite has been
used for reinforcing water-soluble polymers, viz. polyvinyl alcohol (PVAl)
[Hoshino et al., 1992a] and hydroxy propyl cellulose (HPC) [Hoshino et al.,
1992b]. Imogolite has several rather broad, low XRD peaks. Conclusive
identification can be made by FTIR and TEM. Its CEC is 1.7 mol/g at pH 7.0, the
calculated specific surface is 1000, while its measured value is 900 to 1100 m2/g.
The density is 2.7 g/ml, hardness = 2 to 3, refractive index (nD) = 1.47 to 1.51.
The crystals are transparent and fragile [Gabriel and Davidson, 2000].
2.1.3.4 Vanadium Pentoxide, V2O5

Since CNTs are expensive and inhomogeneous (because of a wide range of
chirality), V2O5 nanofibres have been proposed as an alternative. These may be
formed by polycondensation of vanadic acid (HVO3) in water. The individual
flat fibres are ca. 10 nm wide, ca. 1.5 nm thick and up to several microns long. A
single fibre has a double layer structure, each consisting of two V2O5 sheets.
Consequently, each fibre consists of only four layers of vanadium atoms and
represents a wire of molecular dimensions. Owing to the disassociation of surface
V-OH groups (V-OH + H2O ↔ V-O– + H3O+) the fibre surface is negatively
charged. The V2O5 fibres are being investigated for electronic applications [Sinn,
1999]. Furthermore, V2O5 can also be formed into ribbons, sheets or nanotubes.
V2O5 is available in a diversity of morphologies. Commonly, it is an orange-
yellow to rust-brown orthorhombic crystalline solid with molecular weight of
304.15, density of 3,350 kg/m3, melting point of 670-685 °C and boiling point
of ca. 1800 °C (it starts losing oxygen at 700 °C) [Macintyre, 1992; Cotton et
al., 1999]. V2O5 is used as a catalyst, e.g., in the oxidation of SO to SO2, of
alcohol to acetaldehyde, of aniline to aniline black, for the manufacture of yellow
leaded glasses with inhibited UV light transmission, for depolarisers, etc. Its main
54
commercial use is as colorant, with colour strengthened by tin and zirconia.

Although yellows can be prepared with antimony, vanadium is stable at higher
temperatures.
Wider V2O5 fibres, e.g., 1×25×(200 to 600) nm, are known as molecular
ribbons. These may also be synthesised at pH2 from VO(OH)3x2H2O. The ribbon
thickness is determined by the molecular structure. A magnetic field aligns the ribbons
in the field direction. The ribbons are promising new materials that may be used as an
important catalyst, a building block for electronic devices and reinforcing material
with a strongly anisotropic structure [Gabriel and Davidson, 2000].
During the hydrothermal synthesis, organic templates control the crystallisation
mode. This method has been used to prepare layered structures of V2O5 in the
presence of coordination compounds, viz. 2,2´-bipyridine and ethylene diamine
[Nesper et al., 2001; Ollivier et al., 1998]. Muhr et al. [2000] prepared V2O5 and
mixed vanadium oxide nanotubes (VONT), reacting either primary n-alkyl amines
(CnH2n+1NH2; 4 ≤ n ≤ 22) or α,ω-diamines (H2N-CnH2n-NH2; 14 ≤ n ≤ 20) with
vanadium (V) alkoxide, followed by hydrothermal treatment. The monoamine
templates tend to form wide tube openings and tube walls consisting of 2 to
10 layers, whereas the diamines lead to tubes with comparatively thick walls with
>10 layers. The amines get intercalated into VONT structures that have 2 to
30 layers, resulting in an outer diameter (OD) = 15 to 100 nm and tube length
L = 500 to 15,000 nm. The interlayer distances (1.7-3.8 nm) increase with the
length of the alkyl chain of the amines. The VONT collapse into amorphous form
at about 250 °C.
In another publication from the same laboratory [Krumeich et al., 2000]
VONT was similarly prepared from vanadium alkoxides and amines by a sol-gel
reaction and a subsequent hydrothermal treatment. The product showed bent
VOx layers rolled into tubes. The layer structure inside the tube walls is frequently
disordered, and several types of defects were identified. Vanadium oxide in the
form of scroll-like nanorolls was prepared for use as a cathode material for
rechargeable lithium batteries [Edström et al., 2001]. The rolls consisted of several
layers, separated by templates, viz. hexadecyl amine (C16H33NH2) or dodecyl
amine (C12H25NH2).
2.1.3.5 Inorganic Nanotubes

Nanotubes are not limited to carbon and V2O5. In 1992 inorganic fullerene-like
nanotubes of tungsten disulfide were described [Tenne et al., 1992]. It seems that
any compound that forms stable two-dimensional sheets can be rolled into a
nanotube. Different synthetic methods may lead to nanotubes having different
type, size and yield. The methods range from substitution of atoms in an already
fabricated tube [Hang et al., 1998], laser heating [Laude et al., 2000] and arc
discharge [Cumings and Zettl, 2000] to template-assisted synthesis [Shenton et
al., 1999; Zhang et al., 2000a].
For example, 2-D tungsten disulfide (WS2) sheets transformed into nanotubes
are extremely inert and durable. They show potential for novel scanning probe
microscope (SPM) tips. A standard AFM tip will rarely remain sharp for more
than a few hours under normal operating conditions. WS2 nanotube tips are so
rigid and inert that they have been used for months with no sign of wear.
Boron nitride (BN) provides another example. These inorganic nanotubes
may be synthesised in a discharge using a tungsten electrode hollowed and filled
with boron nitride powder [Chopra et al., 1995]. In contrast to CNTs, the ones
55
from BN should all be insulating with a band gap of about 5 volts. Another
method of preparation is by means of a solid-state process. Graphite and
hexagonal boron nitride powders were ball milled at room temperature, then
annealed below the melting points for both graphite and boron nitride, at
T ≤ 1300 °C. The latter stage leads to the nucleation, re-ordering and crystal
growth of hexagonal C and BN nanotubes of both cylindrical and bamboo-like
morphology. High energy ball milling was found to result in solid-state phase
transformations and chemical reactions [Chen et al., 1999a].
Gole et al. [2003] prepared and characterised silica-based nanospheres
(monodispersed, with d ≤ 30 nm diameter), nanotubes, nanofibre arrays, and
nanowires. The agglomeration of small nanospheres (d ≤ 10 nm) into wire-like
groupings has suggested a possibility of growing silica nanotubes (SiNT) by a
more efficient agglomeration process. The SiNT were generated from silicon
particles at 1400 oC. Their outer diameter was, OD = 70 to 80 nm, with wall
thickness of ca. 20 nm. Biaxially structured SiC-SiOx nanowires have now also
been generated from C/Si/SiO2 mixtures. Depending on the size, the Young’s
modulus of these structures is 50 to 100 GPa.
2.1.4 Other Nanoparticles
2.1.4.1 Spherical or Nearly-Spherical Particles

For several decades carbon black and fumed silica with particle size below 50 nm
have been used in tyres, tubings, sealants, etc. More recently, functionalised silica
nanoparticles were copolymerised with methyl methacrylate to generate transparent
films with good surface finish and controllable (by silica content, x) refractive index:
nD = 1.509 – 0.00035x [Yu et al., 2003].
Newer, nanosized particles are metal, metal oxide, nitride, sulfide or carbide
powders. They find use in the preparation of materials with specific electrical
and/or magnetic properties. CdSe, ZnS, CdS, PbS, and many others have been
used for the preparation of functional PNC, for example showing non-linear
optical quantum-size or other semiconductive properties. For example, nanosized
dispersions of ZnS and CdS in PVAl were prepared by a hydrothermal method.
Thus, ZnCl2 or CdCl2 were dissolved in an aqueous solution of PVAl, then CS2
was added and the mixture was heated in an autoclave for 8 h at 120 °C. Uniform
particles of ZnS and CdS had a diameter of ca. 60 to 100 and 80 to 120 nm,
respectively [Qian et al., 2000]. The same solvo-thermal method was used for
the preparation of nanocrystalline particles of tin chalcogenide or chromium
nitride [Qian et al., 1999a].
Electrolytic precipitation of Cu in pores of solvent crazed polymers (e.g., PVC
or PP) resulted in the formation of ca. 15 to 20 nm diameter particles [Arzhakowa
et al., 2003]. The size and concentration of metal particles depended on the
extent of the crazing.
2.1.4.2 Sol-Gel Hybrids

Sol-gel hybrids are produced by methods which are based on the reaction of
precursors (e.g., metal alkoxides M(OR)n) that result in the formation of a
nanometric dispersion of an inorganic phase [Mauritz et al., 1995; Wen and
Wilkes, 1996; Deng et al., 1998; Hand et al., 1998]. Hydrolysis and condensation
leads to the formation of metal oxopolymers. The sol-gel process takes place
56
under relatively mild, well controlled conditions, hence inorganic and organic
components can be formed at the nanometre scale, at a wide range of composition.
The hybrids usually have ≥ 10% dispersed phase. Two types of hybrids are
recognised:
1. Those where only weak interactions between the organic and inorganic species
exist (viz. van der Waals, hydrogen bonding or electrostatic interactions).
2. Where the inorganic and organic components are chemically bonded by either
covalent or ionic-covalent bonds. Examples of PNCs prepared by the sol-gel
methods are provided in Table 2.
Several methods of PNC preparation by the sol-gel method have been developed
[Brinker and Scherer, 1990]:
The principal sol-gel process involves the formation of a colloidal suspension

(sol) and gelation of the sol to form a network in a continuous liquid phase (gel).
Often the hydrolysis is catalysed using either acids (acetic acid, HCl, HF, etc.),
bases (ammonia, amines, KOH, etc.) or salts (e.g., KF). The rate and extent of
the hydrolysis reaction depend on the strength and concentration of the catalyst.
From a homogeneous solution of an oligomer or polymer with inorganic precursor,
chemical reactions lead to dispersion of the inorganic phase in the polymeric
matrix. The precursors consist of a metal or metalloid compound with reactive
ligands. Metal alkoxides are most popular because they readily react with water.
However, other compounds, viz. aluminates, titanates, and borates are also used,
often mixed with silicon alkoxides. After the reaction, the solvent must be removed
before the dispersed phase has time to aggregate. Control of the interface is crucial.
The use of electrostatic charge or hydrogen bonding interactions may be required.
For example, silica nanoparticles can be generated by hydrolysis and condensation
of silicon tetraalkoxides, Si(OR)4, in polyoxazoline ethanol solution. Hydrogen
bonding between Si-OH silanol groups and the carbonyl and amide functionalities
of the polymer ascertained homogeneous and stable dispersion. It is noteworthy
that these advantageous properties could be enhanced by grafting the polymer
with -Si(OR)3 groups, which after hydrolysis increase the chemical affinity between
organic and inorganic components.
From a homogeneous solution of an inorganic precursor and a monomer,
chemical reactions lead to the formation of inorganic gels, followed by
polymerisation. For example, hydrolysis and polycondensation of silicon alkoxides
in the presence of methyl methacrylate (MMA) leads to PNC with superior optical
and mechanical properties.
57
The pre-formatted building blocks (e.g., oxometallic clusters, CdS or CdSe

nanoparticles, metallic or oxides colloids) are functionalised, saturated with an
oligomer or monomer, and polymerised. A review of this strategy has been
presented [Anonymous, 1999a].
The sol-gel methods lead to the preparation (often at room temperature) of
PNC with inorganic nanoparticles that engender improved hardness, optical
transparency, chemical durability, tailored porosity, and thermal resistance. The
materials are used in optics, protective and porous films, optical coatings, window
insulators, dielectric and electronic coatings, high temperature superconductors,
reinforcement fibres, fillers, and catalysts [Zeigler and Fearon, 1990].
The phase separated morphologies of certain copolymers and ionomers can
act as 3-dimensional templates during the sol-gel polymerisation of silicon alkoxide
and organo-alkoxysilane monomers. In the presence of these templates the
inorganic oxide or organically modified silicate nanophases grow within specific
nanoscopic domains. For example, Mauritz et al. [2001] prepared a variety of
organic/inorganic nanocomposites via in situ sol-gel polymerisation of metal
alkoxide and organo-alkoxysilane monomers as well as copolymerisation of their
mixtures. Thus, poly(styrene-b-isobutylene-b-styrene) was first sulfonated and
neutralised, then tetraethoxy silicate was dissolved into the ionic domains.
Nafion® perfluorosulfonic acid membrane and Surlyn® ionomer have been
used as a templates for several silicate and titanate compounds. After hydrolysis
and condensation of the ≡Si-OH groups, PNC with highly regular structure of
spherical dispersions, d = 2 to 5 nm, was obtained. The polymer ionic groups are
entrapped within the silicate or titanate nanoparticles.
2.1.4.3 Polyhedral Oligomeric Silsesquioxanes (POSS)
2.1.4.3.1 Origin and Structure

Ladenburg first described the synthesis of silsesquioxanes in 1875. In 1915 Meads
and Kipping studied the hydrolysis and condensation reactions of trifunctional
silanes, concluding that polycondensation of ‘siliconic acids’ leads to complex
mixtures of little synthetic value. This delayed investigation on silsesquioxanes
until 1955, when Barry et al. [1955] described crystallisable
organosilsesquioxanes, defining the atomic ratio as: O:Si = 3:2, as for example,
in H8Si8O12 – the siloxy analog of cubane (C8H8) in which C-C bonds are replaced
by Si-O-Si. However, silsesquioxane does not have to be cubic – amorphous and
ladder-like structures are also known. In 1965 Brown and Vogt conducted a
controllable synthesis of silsesquioxanes.
According to Marcolli and Calzaferri [1999] three synthetic routes have been
used: cohydrolysis of trifunctional organo- or hydro-silanes, substitution reactions
with retention of the siloxane cage, and corner-capping reactions. Murugavel et
al. [1999] discussed the chemistry of silanetriols and triaminosilanes as useful
synthons for the generation of three-dimensional metallosiloxanes. Starting from
stable N-bonded silanetriols and triaminosilanes, metallosiloxanes and
iminosilicates with aluminium, gallium, indium, titanium, zirconium, tantalum,
tin and rhenium incorporated, a heterosiloxane framework could be prepared.
Since some of these contain hydrolysable functionalities they may be used as
starting materials for the preparation of supramolecular cage structures.
Functionalised POSS may be synthesised by polycondensation of trifunctional
RSiY3, where R is a hydrocarbon and Y is a hydrolysable functionality such as
58
chloride, alkoxide or silanol. However, this route does not control the placement
of the functionality on the cage. Functionalisation of fully substituted silane
compounds by hydrosilylation or chlorination also does not lead to controlled
substitution. Silylation of anionic species has been reported to produce
functionalised species, e.g., via: (a) the addition of hydrogen atoms bonded directly
to silicon atoms onto aliphatic unsaturated compounds, or (b) the addition of
sulfur onto aliphatic unsaturated compounds. The type of organic functionality
that can be incorporated on the cage is limited. These methods have low yield
and a large percentage of impurities from side reactions that must be removed.
The reaction between trisilanol with a variety of compounds of the type R´´MX3
(R´´ = alkyl, alkenyl, aryl, H; M = Si, Ge, or Sn; X = halogen or alkoxide) leads to
a variety of monomeric Σ8 silsesquioxanes.
In the early 1990s, Lichtenhan reacted trisilanol with R´SiCl 3 or
R´Si(OCnH2n+1)3 starting a new class of monomers called polyhedral oligomeric
silsesquioxanes, or POSS (see Figure 9). In this case the R´ group was polymerisable
or useful for grafting reactions, or sol-gel processing, e.g., acidic, acrylic, alcohol,
amine, α-olefin, epoxy, ester, halides, isocyanate, organo-halides, phenol, silanes,
silanols, styrenic, vinyls, etc. The process that leads to functional POSS was
patented [Lichtenhan et al., 1999]. In the presence of a metathesis catalyst an
effective amount of olefins of alkyls, cyclics, aryls, siloxyls or their isomersis able
to provide POSS with 1-8 reactive functionalities. The process has been used in
the US Air Force Laboratory to synthesise dozens of types of POSS. The products
are soluble in common solvents, e.g., chloroform, hexane or THF.
The chemical structure of POSS is: (RSiO1.5)Σn, thus as the name indicates
(sesqui = ‘one and a half’) intermediate between silicas (SiO2)n and silicones
(R2SiO)n. For most POSS: Σn = 8, but Σn = 6, 10 or 12 are also available. The size
of the cage varies from about 0.7 to 3 nm. Polyhedral siloxanes or silsesquioxanes
sensu stricto are topologically equivalent to a sphere and are also called sphero-
siloxanes. Most POSS compounds are crystalline, but changing the R-group may
result in liquid crystal or liquid-like behaviour.
The octasilsesquioxanes (Σn = 8) have cube-shaped molecules that consist of
a Si8O12 core and eight reactive sites that may be differently functionalised. From
the point of view of polymer technology the mono-substituted species, R´R7Si8O12
Figure 9 Reaction between trisilanol and a compound of the type R´SiX3 (R´ =
reactive group; X = halogen or alkoxide) leads to a variety of monomeric Σ8
silsesquioxanes, or POSS monomers [Lichtenhan et al., 1999].
59
(where R´ ≠ R are substituents) are the most interesting – the group R´ may provide
an ability to the octasilsesquioxane to enter polymerisation, copolymerisation or
grafting reaction, whereas the other functionalities, R, make the system miscible.
It should be noted that incorporation of POSS into crystallisable macromolecules
reduces the crystallinity, which in turn tends to lower the chemical and solvent
resistance.
A new type of PNC formation was recently proposed by Ricardo et al. [2001].
The authors started with octakis(hydrido dimethyl siloxy) octasilsesquioxane
Q8M8H, converting it to octa-ethylbenzyl chloride. Using bromoester as an initiator
and CuCl as a catalyst, atom transfer radical polymerisation (ATRP) was employed
to produce star-type PMMA with arms having controlled molecular weights.
The concentration of catalyst and initiator control MW, MWD and the star-star
coupling reactions. The arms had Mn = 4 to 15 kg/mol (varying with conversion),
and the polydispersity MW/Mn = 1.2 to 1.5. The number of arms per Q8M8H-unit
was found to vary from 6.2 to 7, hence less than the maximum of 8. The lower
number of arms may result from star-star coupling reactions. The new PNCs
should have unique properties, combining those of nanocomposites with those
of the controlled star-branched polymers [Roovers, 1985]. Mechanical properties
of these PNCs have not yet been reported.
2.1.4.3.2 Properties
POSS with reactive groups may be incorporated into virtually any polymer either
by compounding (as a nanofiller), copolymerisation or blending [Lichtenhan et
al., 1993; Lichtenhan, 1995; Haddad and Lichtenhan, 1996; Shockey et al., 1999;
Feher et al., 1999].
POSS may provide a variety of property enhancements to existing resin systems.
Owing to its chemical nature, POSS can be used to upgrade the thermal and
physical properties of most plastics. The following isotropic enhancements have
been reported for POSS-copolymers and blends: higher decomposition
temperature, Tg increased by 100-200 °C, lower flammability (delayed combustion
and reductions of heat evolution), bulk density reductions of up to 10%, increased
O2 permeability, reduced thermal conductivity, improved resistance to oxidation,
increased modulus and hardness while maintaining the stress and strain
characteristics of the base resin, good processability and mouldability (viscosity
reduction of up to 24% was reported) [Lichtenhan, 1996; Tsuchita et al., 1997].
Substituted POSS have been used as Wittig reagents, precursors to SiC powders,
low dielectric constant materials, alumino-and gallio-silicates, silica-reinforced
composites, a variety of microporous materials, etc. A variety of functional groups
have been attached to POSS, viz. acrylates, silanes, silanols, olefins, epoxies,
amines, esters, phenols, styrenics and thiols. Functionalised POSS was polymerised
to yield hybrid inorganic-organic homopolymers or copolymers [Tsuchita et al.,
1997].The free radical reaction of propyl-methacryl-POSS gives POSS macromers,
which can undergo hydrosilylation into oligomers and polymers with improved
mechanical properties, increased thermal stability to oxidation and resistance to
degradation by UV [Lichtenhan, 1995]. Properties and performance of POSS-
based polymers continue to be explored [Zheng et al., 2001; 2002a,b; Li et al.,
2002]. The modern POSS is only about 10 years old, but between 1993 and
2002 over 160 articles on POSS were published.
POSS have been successfully incorporated into a number of thermoplastic
matrices such as styrenics, acrylics, LCP, siloxanes, polyamides and more recently
60
PO. The resins are inherently reinforced by the presence of the inorganic cages of
size between a molecule and a macromolecule. By controlling the nature of the
substituted groups, R and R´, POSS has controllable reactivity, miscibility, low
density, neutral pH and low VOC. Their polymers or copolymers are isotropic,
free of metals, and transparent.
In Figure 10, the compositional variation of Tg and the decomposition
temperature for 10 wt% mass loss (Td) is shown for a series of copolymers. These
were prepared by free-radical polymerisation of α-methyl styrene with styryl-based
POSS. The latter contained one styryl-ethyl polymerisable group and seven inert
R-groups, either cyclohexyl (-c-C6H11) or cyclopentyl (-c-C5H9). Thus, the
macromer had a spherical (Si8O12) core, surrounded by seven inert groups for
solubility and one reactive. It was found that the cyclohexyl derivative is about
twice as soluble as cyclopentyl [Haddad and Lichtenhan, 1996]. The difference
in behaviour between these two types was small, but cyclohexyl-substituted POSS
showed better performance.
Figure 11 shows the variation of Tg for two series of isobutyl-styryl-POSS
copolymers with either vinylpyrrolidone (P4VP-POSS) or acetoxylstyrene (PAS-
POSS). The Figure demonstrates that POSS may increase the Tg, but at a relatively
high POSS content – for both systems incorporation of POSS initially leads to a
reduction in the HDT. Since the ratio of molecular weight of POSS to P4VP is
8.3 the observed minimum at about 2 mol% is equivalent to 14 wt% of POSS.
The authors [Xu et al., 2002] rationalised this behaviour by noting that the POSS-
containing copolymer had reduced molecular weight and narrower molecular
weight distribution. Furthermore, the Tg depends on:
Figure 10 Composition dependence of the glass transition (Tg) and decomposition

(Td) temperatures for copolymers of 4-methyl styrene with styryl-based POSS. In
the latter C5 and C6 stand, respectively, for R = -C5H9 and -C6H11 [1addad and
Lichtenhan, 1996].
61
Figure 11 Variation in glass transition temperature for two series of

vinylpyrrolidone random copolymers with POSS (P4VP- POSS) and
acetoxylstyrene with POSS (PAS-POSS). Data [Xu et al., 2002].
1. A diluent role of POSS that reduces the dipole-dipole interaction of the matrix
monomer,
2. The dipole-dipole interaction between POSS siloxane and the polar carbonyl
of organic polymer, and
3. The POSS-POSS intermolecular interaction.
At a relatively low POSS content, the diluent role dominates, thus Tg decreases.
At a high POSS concentration, the POSS-PAS, POSS-P4VP and POSS-POSS
interactions cause the Tg to increase.
Figure 12 illustrates the variation of Tg for copolymers of butyl methacrylate
(BM) with up to 50 mol% of cyclopentyl-POSS-methacrylate – a significant
increase from 50 to 245 °C was observed. The experimental data may be described
by the dependence:
[ 3/2
Tg = ( 1+ K * w 1w 2 ) ⋅ w 1Tg1
3/2
+ w 2Tg 2 ] (12)
where wi and Tgi are, respectively, the weight fraction and glass transition temperature
of component i, and K* is the binary interaction parameter between them.
The relation was derived for strongly interacting miscible blends [Utracki,
1989], thus the agreement implies that there are strong thermodynamic
interactions between the two types of mers expressed by the high value of the
binary interaction parameter: K* = 6.39 ± 0.52. Since such an effect has not been
observed in copolymers of BM with methyl methacrylate (MM), it is evident that
stiffening of the copolymer macromolecules involves the POSS units. The
correlation coefficient squared for the dependence in Figure 12 is r2 = 0.999. The
dependence predicts that Tg should decrease at POSS loadings over 50 wt%.
62
Figure 12 Glass transition temperature of polybutyl methacrylate and its

copolymers with up to 50 mol% of heptacyclopentyl methacrylate (CpPOSS-MA)
[Lichtenhan, 1995].
Points – experimental, line calculated from Equation 12.
Figure 13 illustrates the effect of melt compounding PP with 10 wt% of POSS =

[CH3SiO1.5]S8. At T < Tg ≈ 0 °C the stiffening effect is negligible, whereas at Tm >
T > Tg the complex tensile modulus (E*) increased by a factor of up to two, or
the usage temperature window increased by 45 °C, i.e., the POSS compound at
145 °C has the same value of E* as neat PP at 100 °C [Schwab et al., 2001]. In
other words, POSS is not effective in the glassy state, but is able to ‘reinforce’ PP
at T > Tg. (Similar effects were observed for norbornyl elastomer with cyclopentyl
or cyclohexyl POSS [Bharadwaj et al., 2000]). Schwab et al. [2001] also provided
numerical values characterising the mechanical performance of these
nanocomposites (see Table 10). Improvement of the tensile and flexural properties
was modest, but of impact strength and HDT were significant. It is noteworthy
that POSS is expected to reside in the amorphous PP phase, which constitutes ca.
40% of the polymer. If so, the local POSS concentration is higher by a factor of
about 2.5.
Using a metallocene catalyst, Zheng et al. [2001] copolymerised ethylene or
propylene with up to 10.4 mol% of norbornylethyl cyclopentyl-POSS macromer
(see Figure 14). As shown in Figure 15, incorporation of the POSS sharply reduced
the crystallinity, while the decomposition temperature and the temperature for
5 wt% mass loss in TGA increased to a plateaux by ca. 20 and 100 °C, respectively.
The latter two properties reached their respective plateaux at POSS ≈ 20 wt%
[Zheng et al., 2001].
Zheng et al. [2002b] carried out copolymerisation of styrene with the POSS-
styryl macromer 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptacyclopentylpentacyclo
octasiloxane. The catalyst CpTiCl3 with methylaluminoxane (MAO) was used.
Random syndiotactic copolymers have been obtained with POSS content up to
24 wt% or 3.2 mol % (see Figure 16).
63
Figure 13 Complex tensile modulus versus temperature for PP and its copolymer
with 10 wt% of [CH3SiO1.5]Σ8 [Schwab et al., 2001].
Table 10 Mechanical properties and HDT of PP and its composites

with [CH3SiO1.5]Σ8 [Schwab et al., 2001]
Property ASTM [CH3SiO1.5]Σ8 content (wt%)
(improvement)
0 2 5 10
Flexural modulus D790A 1.655 1.730 1.757 1.80

(GPa) (4.5%) (6.2%) (8.8%)
Tensile strength D638 34.5 34.5 35.1 35.8

(MPa) (0%) (1.7%) (3.8%)
Izod impact D256A 26.7 29.3 33.1 40.0

strength (kJ/m) (9.7%) (24%) (50%)
HDT (°C) D468 99 105 115 124

(6°) (16°) (25°)
Incorporation of 24 wt% POSS increased the T g by 4 °C, destroyed sPS

crystallinity, did not affect the decomposition temperature under N2, but increased
that in air by 37 °C (reduced oxidative degradation).
Li et al. [2002] copolymerised vinyl ester (VE) and 50% styrene (St) with 0, 5 or
10 wt% of POSS (MW = 1305: (C6H5CHCHO)4(Si8O12)(CH=CHC6H5)4). At
5 wt% of POSS the system was homogeneous, but at 10 wt% silicon-rich crosslinked
domains of irregular shape were observed – these ranged in size from a few to
about 75 nm. Incorporating POSS into the VE/St resin had almost no influence on
Tg or on the width of the loss peak in the glass transition range.
64
Figure 14 Norbornenylethyl cyclopentyl-POSS, C44H76O12Si8, with MW = 1021.77

g/mole; soluble in THF, chloroform or hexane [Zheng et al., 2001].
Figure 15 Thermal properties of (norbornenyl-ethyl-cyclopentyl)-POSS-co-

ethylene. Incorporation of POSS sharply reduced crystallinity. The decomposition
temperature, Td, and the temperature for 5% wt loss during TGA, T5%, reached a
plateaux at POSS content of about 20 wt% [Zheng et al., 2001].
65
Figure 16 Coordination copolymerisation of styrene with the POSS-styryl macromer

1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptacyclopentylpentacyclo octasiloxane
Reproduced from Zheng et al. [2002b], copyright 2002, with permission from
John Wiley & Sons, Inc.
Similar absence of effect on Tg was also observed in specimens prepared by blending

in non-reactive POSS units into VE resin. Copolymerisation with 10 wt% POSS
resulted in a two-phase, crosslinked system. There was no measurable effect of
POSS incorporation on Tg ≅ 131 ± 1 °C. At 40 °C the bending storage modulus, E´,
of the VE/styrene resin and its copolymer with 10 wt% POSS was E´ = 1.24 and
1.58 GPa, respectively. The flexural modulus of these specimens was 1.89 to 2.14
GPa, respectively. However, addition of POSS reduced the flexural strengths by
about 21%. The VE and composite samples showed poor solvent resistance to
THF.
The following property improvements have been cited for POSS in
thermoplastic or thermoset systems:
• Controlled miscibility for mixing and blending.
• Maintained processability and mouldability of neat polymer.
• Viscosity reductions of up to 24% (relative to silica-filled composites!).
• Low density, by eliminating the need to use common fillers. For example, by
replacing silica as filler the bulk density may be reduced by up to 10%.
• Extended temperature range, and resistance to oxidation and wear.
• Reduced flammability by delayed combustion and low heat evolution rate.
• Increased modulus and hardness while maintaining the stress and strain
characteristics of the base resin.
• Increased O2 permeability and low thermal conductivity.
• Simple disposal as of silica.
2.1.4.3.3 Sources
POSS is available from Sigma-Aldrich Chemical Co. (www.sigma-aldrich.com),
Gelest Inc. (www.gelest.com), The Mather Group at UCONN (University of
Connecticut), Hybrid Plastics (www.hybridplastics.com), etc.
66
Sigma-Aldrich Fine Chemicals is a global supplier. The company offers

68 POSS compounds (monomers, polymers, silanols, reagent and precursors) in
quantities of 1 to 10 g. Gelest was founded in 1990 to serve the advanced
technology applications market. The company offers a dozen POSS compounds
at a cost of 100 to 450 US$/kg. The main source of POSS is Hybrid Plastics, a
spin-off from the US Air Force Research Labs (AFRL). Lichtenhan and Schwab
launched the company in 1998, on a license from AFRL and an Advanced
Technology Program (ATP) startup grant from the US National Institute of
Standards and Technology (NIST). The continuing cooperation with AFRL is for
the application of POSS-technology to rocket, aero, and space vehicle systems.
Starting with six products, in 2003 Hybrid Plastics has a list of nearly 300
(guaranteed 97% pure) products, grouped into four categories:
1. POSS® Molecular Silicas™ with Si–O core surrounded by non-reactive organic
groups providing miscibility with an organic matrix. These may be added
(up to 50 wt%) to polymers, yielding nanocomposites with nanoscale
reinforcements.
2. POSS® Silanols have 1 to 4 ≡Si–OH silanol groups. These may react with
metal or glass surfaces (or with inorganic fillers) rendering them hydrophobic.
Silanols containing epoxide, methacrylate, and olefinic groups are available
for copolymerisation or grafting.
3. POSS® Functionalised Monomers have 1 to 8 reactive groups, such as amines,
esters, epoxies, methacrylates, olefins, silanes, styryls and thiols. In most
cases they are available as: 1-R-3,5,7,9,11,13,15-heptacyclopentyl cyclo
octasiloxane (R-POSS).
4. POSS® Polymers possess a hybrid inorganic-organic composition and can be
either thermoplastic or thermoset. They are either (1) co-polymers with
standard monomers, or (2) neat POSS resins. The types available include:
silicones, styrenics, acrylics and norbornenes.
The price depends on quantity: viz. for R&D gram quantity the price is US$200 to
2,000/kg, for semi-bulk it is US$60 to 200/kg, and for production level it is
> US$20/kg. ‘Sampler Kits’ contain 5 to 7 types of a specific type of POSS (e.g., POSS-
methacrylate, POSS-epoxy, or POSS-silanol, 20 g each) at US$650 to US$1200 per set.
Multi-ton quantities can be produced using a continuous process. In 2002 POSS cost
was ca. US$400/kg. New plant for making POSS may push the price of some POSS to
about US$33/kg. Hybrid Plastics’ sales and marketing arm is Divex, Inc.
2.1.4.3.4 Applications
The method of POSS incorporation depends on the category (see above) and the
expected application. Evidently, it is advisable that the molecular silicas are dissolved
in a monomeric or polymeric liquid. The dissolution should be carried out in a
suitable mixer, e.g., a twin-screw extruder (TSE), as dispersing [CH3SiO1.5]Σ8 in
molten PP [Schwab et al., 2001]. The functionalised POSS monomers are mainly
copolymerised, e.g., as butyl methacrylate with heptacyclopentyl methacrylate
(CpPOSS-MA) [Murugavel et al., 1999], but homopolymerisation, grafting and
crosslinking may also be carried out. However, since the cost of POSS is high (even
in comparison to engineering resins) the recommended use is < 50% incorporation
into high performance resins. In the case of POSS® Polymers, blending with other
resins in a TSE may provide a suitable solution.
67
POSS can be used in many guises as:

• Additives – for heat/abrasion resistant paints and coatings. Used as
crosslinking agents, viscosity reducers, fire retardants, also to increase
mechanical properties, HDT and gas permeability, to decrease dielectric
properties (in photoresists, interlayer dielectrics), etc. Thus, for example,
Weidner et al., from Wacker-Chemie used POSS as a crosslinking agent.
• Plastics – in aerospace, electronic, optical, medical, biomedical and
pharmaceutical applications, for catalysis, packaging, coatings, liquid crystal
display elements, magnetic recording media, as coupling agents, fire
retardants, nanofillers in speciality polymers, dendrimers, etc. Optical disks,
microelectronics, and medical products are target niches. Takamuki et al., of
Konica Corporation used POSS for transparent printing plates; Zank and
Suto of Dow Corning Asia for electronic materials; Nguyen of American
Dye Source as hot melt inks; Canon for LED, etc.
• Pre-ceramic coatings that, depending on the oxidising conditions, convert to
silicon dioxide, silicon oxy-carbide or silicon carbide. These POSS may be used
as ablative materials (for nozzles, insulations, etc.), for cladding and coatings in
the electronics industry, etc.
• Reagents, POSS have been used for catalysis supports, as monomers, crosslinkers,
biological scaffolds, reactive ion-etch resistant layers; they find application in
microelectronics, for drug delivery, etc. For example, POSS silanols are formulated
at room temperature. At T > 40°C the resin becomes tacky, and then a viscous
liquid at 120 °C. The cure is catalysed by dibutyl tin diacetate, zinc acetate or
zinc-2-ethylhexanoate. After condensation the resin becomes tough binder or film.
Shell Oil Co. and Solvay used POSS as an epoxidation catalyst (US Patents
5,750,741 and 6,127,557), etc.
• Surface Modifiers, as silane replacement in corrosion and abrasion resistant
coatings, lubricants and compatibilisers, for controlled drug release, and
optical fibre coatings.
Table 11 summarises the relative merits of three types of PNC systems: CPNCs
with organoclay, those with POSS, and other PNCs with other nanofillers.
By the end of 2002, Pentron Clinical Technologies had introduced the Nano-
Bond Universal Bonding System, a POSS-reinforced adhesive. The resin infiltrates
etched surfaces and provides a strong bond between the tooth and dental restorative
material. The kit includes a primer, the adhesive and a dual cure activator.
Finally, it is worth mentioning that not only cage-type POSS are known. A
ladder-like variety (L-POSS):
shows superior heat, radiation, water and fireproof resistance, outstanding

electrical properties as well as the formation of high-strength film (for coatings,
electronic and optical devices). Changing the side and/or end groups may modify
the molecular structure of L-POSS.The compound is used in photoresists,
interlayer dielectrics and protective coating films for semiconductor devices.
68
Table 11 Comparison of the three basic PNC technologies (after

Hybrid Plastics, 2002)
Properties Organoclay POSS Nanofillers
Characteristics Mineral or Nanosized chemical Nanosized, fillers
synthetic clays: molecules that (fibres, whiskers,
nanosized directly interact and tubes, spheres,
organically treated bond with polymers etc.) for
platelets, indirectly polymeric
interacting with matrices
polymers
Size 1 by ≥ 100 nm, 0.7-3 (mostly 1.2) ≥ 20 nm
anisotropic nm
Size distribution Polydispersed Mono or Polydispersed
polydispersed
Physical appearance Solid Transparent oils or Solid
solids
Density Moderate Low High
Hygroscopic No No Possible
High T stability No Yes Yes
Trace metals Possible None Possible
Biocompatibility Possible Yes Yes
O2 permeability Low High Poor
Recyclability Yes Possible Limited
Dispersability Possible Dissolves Limited loading
molecularly
Interfacial Possible Adjustable Limited
properties
Melt compounding Yes Ye s No
Glass transition, Tg Small change Significant in Minor change
amorphous
Viscosity Increased Reduced Increased
Hardness Increased Increased Variable
Modulus, E Increased, Increased Increased
anisotropic1
HDT Increased Increased Increased
Creep Improved Improved Poor
1
Impact/toughness Anisotropic Increased Reduced
Fire retardance Improved Improved Improved
Impact/toughness Variable Improved Variable
Cost Moderate High Low
Notes: 1 Nanoclays may be flow-oriented, which will impart anisotropy to the

modified polymer system
69
Applications for liquid crystal display elements, magnetic recording media and
optical fibre coatings have also been disclosed. L-POSS may also be used for gas
separation membranes, binders for ceramics and controlled release drugs as well
as additives in cosmetics and resins.
The ladder-like poly(methyl silsesquioxane)s (PMSQ) are used for coatings,
particularly in electronics and optical devices. To improve the barrier, mechanical
and thermal properties Ma et al. [2002] tried to disperse MMT in PMSQ. The
aim was to develop high heat-resistant coating. The Na-MMT was pre-intercalated
with trimethyl hexadecyl ammonium bromide (3MHDA), dried and ground.
Dispersing the organoclay in chloroform, then adding methyl trimethoxysilane,
hydrolysing it, neutralising and polymerising, resulted in the PMSQ/MMT
nanocomposite:
XRD and TEM showed that MMT was only intercalated with d001 = 3.42 nm.
Annealing the nanocomposite at 150 °C for 3 h did not change the spacing, but
annealing at 300 °C for 3 h did reduce d001 to 3.0 nm. Furthermore the relative
intensity of the peak significantly increased. The stability of interlayer spacing at
T ≤ 150 °C was explained by the molecular structure of the in situ polymerised
PMSQ. The decrease of spacing at 300 °C is most likely due to decomposition of
the quaternary ammonium ion complex on MMT. Unfortunately, the authors
did not report on the performance of these interesting materials.
The commercial success of a material depends on delivery of enhanced
performance at low cost. Currently, the PNCs available on the market contain
2 to 5 wt% of organoclay. The market price for PA-6 and PP is about US$3,000
and 1,000/ton, respectively. Assuming that a 10% increase of cost would be
acceptable (if performance warrants it), the cost of compounding and organoclay
must not exceed US$300 and 100/ton, respectively. At the current cost of
compounding (at least US$50/ton) and clay the incremental cost is ca. US$300
to 400, leaving little room for profit. Thus, in the case of CPNC the commercial
success of PNC hinges on the intercalation and compounding costs.
Applying a similar algebra to POSS with the lowest projected price of
US$33,000/ton the situation is difficult. Furthermore, to achieve an interesting
enhancement of properties relatively large amounts of POSS must be added (from
10 to 50 wt%). For applications as a structural material the cost would be
prohibitive. Obviously, the economics look better when more expensive
70
engineering or speciality resins are modified by POSS. However, by the same

token POSS use is automatically diverted from structural (large production
volume) to functional speciality products.
From the point of view of structural performance, incorporation of POSS
resulted in relatively minor gains, viz. mechanical performance about 10 times
smaller than that obtained by incorporation of the same quantity of organoclay.
The effect on the transition temperatures, Tg or Tm, was found to depend on the
type of POSS, the polymeric matrix and the method of its incorporation –
variations from a decrease by 100 to an increase by 200 °C were reported. Finally,
the ‘lightweight’ of POSS systems is in comparison with mineral-filled composites
and it does not seems to offer much above the virtually ‘neutral’ effect on matrix
density of organoclay.
In consequence, CPNC and POSS find applications in different domains, the
former as structural material, e.g., for the automotive or packaging industries,
the latter as a functional material in electronic, space or bio-applications. Vive la
différence!
71
72
Clays
2.2
Clays
2.2.1 General Characteristics

Clays originate from the hydrothermal alteration of alkaline volcanic ash and
rocks of the Cretaceous period (85-125 million years ago). The airborne ash
carried by winds formed deposits characterised by high volume bedding of ash,
deposited in seas and alkaline lakes. Different opinions have been expressed
regarding the mechanism of the ash to clay transformation. Probably the change
began in marine water in reactions involving sufficient amounts of Mg+2 and
Na+. Several geological processes may have lead to the formation of clays during
millions of years [Keller, 1979; Giese and van Oss, 2002; Drits, 2003; Lagaly
and Zismer 2003].
Clays are distinctive from rocks in several aspects:
1. Wet clays can be formed by application of light force and after release of the
pressure they retain the imposed shape.
2. Clays are composed of extremely fine crystals, usually plate-shaped, less than
2 μm in diameter and less that 10 nm thick. They are mostly phyllosilicates,
i.e., hydrous silicates of Al, Mg, Fe, and other elements. Having at least one
small dimension and large aspect ratio they have large specific surface areas.
This in turn makes clays physically sorptive and chemically surface active.
Several clay types carry an excess negative electric charge owing to internal
substitution by lower valency cations, viz. Mg2+ substituted for Al3+, which
makes clay slightly acidic. A clay deposit usually contains non-clay minerals
as impurities, viz. quartz, sand, silt, feldspar, mica, chlorite, opal, volcanic
dust, fossil fragments, heavy minerals, sulfates, sulfides, carbonate minerals,
zeolites, and many other rock and mineral particles ranging in size from
colloidal to pebbles.
Clays are classified on the basis of their crystal structure and the amount and
locations of charge (deficit or excess) per basic cell. In the context of PNCs, the
amorphous clays are a great nuisance as they are difficult to remove from the
crystalline ones. The crystalline clays range from kaolins, which are relatively
uniform in chemical composition, to smectites, which widely vary in their
composition, cation exchange properties, and the ability to expand. The ease of
separation of the individual layers is related to the interlamellar charge, x. The
latter parameter changes from zero (talc) to x = 0.2 to 0.6 for smectites, to x = 0.6
to 0.9 for vermiculites, and to x = 1 to 2 for micas [Giese and van Oss, 2002].
Clay particles are usually plate-shaped, less often tubular or scroll-like.
Individual clay particles are nanometre-sized at least in one dimension. Aqueous
suspensions of clays are thixotropic and sensitive to ion concentration.
73
The synthesis of clays has been extensively studied [de Kimpe et al., 1961;
Roy, 1962; Weaver and Pollard, 1973; Velde, 1977]. For example, organic
compounds facilitate the synthesis of kaolin at low temperature by condensing
aluminum hydroxide into octahedrally coordinated sheets [Linares and Huertas,
1971]. More recently, Carrado [2000] published an excellent review on synthetic
clays and the resulting CPNCs.
2.2.2 Crystalline Clays

Most clays are crystalline, composed of fine, usually plate-shaped crystals about
1 nm thick with high aspect ratio, and have large specific surface areas. They
absorb up to a 30-fold amount of water, and when wet, can be easily shaped –
pottery is as old as human civilisation.
2.2.2.1 Kaolins
These include kaolinite, dickite, nacrite and halloysite-endellite. The structural
formulae for kaolinite and endellite are A1 4 Si 4 O l0 (OH) 8 and
A14Si4Ol0(OH)8.4H20, respectively. The kaolinite lattice consists of one sheet of
tetrahedrally coordinated Si (with O) and one sheet of octahedrally coordinated
Al (with O and OH), hence a 1:1, or a two-layer structure. A layer of OH
completes the charge requirements of the octahedral sheet. Adjacent cells are
spaced about 0.71 nm across the (001) plane. When solvated in ethylene glycol,
endellite expands to 1.0 nm in the c-direction. Halloysites are usually tubular or
scroll-shaped; they may be differentiated from kaolinite and dickite by treatment
with potassium acetate and ethylene glycol.
For example, kaolin (KGa-1) from Georgia [van Olphen and Fripiat, 1979]:
• Contains (wt%): SiO2 = 44.2, Al2O3 = 39.7, TiO2 = 1.39, Fe2O3 = 0.13,
FeO = 0.08, MnO = 0.002, MgO = 0.03, Na2O = 0.013, K2O = 0.05,
F = 0.013, P2O5 = 0.034.
• Loss on heating to 550 °C is 12.6 wt%.
• CEC = 0.02 meq/g, the specific surface area = 10.05 ± 0.02 m2/g.
• DTA: endotherm at 630 °C, exotherm at 1015 °C, dehydroxylation weight
loss 13.11% (theory 14%).
• The unit cell composition is:
(Mg0.02 Ca0.01 Na0.01 K0.01)[Al3.86 Fe(III)0.02 Mntr Ti0.11][Si3.83l0.17]O10(OH)8,
octahedral charge: 0.11, tetrahedral charge: -0.17, interlayer charge: -0.06.
2.2.2.2 Serpentines
Substituting Mg for Al in the kaolin structure results in the serpentine,
Mg3Si2O5(OH)4. Here all three possible octahedral cation sites are filled, yielding
a tri-octahedral group carrying a charge of +6. In kaolinite only 2/3 of the sites
are occupied by Al, yielding a di-octahedral group, also with a charge of +6.
Most serpentines are tubular or fibrous. Chrysotile occurs in both clino- and
ortho-structures.
2.2.2.3 Illite Group (Micas)

‘Mica’ is a generic term applied to a group of complex aluminosilicates having a
sheet or plate like structure with a wide range of chemical compositions and
74
Clays
physical properties. All micas form flat six-sided monoclinic crystals with a
remarkable cleavage in the direction of the large surfaces, which permits them to
split easily into optically flat films, as thin as one micron. When split into thin
films, they remain tough and elastic even at high temperature. The dictionary
defines mica as ‘a class of silicates having a prismatic angle 120o, eminently perfect
basal cleavage, affording thin tough laminae or scales, colorless to jet black,
transparent to translucent, of widely varying chemical composition, and
crystallising in the monoclinic system’.
Illites or micas are not pure minerals. The mica structure consists of a pair of
tetrahedral sheets enclosing an octahedral sheet. Between each such sandwich
there are interlayer sites, which can contain large cations. Considerable variation
exists in the composition and polymorphism of the illites. A basal spacing exhibited
in XRD, d001 ≅ 1.0 nm, is somewhat broad and skewed toward wider spacings.
Muscovite derivatives are typically dioctahedral; phlogopite derivatives are
trioctahedral. The cation-exchange capacity of illite is CEC = 0.2-0.3 meq/g of
dry clay. The interlayer potassium exerts a strong bond between adjacent clay
structures. Thus, mica possess a 2:1 sheet structure, similar to MMT, except that
the maximum charge deficit in mica is typically in the tetrahedral layers and
contains potassium held tenaciously in the interlayer space. As a result, micas are
difficult to exfoliate. However, once exfoliated they form dispersions of platelets
with the highest aspect ratio, thus they are particularly useful for the control of
gas or liquid permeability. Several examples of CPNC with mica are provided in
this book. Pironon et al. [2003] proposed the use of FTIR of clay-NH4+ to
distinguish illite from smectite clay.
The coordination of the octahedral sheet is completed by OH anions. The
general formula of mica group minerals is XY2-3Z4O10(OH)2, where X represents
the interlayer site, Y the octahedral sites and Z the tetrahedral sites. The octahedral
sheet can be made up in two ways: either dominantly of divalent cations such as
Mg2+ or Fe2+, in which case all three sites are filled (trioctahedral mica), or else
dominantly trivalent cations such as Al3+, in which case one of the three sites is
left vacant (dioctahedral mica). If solely Si occupies the tetrahedra, the sandwich
is charge-balanced and there is no need for interlayer cations – the resulting
minerals are talc (trioctahedral) or pyrophyllite (dioctahedral). In true micas Al
substitutes for Si in the tetrahedra, and charge balance is maintained by K, Na or
Ca, in the interlayer site. The important rock-forming micas are the trioctahedral
phlogopite and the dioctahedral ‘white’ micas:
• Phlogopite: KMg3[AlSi3]O10(OH)2
• Wonesite (or sodium phlogopite): NaMg3[AlSi3]O10(OH)2
• Annite: KFe3[AlSi3]O10(OH)2
• Eastonite: K[Mg2Al][Al2Si2]O10(OH)2
• Muscovite: KAl2[AlSi3]O10(OH)2
• Paragonite: NaAl2[AlSi3]O10(OH)2
• Margarite: CaAl2[Al2Si2]O10(OH)2
• Mg-Al-celadonite: K[MgAl][Si4]O10(OH)2
• Fe-Al-celadonite: K[FeAl][Si4]O10(OH)2
The average composition of mineral mica is (wt%): SiO2 45.57; Al2O3 33.10;
K2O 9.87; Fe2O3 2.48; Na2O 0.62; TiO2 trace; CaO 0.21; MgO 0.38; moisture
75
at 100 °C 0.25; P 0.03; S 0.01; graphite C 0.44; loss on ignition (H2O) 2.74. The
physical properties of a typical phlogopite and muscovite are listed in Table 12.
2.2.2.4 Chlorites and Vermiculites

Chlorite was identified as a mineral yielding a 1.4 nm basal spacing in clays.
Chlorite is a three-layer phyllosilicate separated by a Mg(OH)2 interlayer. Chlorite-
like structures have been synthesised by precipitating Mg and Al between MMT
sheets [Slaughter and Milne, 1960].
The interlayer sheet in vermiculite is octahedrally coordinated, 6H2O about
Mg2+. The basal spacing of vermiculite varies from 1.4-1.5 nm with the nature of
the interlayer cation and its hydration. The cation-exchange capacity of vermiculite
is relatively high and it may even exceed that of MMT. Vermiculites are known
to have high aspect ratio (p ≤ 2,500), exceeding that of MMT by nearly one
order of magnitude.
2.2.2.5 Other Clays
2.2.2.5.1 Glauconite
Glauconite is green, dioctahedral, micaceous, rich in Fe3+ and K+ ions. It has
many characteristics common to illite. Glauconite may contain randomly placed
expandable layers of the montmorillonite-type. The glauconitic green sands of
New Jersey have been used in ion exchange, water-softening installations, and as
a source of slowly released potassium in soil.
2.2.2.5.2 Sepiolite, Palygorskite and Attapulgite

Sepiolite and palygorskite contain a continuous two-dimensional tetrahedral sheet
and thus differ from the other layer silicates by absence of the octahedral sheet.
Details of the structures were described by Jones and Galan [1988]. The attapulgite
structure is similar to palygorskite minerals resembling cardboard, paper, leather,
cork, or even fossil skin. These clays have distinctive properties, not shown by
platy clays. Attapulgite and palygorskite sorb both cations and neutral molecules.
Typical CEC is about 0.2 meq/g of dry clay. Sepiolite and attapulgite are best
identified by their 110 reflections in XRD, 1.21 and 1.05 nm, respectively.
2.2.2.5.3 Mixed-Layer Clay Minerals

In mixed-layer clay sheets illite may be interspersed with MMT or chlorite.
Corrensite has regular alternation of chlorite and vermiculite layers.
2.2.2.6 Smectites or Phyllosilicates

Smectites are the most frequently used clays for a variety of non-ceramic
applications. These 2:1 phyllosilicates have a triple layer sandwich structure that
consists of a central octahedral sheet dominated by alumina, bonded to two
silica tetrahedral sheets by oxygen ions that belong to both sheets (see Figure 17).
Smectites are structurally derived from pyrophyllite [Si8Al4O20(OH)4], or talc
[Si8Mg6O20(OH)4] by substitutions mainly in the octahedral layers, viz. Al can
be substituted by Mg, Fe, Cr, Mn or Li. When substitutions occur between ions
of unlike charge, deficit or excess charge develops on corresponding parts of the
structure. The charge imbalance is compensated by the presence of cations (usually
76
Clays
Table 12 Physical properties of micas

Characteristic Unit Phlogopite Muscovite
Colour Amber/ Ruby/

yellow green
Density g/ml 2.6-3.2 2.6-3.2
Specific heat 0.21 0.21
Hardness Moh’s Scale 2.3-3.0 2.8-3.2
Hardness Shore Test 70-100 80-105
Optic axial angle 5-25 55-75
Tensile strength MPa ≈ 100 ≈ 1.75
Shear strength MPa 100-130 220-260
Compression strength MPa - 190-280
Modulus of elasticity GPa 140-210 140-210
Thermal expansion x106 ⊥ to 1/°C 30-60 9-36

cleavage plane
Calcination temperature °C 900-1000 700-800
Maximum operating temperature °C 800-900 500-600
Thermal conductivity, ⊥ to J/s/cm/°C ≈ 0.00042 ≈ 0.0054

cleavage planes
Thermal conductivity to J/s/cm/°C ≈ 0.050 -

cleavage planes
Water of constitution % 3.0 4.5
Moisture absorption Very low Very low
Apparent electric strength; thin KV/mm - 120-200
RMS at 15 °C KV/mm 30-60 40-80
Permittivity at 15 °C 5-6 6-7
Power factor (loss tangent) ×10-3 1-5 0.1-0.4

at 15 °C
Volume resistivity ×10-12 at Ω cm 1-100 400-

25 °C 200,000
Chemically affected by acid Sulfuric Hydro-

fluoric
77
Figure 17 Idealised structure of dry phyllosilicate with the unit cell:

[Al2(OH)2(Si2O5)2]2 + 5 wt% H2O. The unit cell molecular weight is 720 + water
and counterions (e.g., Na+); the minimum d001 spacing for dry MMT is 0.96 nm
(the interlamellar gallery height 0.30 nm), the surface area of the unit cell is
0.458 nm2. After van Olphen and Fripiat, 1979.
Na+, Ca2+, K+) sorbed between the three-layers. The cations are stoichiometric,
but held relatively loosely and are readily exchanged by other cations. The triple-
sheet layers form stacks with the interlamellar gallery between them. Their cation-
exchange capacity (CEC) is high, 0.8-1.2 meq/g of air-dried clay, and may be
used as a diagnostic criterion of the group.
Characteristically, smectites expand in H 2O or alcohol. The size and
composition of the interlamellar gallery is highly variable – its minimum thickness
is 0.26 nm, which corresponds to a monolayer of water molecules. With each of
the three sheets 0.22 nm thick, the minimum thickness of the phyllosilicate
interlayer spacing as read by XRD is d001 = 0.92 nm. The flat thin sheets of
smectite crystals have irregular shape and can be up to 1,500 nm in the largest
dimension. Thus, the aspect ratio of smectites is: p ≤ 1500. Owing to
counterbalancing ions present, the nominal value for d001 is taken as 0.96 nm. As
shown in Figure 18, the van der Waals interaction energy (EA) that holds the
stacks together depends very much on the distance between the platelets (h), or
on the interlamellar spacing.
In the early literature, the term montmorillonite was used for this group. In
the natural state these minerals are partially hydrated, with XRD basal spacing
d001 = 1.2-1.4 nm. Solvating them in ethylene glycol expands d001 to 1.7 nm,
while heating to 550 °C collapses it to 0.96 nm. The DTA curves for smectites
show three endothermic and one exothermic peak, within the ranges 150-320,
78
Clays
Figure 18 Van der Waals attraction energy between two phyllosilicate layers
separated by a distance h (nm) (after van Olphen and Fripiat, 1979).
695-730, 870-920, and 925-1050 °C, respectively. The crystal lattice is weakly
bonded. The smectite lattice is expandable between the silicate layers, hence when
soaked in water it may swell to several times its dry volume (e.g., bentonites of
Badlands). A broken surface of these clays typically shows a ‘corn flake’ or ‘oak
leaf’ texture.
There are several species of smectite clay, but the two of greatest commercial
importance and value are montmorillonite (MMT) and hectorite (HT). MMT
tends to have sheet morphology whereas hectorite has a lath or strip morphology.
Commercial availability of hectorite is limited whereas MMT deposits are large
and widely spread around the globe, e.g., 7 in Canada, 6 in the USA, two in
South America, 15 in Europe, 7 in Africa, 3 in Australia, and 8 in Asia. Typical
chemical formulae of the smectite clays are listed in Table 13.
2.2.2.6.1 Bentonite
Bentonite (named after Ford Benton, Wyoming) is rich in MMT (usually > 80%).
Its colour varies from white to yellow, to olive green, to brown to blue. Grades of
this mineral show a broad spectrum of properties and consequently find a variety
of applications and uses. Its origin is a hydrothermal alteration of volcanic ash
deposited in a variety of freshwater (e.g., alkaline lakes) and marine basins
(abundant marine fossils and limestone), characterised by low energy depositional
environments and temperate climatic conditions. The deposits date from Jurassic
to as recent as the Pleistocene epoch, but most are from the Cretaceous period
(85-125 million years ago).
Bentonite beds range in thickness from several centimetres to tens of metres
(most 0.3 to 1.5 m) and can extend for hundreds of kilometres. Bentonite is
widely distributed on all continents. In Canada large deposits are located in British
79
Table 13 Typical smectite clays

Mineral Chemical composition of 1/2 crystalline unit cells
Montmorillonite [All.67Mg0.33(Na0.33)]Si4Ol0(OH)2
(MMT)
Hectorite [Mg2.67Li0.33(Na0.33)]Si4O10(HOOFF)2
Beidellite A12.17[Al0.33(Na0.33)Si3.17]O10(OH)2
Nontronite Fe(III)[Al0.33(Na0.33)Si3.67]O10(OH)2
Saponite Mg3[Al0.33(Na0.33)Si3.67]O10(OH)2
Sauconite [Znl.48Mg0.l4Al0.74Fe(III)0.40][Al0.99Si3.01]O10(OH)2X0.33
Volkhonskoite contains Cr2+
Medmontite contains Cu2+
Pimelite contains Ni2+
Note: Na0.33 or X0.33 refers to the exchangeable cation in the interlamellar gallery,
of which 0.33 equivalent is typical
Columbia (French Bar, Hat Creek, Princeton, Quilchena, etc.), Alberta (Rosalind),
Saskatchewan (three ca. 1 m thick beds of Na-MMT near Truax), and Manitoba
(Morden). In the USA, it occurs mainly in Wyoming (overburden: 12 m thick;
1997 price: US$25 to 40 a short ton; estimated deposits: ≥ 1 billion ton), Georgia,
Florida, Mississippi, South Dakota, Montana, Utah, Nevada, and California.
Other known deposits are located in Algeria, Tasmania, Mildura and Scone
(Australia; estimated deposit of 70 million tons), San Juan (Argentina), Sarigyugh
(Armenia), Campina Grande (Brazil), Guangxi and Hangzhou Linan (P. R. China),
Hamza (Egypt), Gewane, Mille and Ounda Hadar (Ethiopia), Landshut
(Germany), Milos (Greece), Kutch (Gujarat, India, estimated deposits: 15 million
ton of good quality sodium bentonite), Java - (Indonesia; estimated deposits
8 million ton), Sardinia (Italy), Annaka and Kuroishi (Japan), Pershwar (Pakistan),
Holy Cross Mountains, Upper Silesia Coal Basin and Sudetes (Poland; deposits:
3 million ton), Eskisehir and Biga Peninsula (Turkey), Tam Bo (Vietnam; deposits:
3 million ton), etc.
Main uses for bentonite are in foundry sands, drilling muds, iron ore pelletising,
absorbents, as a variety of composite liners, food additive for poultry and domestic
animals, in filtration, foods, cosmetics and pharmaceuticals. Bentonite has been
used for clarification of liquids (especially white wine and juice). Bentonite is part
of most adsorbent, bleaching and catalyst clays. About 6 million tons of bentonite
is produced annually [Harben and Bates, 1990; Carr, 1994].
2.2.2.6.2 Montmorillonite (MMT)

Montmorillonite (MMT) is the name given to clay found near Montmorillonite
in France, where MMT was identified by Knight in 1896. It is the most common
80
Clays
phyllosilicate used for the production of commercial CPNC. MMT has been
known under several names, viz., smectite; sodium montmorillonite; sodium
bentonite or swelling bentonite (Wyoming bentonite (US)); sodium-activated
bentonite (UK); sodium-exchanged bentonite, etc.); the non-swelling (in water)
bentonite is calcium montmorillonite or bentonite (Mississippi bentonite (US));
Sub-bentonite (Texas bentonite, US)). Also known are magnesium montmorillonite
(Saponite & Armargosite), potassium montmorillonite (Metabentonite), lithium
montmorillonite (Hectorite), etc.
The idealised structure of Na-MMT is shown in Figure 17. The unit cell is
usually written as:
Triple layer sandwich of two silica tetrahedron

sheets and a central octahedral sheet with 0.67
[
Al3.33 Mg0.67 ]
− ( 0.67 )
Si8 O20 (OH )4
negative charge per unit cell ⇓

Aqueous interlamellar layer containing 0.67 Na+ (n × H2 O) Na0+.67
cations per unit cell
Thus, an idealised MMT has 0.67 units of negative charge per unit cell, in other
words, it behaves as a weak silicilic acid. Since the molecular weight of a unit cell
is Mu = 734 + water, the CEC of idealised MMT is: CEC = 0.915 meq/g (one ion
per 1.36 nm2), i.e., the anionic groups are spaced about 1.2 nm apart. The charge
is located on the flat surface of the platelets. As Thiessen demonstrated in 1947,
a small positive charge is also present at the platelet edges.
MMT composition varies across a relatively wide range not only with the
geographic location but also with the deposit strata [Ross and Hendrics, 1945;
Ross, 1960]. The data for 100 samples gave the following ranges of composition:
1. The octahedral layer: Al3.0 - 4.0 Mg0 - 1.4 Fe3+0 - 1.0
2. The tetrahedral layers: Al0 - 0.8 Si7.2 - 8.0
3. Exchangeable cation in the aqueous layer: Na0.67 - 0.8
Chemical analysis of a typical MMT yields: SiO2 = 51.14, Al2O3 = 19.76, Fe2O3
= 0.83, ZnO = 0.1, MgO = 3.22, CaO = 1.62, K2O = 0.11, Na2O = 0.42 and
water 22.8 wt%. Drying at 150 °C eliminates 14.81 wt% of water, with 7.99 wt%
remaining. Another chemical analysis of MMT gave: Al 9.98 wt%, Si 20.78 wt%,
H 4.10 wt%, and O 65.12 wt%. Depending on composition, MMT colour varies
from brick red (due to Fe+3) to pale yellow or blue-grey. The CEC ranges from
0.8 to 1.2 meq/g. In the montmorillonite-nontronite series, as the Fe3+ content
increases from 0 to 28%, the refractive index ranges from 1.523 to 1.590. XRD
patterns of a hydrated MMT yield typically d001 = 1.2-1.4 nm basal spacing.
These values, along with expansion to ca. 1.8 nm in glycerol, have been used for
MMT identification.
The specific surface area of MMT is Asp = 750-800 m2/g (theoretical value is
834 m2/g). From the cited values it follows that the density of the triple sandwich
is 4.03 g/ml and that the interlamellar gallery thickness is 0.79 nm, hence the
interlayer thickness of hydrated MMT should be d001 = 1.45 nm and the average
density ρ = 2.385 g/ml. Drying MMT at 150 °C reduces the gallery height to
0.28 nm (which corresponds to a water monolayer), hence the interlayer spacing
decreases to d001 = 0.94 nm and the average density increases to ρ = 3.138 g/ml.
Assuming that MMT platelets are fully exfoliated and that locally they are parallel
81
to each other, the interlayer spacing should be inversely proportional to the clay
volume fraction, φ,
d001 = h/φ
where h ≅ 0.96 nm is the thickness of a single (exfoliated) clay platelet. This
simple relation predicts that the interlayer thickness, e.g., of PA-6 containing,
respectively, 4 and 25-wt% of clay should be 32 and 4.6 nm, which is not far
from the measured values (see Figure 3).
Commercially, MMT is supplied in the form of powder with about an 8 μm
particle size, each containing about 3000 platelets with a moderate aspect ratio p
= 10 to 300. Typical properties and applications are listed in Table 14.
For example [van Olphen and Fripiat, 1979] Na-MMT from Wyoming, SWy-1,
has the composition (wt%): SiO2 = 62.9, Al2O3 = 19.6, TiO2 = 0.090, Fe2O3 = 3.35,
FeO = 0.32, MnO = 0.006, MgO = 3.05,CaO = 1.68, Na2O = 1.53, K2O = 0.53,
F = 0.111, P2O5 = 0.049, S = 0.05. Weight loss on heating to 550 °C = 1.59 and to
Table 14 Properties and applications of montmorillonite

[Grimshaw, 1980]
Physical Constants Applications
Unit cell molecular 540.46 To slow down water flow
wt. (g/mol) through soil
Density (g/ml) (2.5) 2.3 to 3.0 To produce nanocomposites
Crystal system and Monoclinic; To de-colour & purify
d-spacing (nm) 1.47x0.442x0.149 liquids, viz. wines, juices, etc.
Moh’s hardness 1.5- 2.0 As filler for paper or rubber
@ 20 °C
In drilling muds to give the
Appearance White, yellow or
water greater viscosity
brown with dull luster
Cleavage Perfect in one As a base for cosmetics and
direction, lamellar drugs
As an absorbent
Characteristic In H2O its volume As a base for pesticides and

expands up to 30-fold herbicides
As food additive for poultry
Field indicators Softness, and soapy and pets
feel
For thickening of lubricating
DSC endothermic 140, 700, 875 oils and greases
peaks, T (°C)
For binding foundry sands
DSC exothermic peak, 920
To generate thixotropy
T (°C)
MMT swells in water Largest for Na-MMT, Absorption of ammonia,
more than any other smaller for multivalent proteins, dyes and other polar,
mineral counter-ions aromatic or ionic compounds
82
Clays
1000 °C = 4.47 wt%. CEC = 76.4 meq/100 g, principal exchange cations are Na+
and Ca2+. DTA endotherms occur at 185 °C (shoulder at 235 °C), desorption of
water occurs at 755 °C, dehydroxylation; shoulder at 810 °C, exotherm at 980 °C.
Weight loss in dehydroxylation = 5.53 wt% (theory = 5%). Cell structure is:
(Ca0.12 Na0.32 K0.05)[Al3.01 Fe(III)0.41 Mn0.01 Mg0.54 Ti0.02][Si7.98 Al0.02]O20(OH)4;
octahedral charge = -0.53, tetrahedral charge = -0.02, interlayer charge = -0.55,
unbalanced charge = 0.05.
The early treatments of MMT involved acid-treatment and preparation of
organoclays. The aim of the former was purification, replacement of Ca2+ for H+
and dissolution of some Fe, Al and Mg ions from the octahedral layers.
Manufacture of organoclays started in the 1940s (NL Industries) for use as
thixotropic additives to control flow behaviour of oils, greases, suspensions, paints,
printing inks, cosmetics, etc.
As described earlier in this text, PNC literature recognises four types of
dispersion of layered silicates in a polymer matrix (see Figure 19):
(A) conventional dispersion of non-intercalated clay particles with the basic dry
structure,
(B) intercalated form where the interlayer spacing d001 < 8.8 nm, and
(C or D) exfoliated structures where d001 > 8.8 nm with the individual platelets
either ordered (because of stress field or concentration effects) or not,
respectively.
In aqueous suspension the clay platelets may adopt more complex structures (see
Figure 20). The platelet association (flocculation) may take place by face-to-face
(FF), face-to-edge (FE) or edge-to-edge (EE) interactions [Qian et al., 2000]. Evidently,
each clay structure results in a different set of suspension properties. It suffice to note
that from the hydrodynamic point of view the encompassed volume of suspended
particles dramatically increases from structure (a) to (g), the increase that is reflected
in rheological properties. The EE and EF structures are especially significant.
Figure 19 Four types of clay platelet dispersions in a polymeric matrix
83
Figure 20 Structures encountered in clay suspensions [1Qian et al., 2000]
Recently, Okamoto et al. [2001a] reported formation of a ‘house of cards’ structure

in PP/clay nanocomposite melt under extensional flow. The authors considered
that high strain hardening and rheopectic effects originate from the perpendicular
alignment of the silicate layers to the stretching direction. When the stress vanishes,
the platelets form the complex structures.
2.2.3 Purification of Clay

The names bentonite, smectite and montmorillonite are often used
interchangeably. However, industrially these terms represent different minerals
with different degrees of purity. Bentonite is the ore that comprises smectite clay
and impurities, such as gravel, shale, limestone, etc. Purification of the ore that
results in extraction of MMT is a complex and expensive process.
Clay is usually mined in open pits. The depth of a deposit can be from a few
centimetres to several metres with a length of up to hundreds of metres. After the
overburden is removed, layers of clay are disked and allowed to sun dry. The
clay is removed from the pit in layers, and stockpiled in multiple layers. Next,
the dry clay is transported to processing facilities in trucks that are loaded from
the stockpile in such a way that each ‘swipe’ of the front-end loader goes through
every layer of the stockpile, insuring homogenisation.
Polymer-grade clay should have < 5 wt% non-smectite impurities. Typical
contaminants include silica, feldspar, gypsum, albite, anorthite, orthoclase, apatite,
halite, calcite, dolomite, sodium carbonate, siderite, biotite, muscovite, chlorite,
stilbite, pyrite, kaolinite, hematite and many others. MMT usually has > 50 wt%
calcium montmorillonite, Ca-MMT. Since Ca-MMT (as well as H-MMT) show
non-uniform expansion in water, purification of clay often involves cation
exchange into Na-MMT [Norrish, 1954]. The purification often involves
reduction of clay particle size either by mechanical means (milling, grinding,
comminuting, etc.) or by application of hydrodynamic means [Cohn, 1967].
84
Clays
Clocker et al. [1976] provided a detailed description of the clay purification

process. Thus, clay is mixed with water, then heated by steam to pressurise
(T ≤ 243 °C; P ≤ 3.5 MPa) and hydrate the clay. Next, the slurry is rapidly
expanded to cause some delamination, non-clay particles removed and large clay
particles recycled through the steaming and expansion cycle. The slurry is left in
a holding zone for up to 2 h, at optimised temperature (e.g., T = 80 to 130 °C)
and pressure (P = 0 to 0.2 MPa) for the intercalation, and again separated (e.g.,
by hydrocyclone) from the non-colloidal particles. Finally, the purified clay with
expanded interlayer spacing is treated with an onium intercalant (e.g., octadecyl
ammonium chloride (ODA)), filtered out, washed and dried. The resulting
organoclay has been used for thickening solutions in various solvents and paints.
Organoclay suitable for use in CPNC must be purified and uniformly intercalated
with great care. For example, one of the principal advantages of CPNC is to
control diffusion of fluids through a polymeric membrane – if the non-colloidal
mineral content exceeds ca. 0.5 wt%, holes can be formed around such a foreign
particle (e.g., quartz) dramatically increasing the penetrant flux.
A patent from AMCOL [Clarey et al., 2000] describes modern purification
technology. The clay (see Figure 21) is ground to > 90 wt% particles having
diameter d < 200 μm. Dry clay is fed from loader (12) into storage tanks (22) and
(24). Using a blower (36) and air injectors (32 and 34) the clay is transported
into a receiving vessel (38), and through an auger (48) into a blunger (50) where
it is mixed with water. The slurry, containing 5 to 50 wt% clay + impurities, is
sedimented to remove stones to a waste hopper (56), while the rest is conveyed
to an attrition scrubber (60). The washed clay is pumped by pump (80) into a
feed tank (84) for a series of hydrocyclones (86, 98, 110, 142, 170 and 181) that
remove impurities of a size > 50 μm.
The purified slurry containing 3 to 7 wt% clay is fed to the ion-exchange
column feed tank (180). At this stage > 90 vol% clay particles have diameter
below 40 μm, with mean particle size of < 7 μm. The suspension is directed
upward through cation exchange columns (212 to 222) that replace Ca2+ by
Na+, giving > 95 wt% Na-MMT. After the ion exchange, the clay is conveyed
through a feed tank (240) to a high speed centrifuge (250) operating at centrifugal
force of 2.5 to 3.5 kG. The product is conveyed to a tank (258) and then through
a vibrating dewatering unit (266) which produces the clay slurry containing about
12 wt% solids. The slurry is transported to a spray dryer (272), where it is dried
to about 9 wt% water. Finally, the material is conveyed to an air filtering baghouse
(276), holding tanks (282 to 286), and then to bagging apparatus (292 and 294)
[Harben and Bates, 1990]. Statistical process control is used to maintain the
product within the accepted limits. The important process control parameters
are: concentration, counterion level, purity, particle size, moisture ratio, dispersive
characteristics, etc.
2.2.4 Reactions of Clays with Organic Substances

MMT crystals are made of flat sheets (individual clay platelets), 0.92 nm thick
and up to 1,500 nm in the largest dimension. Their specific surface area is 750 to
800 m2/g. The crystals form large particles or aggregates, even after purification
the Na-MMT particles are ca. 8 μm in diameter, each containing about 3000
platelets with an aspect ratio of p = 50 to 300. To be incorporated into a polymeric
matrix these particles must be dispersed into individual stacks of platelets, then
delaminated into a uniform dispersion of individual platelets in the matrix. The
85
Figure 21 Process for clay purification (see text)

Reproduced from Clarey et al. [2000], with permission from AMCOL.
86
Clays
process of delamination usually goes through two stages: intercalation and

exfoliation. As evident from the definition of these terms, they differ not in
character, but in the magnitude of the achieved platelet separation.
The attraction energy (Uattraction) of two platelets of equal thickness is given
by Equation 13 [Stokes and Evans, 1997]:
A11 ⎡1 1 2 ⎤
U attraction = − ⎢ 2 + − ⎥ (13)
12π ⎢ h
⎣ (h + 2δ) (h + δ) ⎥⎦
2 2
where, A11 is the Hamaker constant, h is the separation distance between plates,
and δ is the platelet thickness. It is noteworthy that the surface energy of inorganic
solids is about 100 times higher than that of organic liquids. According to Equation
13 the interactions between two crystalline planes decrease with the inversed
square of the separation distance (see Figure 18). Thus, the logical approach to
the process of delamination is to increase the gallery space in several steps, inserting
progressively larger molecules – this is indeed the most common intercalation/
exfoliation strategy.
However, before discussing the methods developed for the intercalation and
exfoliation that lead to CPNC it is advisable to summarise the chemistry of clays.
Several books and reviews are available on the topic, viz. the ever popular early
text by Weiss [1969], Mortland’s review [1970] and other such publications
[Weaver and Pollard, 1973; van Olphen and Fripiat, 1979; Grimshaw, 1980;
Theng, 1974; Raussell-Colom and Serratosa, 1987; Mark et al., 1995], a review
on synthetic clays [Carrado, 2000], etc.
Several active sites on the MMT crystal surface have been identified. In the
absence of water, for molecules not fully coordinated Al constitutes an electron-
pair accepting site. Ions of Fe+3 and Fe+2 provide, respectively, oxidising (electron-
accepting) and reducing (electron-donor) sites (similar activity in the presence of
other metallic impurities is expected). Interactions between the clay surface and
organic molecules by van der Waals forces and by entropic rearrangement effects
have also been observed.
From the point of view of intercalation/exfoliation that may lead to CPNC
the following three active sites are the most important [Brown et al., 1952]:
1. The platelet edges have a few positive charges that attract negatively charged
ions or molecules. These sites have been used to attach organic molecules
making MMT organophilic. However, the reactions involving edge ions do
not increase the interlayer spacing, hence they are not useful for intercalation.
Evidently, once MMT is intercalated, these sites can be used, e.g., to enhance
platelet miscibility with polymeric matrix or mechanical dispersability during
melt compounding. For example, Na-MMT is able to react with weak organic
acids, viz. tannin or ligno-sulfonates. This method has been used for dispersing
clay particles in drilling mud. The reaction does not increase the interlayer
d001 spacing.
2. The –OH groups (four per unit cell) may participate in hydrogen bonding
and chemical reactions. These are mainly located at the crystal edges, bound
to Si, Al or other octahedral ions. The face surface location of –OH groups
has also been postulated [Deuel, 1952; Uytterhoeven, 1960; 1962]. The
concentration of –OH groups can also be enhanced by digesting MMT with
NaOH solution.
87
Hydrogen bonding to the surface oxygen atoms provides the mechanism

responsible for adsorption of organic molecules by clay particles. The reaction
depends on the suspending medium. In water, hydrogen bonding by a water-
soluble polymer is much less likely to take place than in an organic medium.
H-bonding is significantly weaker than that with exchangeable ions. It depends
on the polarity of the interacting group, hence its strength decreases from
–NH3+, to –OCH2- to –CH3 [Gonzales-Carreño et al., 1977] as well when the
charge is tetrahedrally located [Farmer and Russel, 1971]. The H-bonding
depends on the pH of the suspension, thus H-MMT is more likely to involve
H-bonding than Na-MMT [Mortland, 1966]. Often H-bonding is a competitive
process, e.g., H-bonding between the alcohol molecules themselves moderates
adsorption of alcohol by MMT [Annabi-Bergaya et al., 1981].
It has been reported that (after cation exchange) clay containing either UO22+
or Fe3+ can be made hydrophobic by acid-catalysed reaction in n-heptane
with octadecyl-trimethoxy silane [Giaquinta et al., 1997; Wasserman et al.,
1998]. The silane film inhibited free exchange of water in and out of the
interlamellar galleries, thus after exposure to water the interlayer spacing
remained stable, similar in magnitude to the dry state. The authors did not
elaborate on the reaction mechanism.
3. The anionic group on the MMT face surface; MMT in aqueous medium behaves
as weak silicilic acid. These sites are of principal interest for diverse intercalation
methods. It has been observed that organic compounds may diffuse into galleries
and coordinate to alkaline cations. The strength of the complex as well as
expansion of the d001 spacing depends on the cation and organic compound.
For example, for a series of crown ethers absorbed by MMT, expansion by
Δd001 = 0.4 to 0.8 nm was reported [Ruiz-Hitzky and Casal, 1978].
The cation exchange reactions in aqueous medium have been extensively studied.
It has been known for 70-odd years that the surface cations can be exchanged for
other cations. A measure of this capacity is given by the cation exchange capacity
(CEC). For example, the CEC of MMT is 0.8-1.2 meq/g hence one negative ion
per 1.36 nm2 is located on the flat platelet surface. These values are considered
to be optimal – sufficient concentration of ions to obtain a good level of chemical
activity, and at the same time not too much of them to engender too strong solid-
solid interactions. To facilitate the ion exchange, an aqueous slurry of sodium
montmorillonite is mechanically mixed either in the shear field (e.g., in a colloid mill)
or subjected to ultrasonics [Pérez-Maqueda et al., 2003]. It is noteworthy that in aqueous
medium clay interlayer spacing expands and platelets interact with each other, increasing
the suspension viscosity. The increase depends on the clay counterion, concentration,
and flow field [Malfoy et al., 2003]. Thus, for practical reasons the clay suspension
during the purification and ion-exchange steps is usually kept below ca. 7 wt%.
The cation exchange reaction is reversible, hence to obtain a high conversion of
Na-MMT into organoclay, an excess of intercalating organic cation RH+ is used:
RH+ + Na+ – MMT RH+ – MMT + Na+
The reaction rate depends on the type of clay, the medium, the type of cation to
be exchanged, the reaction conditions, viz. temperature (T), pH, concentrations
and geometry of clay particles, etc. For example, recently, natural smectite (Na-
MMT) was intercalated with 3-methyl hexadecyl ammonium bromide (3MHDA)
with a molar excess ranging from 0 to 3 CEC. The interlayer spacing increased
88
Clays
from the original value of d001 ≅ 1.4 nm to 1.9, 3.2 and 3.9 at a 3MHDA loading
of 1, 2, and 3 CEC, respectively. When heated at a rate of 2 oC/min the interlayer
spacing started to collapse at T ≥ 200 oC [Lee and Kim, 2003].
To ensure that free cations are in the system, the pH is usually adjusted to at
least one unit lower than pK; a too acidic medium may cause cations to leach out
from the clay and interfere with the desired exchange reaction.
The type of cation present within the interlamellar galleries affects the magnitude
and uniformity of interlayer spacing. For example, H+ and Ca2+ show a non-uniform
expansion in water, whereas Na+ and Li+ provide easy expansion up to total
exfoliation. Under ambient humidity the d001 depends on the cation, viz. for Na+ it
is 1.4 nm, for Ca2+ it is 1.5 nm and for UO22+ it is 1.48 [Giaquinta, 1997].
The fastest rates of exchange are reported for Na-MMT. The presence of
less hydrated monovalent ions (e.g., K+, Rb+, Cs+) and of multivalent ions (e.g.,
Ca2+, Mg2+, etc.) reduces the rate. It seems that multivalent cations are capable
of simultaneous interaction with anions on adjacent MMT platelets, making
intercalation more difficult. However, since the thickness of the triple sandwich
is 0.66 nm (see Figure 17) compounds having the smallest dimension below
0.6 nm may diffuse into the interlamellar gallery when d001 > 1.4 nm.
The reaction rates in water are faster than those in aqueous solutions of organic
liquids, viz. alcohols, but there are exceptions to this rule, e.g., during intercalation
with organic cations. Increased T accelerates the process, hence the recommended
range is T = 60-80 °C. Similarly, an increase of pressure (P) has been also reported
to speed up the reaction. The particle shape and size also affect the kinetics. The
reaction is diffusion controlled. It starts at the rim and the rate of the linear
diffusion down the slit of diameter d, is proportional to the diffusion time, td,
viz. δd/δtd∝td , hence the diffusion time is proportional to the square root of d.
This prediction is almost confirmed by data from Mackintosh et al. [1971]. As
shown in Figure 22 the experimental exponent a = 0.45, instead of 1/2 was found.
Figure 22 Diffusion time of K+ in exchange reaction for dodecylammonium

cation as a function of the biotite clay diameter. Data [Mackintosh et al., 1971].
The broken line follows the empirical relation: td = aoda, with ao =15.63, a = 0.45
and the correlation coefficient, r = 0.9967.
89
Thus, modification of clay involves mainly a reaction with the anionic silicilic
groups on the platelet surface. In the presence of strong, but small in size cations
the interaction is mainly ionic, e.g., silicilic acid with Na+. However, when the
latter ion is replaced with a quarternary ammonium one, the van der Waals
interactions become more important. Their importance increases with the
hydrocarbon chain length [Theng, 1964]. Another type of interaction involves
the disruptive effects large cations have on the hydration shell around the interlayer
cation – the entropic effects. It has been found that the effect is more important
for Na+ than for Ca2+ or Mg2+ [Theng, 1967].
2.2.4.1 Clay in Aqueous Medium
2.2.4.1.1 General
Clays are hydrophilic hence the first step in their modification involves reactions in
the aqueous medium. The small and highly mobile water molecules easily diffuse
into interlamellar species, causing a lateral expansion of the clay crystals. The
process is diffusion controlled, hence to swell platelets that are twice as large requires
four times longer. The rate depends on many factors and the time required to reach
equilibrium swelling varies from minutes to days. Since water monolayer thickness
is about 0.28 nm, the first step involves expansion of d001 from 0.96 to about
1.25 nm. Further expansion up to complete exfoliation can be accomplished by
judicious control of conditions, especially the ionic strength and counterion type.
MMT exposed to water vapour expands its basal spacing in steps (which
correspond to one to four molecular layers of water) to d001 = 1.25 to 2.0 nm.
The origin of the water absorption by MMT is on the one hand hydration of the
counterions in the interlamellar galleries and on the other hydrogen bonding to
the clay surface. The work to remove the last monolayer of H2O is about 0.1 J/m2
at the equivalent pressure of 400 MPa.
Dispersing Na-MMT in distilled water causes the ions that are associated
with the clay surface to diffuse out. The osmotic pressure pulls the ions away
from the clay surface, whereas the electrostatic charge tends to hold them near
the surface. Eventually a steady state is achieved and an electrostatic double
layer is formed that keeps the clay platelets apart. The counterions in the double
layer are fairly mobile and can readily be exchanged. The reaction constant
depends on the ionic concentration in the double layer and in the supernatant
solution.
The double layer is formed by adsorption of solvated ions. Their concentration
and the associated electric potential decrease with the distance from the platelet
surface, following the Nernst equation:
Φ = (kBT/νe)ln(c/co) (14)
where: kB is the Boltzmann constant, v is the valence, e is the electronic charge, c
and co are the ion concentration in the solution and where the potential Φ = 0,
respectively.
Thus, the thickness of the double layer depends on the counterion
concentration and valency. Clay platelets can be fully exfoliated in aqueous media,
but on standing, since the surface and edges have different charge, the EF
interactions may lead to formation of a ‘house of cards’ structure. If enough clay
is present, all the water will be tied resulting in a gel formation. Shearing may
90
Clays
disrupt the structure, dramatically reducing the viscosity. The gelation is reversible,
as evidenced by the thixotropic effects [van Olphen and Fripiat, 1979].
Another type of structure that may be formed is a tactoid – a parallel alignment
of clay platelets, up to 10 nm distant from each other, forming high clay
concentration regions in suspensions. In some systems there is a sharp transition
between the gel and tactoid phase. For example, an aqueous suspension of n-
butyl ammonium vermiculite, n-butyl ammonium chloride and either PVME or
PEG has a phase transition temperature between the tactoid and gel phases of
the clay system, Tc = 13 ± 1 °C [Jinnai et al., 1996; Hatharasingle et al., 1998].
Tactoid formation is caused on the one hand by the presence of a repulsive double
layer and on the other by the attractive van der Waals forces. Tactoids have
smaller effects on flow behaviour than the ‘house of cards’ structures.
2.2.4.1.2 Reactions with Edge Cations

Tannates have been used as dispersing agents in drilling fluids. The most popular
tannate is quebracho tannin, a red-coloured tannin extracted from the South
American quebracho tree. Since the tannin is a weak acid, the sodium salt solution
is alkaline. Clay suspensions are dispersed by the addition of a small amount of a
tannate. The tannate anions are adsorbed at the edge surfaces of the clay particles
by complexing with the exposed octahedral aluminium ions. Consequently, the
edge charge is reversed and a negative double layer is created by which EF and EE
association is prevented. The anion adsorption on the clay edges is absent on the
faces of the clay plates. As a result, the basal spacing does not increase after tannate
adsorption. To be effective, a phenol must contain at least three phenolic groups in
the molecule, two of which should be adjacent. Thus, 1,2,3-hydroxy benzene is
effective for dispersing MMT, but 1,3,5-hydroxy benzene is not. Similarly alizarin
dyes react with the platelet edges, causing dispersion [Schott, 1968; Freudenberg
and Maitland, 1934].
2.2.4.1.3 Reactions with –OH Groups

The vibration stretching frequency of structural –OH groups in MMT are slightly
lower than those of unperturbed –OH groups, but easily distinguishable from
the broadband of hydrated minerals [Farmer, 1971]. Thus, in aqueous medium
these groups form hydrogen bonds with water molecules. The strength of these
interactions is expected to be higher than those between water molecules and
=Si=O surface groups.
2.2.4.1.4 Reaction with the Silicilic Surface Anions

As stated before, anions are adsorbed on the edges of the clay particles and organic
cations on the anionic inner surfaces of the clay platelets. This is evident from
the high adsorption capacity of the clay as well as the resulting expansion of the
d001 spacing.
The exchange reactions between Na-MMT and ammonium ions, R-NH3+Cl–,
or R4N+Cl– were studied in the early 1930s [Smith, 1934; Gieseking 1939]. When
onium salt is added to aqueous clay suspension, the organic cations replace the
cations present on the clay surfaces. There is a strong preference for the less
mobile organic cations. Often they are adsorbed quantitatively until all the
exchange positions are exhausted. The ammonium groups become ionically
attached to the clay surface while the hydrocarbon chains interact with the clay
91
surface and displace the adsorbed water molecules [Hendricks, 1941; Jordan,
1949; Jordan et al., 1950]. When the chains are too long to lie flat in the available
space they may tilt, crowding within the interlamellar space. Depending on the
conditions, the hydrocarbons may crystallise, hence the spatial organisation of
the hydrocarbon segments is given by the appropriate crystalline cell unit and
the performance of such organoclay depends on temperature – whether below or
above the hydrocarbon melting point. When the hydrocarbon chains cover the
clay surface, it precipitates from the aqueous suspensions. However, the formed
hydrophobic clay can be homogeneously dispersed in organic medium.
Often the concentration of the organic cations exceeds the amount equivalent
to the clay CEC. For example, commercial organoclays contain from 98 to 153%
of intercalant per nominal CEC of MMT. The reason for the excess is to force
the reversible reaction of ion exchange towards the organocomplex and to increase
the interlayer spacing to maximum.
The orientation of the interlayer cations, hence the d001 spacing, is usually
determined by the projected surface area of the cation (in a given orientation)
provided that it does not exceed the available surface area per surface anion.
Aromatic cations assume either a parallel or an upright position between the
layers, depending on the available space. Weiss and Kantner [1960] proposed a
method of estimating the surface charge density from the d001 spacing of complexes
with mono- and di-alkylammonium cations of different chain lengths. When the
modifier molecules are large and bulky the steric effect precludes total cation
exchange. The average distance between the silicilic anions on the MMT surface
is about 1.2 nm.
However, when the concentration of the organic cations is high, their
adsorption may exceed the amount equivalent to the clay CEC. For example,
quaternary ammonium compound having long hydrocarbon chains can be
absorbed in the amount equivalent of two-and-half times the CEC. The excess
enters the interlamellar galleries in a head-to-tail configuration, profiting from
the hydrocarbon/hydrocarbon chain solubility and the tendency to crystallise.
Under these circumstances, the excess ammonium compounds form a layer with
the cationic groups facing the water phase, forming a diffused electric double
layer that prevents the particles from precipitation. Thus the resulting organoclay
is hydrophilic, hence unsuitable for use in organic medium, e.g., for the preparation
of CPNC [Cowan and White, 1958; McAtee, 1962; Diamond and Kinter, 1963].
Often, the excess modifier can be removed by washing with hot water or alcohol
solution, provided that the cations are not too large [Furukawa and Brindley,
1973]. To avoid formation of the ionic double layer the ionic intercalant is used
to stoichiometry, and then its amine is added to form the head-to-tail, non-ionic
complex.
The perfidy of Nature also provides for an opposite effect – adsorption of less
than the stoichiometric number of organic cations. This situation has been
observed for large molecules (e.g., codeine on MMT) adsorbed from dilute
solutions to form a monolayer on the clay surface, hence shielding adjacent anionic
sites on the clay surface by steric hindrance [Weiss, 1963].
2.2.4.1.5 Stabilisation by Polyelectrolytes

Addition of water-soluble polyelectrolytes is a powerful method for controlling
clay dispersion [Hesselink, 1971; Hesselink et al., 1971]. Polyelectrolyte consists
92
Clays
of long-chain molecules with ionic groups usually located along the entire length
of the chain. The polyion may be a polycation with amino groups, or a polyanion
with carboxyl, sulfate, sulfonate, or other negative groups. A single polymer
molecule may contain both positive and negative groups, as is the case for proteins
with amino and carboxyl groups [Hauser, 1950].
Bio-polyelectrolytes (e.g., gum arabic, gelatin, alginates, pectin), modified
biopolymers (e.g., oxidised starch, carboxymethylcellulose) and synthetic
polyelectrolytes are becoming available, viz. polyacrylic acid [Warkentin and
Miller, 1948], polyacrylonitrile [Mortensen, 1962], polyvinyl alcohol [Greenland,
1963], etc. Addition of polyelectrolytes improves the stability of clay dispersion
in the aqueous medium.
2.2.4.2 Clay Dispersion in Polar Organic Liquids

Like water molecules, polar organic compounds may be adsorbed on the clay
surface. The adsorption energy of many of these compounds is comparable with
that of water. Depending on the concentration, they can displace adsorbed water
from clays, and be removed from the clay by washing with water. When MMT is
dispersed in a polar organic liquid (e.g., alcohol, glycol or amine) the suspending
liquid molecules penetrate into the interlamellar galleries and displace water.
The basal spacing of the complex depends on the size of the organic molecules
and on their orientation and packing geometry. The extent of d001 expansion in
polar organic liquids is so well defined that it can be used to identify MMT, e.g.,
ethylene glycol that gives d001 = 1.7 nm has been used to identify MMT [MacEwan,
1948; Bradley, 1945].
The exact mechanism of association between clay and polar molecules is not
known (similarly for water!). They may interact through the ionic groups of clay
and/or through hydrogen bonding. However, there is little spectroscopic evidence
for the interaction between -CH2- or -CH3 and =SiO groups. FTIR indicates that
hydrogen bonding is less important [Greene-Kelly, 1955; Brindley and Rustom,
1958]. For adsorption of ammonium ions it was shown that entropic effects
provide the driving force [Vansant and Uytterhoeven, 1972].
When the clay surface becomes covered with polar molecules containing a
substantial proportion of hydrocarbon groups, the surface becomes oleophilic,
and under these conditions the organoclay can be used as an oil or grease thickener.
However, since the exchange cations are still present, the complexes are usually
sensitive to water. For example, as shown by XRD, the MMT-pyridine complex
at low water concentration hydrates stepwise and then exfoliates when a large
amount of water is added [van Olphen and Deeds, 1962]. Similarly low molecular
weight alkane ammonium complexes (e.g., n-butyl ammonium) show a spectacular
interlayer swelling in water [Garrett and Walker, 1962]. However, pyridinium
and other large organic cation exchange complexes are not sensitive to H2O.
Apparently here the steric shielding of unused silicilic anions provides sufficient
protection.
Polar, water-soluble macromolecules such as polysaccharides or polyethylene
glycol are readily sorbed by MMT, which leads to expansion of the interlamellar
space, d001. Edge sorption may also take place [La Mer and Healy, 1963].
2.2.4.3 Absorption of Organic Molecules by Organoclay

The initial adsorption of organic molecules (as described above) may lead to change
of the clay character from hydrophilic to hydrophobic and to an expansion of the
93
interlayer d001 spacing. Both factors tend to facilitate further absorption of organic
substances by the interlamellar organic phase. The absorption may take place from
the vapour phase, from solution or from melt. It constitutes a vital element in the
strategy of CPNC manufacture.
The mechanism of the secondary absorption is based on the miscibility
principle – only the substances that either can chemically react or are miscible
with the interlamellar organic phase can be absorbed. Furthermore, the
thermodynamic free energy of mixing must be able to compensate for the energy
of increasing separation of the clay platelets. Thus, for example, absorption of a
base requires that the interlamellar phase comprises active acidic functionalities,
while absorption of nonionic compounds requires that their solubility parameter
is comparable to that of the interlamellar phase [Utracki, 1989; 2002b; Utracki
and Kamal, 2002a; Utracki, 2004]. The absorption leads to further expansion of
the interlamellar space, proportional to the total number of -CH2- groups within
the space. The process is diffusion controlled, hence a long residence time and
intensive mixing may be required.
Maximum swelling is facilitated by the organophilic nature of treated clay
and by the high polarity of the organic penetrant. Thus, the initial modification
(in the aqueous phase) should result in the exchange of at least 50% of Na+ by
organic cations and the interlamellar space should be at least 0.8 nm. The best
secondary intercalant should have high polarity and be organophilic, e.g.,
nitrobenzene or benzonitrile. When the secondary intercalant is hydrocarbon,
unsaturation is a definite asset otherwise swelling may have to be aided by addition
of a well miscible (with it) polar organic liquid [Grim, 1968].
Certain organic molecules may also penetrate the interlamellar space to form
coordinated compounds by not directly interacting with the clay surface, but
rather with the cations ionically bound to it. Two types of molecules are suitable,
with either polar or aromatic functionalities. Since this secondary intercalation
is usually conducted using air-dried organoclay (often suspended in an alcohol),
the process must (1) replace the adsorbed water, and (2) form the coordination
shell around the cation. The presence of residual moisture enlarges the
interlamellar space, hence easier diffusion, but at the same time the energetics of
step (2) must be sufficient to compensate for it. When the secondary intercalant
was either ethanol or acetone the number of molecules in a complex depended
on the interlamellar cation. Thus there were 2 for each K+, 3 for each Na+, 8-10
for each Ca2+ or Ba2+, etc. The interlamellar spacing also varied, respectively
from 1.3-1.4 to 1.7 nm [Bruque et al., 1982]. The complexes of Cu-, Ni-, Zn-,
Cd-, Hg- or Ag-MMT with PA or thiourea are highly stable [Peigneur et al.,
1978].
Complexes with water molecules forming bridges between the metal cation
and the organic molecules are known for, e.g., pyridine, nitrobenzene, benzoic
acid, aniline, nitriles, ketones or PEG. The latter compound forms complexes
with M+-MMT even in aqueous suspensions [Parfitt and Greenland, 1970]. The
presence of H2O on the one hand causes expansion of the interlamellar space,
but on the other it makes the system less stable at higher temperatures.
Complex formation of M+-MMT with neutral organic molecules results in
their protonation and stronger bonding. Protonation may originate directly from
the cations present in the system, viz. H+, NH4+ or in general M+, or from the
water molecules that are coordinated to a cation, viz. [M(H2O)x]n+. FTIR or
94
Clays
NMR readily detects protonation. The molecules that undergo these reactions
are amines, azoles or phenols [Raussell-Colom and Serratosa, 1987].
In non-aqueous systems hydrogen bonding of organic molecules to the clay
surface takes place. The positive charge deficiency in the tetrahedral layer results
in negative charge that is spread out on several surface oxygen atoms coordinated
to Al3+ or Si4+ ions [Farmer and Russel, 1971]. The molecules capable of forming
the hydrogen bonds are mainly alcohols, amines, ketones, etc. Identification of
these reactions by spectroscopic means is difficult.
In MMT at the platelet edges there is a limited number of silanol groups that
can be reacted with a diversity of organic compounds, viz. alcohols,
organochlorosilanes, isocyanates, epoxies, diazomethane:
⎧ R − OH → ≡ Si − OR + H 2 O
⎪
⎪ Cl − Si(R)3 → ≡ Si − OSi(R)3
≡ Si − OH + ⎨
⎪ O = C = N − R → ≡ Si − O − CO − NH − R
⎪⎩ R − CH (O) = CH 2 → ≡ Si − O − CH (CH 2 − OH ) − R
Since the number of silanol groups in MMT is small, only a limited number of
organic molecules can be grafted. The grafting does not affect the interlayer
spacing, but may provide for better miscibility with the organic matrix. However,
the silanol groups can also be formed by treating a suspension of MMT in alcohol
with HCl [Lentz, 1964; Zapata et al., 1972]. The treatment removes surface
cations from octahedral layers:
≡ Si − O − Mg − O − Si ≡ + 2H + → 2(≡ Si − OH ) + Mg2 +
The silanol groups in turn can be reacted with a diversity of compounds, e.g.,
having groups susceptible for subsequent polymerisation: polycondensation or
polyaddition.
95
96
Intercalation of Clay
2.3
2.3.1 Introduction
The first step in the preparation of clays for use in PNC is purification of the
mineral (see Section 2.2.3). Depending on the ultimate use of the resulting Na-
MMT, before intercalation the powder may be subjected to further preparatory
steps, either to reduce the particle size and/or to reduce the particle size distribution.
Since the time (t) that intercalant needs to diffuse a distance (l) is given by the
proportionality: t ∝ l2, a decrease of clay particle diameter by 30% results in
reduction of the intercalation time by half. Thus, as described in patents from
Southern Clay [Knudson and Jones, 1986; 1992a,b], the interdiffusion of
intercalating molecules is facilitated by reduction of the clay particle size – high
stresses not only reduce the diameter but may also cleave the stack, reducing the
required force to bend the middle layers during intercalation. Earlier patents similarly
focused on the reduction of clay particle size either by mechanical grinding,
comminuting or by hydrodynamic forces [Cohn, 1967; Clocker et al., 1976].
Since the exchange reaction of the inorganic cation (such as Na+) for the
organic one proceeds from the clay platelet edge toward the centre as a regular
front, reduction of platelet size reduces the time required for the intercalation
(increasing the reaction temperature to ca. 70 oC also helps) [Newman, 1987].
Ion exchange strongly depends on pH – the optimum is about one unit below the
pK-value of the organic salt.
It is noteworthy that reduction of particle diameter is detrimental for the
control of barrier properties, but it may not be essential for the other performance
criteria. Intercalation of clay that has a wide distribution of platelet size often
results in an uneven degree of intercalation, evidenced by broad XRD diffraction
peaks [Ho et al., 2001]. The peak is much sharper when more uniform size Na-
MMT particles are used.
The aims of intercalation are to:
1. Expand the interlayer spacing,
2. Reduce solid-solid interaction between the clay platelets and
3. Improve interactions between the clay and the matrix.
The first goal has been traditionally achieved by making use of the anionic charge
within the interlamellar galleries. Since the van der Waals interactions between
solid surfaces decrease with the square of the separating distance (see Figure 18),
insertion of organic or inorganic molecules into the interlamellar space greatly
helps to achieve the second aim. To reach the third goal, to compatibilise the
system, the principles developed for compatibilisation of polymer blends should
be used [Utracki, 1994; 1998; 2000; 2002a; Ajji and Utracki, 1997; Utracki and
Kamal, 2002b; Ajji, 2002; Brown, 2002].
97
For successful intercalation the selected clay should have a cation-exchange

capacity: CEC = 0.5-2.0 meq/g, as for CEC < 0.5 the ion exchange is insufficient,
while for CEC > 2.0 meq/g, the interlayer bonding is too strong for easy
intercalation, thus smectites and vermiculites have the optimum CEC –
theoretically 1.39, experimentally 0.8 to 1.2 meq/g. By contrast, kaolin has a
cation-exchange capacity < 0.1 meq/g, while mica, illites, attapulgite and sepiolite
are about 0.2 meq/g. As a consequence, MMT, saponite and hectorite are the
preferred clays for CPNCs, but since MMT is more abundant and it has a fairly
large aspect ratio, p ≅ 300, (natural hectorite has the smallest) it became the
main nanofiller for PNC technology. Owing to the large aspect ratio, p ≤ 2,000,
of synthetic micas, natural vermiculites and natural micas, several attempts have
been made to use them in CPNC as barrier material against permeation of gases,
vapours and liquids.
Purification and intercalation can be quite abrasive, significantly reducing
the clay aspect ratio [Ferreiro et al., 2001; Jeon et al., 2004]. According to the
former authors, synthetic hectorite (Ilaponite LRD) had p ≅ 30, whereas MMT
had p ≅ 100. Jeon et al. estimated the aspect ratio of MMT-based organoclay to
be ca. 80. Both teams reported that in solution organoclay tends to form spherical
particles of diameter varying from about 20 to 240 nm.
Traditionally, the main use of the intercalated clays has been to produce
thixotropic effects in aqueous or non-aqueous systems, e.g., to improve paper
coating, lubricant thickening or to prevent sedimentation of dispersed solids.
During the last 20 years or so additional uses for clay for CPNC technology have
emerged. Intercalation and exfoliation for fine chemical delivery systems is the
most recent. Thus, intercalated organoclays have had numerous uses:
• As water-based or organic liquid-based (e.g., ethanol, acetone) thickener for
insecticide paste [Hamilton, 1936].
• ‘Bentonite’ intercalated with either ammonium (e.g., with dodecyl ammonium,
octadecyl dienyl ammonium, dimethyl dicetyl) or phosphonium (e.g., with
triphenyl lauryl) cation has been used, e.g., for thickening lubricating oils
and greases, oil-based muds, packer fluids, paint-varnish-lacquer removers
[Jordan et al., 1950].
• Application of onium intercalated layered silicates as organophilic thickeners
of organic liquids [Hauser, 1950]. A wide diversity of onium salts have been
described in the patent literature, viz. ammonium, phosphonium, sulfonium,
etc.
• Use of MMT intercalated with quaternary ammonium (commercially available
as ‘Bentone®’ from the National Lead Co.) as an inherently thixotropic
additive in nail enamel applications. The organoclay provided suitable
rheological behaviour and prevented settling of nacreous pigments [Kuritzkes,
1969].
• In CPNC to facilitate diffusion of monomers and/or macromolecules into
the interlamellar space, that eventually would lead to exfoliation [Fujiwara
and Sakamoto, 1976; Okada et al., 1988].
• For delivery of cosmetic, medical or agro-active compounds, e.g., sunscreen,
antibacterial, antifungal, and many others [Beall et al., 1998].
• For delivery of fungicides, pesticides, insecticides, acaricides and other
agriculturally active compounds [Beall et al., 1999a].
98
Intercalation of the clay particles is diffusion controlled. Water is a ‘natural’

intercalant for clays, but it can hardly be considered unique. Its efficiency is most
likely related to the good balance between the dipole moment that drives the
process and the molecular size that restricts its motion. In aqueous systems, water
molecules can easily diffuse in and the electrostatic double layer can push the
individual platelets apart and keep them away from each other – at low clay
concentration total exfoliation can be achieved.
On a molecular scale, intercalation can be visualised as inserting peas between
each pair of play-cards in a stack. Evidently, to be able to do that the cards must
be pre-spaced and there must be a driving force for the peas to enter the narrow
space bending the cards from the edges. Thus, the way to intercalate clay is to
use progressively larger molecular species. To prevent re-assembly of layers it is
desirable that at least some intercalant is bound to the clay surface.
For the application of clays in CPNC technology intercalation should increase
the interlamellar spacing to about 3-4 nm and make the clay organophilic. The
goal is usually reached in stages.
1. In dry clay the solid-solid interactions keep the interlamellar gallery at a
water monolayer level, of about 0.26 nm. The sheets are strongly bound to
each other (see Figure 18). The traditional method for reducing the solid-
solid interactions, hence to reduce the resistance to intercalant diffusion into
interlamellar space, is to disperse the clay in water or an aqueous solution of
water-soluble organic solvents, e.g., alcohol or glycol.
2. The second step usually involves exchange of Na+ for an organic cation.
Since the pK of onium salts increases with the degree of substitution, in most
cases the quaternary onium is used. However, for the use of organoclay as a
reactive component (e.g., in thermosets) a primary or secondary onium salt
may be preferred. Furthermore, depending on the expected application the
onium salt may have a functional group (e.g., a vinyl functionality).
3. In the third step the organoclay may be further treated with reactive compound
to compatibilise the clay/polymer systems. Three classes of reactive
compounds have been used: known glass-fibre sizing agents (e.g., silanes,
titanates, zirconates), known reactive compatibilisers (e.g., oligomeric or
polymeric compounds with glycidyl, maleic, isocyanate and other reactive
groups), and organometallic compounds. This third step may be a part of
the last step in the preparation of CPNC, the exfoliation of organoclay and
dispersion of individual platelets in the polymeric matrix.
Several routes have been used to intercalate clay particles. They can be classified
as follows:
1. Use of solvents or low MW solutions, such as water, alcohols, glycols, crown
ether or monomer solutions.
2. Use of organic cations, viz. ammonium, phosphonium or sulfonium.
3. Silylation of clay platelets.
4. Incorporation of inorganic compounds that form interlamellar pillars.
5. Use of organic liquids, viz. monomers, macromers, oligomers, polymers (PEG,
PVAl, PDMS, PVP), copolymers, and their solutions.
6. Melt intercalation.
7. Others.
99
2.3.2 Intercalation by Solvents and Solutions

As was shown in Figure 17, the basal spacing of MMT is 0.96 nm. In the presence
of ambient humidity it expands to about 1.25 nm and upon addition of ethylene
glycol to 1.7 nm. Intercalation using aqueous solution of glycols, glycerol or
sorbitol was reported to be facilitated by the addition of Mg(OH)2 in the amount
that changes pH to about 9.4 [Buffett, 1965; Burns, 1974].
Vaia et al. [1995a] directly intercalated Na-MMT or Li-MMT with PEG by
heating the suspension to 80 °C for 2 to 6 h. The PEG displaced water molecules,
expanding the interlayer spacing to d001 = 1.77 nm, but the clay could not have
been exfoliated.
Thixotropic thermoset polyester resin was prepared for hand lay-up mouldings
by incorporating clay intercalated with polyols. Similarly, Kornmann et al. [1998]
produced CPNC based on MMT and unsaturated polyester (UP). Na-MMT was
intercalated at 50 °C in MeOH with methacrylate then dried. The treated MMT
was dispersed in UP (containing 42 wt% styrene and co-octanoate). The mixture,
after curing at room temperature and post curing at 70 °C, was found to be
exfoliated.
In 1998 Katahira et al. [1998a,b,c,d] published a series of articles on the use of
mica for the production of PA-6-based CPNC. First, Na-mica flakes were cleaved
and dispersed into hydrolysed and protonated ε-caprolactam (ε-CL). Phosphoric
acid has been used as a catalyst for the protonation of ε-CL. The intercalation was
found to occur in two steps: a rapid (even at 20 °C) exchange of Na+ in mica galleries
with protonated ε-CL, then a significantly slower exchange of water solvated Na+
ions – the latter step could be accelerated by heating to T > 60 °C. The intercalated
mica had the interlayer spacing of d001 = 1.47 nm.
Serrano et al. [1998a] patented exfoliated CPNCs containing ≤ 99.95 wt%
EVAl. No onium ion or silane coupling agent was needed for the intercalation.
The intercalant was selected from between water-soluble oligomers (degree of
polymerisation (DP) = 2-15) or polymers (DP > 15) having dipole moment greater
than that of H2O (1.85 D). For example, P4VP, PVAl, copolymers of vinyl acetate
and vinyl pyrrolidone, or their mixtures could be used. The intercalant was
absorbed between the silicate platelets increasing the interlamellar galleries by
Δd001 = 0.5 to 10 nm. The authors speculated that on the clay surface the
intercalant molecules were ionically complexed with interlayer cations. Depending
on the intercalant concentration the adsorbed molecules formed from 1 to 5 layers
on the clay surface.
In the following patent from the same laboratory [Serrano et al., 1998b] it was
reported that the best results were obtained using an oligomer with DP = 2-15 or a
polymer containing 50-80 wt% of an oligomer. The optimum performance was
achieved by expanding the interlayer spacing to d001 = 3.0-4.5 nm. The preferred
intercalants were P4VP, PVAl, or their mixtures. Intercalation was conducted in
a twin-screw extruder (TSE) using intercalant solution at T = Tm + 50 °C. A
masterbatch containing 20-80 wt% of clay was prepared. The recommended
presence of oligomers and relatively high mixing T indicate recognition of the
critical role diffusion has in the process. The method was extended to non-aqueous
systems, but using Na-MMT that contained 10-15 wt% H2O (exfoliation was
not obtained when the water content was below 8 wt%). For example, when
80 wt% PA was compounded under N2 with Na-MMT at T = Tm + 50 ≈ 230 °C,
the clay platelets were exfoliated. Similarly, mixing PET with 10 wt% of
Na-MMT or PC with 50 wt% of Na-MMT resulted in exfoliation.
100
N-Vinylcarbazole (NVC) was cationically polymerised by Biswas and Ray [1998;

1999], in the presence of well-dried MMT, either directly at T > Tm = 64 °C, or in
benzene at 50 °C. The resulting CPNC of polyvinylcarbazole (PVK) was
intercalated, but during 100 min of polymerisation the interlayer spacing increased
from d001 = 0.98 to 1.46 nm. However, intercalation was not the aim of this
work. The authors reported two important discoveries of PVK grafting to the
MMT surface and of the possibility of achieving clay intercalation under
anhydrous conditions. Evidently, the dipole moment and aromatic character of
NVC provided a large driving force.
Srikhirin et al. [1998] intercalated two polydiacetylenes: 14-amino-10,
12-tetradiynoic acid (a diacetylenic mono-amino acid, MADA) and 10,
12-docosadiyndiamine (diacetylenic diamine, DADA) into layered silicates: MMT
from Wyoming (CEC = 0.33 meq/g) or from Arizona (CEC = 0.57 meq/g) and
vermiculite (VMT). The intercalation was conducted in an aqueous ethanol
suspension for MMT and VMT over 1 and 7 days, respectively. The intercalation
was confirmed by XRD and FTIR. The d001 spacing and polymerisability of the
diacetylenes depended on the length of the diacetylene molecule, the layer charge
density of the clay, and the solvent treatment. The DADA dichloride was
intercalated into both MMT and VMT. The d001 = 1.41 and 3.1 nm was obtained
for MMT and VMT, respectively. Intercalation with MADA resulted in d001 =
1.91 and 3.68 nm for the two MMT types, and d001 = 4.5 nm for VMT. Irradiation
produced polymer only in the latter case. In the final product the interlayer spacing
changed but a little: d001 = 4.2 nm was obtained. The authors concluded that
when the intercalated diacetylene in MMT lays flat on the clay surface it is unable
not be polymerised owing to the lack of proper packing density. In VMT the
intercalated MADA is tilted with respect to the clay surface and the diacetylene
has proper packing for propagation of radical polymerisation.
As was already mentioned, organic compounds may diffuse into galleries and
coordinate to alkaline cations [Ruiz-Hitzky and Casal, 1978]. The strength of the
complex as well as expansion of the d001 spacing depends on the nature of the
cation and the organic compound. Recently, on separate occasions, Gilman et al.
[2001] and Yao et al. [2001] used crown ethers and cryptands to intercalate clays
that were subsequently dispersed in polymers (PA-6 and PS, respectively). Similarly,
MMT has been intercalated with C60-fullerene [Ishikawa et al., 1997]. The process
was conducted in a phenol-formaldehyde-N-vinyl-2-pyrrolidone mixture at 60 °C,
in the presence of HCl, subjecting the system to ultrasonics. The resulting thermosets
with good electrical conductivity were used in Li-batteries.
In 2001 Yao et al. used Na-MMT and K-MMT swollen overnight in water,
then added a 1~3 % solution of crown ether in acetone. The complexation was
conducted for 24 h at 20 to 45 °C, then the clay complex was filtered, washed and
finally dried in a vacuum oven. The crown ethers were found to increase the d001
spacing by Δd001 = 0.4 to 0.7 nm, hence they complexed with either K+ or Na+. PS-
type CPNCs were prepared by dispersing ca. 1 wt% of crown ether-modified clay
in styrene (St). The radical polymerisation of St in the presence of these clays was
conducted overnight at 80-120 °C. For Na-MMT-based systems XRD showed no
significant change in the d-spacing, but CPNCs were formed from K-MMT
intercalated with cis-di-cyclohexano-18-crown-6 and the interlayer spacing
increased to d001 = 7.7 nm. It is noteworthy that the complexation constant of
crown ethers with K+ is higher than that with Na+. The larger is the constant, the
stronger is the complex and the more organophilic the clay.
101
2.3.3 Intercalation by Organic Cations

This method of intercalation by organic cations has been dominant for 70 years
or so. As mentioned, the fastest exchange rates have been reported for Na-MMT.
The reactions in water are faster than those in aqueous solutions of organic
liquids, especially at higher temperatures, viz. T = 60 to 80 °C. Increased pressure
(P) also speeds up the reaction. The diffusion-controlled, reversible reaction starts
at the rim and the distance it travels is proportional to the square root of time
(see Figure 22).
As shown in Table 17, there is a great diversity of intercalants for layered
clays. Functionally, these compounds are similar to compatibilisers or emulsifiers
– they must diffuse into interlayer space and ascertain good thermodynamic
interactions between the modified clay and polymeric matrix. Furthermore,
similarly like compatibilisers, intercalants must provide good stress transfer
between the two principal CPNC components – clay and polymer. Thus, the
three criteria for selecting intercalant are: (1) the kinetics for diffusion into the
interlamellar galleries, (2) high bonding strength with clay platelets, and (3) strong
interaction with the polymer matrix.
To facilitate selection, Tanaka and Goettler [2002] used molecular dynamics
(MD) computation. The authors built a model comprising a MMT platelet, an
intercalant (12 were considered), and a matrix (PA-66). Next, using MD methods
the binding energies were computed for 600 K within each of the three model
components, as well as the binary interaction energies between them. Finally, the
fracture toughness parameter, Gc, was equated with the computed binding
energies. The simulation showed that the positive charge initially placed on R4N+
spreads over the intercalant molecule; the charge is not localised on the nitrogen
atom, but primarily on the substituent groups bonded to it. The charge
equilibration method showed that the binding energy between PA-66 and the
clay platelet decreases almost linearly with the intercalant volume. Thus, pristine
clay/PA-66 showed the highest binding strength (hence toughness). The second
best performance was found for MMT intercalated with ω-amino dodecyl acid
(ADA), and the worst for MMT with dimethyl di-octadecyl ammonium (2M2OD).
Similar MD simulations were carried out for CPNC comprising MMT, intercalant,
and PA-6 [Fermeglia et al., 2003]. The results on the one hand paralleled the
previously data for PA-66, and on the other indicated that the intercalants
originally selected in Toyota R&D laboratories were indeed the best.
Clay reactions with ammonium ions were studied in the early 1930s [Smith,
1934; Gieseking, 1939]. Later on attention shifted to the whole class of onium
salts defined as organic compounds of the type RXHv. The element X (in its
highest valency) may be pentavalent, as in ammonium, phosphonium, arsonium
and stibonium; tetravalent, as in oxonium, sulfonium, selenonium and
stannonium; or trivalent, as in iodoium [Hauser, 1950]. Clays readily react with
less mobile organic cations, ionically bonding them to the surface. The organic
part is selected considering three aspects of intercalation:
1. Ability to non-ionically interact with the clay surface,
2. Ability to expand the interlamellar space, and
3. Miscibility with the polymeric matrix.
In 2003, Lagaly and Ziesmer published an excellent review on clay chemistry
[Lagaly and Ziesmer, 2003].
102
Traditionally, for the preparation of organophilic thixotropic additives used

in lubricants, quaternary ammonium chlorides with aliphatic hydrocarbons were
introduced. Later, for paints and varnishes, mixed aliphatic/aromatic ammonium
salts were used. For latex systems, it has been found advantageous to use
hydrocarbons with -OH groups, viz. hydroxyethyl, carboxyl, etc. Owing to low
cost and suitable hydrocarbon lengths, tallow oil derivatives have frequently been
used. Commercial hydrogenated tallow oil typically contains (in wt%): 2.0 C14,
0.5 C15, 29.0 C16, 1.5 C17, 66.0 C18 and 1.0 C20 alkyl groups. It is obtained from
natural oils, e.g., corn, soybean, cottonseed, castor, or animal oils and fats. Other
oils, e.g., coco or coconut, are also being used. The commercial organoclays are
still intercalated with ammonium salts having these three types of organic chains.
Unfortunately, as discussed in Part 3.2, quaternary ammonium ions decompose
at the processing temperatures of most thermoplastics, viz. at T ≥ 200 °C. This
decomposition leads to reduction of the interlayer spacing (reversed intercalation)
and it may discolour the product, reduce mechanical properties, decrease impact
strength, etc. Nevertheless, these quaternary cations are the principal intercalants
used in the industry [Hamilton, 1936; Maloney, 1939]. It has been found that
the d001 spacing of layered clays intercalated with alkylammonium salts depends
on the length of the alkyl radical as well as on the CEC. As shown in Figure 23
the spacing changes in steps [Hackett et al., 1998]. Molecular modelling and the
FTIR measurements led to the model shown in Figure 24 [Vaia et al., 1994].
One of the early applications of organophilic clays was to ‘thicken’ low
viscosity liquids. Such gellants had to have good dispersability in aqueous or
organic systems. Owing to the hydrophilic character of clays, development of
gellants for organic solvents and solutions was more challenging. To minimise
Figure 23 The interlayer d001 spacing of clays with CEC = 80, 100 and 150 as a
function of the alkyl chain length in a primary ammonium salt: RNH3+Cl-.
After Hackett et al. [1998].
103
the amount of clay that was necessary for creating the desired effects two
conditions had to be met:
1. The clay had to have the largest possible aspect ratio; and
2. The organoclay had to be miscible in the matrix liquid.
In other words, the clay had to be exfoliated. Knowing the aspect ratio the required
concentration could be calculated from Equation 1 as φ > φm. The conditions for
miscibility could be calculated considering the molecular structure of the matrix
liquid and the intercalating radical using, e.g., Hansen’s solubility parameter
approach [van Krevelen, 1993], or the equation of state approach [Utracki, 2004].
Figure 24 FTIR-based alkyl ammonium chain ordering model as a function of

alkyl length: (a) isolated, short chains in a monolayer; (b) intermediate chains
disordered, forming a quasi-bilayer; (c) long chains with increased order and
multi-layer spacing.
Reproduced from Vaia et al. [1994], copyright 1994, with permission from the
American Chemical Society.
104
For example, Finlayson and Jordan [1978] prepared organophilic smectite

(CEC = 0.75-1.20 meq/g) by reacting it with methyl benzyl dihydrogenated tallow
ammonium chloride (MB2HTA). The clays were hectorite and Wyoming bentonite
(CEC = 1.0-1.2 meq/g), purified and converted to sodium form. Other quaternary
ammonium intercalants, viz. dimethyl dihydrogenated tallow (2M2HTA), methyl
trihydrogenated tallow (M3HTA), benzyl trihydrogenated tallow (B3HTA) and
dimethyl benzyl hydrogenated tallow (2MBHTA), were described as suitable as
well – selection of one or the other depends on the character of the liquid to be
thickened. The intercalation was carried out at T = 66-77 °C by mixing an aqueous
suspension of 3-7 wt% Na-MMT and the quaternary ammonium compound for
sufficient time to achieve adequate intercalation. The product was filtered and
washed at 60 °C, then dried and ground. When the organophilic clays are to be
used in emulsions, the drying and grinding steps may be eliminated. These
organophilic clay complexes were used as additives to lubricating greases, oil-based
muds, oil-based packer fluids, paint-varnish-lacquer removers, paints, foundry
moulding sand binders, etc.
A simple test was devised to determine the thickening characteristics of the new
organoclays. Thus, low viscosity oil was mixed with 4.5 wt% of organophilic clay
for 0.5 min at 1800 rpm, then 0.12 wt% of water was added and mixing continued.
After 6-9 min the viscosity η > 200 Poises was obtained.
MMT reacted with dimethyl-dioctadecyl ammonium ion (2M2ODA) has been
industrially produced as a thickener for coatings in solvents with low polarity
(e.g., toluene and xylene). For polar solvents (e.g., DMF, methanol and ethanol),
clay with a dimethyl-benzyl-octadecyl ammonium ion (2MBODA) has been used,
but the gelling efficiency of this system was low. As a solution to the latter problem,
Iwasaki et al. [1994] developed organophilic clay with hydroxy-polyoxy-ethylene-
alkyl ammonium ions. The authors used clay with CEC = 0.85-1.30 meq/g and
ammonium salt of mono-hydroxy-polyoxy-ethylene-tri-alkyl-, mono-hydroxy-
polyoxy-ethylene-di-alkyl-, di-hydroxy-polyoxy-ethylene-di-alkyl-, di-hydroxy-
polyoxy-ethylene-alkyl-, tri-hydroxy-polyoxy-ethylene-alkyl- or tri-hydroxy-
polyoxy-ethylene-. The number of statistical segments (n) in polyethylene glycol,
-(CH2CH2O)n- was n = 2-20. A three step method of preparation was used:
1. 1 to 15 wt% clay was dispersed in water,
2. The quaternary ammonium salt solution was added 0.5 to 1.5-fold on the
clay CEC,
3. The organophilic clay was washed with water, dried and pulverised.
According to XRD, the dehydrated smectite had the basal spacing d001 = 0.96 nm.
Under ambient temperature and humidity the spacing increased to 1.2-1.6 nm.
The organoclay intercalated with quaternary hydroxy-poly(oxy-ethylene)-alkyl
ammonium ions had d001 ≥ 1.8 nm – the actual value depended on the degree of
polymerisation of the PEG segment, -(CH2CH2O)n-. Since these groups have a
high affinity to molecules of a polar solvent, the solvent expanded the interlayers
and exfoliated the clay. The organoclay was used as gellant in the production of
coatings, plastic products, films and adhesives containing highly polar organic
solvents such as DMF or ethanol. Good film-forming ability was achieved. In a
cited example 20 g of hectorite (d001 = 1.25 nm, CEC = 1.1 meq/g) was dispersed
in 1 L of tap water, and 21.4 g of a quaternary ammonium salt. The mixture was
stirred at room temperature for 2 hours. The product was separated, washed,
dried and pulverised. XRD confirmed formation of organoclay with d001 = 2.1 nm.
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The product formed a transparent dispersion in N,N-dimethylformamide showing

good affinity to highly polar organic solvents.
In another patent from NL Industries [Finlayson, 1980], several quaternary
ammonium salts were used, viz. methyl benzyl or dibenzyl dialkyl ammonium
chloride, methyl benzyl dihydrogenated tallow ammonium chloride or methyl
benzyl dicoconut fatty acid ammonium chloride. The intercalation was conducted
as described in the previous patent. On an industrial scale the organoclay could
be prepared in colloid mills or other high speed dispersers. The non-aqueous,
self-activating organophilic clays were useful in paints, varnishes, enamels, waxes,
epoxies, mastics, adhesives, cosmetics and the like. The use of benzyl or dibenzyl
radicals in the intercalant indicates that the paints that needed thickening were
dispersed in at least partially aromatic solvents.
In a later patent [Finlayson and Mardis, 1983], the intercalating cation could be
any quaternary onium, viz. ammonium, phosphonium, sulfonium or their mixtures.
The intercalant should contain at least one alkyl group having 12-22 carbon atoms,
derived from natural oils, e.g., tallow. Additional onium radicals may include
methyl, ethyl, decyl, lauryl, stearyl, benzyl and substituted benzyl, phenyl (as in
N-alkyl and N,N-dialkyl anilines), alkyl phenyl, naphthalene, anthracene and
phenanthrene. The clay-onium complex was reacted with organic anion. The
latter should have molecular weight < 1 kg/mol and be derived from an organic
having a pKA < 11.0. Suitable acids include:
• Carboxylic acids (benzoic, phthalic acid, benzene tri-, tetra- and hexa-carboxylic
acid); alkyl carboxylic acids: H-(CH2)n-COOH, wherein n is a number from
1-20; alkyl dicarboxylic acids: HOOC-(CH2)n-COOH, wherein n = 1-8;
hydroxy alkyl carboxylic acids (citric, tartaric, or 12-hydroxystearic acid);
unsaturated alkyl carboxylic acids (maleic, fumaric or cinnamic acid); fused
ring aromatic carboxylic acids (naphthalenic or anthracene carboxylic acid);
cycloaliphatic acids (cyclohexane-, cyclopentane-, or furan carboxylic acids).
• Organic sulfuric acids: (a) sulfonic (benzene-, phenol-, dodecyl-, benzene di-
or tri-sulfonic, p-toluene sulfonic acid); alkyl sulfonic or di-sulfonic acids
(e.g., of butane); and (b) half-esters of sulfuric acid with lauryl or octadecyl
alcohol.
• Organophosphorus acids including: phosphonic; phosphinic (e.g., dicyclohexyl
phosphinic), thiophosphinic acids, phosphites, phosphates, e.g., dioctadecyl
phosphate.
• Phenols, viz. phenol, hydroquinone, t-butyl catechol, p-methoxy phenol, and
naphthols.
• Thio-acids (thio-salicylic, -benzoic, -acetic, -lauric, -stearic, etc.).
• Amino acids, e.g., 6-aminohexanoic or 12-aminododecanoic.
• Polymeric acids, e.g., low molecular weight acrylic acid polymers and
copolymers; styrene-maleic anhydride copolymers.
• Miscellaneous acids and acid salts, which form a water insoluble precipitate
with an organic cation.
The intercalation was carried out in aqueous medium by mixing the ingredients
for 1 to 60 min, at T = 60 to 77 °C, and then filtering, washing, drying and
grinding. The amount of anion should be 0.1 to 0.5 meq/g of clay, that of organic
cation 1.0 to 1.6 meq/g.
106
The preferred process involves:

(a) Preparing water slurry with 1-80 wt% smectite and heating to T = 20-100 °C
(b) While agitating the suspension adding organic anion and organic cation in a
sufficient amount to satisfy the clay CEC and the cationic activity of the
anion
(c) Continuing the reaction for a sufficient time to form a reaction product
comprising an organic cation-organic anion complex, which is intercalated
into clay, and then recovering the product.
In 1986, Knudson and Jones from Southern Clay Products (SCP) [Knudson and
Jones, 1986] reported further improvements of the intercalation method. Prior
to the reaction with the ammonium intercalant the authors subjected clay to
high-energy pugmilling in a machine. The device had a short barrel (L/D = 4-10),
a motor driven screw, and perforated die plate. The reasons why the extrusion
improved the intercalation were not discussed. The authors observed that
intercalation was improved if prior to the reaction with onium salt the clay is
subjected to high energy milling, dispersing or grinding. However, pugmilling
with energy of 30, 51 and 108 HP-hr/ton reduced the smectite clay particle size
from 475 nm to, respectively, 391, 277 and 276 nm. Since, according to the
diffusion mechanism the process depends on the diffusion path length, this would
considerably reduce the diffusion time. The high shear stress may not only reduce
the stack diameter, but also its height.
In a typical procedure, the crude clay, e.g., bentonite, was wetted with 25 to
40 wt% water, and then passed through the pugmill under conditions which impart
at least 40-50 HP-hr per ton of dry clay. When the crude clay is not Na-clay,
Na2CO3 may be added during the pugmilling. The clay is then dispersed in water
at a concentration below 10 wt%, screened and centrifuged to remove non-clay
contaminants, such as quartz. The fine fraction from the centrifuge (d < 4 μm at
4-5 wt% solids), was reacted with a quaternary amine chloride, e.g., 2M2HTA,
2MBHTA, M3HTA, etc. The organoclays had high gelling efficiency so only a
small amount was needed to achieve the desired result.
Knudson and Jones [1992a] disclosed further improvements of this technology.
The organoclay manufacture followed the standard steps: clay purification,
conversion to Na-smectite, reduction of the platelet size by high stress shearing,
and reacting it with quaternary ammonium salt. The key improvement was the
use of a Manton-Gaulin colloid mill (also known as a ‘Gaulin homogeniser’). In
the mill the clay suspension that entered the valve area at high pressure and low
velocity was subjected to high acceleration, turbulence and cavitation. As it passed
through a narrow orifice the velocity increased to about sonic level. Directing
this high velocity stream to impact on a ring enhanced the milling effectiveness.
As a result, the particle size was reduced from 756 to 438 or 352 nm for an
energy input of 210 or 700 HP-hours per ton, respectively. Another patent
describes the use of Cowles disperser and Greer mill for subjecting the clay slurry
to high shear flow [Knudson and Jones, 1992b]. In the Cowles disperser the clay
particles are subjected to laminar flow, while in Greer mill the clay slurry is
forced to flow at high speed through a 0.254 mm gap and to impact on a deflector
plate. The gelling capacity of such treated clays was improved.
In Jordan’s patent [Jordan, 1994] another approach to intercalation was
adopted. The organoclay was to be used as a thickener or a gelling agent, especially
107
for paints. The author noted that intercalation in aqueous slurry is advantageous
as ‘solvation relaxes the clay’s structure in order to permit penetration of the
organic cations’. However, it is preferable to avoid too dilute a reaction because
the slurry preparation takes time and space and dewatering of product is energy-
intensive. A new, waterless method was developed, based on reacting preblended
clay with quaternary cations by mixing the dry materials in a high pressure reaction
vessel. The process can be batch or continuous. MMT, hectorite, saponite,
attapulgite, sepiolite and their combinations can be used. The onium cation has
a formula R4M+ X-, wherein M is nitrogen or phosphorous, R is alkyl, aryl, or
alkyl-aryl and X is halogen or methyl sulfate. To facilitate the process 3-15 wt%
of a dispersant (neopentyl glycol, pentaerythritol, hydrogenated castor oil,
sulfonated castor oil, a plasticiser, toluene sulfonamide, trialkoxyphosphate, etc.)
might be added. It is preferred that the dispersant has beneficial effects on the
final product.
For example, a mixture of clay, quaternary salt and dispersant passes from a
ribbon blender to a high pressure mixing auger-extruder with a perforated die.
At the downstream end a mixing blade assembly stirs the highly compressed
mixture at pressures of 20-55 MPa. The temperature should be near, but not
above 80 °C. The mixture may be either cycled through the same or another
mixer/reactor, or it may be transferred for further processing or milled to suitable
particle size. Since the process obviates the need for slurring the clay, sand and
other particulates may be present in the product. The material (10 wt% of
organoclay with the remaining constituents) was successfully used in a cable
filling application as an oil gelling agent. The dielectric constant was almost
invariant at T = 21-148 °C.
Two years later, Jordan [1996] published a refinement of the above method.
Thus, a mixture of two quaternary cations was found to induce superior
performance in a variety of applications. The mixture comprised at least 5% of
each: X2R2N+ and XYR2N+ where X is methyl, Y is benzyl and R is an alkyl,
derived from saturated tallow oil. The clay may include 3-15 wt% of a dispersant,
e.g., hydrogenated castor oil.
The organoclay comprised 50-90 wt% of a smectite (MMT, hectorite, saponite,
attapulgite, sepiolite, or their mixture) having exchangeable, inorganic cations
at least in part substituted by a mixture of 10-50 wt% of two organic X2R2N+
and XYR2N+ cations. The composition may include 3-15% (based on clay) of a
dispersant (e.g., neopentyl glycol, pentaerythritol, hydrogenated castor oil,
sulfonated castor oil, toluene sulfonamide, trialkoxyphosphate). As in the previous
patent, the pre-blended mixture was processed using a blender and an auger-
extruder with perforated die. The product was milled to usable particle size. The
interlaminar spacing was not determined.
The modified clay was evaluated for paint and grease thickening applications.
In the first case, the thixotropic index and the number of oversized particles were
measured – the new organoclay was found to equal or exceed the best
commercially available materials made using a high-cost slurry process. The
greases were tested for consistency by utilising a Helipath instrument. Again, the
results showed that the new organoclay offered significantly better performance
than the standard materials.
Eilliott and Beall [1989] patented an organoclay composition for use as a
rheological additive in a variety of non-aqueous liquids, such as paints, varnishes,
enamels, waxes, adhesives, inks, laminating resins, gel coats, etc. To obtain
108
maximum dispersability and thickening (or gelling) efficiency, it was necessary

to add a low molecular weight polar organic to the clay. Such compounds have
been called polar activators, dispersants, dispersion aids, solvating agents, etc.
An organosilane of the type RnSiX4-n was a new alternative. In this formula, n = 1-3,
R is an organic radical having C-Si link and X is a hydrolysable alkoxy, acryloxy,
amino or halogen group. The new organoclay of Na-MMT (CEC ≥ 0.75 meq/g)
with a quaternary ammonium ion and 0.5 to 5 wt% organosilane has been used
for preparing thixotropic thermoset compositions from unsaturated polyesters
and unsaturated aromatic monomers, e.g., styrene. The composition was
crosslinked by peroxide, and used in the preparation of glass fibre (GF) laminates.
The smectite-type clays of CEC ≥ 0.75 meq/g, e.g., Na-MMT or hectorite
were preferred. The onium was R1R2R3R4N+M-, where M is an anion, R1 is an
alkyl containing 12-22 C-atoms and R2-R4 are alkyls containing 1-22 C-atoms,
arylalkyl groups containing 7-22 C-atoms, aryl groups containing 6-22 C-atoms
and their mixtures. The long chain alkyls can be derived, e.g., from hydrogenated
tallow oil. Aryl groups include phenyl and substituted phenyl. Arylalkyl groups
include benzyl and substituted benzyl groups. Examples of useful quaternary
ammonium compounds are 2M2HTA (preferred), M3HTA, 2MBHTA, MB2HTA,
etc. The organosilanes used in this patent are the same coupling agents as used in
plastics composites [Plueddemann, 1982], viz. methyl-, ethyl-, or propyl-
trimethoxy silane, di-methyl- or diethyl- di-methoxy silane, tri-methyl- or tri-
ethyl- methoxy silane, phenyl triethoxy silane (preferred), etc. Furthermore, the
thixotropic properties of the organophilic clays can be improved by the addition
of ≤ 25 wt% of hydrogenated castor oil.
Intercalation took place in a slurry process. A purified aqueous suspension of
1.5-5 wt% clay was heated to 60-75 °C, then quaternary ammonium salt and the
organosilane (as an emulsion in water or alcohol) were added. To complete the
reaction, agitation and heating continued for 15 to 120 min, then the organophilic
clay was filtered, washed and dried at 90 °C for 24 hours. The dried product,
ground and screened through a 170 mesh screen, was used as a rheological additive
in a wide variety of non-aqueous liquids, viz. paints, varnishes, enamels, waxes,
adhesives, inks, laminating resins, gel coats and the like. The new clays were
particularly useful for preparing thixotropic crosslinkable compositions from
unsaturated polyesters and styrene. The developed compositions were used in
the ‘pre-gel’ and ‘directly add’ processes.
MMT intercalated with 12-amino-dodecanoic acid (ADA) was used to prepare
CPNC based on PA-6, which in turn could be blended with polypropylene/
ethylene-propylene rubber (PP/EPR) [Fukui et al., 1992]. For example, 100 g of
MMT (d ≈ 100 nm) were dispersed in 10 l of water, then 51.2 g of ADA and
24 ml of HCl were added. The mixture was stirred for 5 min, filtered, washed
and vacuum dried.
Some degree of dissatisfaction with onium ion as the principal intercalant is
evident from patents deposited by Toyota Central Research and Development
Laboratories (Toyota – for short). For example, [Usuki et al., 1996] described the
preparation of CPNC in three steps:
(i) Intercalation of clay with an onium ion (having ≥ 6 carbons) rendering it
compatible with a ‘guest molecule’ with a polar group in its chain and length
equal to or larger than that of the onium alkyl;
(ii) Contacting the organo-clay with the ‘guest molecule’ at T ≤ 250 °C; and
109
(iii) Transferring the modified clay to a reactor (the preferred reactive exfoliation
method) or compounding it with a resin.
The patent listed thermoplastic and thermosetting resins as well as elastomers
(e.g., PE, PP, PS, PIB, acrylics, TPU, SBS, liquid BR, PB or IR, etc.) as potential
matrix polymers. However, the main interest was to produce CPNC in low polarity
polymers, such as PO or rubbers. The guest molecule should have a polar group
at the chain-end. The following groups might be used: hydroxyl (-OH), halogen
(-F, -Cl, -Br, or -I), carboxyl (-COOH), anhydrous-carboxylic acid (maleic), thiol
(-SH), epoxy radical, or primary, secondary or tertiary amine (-NH2, -NH, -N).
In the described examples the authors used as onium salts 2M2ODA, 2M2TDA,
or TDA; as a ‘guest molecule’ hydrogenated, low molecular weight polybutadiene
with an -OH group at the chain end (HTBR), stearic acid or alcohol alone or
with HTBR, maleated PP (PP-MA with high acid value hence low MW), etc. To
ascertain good miscibility of organoclay with the matrix polymer a second ‘guest
molecule’, e.g., low molecular weight polyisoprene (IR) or oligopropylene, could
be used. The process resulted in a high degree of clay dispersion [Kato et al.,
1997].
The patent on CPNC with PA as matrix [Okada et al., 1988] described the
following method for uniformly dispersing clay platelets with interlayer distance
d001 ≥ 2.0 nm. The manufacturing process comprised three steps:
1. Intercalation of a clay (CEC = 0.5 to 2.0 meq/g, e.g., smectite, vermiculite or
halloysite);
2. Mixing the organoclay with a PA-monomer and
3. Polymerisation.
Only the first step is of interest in the present discussion.
The intercalation was accomplished by dispersing clay in an aqueous, acidified
intercalant solution, followed by washing the organoclay with water to remove
excess ions, or by mixing an aqueous suspension of clay with a cation-exchange
resin previously treated with an intercalant. The easiest to treat were the sodium-
substituted clays, viz. Na-MMT (CEC = 0.8-1.0) or Na-vermiculite (CEC = 1.8).
Inorganic (viz. Cu2+, Al3+), or organic cations were used. In the latter case α,ω-
alkyl acids H3N+ CnH2n COOH were used, with n = 12 for the preferred dodecyl
(ADA), n = 14 for tetradecyl (ATDA), n = 16 for hexadecyl (AHDA), or n = 18
for octadecyl (AODA). For example, to a suspension of 100 g Na-MMT in 10 L
of water, 51.4 g of ADA and 24 ml HCl were added, and the mixture was stirred
for 5 min. After filtration, the organoclay was thoroughly washed and vacuum-
dried. After execution of steps 2 and 3 (dispersion in a monomer, then
polymerisation) the resulting CPNC contained fully exfoliated clay platelets and
showed significant improvement of the mechanical and thermal properties. As
displayed in Figure 25 the intercalation effect on the interlayer spacing depended
very much on the paraffin chain length and the presence of monomer; only after
polymerisation was full exfoliation obtained.
A patent from Toyota [Kawasumi et al., 1989] reported that clays may be
intercalated in an aqueous medium with ammonium salt of a primary, secondary
or tertiary linear organic amine. However, owing to the envisaged use of the
organoclay in polymerisation, the preferred intercalant has remained ADA.
Several patents on the intercalation of clays with onium ions originate from
SCP. Thus, Dennis [1998] described the preparation of organoclay compositions
110
Figure 25 Interlayer spacing after intercalation with ω-amino acid (AA) having
n CH2 segments in the molecule. The lower curve is for intercalation with AA only,
the upper curve is for AA with ε-caprolactam at 100 °C (2 g of lactam per 0.5 g of
Na-MMT + AA). Data Okada and Usuki [1995].
useful in grease and ink formulations. The organoclay was the reaction product of
a smectite-type clay having CEC ≥ 0.50 meq/g and a branched chain alkyl quaternary
ammonium compound. Useful clays include bentonite, hectorite, as well as, synthetic
smectite-type clays, such as MMT, beidellite, hectorite, saponite and stevensite.
The branched quaternary ammonium intercalant has the formula: R1R2R3C(R4
R5R6)N+M–, where M– is an anion (preferably methyl sulfate, chloride or bromide),
R1 = R2 = -CH3, R3 is a linear or branched saturated or unsaturated alkyl group
having 12-22 carbon atoms, R4 is hydrogen or a saturated lower alkyl group of
1-6 carbon atoms; R5 is hydrogen or a linear or branched saturated alkyl group of
1-22 carbon atoms; R6 is a linear or branched saturated alkyl group of 5-22 carbon
atoms; and M is the salt anion. Especially preferred are the quaternary ammonium
salts wherein R3 is hydrogenated tallow and R4, R5 and R6 are together a
2-ethylhexyl.
Organo-MMT was prepared using the following steps:
1. Aqueous bentonite slurry (2 wt% solids) was passed three times through a
homogenising Manton-Gaulin mill (MG-mill).
2. The slurry was then heated to 66 °C and reacted for 30 min with dimethyl-
hydrogenated tallow-2-ethyl-hexyl ammonium methyl sulfate (2MHTL8, a
commercially available quaternary ammonium salt as Arquad HTL8), a blend
of Arquad HTL8 with dimethyl dihydrogenated tallow ammonium chloride
(2M2HTA, a commercially available quaternary ammonium salt as Arquad
2HT), or other quaternary amines.
3. The reacted slurry was sheared again through an MG-mill at 29 MPa.
4. The organoclays were vacuum filtered, fluid bed dried at 80 °C, and milled
through a 0.2 mm screen. Several commercial organoclays from SCP, e.g.,
Cloisite®-25A, -6A, -15A and -20A comprise these compounds.
111
The following patent [Gonzales et al., 1998a], specifically describes the preparation
of MMT organoclays to be used for the production of CPNC. The organoclay is the
reaction product of smectite-type clay having a CEC ≥ 0.50 meq/g and a mixture of
a first quaternary ammonium salt (e.g., 2M2HTA) with either a second quaternary
ammonium salt containing a -C=C- double bond, or a chain transfer agent. The
second ammonium salt has the formula: R1R2R3R4N+M–, where M– is an anion
(preferably methyl sulfate, chloride or bromide), and Ri are independently selected
from the group consisting of (a) linear or branched, saturated or unsaturated
alkyl groups having 1 to 22 carbon atoms, (b) aralkyl groups which are benzyl
and substituted benzyl moieties, (c) aryl groups, (d) β,γ-unsaturated groups having
≤ 6 carbon atoms or hydroxy-alkyl groups having 2-6 carbon atoms, and (e)
hydrogen, with the proviso that at least one of the substituents is a linear or branched
unsaturated alkyl group. The chain transfer agent may be a thiol, DL-cysteine,
α-methylketone, or a halogen compound.
The intercalation process comprises the following steps:
1. Dispersing a clay in an aqueous medium,
2. Heating the dispersion to T ≥ 30 °C,
3. Adding a first quaternary ammonium salt, then the second quaternary
ammonium compound or the chain transfer agent, and
4. Agitating the mixture to complete the reaction.
For example, MMT was intercalated with 2M2HTA and either DL-cysteine, or
N,N-dimethyl-amino-methacrylate. For the first system d001 spacing was determined
as 2.3 nm, whereas for the second two peaks were found at d001 = 1.4 and 2.6 nm
– evidently in the latter case not all MMT tactoids were intercalated.
Another patent from SCP describes the preparation of organoclays for use as
a rheological additive in an unsaturated polyester resin/styrene system [Farrow
et al., 1998]. Thus, a mixture of two clays was treated with 0.35 to 0.65 meq of
the alkyl quaternary ammonium salt per 1 g of the clay mixture. The mixture
contained 70 to 90 wt% of clay (a) selected from between sepiolite, palygorskite
and their mixtures; and 30 to 10 wt% of clay (b) selected from a smectite group
consisting of hectorite, MMT, bentonite, beidellite, saponite, stevensite and their
mixtures. The alkyl quaternary ammonium cation was either 2M2HTA,
MB2HTA, 2MBHTA or 2MHTL8, with the counterion being chloride, bromide,
methyl sulfate, nitrate, hydroxide, acetate, phosphate, etc.
Production of organoclay followed five steps:
1. The clays (sepiolite, palygorskite, hectorite) were crushed, ground, slurried
in water and screened to remove grit and other impurities.
2. Dilute (1 to 6% solids) aqueous slurry of the clays was then subjected to
high shearing in a homogenising Manton-Gaulin mill, operated with a pressure
differential across the gap from 14 to ≥ 55 MPa.
3. The clay slurries may be mixed together, e.g., 80 wt% sepiolite with 20 wt%
hectorite or 70 wt% palygorskite with 30 wt% MMT.
4. The mixture was treated with a quaternary ammonium salt.
5. The resulting organoclay was dewatered, dried and ground.
The products were found to display highly desirable properties when used as a
thixotrope in the gelling of an unsaturated polyester resin. Thus, the organoclay
(0.1 to 4 wt%) may be directly dispersed in an unsaturated polyester
112
resin/monomer solution. The organoclays also showed excellent performance in

high temperature drilling fluids, offering high gel strength at T ≤ 230 °C. When
used with PA-66, they improved the mechanical properties, e.g., tensile strength
by 20%, tensile modulus by 31% and flex modulus by 28%.
In a patent from Ciba [Zilg et al., 1999] phyllosilicates were intercalated
with a salt of a cyclic tertiary amidine or amidine mixture. In Figure 26 (a), the
basic structure of the now patented intercalant family is presented. In the suitable
compounds: R1 is the alkyl radical (C2 to C8), R2 is hydrogen or an aliphatic
radical containing an unsaturated bond, which may be substituted by a carboxyl
or carbonyl group, R3 is hydrogen or alkyl; each of A and B is –CH2–, or A and
B together are the radical –(CH=CH)–, and X– is an anion. In Figure 26 (b) the
radical R´´ = -CnH2n+1, where n = 0, 1, 2, 3 or 4. Owing to the presence of a
reactive moiety in the second radical (–OH or –CH=CH–), the intercalant may
be modified to bond with a matrix polymer. By contrast with ammonium-
intercalated clays those with amidine have greater thermal stability during
processing, higher interfacial adhesion and better dispersability. Another
advantage of the amidine intercalants is that they do not change the stoichiometry
of the thermoset matrix reaction.
According to the patent, the phyllosilicate may be synthetic or mineral, preferably
MMT and/or hectorite, with d001 = 0.7 to 1.2 nm and CEC = 0.5-2.0 meq/g. The
cyclic tertiary amidine should have two substituted groups, one aliphatic with
unsaturated bonds and/or functional groups, and the other either a hydrogen or
a linear or branched aliphatic radical with one or more unsaturated and/or
functional groups.
The following amidine compounds have been synthesised:
• ricinyl-4,5-dihydro-1-H-imidazole hydrochloride (RDI, from castor oil),
• hydroxyethyloleyl-4,5-dihydro-1-H-imidazolinium hydrochloride (HDI),
• aminoethyloleyl-4,5-dihydro-1-H-imidazolinium hydrochloride (ADI), and
• 1-methyl-2-nortallowalkyl-3-tallow-fatty acid amidoethylimidazolinium
methosulfate (MNTFA).
(a) (b)
Figure 26 (a) The basic structure of the cyclic amidine intercalant family;
(b) Derivatives of (a) particularly suitable as intercalants (see text).
Reproduced from Zilg et al. [1999], with permission.
113
Synthetic MMT was intercalated and XRD showed that the interlayer spacing
increased from d001 = 0.94 to 2.67 (for RDI), 3.27 (for HDI and ADI), and 4.01 nm
(for MNTFA). The intercalation started with dissolution of the intercalant in
acidified, hot water, followed by addition (while stirring) of a synthetic clay
suspension. As a result of the cation exchange, flocculated clay precipitated, it
was filtered, washed (until Cl– could not be detected with AgNO3 solution), and
then dried under vacuum at 80 °C for 72 h.
According to the Ciba patent, the amidine-intercalated clays may be used for
the production of CPNC with virtually any polymeric matrix (thermoplastic,
thermosetting or elastomeric), viz. PO, vinyls, styrenics, acrylics, PA, thermoplastic
polyesters (PEST), PC, polyphenylene sulfone (PSF), polyarylethers, diverse
polycondensates or polyadducts, rubbers, etc. Preferred polymers are PEST, PU,
thermosetting epoxy and polyurethanes.
A recent invention for polymeric (primarily PEST) composition with high barrier
properties [Barbee and Matayabas, 2000; Matayabas et al., 2000] again uses
layered clay that has been cation exchanged with onium salt represented by the
formula [R1R2R3R4M]+ X-, where M is N or P; X- is a halide, hydroxide, or acetate
anion; R1 is a straight or branched alkyl group having at least 8 carbon atoms; R2,
R3 and R4 are independently hydrogen or a straight or branched alkyl group having
1 to 22 carbon atoms. The polymer barrier properties were improved by the addition
of up to 30 wt% of a mixture of onium-intercalated clay (e.g., MMT-MT2EtOH)
with an agent, which expands the interlayer spacing to d001 ≥ 3 nm and is miscible
with the polymer. The ratio of clay to the ‘expanding agent’ varied from 1:4 to 4:1.
Suitable ‘expanding agents’ are mainly low molecular weight compounds (from
monomers to Mn = 25 kg/mol), viz. PCL, PDMS, polyepoxides, PS, polyacrylates,
PC, PU, PSF, PA, PEST, polyethers, polyketones and vitamin E. The ‘expanding
agents’ used in examples were: PETG 6763, PEG (MW = 3.35 kg/mol), PCL (MW
= 2 kg/mol), carbinol-terminated PDMS, etc.
The process recommended by these authors for manufacturing PET
nanocomposites comprised:
1. Preparing the organoclay
2. Pre-swelling the organoclay with an ‘expanding agent’ and
3. Incorporating the expanded organoclay in a polyester.
For example, an aqueous suspension of Na-MMT (CEC = 0. 95 meq/g) was
mixed at 50 to 80 °C in a blender to form a 2 wt% slurry. The methyl tallow bis-
2-hydroxyethyl quaternary ammonium (MT2EtOH) (Ethoquad T/12) was added
in sufficient amount to exchange most of the cations present in the galleries. The
precipitate was filtered out, washed and dried. XRD of the product showed that
d001 = 2.0 nm. Next, the expanding agent (PET modified with 30 mol% of 1,4-
cyclohexane dimethanol available as PETG 6763) was dissolved in methylene
chloride, the organoclay was added and the mixture was blended at high speed.
Next, the suspension was poured over PET pellets, followed by evaporation of
the methylene chloride, and drying the coated pellets in a vacuum oven at 110 °C.
The coated pellets were finally compounded in a TSE at 275 °C and 200 rpm.
For the manufacture of polycarbonates, polyesters and polyphenylene ethers
(PPEs) from low viscosity macrocyclic oligomers, layered minerals were
intercalated with novel cations [Takekoshi et al., 1996]. The preferred type cations
were guanadinium and amidinium, viz. hexa-butyl-guanidinium. However, more
traditional onium cations were also acceptable, especially of pyrrolidine,
114
piperidine, piperazine and morpholine as well as heterocations derived from

cyclododecanes. Intercalation was performed by dispersing Na-MMT (10% H2O;
CEC = 1.19 meq/g) into an aqueous methanol solution. To the resulting
homogeneous dispersion a solution of either dodecylammonium (DDA) or
hexadecylpyridinium (HDP) chloride was added. A white precipitate was
recovered by filtration and subsequently washed with water and dried. There is
no data on interlayer spacing, but upon incorporation of 5% of MMT intercalated
with DDA or HDP the modulus of CPNC with PPE as the matrix increased by
15% or 29% (in respect to neat PPE), respectively. Quaternary ammonium ions
with heterocyclic rings have also been used for rubbers [Weber and Mukamal,
1984].
It has been frequently shown that the size of the intercalating onium ion
determines the resulting interlayer spacing. The most exhaustive list of these
effects can be found in Miyanaga et al. [1999] patent. Four different clays were
used, but for illustrating the effects only data for MMT (Kunipia F; CEC =
1.19 meq/g) will be cited in Table 15. Intercalation was performed by dispersing
15 g of clay in 1 l of deionised water at 70 °C. To the suspension a water/ethanol
solution of onium salt was added in the amount of 1.05 times the equivalent of
the clay CEC with vigorous stirring for 30 min, and then allowed to stand. The
organoclay was filtered, washed, and then dried under vacuum at 80 °C for
72 hours. The d001 spacings as determined by XRD are listed in Table 15. The
results indicate that the best correlation between d001 and the size of the onium
salt involves the three largest radicals.
To prepare CPNC with high temperature processable fluoroplastics as the
matrix, MMT was intercalated with phosphonium cations of the general formula:
R1P+(R2)3 [Ellsworth, 1999]. The fluoroplastics of interest have either melting
point or glass transition temperature Tm, Tg > 220 °C. Thus, for example, 10 g of
sodium hectorite (10 g) was dispersed in alcohol/water 1:1 mixture (200 ml) at
90 °C. To the suspension 50 ml hexadecyl-tributyl-phosphonium bromide in
isopropyl alcohol was added. Next, the reaction mixture was heated at 90 °C for
8 h with stirring. The organoclay was filtered, washed, dried at 120 °C for 24 h,
milled and screened through a 325 mesh (40 micron) sieve.
To produce rubber compositions with enhanced mechanical performance
intercalated clay was incorporated [Weber and Mukamal, 1984]. As the patent
claim specifies, the intercalant can be a quaternary onium ion of the traditional
aliphatic-substituted type or selected from between: imidazolium, pyridinium,
pyrrolidinium, pyrrolium, pyrrolinium, pyrazolium, triazolium, pyrimidinium,
pyridazinium, pyrazinium, triazinium, indolium, indazolium, benzimidazolium,
quinolinium, isoquinolinium, cinnolinium, phthalazinium, quinazolinium,
quinoxalinium, naphthyridinium, quinolizinium, carbazolium, acridinium,
phenazinium, phenanthridinium, phenanthrolinium, benzo[H]isoquinolinium,
purinium, porphinium and pteridinium. In these compounds the heterocyclic rings
could be substituted by alkyl(s) or not, and they could be partially hydrogenated.
Preparation of CPNC in PEST matrix requires high temperature thus thermally
stable organoclay. Furthermore, the organoclay usually induces a brownish color that
must be compensated for by addition of suitable dyes. A patent from Eastman elegantly
solves these problems by using cationic dyes (e.g., optical, fluorescent brighteners)
[Barbee et al., 2000c]. The preparation of these CPNCs is by melt compounding of the
pre-intercalated clay with molten polymer. The clay is pre-intercalated with a dye,
having the cation group (a quaternary ammonium) separated from the chromophore
115
Table 15 Interlayer spacing of MMT (CEC = 1.19 meq/g) intercalated

with, R1R2R3R4N+. Data [Miyanaga et al., 1999]
R1 R2 R3 R4 d001
(nm)
— — — — 1.23
C10H21 C10H21 C10H21 C10H21 2.80
CH3 C18H37 C18H37 C18H37 4.11
CH3 C4H9 C18H37 C18H37 2.85
H CH2-Ph C18H37 C18H37 2.65
CH3 CH3 C18H37 C18H37 2.81
CH3 CH3 CH3 C18H37 2.13
CH3 CH3 C10H21 C10H21 1.98
CH3 C8H17 C8H17 C8H17 1.83
C4H9 C4H9 C4H9 C4H9 1.55
CH3 CH3 CH3 [CH2CH(CH3)O]30H 4.58
CH3 CH3 C12H25 [CH2CH(CH3)O]30H 3.87
CH3 [CH2CH(CH3)O]10H [CH2CH(CH3)O]10H [CH2CH(CH3)O]10H 5.19
CH3 CH2CH(CH3)OC8H17 CH2CH(CH3)OC8H17 CH2CH(CH3)OC8H17 3.69
CH3 CH3 (CH2CH2O)2(CO)C17 (CH2CH2O)2(CO)C17H35 2.98
H35
CH3 [CH2CH(CH3)O]10H [CH2CH(CH3)O]10H CH2CH2(COO)C12H25 3.46
CH3 [EO/PO(1/2)]10H [EO/PO(1/2)]10H [EO/PO(1/2)]10H 3.62
CH3 CH3 [C3H7CH(CH3)C4H8]2 [C3H7CH(CH3)C4H8]2 2.73
CHCH2 CHCH2
CH3 CH3 C9H19CH(CH3)CH2 C9H19CH(CH3)CH2 2.56
CH3 CH3 CH3 C14H29CH(C12H25)CH2 2.89
CH3 CH3 CH3 C18H37 2.13
CH3 CH3 C18H37 C18H37 2.81
CH3 C18H37 C18H37 C9H19CH(CH3)CH2 2.65
CH3 CH3 CH3 [C3H7CH(CH3)C4H8]2 2.45
CHCH2
Note: EO/PO (1/2) represents poly(ethylene glycol-co-propylene glycol) with the
monomer ratio 1:2
116
by at least two C-groups. Colourless CPNC was prepared by dry blending a mixture
of clay pigments with Claytone‚ APA and PET. The well-dried mixture was extruded at
275 °C. Unfortunately, there is no information on the extent of intercalation/exfoliation
in, or the properties of the CPNC. Similarly for PET, Imai et al. [2002] developed
intercalant able to react with PET, with a cationic group to bind to clay and stable at
least up to 275 °C. The selected compound was a dimethyl isophthalate substituted
with a triphenyl-phosphonium group (dimethyl isophthalate triphenyl phosphonium,
DIP). In spite of lack of exfoliation, 8 wt% of the pre-intercalated clay increased the
matrix modulus by 80%.
TNO patented the use of dyes as intercalants [Fischer et al., 2001], such as,
e.g., methylene blue:
N
H3 C CH3
N S N+
CΓ
CH3 CH3
Virtually any polymer can be used as a matrix, but for the coating applications
the preference goes to PU, acrylics, siloxanes, polyesters and polyethers. The
new intercalants offer better thermal stability, controllable amount of intercalation,
ability to introduce functional groups for end-tethering the matrix
macromolecules, etc. The technology was commercialised for the production of
Planomers®, PlanoCoatings® and PlanoColors®. The Planomer range is an
organoclay tested in diverse polymeric matrices, viz. PO, PMMA, PA, PU, PS,
PC, phenolics, and biopolymers. The second material is used as a transparent
barrier material in packaging or for protection. The PlanoColors® are offered as
highly UV stable, clay-based, metal-free nanopigments in a variety of colours.
Conroy et al. [2002] prepared high temperature CPNC by dispersing up to
10-wt% of clay in molten phthalonitrile monomer or oligomer that in turn was
polymerised into CPNC, stable to T ≥ 450 °C. The authors replaced the customary
(and thermally unstable) ammonium intercalants by compounds with nitrile
groups. This new type of organoclay may be used with a variety of polymers,
such as, PA, PC, PO, PEI, PI, TPU, PVP, PVAl, PEG, epoxy, etc. Unfortunately,
this patent application does not provide examples of CPNC preparation or
performance characteristics.
In summary, the standard method of clay intercalation with organic cations
usually starts with purified bentonite or MMT. The clay has a layer of Al and Mg
hydroxides between two layers of silica that are negatively charged and ionically
balanced by Na+, K+, Ca2+and Mg2+. The repeating layers are 0.96 nm thick and
under ambient conditions the basal or d-space is d001 = 1.2-1.5 nm, hence the
interlamellar space in the gallery is about 0.2 to 0.5 nm. At this stage the clay is
unsuitable for use in PNC technology - the interlamellar gap is too narrow for
the diffusion of macromolecules, the solid-solid interactions between the clay
platelets are too high. The oldest and still most frequently used method has been
to replace the inorganic cations with onium ones. This increases the interlayer
distance to d001 ≥ 2.5 nm, reduces the interlayer forces, makes the clay more
hydrophobic and makes it amenable to dispersion in a monomer or polymer.
However, the most common intercalant, quaternary ammonium has limited
thermal stability. Ammonium-modified clay may be used to prepare CPNC by first
dispersing it in a monomer that in turn is polymerised by UV, acid, base or heat.
117
This approach is suitable, provided that the polymerisation is conducted at T <

250 °C. Alternatively, CPNC may be prepared by melt blending ammonium-
modified clay with a polymer that can preferably be processed at T < 200 °C. With
the exception of elastomers, there are few industrially interesting polymers that
can be processed at these low temperatures. It is customary to process a polymer at
temperatures about 40-50 °C above its transition temperature, in the case of an
amorphous polymer the glass transition, Tg, or in the case of a semicrystalline
resin, the melting point, Tm. In several patents besides quaternary ammonium,
phosphonium and/or sulfonium salts are also listed. It is noteworthy that clay
modified with organophosphonium cations may be thermally stable up to 370 °C
hence it is suitable to prepare CPNCs with a high temperature matrix polymer.
The most common cation-exchange method uses onium salt, the quaternary
ammonium being the most common (the primary or secondary have been used in
specific cases to ascertain chemical reactivity, e.g., with PA-6 or thermosets). The
reason for using the quaternary ammonium salts originates from consideration of
the binding strength to MMT. The strength increases with the number of substituents
in the ammonium cation [Maes et al., 1980], viz.
NH4+ < RNH3+ < R2 NH2+ < R3 NH + < R4 N +
The authors observed that the exchange reaction between either Na-MMT or
Ca-MMT and ammonium salt is thermodynamically reversible, and that the ionic
charge (usually assigned to the N-atom) is delocalised over the R-alkyl substituents.
The delocalisation increases with the number of substituents (from 0 to 4) and
their molecular weight.
Most commercially available organoclays are intercalated with quaternary
ammonium – examples are listed in Table 16. The typical dry particle size of
these materials is ca. 5 μm, with the sieve analysis: 10 vol% less than 2 μm; 50%
less than 6 μm; and 90% less than 13 μm. The quaternary onium ions can
quantitatively replace Na+ in Na-MMT. It can be calculated that stoichiometric
replacement by means of 2M2HTA would result in organoclay containing 34 wt%
of organic phase. As the tabulated data indicate, there is up to 50% excess of the
intercalant present. Elimination of this excess improves thermal stability.
Industrially Na-MMT undergoes ion exchange mainly with a quaternary
ammonium chloride: R1R2R3R4N+ Cl-, to produce hydrophilic or hydrophobic
intercalated MMT. The character and the interlayer spacing depend on the Ri- radicals.
In several commercial organoclays R1 = R2 = -CH3 and R3 = R4 = hydrogenated
tallow oil. Other radicals used to control interactions with the matrix are benzyl,
hydroxyethyl, 2-ethylhexyl, etc. Intercalation involves a slow chemical reaction:
MMT- Na+ + R4N+ Cl- ↔ MMT- R4N+ + Na+ Cl-
Owing to low mobility of the MMT- R4N+ ionic pairs, the equilibrium is shifted
to the right hand side (RHS). Nevertheless, intercalation in aqueous medium at
T = 25-80 °C takes from t = 10 to 480 min, while the second stage intercalation
in non-aqueous solvent may take up to 15 days. It results in a complex of MMT
with two ammonium ions and two amines: MMT2- 2RN+H3 + 2RNH2. Typical
characteristics of commercial organoclays are shown in Table 16 with
abbreviations for intercalants listed in Table 17 and Appendix 6.3. The four
types of Cloisite® organoclay produced by Southern Clay Products, Inc. are shown
in Figure 27. Typically, their dry particle size is ca. 5 μm, with the sieve analysis:
10-vol% less than 2 μm; 50% less than 6 μm; and 90% less than 13 μm.
118
Table 16 Typical physical properties of commercial organoclays
Organoclay Intercalant Weight loss on H2O Spacing, Modifier

combustion (%) d001 (nm) conc. (meq/g
(%) & mmol/g*)
Somasif™ from CO-OP Chemical Co., Ltd.
ME-100 none 1.25 (CEC = 1.2
synthetic mica meq/g)
MAE 2M2TA 3.0
MTE M3O 2.5
MEE M2EtOHC 2.3
MPE M 2EPPOH 5.0
®
Cloisite from Southern Clay Products, Inc.
Na-MMT none 7 4 1.23 0
6A 2M2HTA 47 2 3.59 1.40 & 0.86
10A 2MBHTA 39 2 1.93 1.25
15A 2M2HTA 43 2 2.96 1.25 & 0.78
20A 2M2HTA 38 2 2.47 0.95 & 0.83
25A 2MHTL8 34 2 2.02 0.95 & 0.69
30B MT2EtOH 32 2 1.86 0.90 & 0.85
93A M2HTA 40 <2 2.36 0.90
Nanomer® Intercalant Density H2O Matrix/ Interca-

from (g/ml) (%) Appl. lant
Nanocor, (wt%)
Inc.
Intercalant (wt%)
MMT none 2.6 12 (CEC = 1.45 meq/g) nil
I.24TL ADA ≤3 PA-6 polymerisation
I.28E 3MSA 1.7 ≤3 Epoxy, urethane 25-3 0
I.30E ODA 1.7 ≤3 Epoxy, urethane 25-3 0
Rheospan 2M2HT 2 Unsaturated
AS polyester, vinyl
esters
I.34TCN MOD2EtOH 1.7 3 PA, PBT, TPU melt
compounding
I.30P ODA 1.7 2 In PO concentrates, 25-30
viz. C.30P, C.30PE,
C.30EVA
I.44PA 2M2HT 2 In PO concentrates,
viz. C.30P, C.30PE,
C.30EVA
119
Organoclays from Süd-Chemie AG based on Na-MMT
Nanofil Intercalant Wt. loss Bulk density Matrix d001
(%) (g/l) (nm)
15 2S2M 35 440 EVAc, PP 2.8
948 2S2M 45 440 EVAc, PP 3.5
32 SB2M 30 300 PET, PBT 1.8
919 SB2M 35 460 PET, PBT 2.0
848 SA 25 180 EVAc, PP, PA 1.8
804 S2EtOH 30 130 PET, PBT, TPU 1.8
784 AC12A 20 180 PA-6, PA-66, PA-12 1.7
Organoclays from Rheox, Inc. based on Na-MMT
B 34 2M2TA 2.47
Note: Commercial hydrogenated tallow oil typically contains (in wt%): 2.0 C14,
0.5 C15, 29.0 C16, 1.5 C17, 66.0 C18, and 1.0 C20 alkyl groups
Figure 27 Four types of Cloisite® intercalated clays

Reproduced with permission from Southern Clay Products, Inc., Gonzales, TX
120
Table 17 Organic cations used as clay intercalants

Dimethyl dibehenyl ammonium chloride; (CH3)2-(C22H47)2-
2M2Bh
N+ Cl–
2M2DA Dimethyl didodecyl ammonium chloride
Dimethyl dilauryl ammonium or dimethyl didodecyl
2M2DDA
ammonium chloride
Dimethyl dihydrogenated tallow ammonium chloride
2M2HTA
(Arquad 2HT)
N,N-Dimethyl-N,N-dioctadecyl ammonium bromide or
2M2ODA
chloride
2M2SA Dimethyl distearyl ammonium chloride
2M2TA Dimethyl ditallow ammonium chloride
2MBHTA Dimethyl benzyl hydrogenated tallow ammonium chloride
Dimethyl benzyl octadecyl- or dimethyl benzyl stearyl-
2MBODA
ammonium chloride
2MBSA Dimethyl benzyl stearyl-ammonium chloride
2MHDI 1,2-Dimethyl-3-N-hexadecyl imidazolium
2MHDODA Dimethyl hexadecyl-octadecyl amine
Dimethyl hydrogenated tallow 2-ethylhexyl ammonium
2MHTL8
methyl sulfate
2MODA Dimethyl octadecyl amine
2MVBDDA Dimethyl vinyl-benzyl dodecyl amine
2S2M Distearyl dimethyl amine = 2M2ODA
3BHDP Tributyl-hexadecyl-phosphonium bromide
3MDA Trimethyl dodecyl amine
3MDDA Trimethyl dodecyl ammonium bromide
3MHDA Trimethyl hexadecyl ammonium bromide
3MODA Trimethyl octadecyl ammonium chloride
3MSA Trimethyl stearyl ammonium chloride
3PDDP Triphenyl dodecyl phosphonium
4MA Tetramethyl ammonium chloride
AC12A α,ω-Dodecyl amino acid (also ADA)
ω-Amino dodecyl (or lauric) acid, or 12-amino dodecyl

ADA
acid
AHA ω-Amino-hexanoic acid
AHDA ω-Amino-hexadecanoic acid

Allyl-16 N,N-Dimethyl-n-hexadecyl allyl ammonium chloride
121
AODA ω-Amino-octadecanoic acid
APB 1,3-Bis(3-aminophenoxy)benzene
APTS γ-Aminopropyl-triethoxy silane
ATDA ω-Amino-tetradecanoic acid

B3HTA Benzyl trihydrogenated tallow ammonium chloride
N,N-Dimethyl benzyl-n-hexadecyl ammonium chloride
Bz-16
(also 2MBHDA)
CPC Cetyl pyridinium chloride
DA Dodecyl amine
DDA Dodecyl ammonium chloride
DDP 1-Dodecyl-2 pyrrolidone
DIP Dimethyl isophthalate triphenyl-phosphonium
HAD Hexadecyl amine
HDA Hexadecyl ammonium chloride
HDP N-hexadecyl pyridinium chloride
M2EPPOH Methyl diethyl polypropylene glycol ammonium chloride
M2HTA Methyl di[hydrogenated tallow] ammonium
M2S2EtOH Methyl stearyl bis[2-hydroxyethyl] ammonium
M3HTA Methyl trihydrogenated tallow ammonium chloride
M3O Methyl trioctyl ammonium chloride
MC2EtOH Methyl coco-alkyl di-2-hydroxy ethyl ammonium chloride
MDD2EtOH Methyl dodecyl di-2-hydroxy ethyl amine
2-Methacryloyl-oxyethylhexadecyldimethyl ammonium
MHA
bromide
MOD2EtOH Methyl octadecyl di-2-hydroxy ethyl amine
MSA Methyl-styrene ammonium chloride
Methyl tallow di-2-hydroxy ethyl ammonium chloride
MT2EtOH
(Ethoquad T12)
OA Octyl ammine or ammonium chloride
ODA Octadecyl amine (C18; also stearyl amine)
N,N-Dimethyl-n-hexadecyl-(4-hydroxymethylbenzyl)
OH-16
ammonium
OM-2 N-[4-(4´-Amino-phenoxy)]phenyl phthalimide
122
OM-l N-[4-(4´-Amino-phenyl)]phenyl phthalimide
P18 Stearyl-tributyl phosphonium bromide
POE-DPA Polyoxyethylene decyl propyl amine
QD1 2-(N-Methyl-N,N-diethyl ammonium iodide) ethyl acrylate
QD4 2-(N-Butyl-N,N-diethyl ammonium bromide) ethyl acrylate
S2EtOH Stearyl di-2-hydroxy ethyl amine = MOD2EtOH
SA Stearyl amine (C18; also ODA)
TADA Tallow diamine chloride
TDA Tetradecyl ammonium chloride
TPP Tetraphenyl phosphonium
N,N-Dimethyl-n-hexadecyl-(p-vinyl benzyl) ammonium

VB-16
chloride
VDAC Vinyl benzyl dimethyl dodecyl ammonium chloride
VM Vinyl benzyl trimethyl ammonium chloride
The production of CPNC ammonium intercalated clays poses several problems.

Alkylamines are not benign – their permissible level is 5 ppm and lethal dose,
LD50 = 0.2-0.4 g/kg. The toxicology of clay complexes with the great diversity of
oniums has not been determined, but as a precautionary measure so far CPNCs
have not been used in direct contact with consumable products.
The second and well-recognised disadvantage of ammonium intercalant,
especially the quaternary one, is the thermal stability. These substances start
decomposing below 200 °C, which may reduce the mechanical properties and
causes discolouration. The ammonium-modified clay may be used to prepare
CPNC at low temperature, e.g., in low temperature emulsion, suspension
reactions, or by dispersing intercalated clay in a monomer that in turn is
polymerised by UV, acid, base or heat. This approach has been found suitable,
provided that the polymerisation is conducted at T < 250 °C. Alternatively, CPNC
may be prepared by melt blending ammonium-modified clay with a polymer
that can be processed at T < 200 °C. However, with the exception of elastomers,
there are few industrially interesting polymers that can be processed at these
temperatures. The thermal stability of ammonium-modified clays may be
somewhat improved by extracting an excess of the intercalating ammonium salt
and/or by reacting it with, e.g., epoxies [Ton-That, 2000]. There are also
indications that secondary ammonium salt has a better thermal stability than the
quaternary one. Some quaternary ammonium complexes are more stable than
others, for example, phyllosilicates intercalated with a salt of a cyclic tertiary
amidine or amidines mixture showed greater thermal stability during processing
123
[Zilg et al., 1999]. Furthermore, it is expected that: (1) ammonium cations with
strong bonding to clay anions will show greater thermal stability, (2) the presence
of unbounded amines or ammonium salts will have deleterious effects on thermal
discolouration, (3) the ammonium ion can be shielded by more stable secondary
intercalants, e.g., epoxies.
2.3.4 Intercalation by Organic Liquids

Intercalation methods described in this part are effectively the next generation of
the methods discussed in the preceding one: intercalation by organic cation. It
has already been mentioned that addition of organosilane or a polar organic
liquid (labelled as polar activator, dispersant, solvating agent, etc.) has a beneficial
effect on the dispersion of clay platelets and their performance in diverse
applications. The present part will focus on the use of macromolecules as the
intercalation aids.
Amcol has published several patents in this domain, for example [Beall et al.,
1996a,b] intercalated clay using 30 to 80 wt% (per weight of the aqueous phase) of
a monomer, oligomer (degree of polymerisation, DP = 2-15) or polymer (DP > 15).
Regardless of the concentration, the amount of the intercalating composition
should be > 4 times that of clay. The intercalant should be sorbed between and
permanently bonded to the clay platelets, increasing the interlayer spacing of the
phyllosilicate from 0.5-10 nm. Useful intercalants should be water-soluble and
must have a functional group (e.g., carbonyl, hydroxyl, carboxyl, amine, amide,
ether, ester, sulfate, sulfonate, sulfinate, sulfamate, phosphate, phosphonate,
phosphinate functionalities) or aromatic rings that provide metal-cation
complexing to the inner surfaces of clay platelets. Binding to the platelet surfaces
is by metal cation either electrostatically bonding or chelating. Another mechanism
involves bonding of the interlayer cations with intercalant aromatic rings. The
intercalants should have sufficient affinity for the clay platelets to provide adequate
interlayer spacing and to bind to the surfaces of the platelets, without additional
coupling agents.
An addition of metal cations (during intercalation and/or exfoliation) increases
the suspension viscosity, most likely by complexing with the polar moieties of
the intercalant molecules. The complexed metal salt-derived cations carry their
dissociated anions along with the cations, in the interlayer space. Such a double
intercalant complexing occurs on the opposed platelet surfaces, resulting in
repulsion between closely spaced dissociated anions carried by the added cations,
which results in increased interlayer spacing and more complete exfoliation. The
concentration of metal salt ranges from 0.01 to 1 wt%, based on the dry weight
of the phyllosilicate.
The intercalated phyllosilicates can be exfoliated before or during mixing with
solvents (e.g., alcohols, glycerols, glycols, aldehydes, ketones, carboxylic acids, amines,
amides, etc.). Such a suspension may be used in a thixotropic composition, or for
delivery of any active hydrophobic or hydrophilic organic compound, such as an
active pharmaceutical, dissolved or dispersed in the carrier or solvent, in a thixotropic
composition. Depending on the intercalation and exfoliation conditions (viz. T, pH,
and ingredient concentration), the system viscosity can be adjusted in the range of
0.1-5,000 Pas. The compositions are thixotropic.
The preferred water-soluble polymer intercalants are: P4VP, PVAl, and their
mixtures. The weight ratio of intercalant to Na-MMT should be 1:5 to 1:3. The
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concentration of intercalant should be 20-90 wt%, increasing the interlayer spacing

to d001 = 3.0-4.5 nm. The intercalating composition should include 25-50 wt%
water. The water-soluble polymer can be added as a solid along with the clay
when extruding or pug milling. Metal salt is dissolved in a suitable solvent (water
or organic solvent) and added to the intercalating composition in the amount of
0.005 to 0.5 wt%.
The intercalated clay was combined with various organic liquids (with and without
water) to determine the effects of intercalate loading as well as temperature, pH and
water content of the intercalating composition on viscosity. For example, mixing
10 wt% clay/P4VP intercalate into 84% glycerol, and 6% water resulted in a viscosity
of 2-3 Pas. Heating the composition to gelation (100 °C) increased the viscosity to
about 8 Pas, and when heated to 145 °C (then cooled to room temperature) it increased
to 200-600 Pas. Addition of ethanol had a more dramatic effect. The composition:
20 wt% water, 70 wt% ethanol, and 10 wt% clay/P4VP complex showed viscosity
in the range from 0.4-1 kPas, without heating.
The development of intercalation technology as described by Beall et al. [1998]
is a part of the technology developed over the years as evidenced by a series of
patents [Beall et al., 1999a,b; Serrano et al., 1998a,b; Beall et al., 1996a,b]. In
another invention, intercalates were prepared by contacting a clay either with
water, or with an aqueous solution of a water-soluble polymer and/or a water-
miscible organic solvent, e.g., alcohol, followed by contact with a monomeric
organic pesticide or its solution. The latter would have a polar moiety, e.g.,
carboxylic acid, ester, amide, aldehyde, ketone, sulfur-oxygen or phosphorus-
oxygen moiety, cyano, or a nitro moiety.
Best results were achieved using an aqueous solution of water-soluble polymer,
to first intercalate the clay [Beall et al., 1999b]. Using > 10 wt% of an organic
pesticide gave better sorption. Probably the organic pesticide displaces water and
water-soluble polymer and bonds to the platelets by chelation with the exchangeable
cation or via electrostatic or dipole/dipole interactions. Extrusion accelerates the
intercalation of pesticide between activated clay platelets. The sorbed pesticide
may increase the interlayer spacing from 0.5 to 10 nm. The intercalated clay
containing a pesticide can be used directly as a pesticide.
To intercalate Na-MMT with a herbicide (e.g., 2,4-dichlorophenoxyacetic
acid butyl ester (2,4-D)) three processes were employed:
1. Mixing a dispersion of 2 wt% 2,4-D with a 2 wt% clay suspension in water
for 4 h at room temperature.
2. Dry clay powder (about 8% by weight moisture) was gradually added to the
2 wt% aqueous dispersion of 2,4-D in water and agitated at room temperature
for 4 hours.
3. 2,4-D was dry-blended with clay, the mixture hydrated with 35-38 wt% of
water and extruded.
All three methods resulted in clay-2,4-D intercalates. The spacing depended on the
quantity of 2,4-D sorbed between clay platelets. Similar results were obtained with
insecticides, e.g., chlorpyrifos, or the pesticide trifluralin. The intercalated Na-MMT
showed d001 = 1.88 nm, an increase from 1.24 nm of untreated clay. When the wet
sample was dried in a vacuum oven (10-3 torr at 60 °C for 48-60 h) causing the
trifluralin to sublimate the spacing decreased to 1.237 nm. The experiment indicated
that trifluralin might be fully released from the interlamellar space.
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2.3.5 Intercalation by Monomers, Oligomers or Polymers

Historically, the intercalation methods described in this part were developed later
than those by organic cation, discussed before. Cation-exchange technology also
profited from the addition of either: (i) an organosilane, (ii) a polar or (iii) an
aromatic component. Thus, elements of this technology were used within the
category of the cation-exchange methods in the two-step intercalation procedures.
The present section will focus on the use of monomers, oligomers, cyclomers
or macromolecules to enhance the intercalation and eventually will lead to total
exfoliation of clay. The many variations of this method can be divided into two
principal groups:
1. Intercalation of purified clay, e.g., Na-MMT.
2. Intercalation of organoclay (a two-step process).
Each of these two can be further subdivided depending on whether monomer,
oligomer, cyclomer or polymer was used, and whether the second step of
intercalation was necessary.
2.3.5.1 Intercalation of Purified Clay by Hydrophobic Compounds

Here intercalation of purified inorganic layered compound is of interest. Following
the analysis of clay chemistry, two types of interactions can be explored: complex
formation between an aromatic molecule and a clay cation that takes place in
organic medium, and hydrogen bonding with water soluble monomers, oligomers
or polymers.
In one of the first patents on CPNC, a vinyl monomer (e.g., styrene) was used
to intercalate the clay [Kamigaito et al., 1984]. Partly due to the high concentration
of clay (85 wt% of MMT, vermiculite or Na-taeniolite) and partly to the small
thermodynamic potential for styrene diffusion into interlamellar spacing, the
effect was small. Thus, the cited values of the interlayer spacing were: before
intercalation, d001 = 1.2-1.3 nm, and after expansion by sorption of styrene: d001
= 1.5 nm. These values indicate that initially the clay contained one to two
monolayers of water. It is doubtful that styrene was able to expel this surface-
bonded water, thus the expansion of d001 by about 0.2 nm may indicate the
formation of a monolayer of styrene coordinated to the inorganic counterions
within the interlayer space. According to the authors, the initial sorption process
took ‘a very short period of time’. After the free radical polymerisation of sorbed
monomer, the polymers showed a broad molecular weight distribution (MWD),
viz. Mw/Mn ≥ 6.
Some vinyl monomers may be converted into polymers with narrow MWD
by anionic or group-transfer polymerisation, but these reactions are not applicable
to condensation polymers (e.g., PA). The Kamigaito et al., patent [1984] also
describes intercalation of MMT by ε-caprolactam in an aqueous medium. The
process for the manufacture of CPNC is a bit convoluted, as it requires addition
of dichlorodimethyl silane, filtering, drying, then addition of PA-66 dissolved in
formic acid, heating the mixture to 200 °C (to effect copolymerisation of
caprolactam with PA-66) and finally extrusion of a dry blend of concentrated
CPNC with PA-66 pellets. The interlayer spacing was not given, but the final
polymer mouldings showed significant improvement of modulus, strength and
heat distortion temperature (HDT) in comparison to neat polymer.
However, in the following patent the authors stated that the achieved degree
of intercalation was low, dispersion of the silicate layers was not uniform, the
126
clay aspect ratio was seriously reduced (thus reducing MMT effects on
performances), the bonding between the clay and the matrix was not strong
enough and the polyamide matrix had a broad molecular weight distribution,
viz. Mw/Mn ≥ 6 [Okada et al., 1988]. Even if the monomer molecules diffuse into
the interlamellar space they rarely bond strongly enough (by ionic or covalent
bonds) to the clay surface, and the CPNC may be exfoliated, but not end-tethered.
Several publications from the Toyota group indicate that even highly polar
and relatively small monomers, such as ε-caprolactam, do not provide sufficient
intercalation and bonding to the clay surface – Na-MMT must be pre-intercalated
[Usuki et al., 1990; 1993a,b; 1995]. The latter process was carried out with
12-aminolauric acid (ADA) in aqueous medium. Obviously, instead of ADA
another highly polar, water-soluble compound may be used, but as in any other
cation-exchange intercalation process, the initial step of intercalation seems to
require the presence of water. The intercalation with ADA results in nearly
quantitative cation exchange; hence after polycondensation the PA-6 matrix is
end-tethered and densely packed near the clay platelet surface.
Prior to the emulsion or suspension polymerisation of styrene, the clay platelets
dispersed in aqueous media (viz. Na-MMT) may be fully exfoliated. However, in
the recovered polymer the interlayer spacing is quite small, d001 ≤ 1.7 nm,
indicating re-aggregation. Thus, as a rule, to achieve a reasonable degree of
intercalation in CPNC the intercalant must bind to the clay surface. The binding
can be achieved by ionic bonding, covalent bonding (e.g., through ≡Si-OH groups)
or at least through hydrogen bonding with hydrophilic compounds.
2.3.5.2 Intercalation of Purified Clay by Hydrophilic Compounds

Owing to the hydrophilic nature of clay, intercalation by water-soluble monomers,
oligomers or polymers is expected to be relatively simple. However, early attempts
to intercalate MMT with PVAl, P4VP or PEG, were not successful. Greenland
[1963] reported that PVAl containing 12% residual acetyl groups increased the
d001 spacing only by ca. 1.0 nm. As the concentration of polymer increased from
0.25 to 4 wt%, the amount of polymer sorbed was reduced, indicating that
sorption might only be effective at polymer concentrations of 1 wt% or less.
Such a dilute process would be too costly, hence no further work was carried out
toward commercialisation.
Intercalation of Na-MMT by P4VP (MW = 40 kg/mol) was carried out in
1 wt% P4VP dissolved in ethanol/water solution. The clay was first repeatedly
washed with ethanol. After dispersing it in the solution, filtering out and drying
the basal spacing expanded to 2.6-3.2 nm [Levy and Francis, 1975]. It was
concluded that:
1. The ethanol was needed to initially increase the basal spacing for the later
sorption of P4VP to take place;
2. Water did not directly affect sorption of P4VP between the clay platelets;
and
3. P4VP sorption was time consuming and difficult.
Since 1995 Nanocor (a subsidiary of the AMCOL International Corp.; known
since 1927 as American Colloid Co.) has patented several methods of chemical
modification of clays. In an early patent, clay was intercalated using 30-80 wt%
of a water-soluble monomer, oligomer (degree of polymerisation, DP = 2-15) or
polymer (DP > 15) [Beall et al., 1996a]. The aim was to have the intercalant
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bonded to the clay platelets, thus increasing the interlayer spacing to d001 = 3-4.5 nm
(the most desirable spacing!). To bond, the intercalant needed either a strong
polar group (e.g., carbonyl, hydroxyl, carboxyl, amine, amide, ether, ester, sulfate,
sulfonate, sulfinate, sulfamate, phosphate, phosphonate, phosphinate) or an
aromatic ring able to form a metal-cation complex. Several types of interaction
were envisaged, viz. by metal cation electrostatic bonding, chelation of the clay
metal cations, bonding between clay inorganic cations and intercalant aromatic
rings, by hydrogen bonding to the surface -OH groups, etc.
The following water-soluble polymers or oligomers were reported useful as
intercalants:
• P4VP (MW = 1-40 kg/mol). Its solubility can be adjusted by hydrolysis or by
forming a sodium or potassium salt. Copolymers of vinylpyrrolidone and
vinyl amide or γ-amine butyric acid, can be similarly treated.
• Fully hydrolysed PVAl (MW = 2 to 10 kg/mol).
• Fully or partially neutralised salts of a polyacrylic acid (PAA) or a
polymethacrylic acid (PMAA, MW = 0.2 to 10 kg/mol).
• Polymethacrylamide, poly(N,N-dimethyl acrylamide), poly(N-isopropyl
acrylamide), poly(N-acetamido acrylamide), poly(N-acetamido
methacrylamide), their copolymers or interpolymers containing PAA, or
PMAA.
• Polyvinyloxazolidone (PVO) and polyvinyl methyl-oxazolidone (PVMO),
PEG, polypropylene glycol (PPG) and their copolymers.
• Polymeric quaternary ammonium salts.
• Sodium salts of acrylate/vinyl alcohol, olefin/maleic acid, polymethacrylate,
polystyrene sulfonate, styrene/acrylate/PEG dimaleate, styrene/PEG maleate/
nonoxynol, etc.
• Styrene copolymers with acrylamide, acrylate-ammonium methacrylate,
maleic anhydride, PVO, etc.
• Diverse copolymers, viz. cornstarch-acrylamide-sodium acrylate, diethylene
glycol-amine-epichlorohydrin-piperazine; dodecanedioic acid-cetearyl alcohol-
glycol, ethylene-vinyl alcohol, hydroxy ethyl-polyethyleneimine, polyvinyl
methacrylate-methacrylic acid, melamine-formaldehyde resin, phthalic anhydride-
glycerin-glycidyl decanoate, metal salts of acrylic and polyacrylic acid, sucrose
benzoate-sucrose acetate, isobutyrate-butyl benzyl phthalate, sucrose benzoate-
sucrose acetate isobutyrate-butyl benzylphthalate-methyl methacrylate, vinyl
acetate-crotonic acid, and polysaccharide copolymers.
• Prepolymers: urea-formaldehyde, urea-melamine-formaldehyde, etc.
In the cited patent [Beall et al., 1996a] the preferred intercalants are P4VP,
PVAl, and their mixtures at the weight ratio of intercalant-to-Na-MMT = 1:5-
1:3. By contrast with the prior publication that indicated significant difficulties
and achieved minor expansion of the interlayer space, the new intercalation in
the presence of at least 10 wt% of water proceeded quite readily using any of the
three methods. For example, to intercalate Na-MMT with P4VP (MW = 10 and
40 kg/mol) or PVAl (75-99% hydrolysed) the following processes were used:
1. Mix for 4 h aqueous 2 wt% solution of P4VP (MW = 10-40 kg/mol) with
2 wt% suspension of Na-MMT clay in water, at a ratio sufficient to vary the
weight ratio of clay to P4VP from 4:1 to 1:4, based on dry mass.
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2. Add the clay (ca. 8 wt% of moisture) to aqueous 2 wt% solution of P4VP in
a ratio as in method (1) and mix for 4 h.
3. Dry blend P4VP with Na-MMT, and then add 35-38 wt% H2O (based on
dry clay) and extrude the paste.
When a dry blend of Na-MMT and powdered P4VP was mixed with 75 wt%
water an exothermic reaction was observed. Apparently, the bonding reaction of
a polymer to the internal face of the clay platelets is sufficient to engender an
exothermic exfoliation.
All of the three methods resulted in intercalation of MMT. The final spacing
did not depend either on the method of preparation or MW of P4VP, but on the
quantity of polymer sorbed between platelets. Exfoliation did not take place
unless the clay contained at least 10 wt% water. The polymer-engendered
expansion of the interlayer was demonstrated by drying the intercalated samples
for 4 h at 120 °C – only a small change in the interlayer spacing was detected.
The generality of the developed technology was demonstrated in later patents
(see below), where Na-MMT was directly intercalated with insecticide or pesticide
(e.g., 2,4-dichloro phenoxy acetic acid butyl ester), provided that their molecules
were water-soluble and had strong polar groups.
As shown in Figure 28 the interlayer spacing increased with the concentration
of P4VP or PVAl in steps. When the intercalating composition contains < 16 wt%
of intercalating polymer a monolayer is sorbed between the platelets, increasing
the interlayer spacing by < 1 nm. When the concentration is in the range from
16 to 35 wt% the interlayer spacing increases by 1 to 1.6 nm. At loadings of
35 to 55 wt%, the interlayer distance is increased to about 2.0-2.5 nm, which
corresponds to three layers of intercalant sorbed between adjacent clay platelets.
At loadings of 55 to 80 wt% the interlayer distance is increased to 3.0-3.5 nm,
Figure 28 Interlayer spacing as a function of PVP or PVAl concentration

(calculated on dry weight of Na-MMT). Data Beal et al. [1998].
129
which corresponds to 4 and 5 layers of sorbed intercalant – this is considered the

optimum interlayer distance for organoclays. When these are incorporated into
polymeric matrix, the platelets with the intercalant molecules attached to the
surface exfoliate.
Such interlayer spacing has not been achieved by direct intercalation of a
monomer, an oligomer or a polymer molecule, without prior sorption of an onium
or silane coupling agent. The new method leads to easier and more complete
exfoliation. The exfoliated compositions, especially the high viscosity gels, may
be used for delivery of active compounds, such as an oxidising agent for hair
lotions, drugs, cosmetics, oil well drilling fluids, paints, lubricants, food grade
lubricants, etc.
An important feature of the AMCOL invention is that the intercalate
compositions can be manufactured in a concentrated form, e.g., as a master gel;
having 20-80 wt% intercalated or exfoliated clay. Exfoliation should provide
delamination of at least about 80 wt% of the intercalated material. For such
relatively thorough exfoliation a shear rate > 10 sec-1 may be required. The
preferred shear rate is 100-10,000 sec-1. The shearing may be imposed by
mechanical means (in a Banbury, Brabender, continuous mixer or extruder), by
thermal shocks (alternatively raising and lowering the temperature), by pressure
alteration (0.05-6.0 MPa sudden pressure changes) or by ultrasonics (vibrations
cause portions of the composition to be excited at different phases).
Development of the intercalation technology described above has continued
in the following patents [Beall et al., 1996a,b; 1999a; Serrano et al., 1998a,b;
Ferraro et al., 1998]. In another document [Beall et al., 1999b], intercalates were
prepared by contacting clay either with water, or with an aqueous solution of a
water-soluble polymer and/or a water-miscible organic solvent, e.g., alcohol,
followed by contact with a pesticide or its solution. The pesticide should have a
polar group, e.g., carboxylic acid, ester, amide, aldehyde, ketone, sulfur-oxygen
or phosphorus-oxygen moiety, cyano, or a nitro. As for P4VP, here also the results
did not depend upon the method, but on the quantity of active ingredient sorbed
between clay platelets. The intercalated Na-MMT showed d-spacing = 1.88 nm,
an increase from 1.24 nm for untreated clay.
In the following patent [Tsipursky et al., 1999] intercalation was also carried
out in the presence of 25 to 50 wt% of H2O using a water-soluble monomer, an
oligomer and/or a polymer. The shearing could be provided by mechanical means,
thermal shock, pressure alteration, or by ultrasonics. The amount of intercalant
in contact with Na-MMT was ca. 20 to 60 g per 100 g of clay. As before, the
intercalant should have an aromatic ring and/or a polar group: carbonyl, carboxyl,
hydroxyl, amine, etc. The preferred intercalants were P4VP, PVAl, polyacrylic or
polymethacrylic acid polymers and copolymers. A wide variety of topically active
compounds (e.g., cosmetics, industrial, medicinal) could be incorporated into a
stable composition and evidently, so could the monomers. As before, the preferred
interlayer spacing was stated as d001 = 3.0-4.5 nm. The viscosity, η = 0.02 to
5,000 Pas, could be adjusted by pH and addition of metal salts. A very long list
of suitable salts was cited, from Al-acetate oxide to Zr-trifluoroacetyl-acetonate.
For example, addition of 0.1 wt% of either AlCl2OH or Mg-acetate increased η
by a factor of 5.
Another disclosure [Lan et al., 1998; Lan et al., 2000] brings AMCOL’s
intercalation methods closer to the mainstream of CPNC technology. Thus, clay
was treated with 30 to 80 wt% of an organic intercalant, having paraffinic Cn-
130
chain with n ≥ 6. The compound must also have a polar group, viz. hydroxyl,
polyhydroxyl, carbonyl, polycarboxylic acids and salts, aldehydes, ketones,
amines, amides, ethers, esters, lactams, lactones, anhydrides, nitrites, halides,
pyridines and their mixtures. The intercalating composition should have a weight
ratio of organic intercalant to clay ≈ 1:4.
According to the authors, bonding by the intercalant polar ends causes the
molecules to stretch in the direction normal to the platelet surface. This increases
the interlayer spacing, while consuming little of the intercalant. As a result, there
is sufficient expansion of d001 and sufficient concentration of the remaining free
cations to ascertain sorption of polymerisable monomer, oligomer, and/or polymer
molecules, e.g., of an epoxy resin. The process does not require either onium
ions or silane coupling agents. It can be applied to all resins, but it has been
specifically designed for the epoxy resins. Diluting the Na-MMT/intercalant
concentrate with a monomer or oligomer, and then curing may lead to exfoliation.
The presence of polymerisable monomer or oligomer in the clay galleries improves
miscibility with the matrix polymer, hence a masterbatch can be mixed with
additional polymer.
Alternatively, the intercalant may be dispersed into a melt processable thermoplastic
or thermosetting matrix oligomer or polymer, then clay and water added. The matrix
polymer may have DP = 10-100, and a melt index MI = 0.01-12 g/10 min at the
processing temperature. For example, Na-MMT (8 wt% water; CEC = 1.2 meq/g)
was mixed at room temperature with epoxy resin and 1-dodecyl-2 pyrrolidone
(DDP) in a 1:1 molar ratio to the Na+. Then, water was gradually added to the
mixture. The solid-like mixture was extruded using a single screw extruder (SSE)
and dried at 90-95 °C obtaining uniform powdered materials. XRD determined
that incorporation of DDP and epoxy increased the interlayer spacings of
Na-MMT, d001 = 1.23 to 3.4 nm. Similar spacing was obtained using different
mixing sequences and methods, viz. by adding DDP and epoxy to clay slurry and
then drying the mixture; by adding DDP/epoxy/water emulsion to clay, extruding
using a twin screw extruder and drying. However, when DDP was eliminated
from the formula the maximum interlayer spacing achieved by adding water and
epoxy was d001 = 1.9 nm. In conclusion, water is the essential element for the
co-intercalation by the epoxy and DDP molecules. Owing to the co-intercalation,
the free liquid phase of DDP/epoxy/water disappears and the mixture becomes
solid-like. DDP molecules bind to the interlayer Na+ and epoxy molecules diffuse
into the interlayer spacing. The co-intercalate has the molar/weight ratio:
DDP/epoxy/MMT = 1:1:0.75.
Several types of polar organic compounds can be used as intercalants, including
long chain ethers, esters or alcohols, having a polar end group that provides the
molecule with a dipole moment greater than that of water. The listed examples
include aliphatic; aromatic; aryl-substituted aliphatic; alkyl-substituted aromatic
alcohols and phenols, e.g., manufactured from coconut, tallow and/or palm oils.
Straight-chain acids can also be used, for example, stearic, oleic, linoleic, ricinoleic,
canola, castor, tallow-based, soybean or coconut. Representative aldehydes include
C6 to C28, phenyl acetaldehyde, etc. Amines (primary, secondary and tertiary) or
amides are also suitable, viz. oleylamine, soya alkylamines, hydrogenated or not
tallow or ditallow alkylamines, palmitamide, hexadecyl amide, stearamide,
oleamide, linoleamide, etc. Suitable nitrites include hexanonitrile,
n-nonadecanitrile and others. Lactones, lactams, pyridines and surface-active esters
can also be used.
131
These clay-intercalate complexes can be dispersed into thermosetting,

thermoplastic matrix or elastomeric oligomers or polymers. For example, the
indicated thermosets are: epoxides, polyamides, polyalkylamides, polyesters,
polyurethanes, polycarbonates, and their mixtures. The cited thermoplastics are:
polyamides (e.g., PA-4, PA-6, PA-66, PA-6,10), polyesters (e.g., PET, PBT,
polycyclohexylene terephthalate (PCT)), and polyolefins (e.g., PE, PP) as well as
many others, viz. PCL, PU, PSF, PPS, polyetherimide (PEI), polyketones, vinyls,
acrylics, polyacrylonitrile, ionomers, and their blends. The elastomers may be
selected from between chlorinated or brominated butyl rubber, TPU, polyester
elastomers, PVC/NBR, polybutadiene (PBD), polyisoprene (IR), EPR, EPDM,
chloroprene (CR), chlorosulfonated polyethylene (CSR), poly(2,3-dimethyl-
butadiene), fluoro-, silicone or polysulfide elastomers, etc.
Exfoliation of the intercalated layered material should affect > 90 wt% of the
layers, which for some systems may require a shear rate: 10 < γ˙ (sec-1) < 10,000,
for others heating, or cycling the pressure between 0.05 and 6 MPa, with or
without heating. The shearing can be either mechanical (e.g., during extrusion,
injection moulding, compounding in a TSE or an internal mixer), or by thermal
shock, pressure alteration, ultrasonics, etc. The amount of intercalated/exfoliated
clay in a liquid matrix depends on the intended use and desired viscosity of the
composition. A relatively high amount, i.e., from 10-30 wt%, may be used in
solvent gels with viscosity η = 5-5,000 Pas. This may be achieved with 0.1-5 wt%
organoclay, by adjusting the pH and/or by heating the composition to T = 75 to
100 °C. A masterbatch with 20-80% organoclay may be prepared, but the final
composition should not exceed 10 wt% organoclay.
The patent applications are quite broad, addressing:
1. Preparation of a wide variety of topically active compounds (e.g., cosmetic,
medicinal, and industrial viz. antiperspirants, deodorants, antidandruff or
antibacterial compounds, antifungal or anti-inflammatory compounds,
anaesthetics, sunscreens, analgesics, antiseptics, antiparasitics, antibacterials,
steroids, herpes treatment drugs, pruritic medications, etc.).
2. Thermoplastic or thermosetting moulding CPNC for the production of sheets
and panels, formable by conventional processes, viz. vacuum or hot pressing,
lamination of, for example, wood, glass, ceramic, metal or other plastics.
The sheets and panels can also be produced by coextrusion.
3. Extrusion of 25-75 μm thick films and film laminates for food packaging,
fabricated by conventional means, followed by biaxial stretching to orient
the clay platelets parallel to the film surface. These films exhibit increased
modulus, wet strength, and dimensional stability as well as decreased moisture
adsorption, permeability to gases and liquids, etc.
From the fundamental point of view, MMT being a weak silicilic acid has a
negatively charged surface that should interact with a cationic monomer or
polymer. For example, as the discussion above demonstrated, poly-4-vinylpyridine
(PVP) may easily be protonated to form water soluble, positively charged
polyelectrolyte, which intercalates the clay. Similarly, such monomers as
protonated vinyl pyridines and their N-alkylated derivatives (4-VPH+X–) are
expected to intercalate by ion exchange. The inserted monomer can be polymerised
within the MMT galleys. Depending on the monomer concentration and acidity
4-VPH+X– may either form 1,2- or the quaternary 1,6-polyelectrolyte with the
pyridinium units in the side or in the main chain, respectively.
132
In polymer technology it is often advantageous to replace one component

by a mixture of similar functional ingredients. For example, compatibilisation
of two immiscible polymers is often more efficient by a mixture of
compatibilisers than by either one. Similarly, blending one polymer with two
fractions often results in better material. This philosophy has also been applied
to clay intercalation [Lan et al., 2003]. Evidently, it is easier to mix known and
available organic intercalants than to design and synthesise new ones. To
illustrate the advantage of the mixing approach, consider the following situation.
For the best performance of CPNC it is essential that the matrix is miscible
with the organic tails of the intercalant attached to the clay surface. A good
miscibility candidate is ethoxylated or polyalkoxylated ammonium salt (e.g.,
ETHOQUAD 18/25 or JEFFAMINE506). However, this compound has a high
molecular weight, and if used alone it would reduce the clay content to less
than 50 wt%. It was found that its 50:50 combination with ODA is easy to
manufacture and use for CPNC.
The new mixed-onium organoclays have a broader range of application in
diverse polymeric matrices (e.g., PVP, PVAl, PEG, PTHF, PS, PCL, PA-6), but
they have been especially designed for thermoplastic polyesters (PEST) such as
PET. The CPNC may be used alone or as one component of the multi-layered
structures with PEST, aliphatic or aromatic PA, EVAl, etc. For example, the patent
describes preparation of CPNC by melt compounding, in a solvent or by reactive
means, using an organoclay that was pre-intercalated with a mixture of at least
two organic cations. In a given example, the PET-based CPNC (with 75 to 90%
of exfoliated clay platelets) showed low permeability and good mechanical
properties, thus it was suitable for bottle blow moulding.
A similar approach was taken by Han et al. [2004]. The authors pre-
intercalated Ca-MMT with trimethyl cetyl ammonium bromide (3MCA), amino-
undecanoic acid (AUA), and a 1:1 mixture of these two. The organoclays were
used to prepare CPNC with PU as the matrix. XRD and TEM showed that PU
containing MMT-AUA was exfoliated, PU with MMT-3MCA was intercalated
(d001 = 3.5 nm) and the one with mixed intercalant had an intermediate behaviour
(small peak of MMT-3MCA remaining). The tensile properties of the CPNCs
containing 5 wt% organoclay demonstrated an advantage of the mixed intercalant
approach – the tensile modulus and strength were the best, with the elongation
at break 35% higher than that of neat PU.
Na-MMT (CEC = 0.83 meq/g) was intercalated in an aqueous solution of
2 wt% of poly-4-vinyl pyridinium bromide (at a level of 5×CEC) [Fournaris et
al., 1999]. Polymerisation of 4-VPH+Br– in the clay galleries was fast and it resulted
in the formation of quaternised ionene, independently of the polymerisation
conditions. The quaternised ionene polymer and partially protonated poly-4-
vinylpyridine could also be dissolved in water and used to intercalate Na-MMT
at a level of 4×CEC. The isotherms for the 1,2-PVPH+Br-, 1,6-PVP+Br–, and P4VP
adsorption by Na-MMT were obtained by adding the appropriate amount of
each intercalant to a suspension of Na-MMT and stirring it for 2 h. The products
were isolated by centrifugation, washed, and then air-dried on glass plates. The
amount adsorbed by the clay was calculated from analysis of the supernatant
solution. Independently of the amount of polymer available for intercalation,
only one macromolecular sheet of P4VP or the quaternised ionene was found to
enter the interlayer space causing the interlayer space to expand by Δd001 = 0.4 to
0.54 nm. Thus, this amount of polymer suffices to coat the clay surfaces, making
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the clay anions not available for additional macromolecules. The surface saturation
coverage increased in the order:
partially protonated P4VP > quaternised ionene form
> completely protonated P4VP.
By contrast with neutral P4VP, the partially protonated P4VP could be adsorbed
at different levels. XRD showed that the d001 spacing increases with P4VP loading
(see Figure 29). At a concentration of P4VP > 70 wt% the XRD peak disappeared
due to delamination. The FTIR spectra provided additional evidence of P4VP
interaction with the clay surfaces.
Fischer [1999] patented the use of block or graft copolymers for the preparation
of CPNCs. By analogy to compatibiliser in immiscible polymer blends, the
copolymer must have two types of structural units, one (A) to interact with clay
the other (B) with polymer. The molecular weight of part A should be MW = 0.1 to
5 kg/mol (DP = 5 to 20), while for part B MW = 0.1 to 20 kg/mol. To interact with
clay the structural units of part A should be hydrogen-bonding, e.g., vinyl
pyrrolidone, vinyl alcohol, ethylene glycol, ethylene imine, vinyl pyridine, acrylic
acid, acrylamide. To interact with the matrix the structural units of part B should
be miscible with the matrix polymer and able to entangle. In the organoclay the
inorganic clay content ranged from 5 to 600%, while in CPNC it constituted from
2 to 55 wt%. Judging by the examples, preferably the intercalant is a block
copolymer, e.g., PS-b-PEG or PS-b-PVP. The intercalation is performed in THF,
followed by solvent evaporation and melt compounding with the matrix polymer.
Fischer et al. [1999; 2001] used this strategy to prepare CPNCs with either
natural or synthetic clay and either PS or PMMA as matrix. The authors started
directly with Na-MMT, Na-saponite, or Na- fluorohectorite (CEC = 0.85 to
Figure 29 XRD peak position(s) for Na-MMT intercalated with partially

protonated poly-4-vinylpyridine. The peaks disappeared for loadings above 65
wt%. Data [Fournaris et al., 1999].
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3.2 meq/g). Block or graft copolymers were used (viz. PS-b-PEG, PMMA-b-PEG,
PMMA-co-polymethacrylic acid, PS-b-P2VP; MWblock = 1 to 27 kg/mol) having
one part either identical to or miscible with the matrix polymer and the other
capable of intercalating with the clay. The interaction between the compatibiliser
and clay was preferentially ionic or hydrogen bonding. The intercalation was
performed either in the melt (copolymers with PEG) or in solution. It resulted in
individual clay platelets and/or short stacks containing 2-10 layers homogeneously
distributed in the matrix. As expected, better mechanical performance was
obtained for block copolymers having the miscible block with molecular weight
above the entanglement molecular weight value: MW > Me.
Several clays (e.g., sodium montmorillonite, hectorite, and laponite) were melt-
intercalated with PEG using microwave irradiation [Aranda et al., 2003]. The
process was found to depend on irradiation time and power, amount and relative
ratio of the reagents, and relative humidity. The process resulted in d001 ≅ 1.8 nm
indicating formation of a hydrated double layer of PEG within the interlamellar
galleries. Thus, 10 minutes of microwave irradiation of moderate power was able
to accomplish a similar task as shear compounding in an internal mixer or TSE.
2.3.6 Two-Step Intercalation

This process usually involves an organoclay that has been pre-intercalated with a
suitable onium cation, then treated with low molecular weight polymerisable liquid
(monomer, oligomer or cyclomer), which in turn may be polymerised. This reactive
last step is essential as it leads to the ultimate level of intercalation – the exfoliation.
An early example of this process has already been discussed in relation to the
preparation of PA-6 nanocomposites [Okada et al., 1988]. The process comprised
three steps:
1. Intercalation of Na-MMT (CEC = 1.8 meq/g) with ω-amino-dodecanoic acid
(ADA) in the presence of inorganic cation, e.g., Cu2+ or Al3+;
2. Mixing the intercalate with ε-caprolactam, and
3. Polycondensation.
As shown in Figure 25, each of the three steps contributed to the expansion of
the interlayer spacing. The clay was first dispersed in aqueous, acidified intercalant
solution, reacted with ADA and the precipitate was washed with water to remove
excess ions. The organoclay paste was then mixed in a mortar with monomer
and the mixture heated at 80 °C for 3 h to ensure dehydration and melting of the
caprolactam. The homogeneous complex was then transferred to a closed stainless
steel vessel and heated at 250 °C for 5 h. The resulting CPNC contained exfoliated
clay platelets and showed significant improvement of the mechanical and thermal
properties.
Over the years several modifications of this basic process have been made.
For example, it was found that the original process resulted in end tethering of
all macromolecules, having the end amino groups of PA firmly attached to the
clay surface. As a result, the CPNC had insufficient dyeability, as well as poor
coating and printing properties. The modified method [Deguchi et al., 1992]
comprised the following steps:
1. Dispersing >1 wt% of Na-MMT (CEC = 1.19 meq/g) in water solution of
ADA and HCl, followed by stirring at 80°C for one hour. After washing, the
mixture was filtered to obtain organoclay complex (abbreviated as 12MMT;
d001 = 1.25 to 1.8 nm) containing 88 wt% H2O.
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2. To the 12MMT-paste H2O and ε-caprolactam were added in a ratio:

12MMT/H2O/ε-caprolactam = 1:9:9, followed by mixing.
3. The produced organoclay/water/ε-caprolactam mixture was compounded with
72 wt% of either PA-6 (MW = 15 kg/mol) or PA-66 (MW = 20 kg/mol) in a
TSE. The extruded strands were pelletised, and then caprolactam was extracted
from the pellets using hot water. Excellent clay layer dispersion was observed
under TEM in the moulded CPNC, with only single platelets or doublets visible.
XRD and swelling tests indicated exfoliation.
The new method resulted in CPNC in which layers of silicate are uniformly dispersed
and not all amino end-groups are tethered. The material showed good mechanical
properties, heat resistance, improved dye-affinity and whitening resistance during
stretching. This process has been used for the commercial scale production of
PA-6 nanocomposites.
Two-step intercalation is particularly important for preparation of CPNC
with non-polar polymers, viz. PO, regardless of whether the selected method is
reactive or by melt compounding. Since these systems will be discussed in greater
detail later, here only two examples are given.
Heinemann et al. [1999] have prepared PO-based PNC starting with hectorite
intercalated with dimethyl benzyl stearyl ammonium chloride (2MBSA), having
d001 = 1.96 nm. When HDPE was polymerised in the presence of the intercalated
clay, the XRD peak shifted to d001 = 1.40 nm. Best results were obtained for
LLDPE-type ethylene-octene copolymers. The authors reported that performance
of the reactively prepared CPNC was better than that prepared by melt
compounding. However, the intercalated clay was found to interfere with
metallocene catalysts.
An early patent on the preparation of PO-based CPNC may serve as an
illustration of the two-step melt intercalation method [Kato et al., 1997; Usuki et
al., 1999]. Thus, MMT was intercalated with ODA and a guest molecule (MW =
0.100-100 kg/mol) having a polar group, e.g., a maleated PO. Alternatively, an
oligomeric guest molecule with a polar group could be added to the onium-
intercalated clay. Next, the complex was compounded with a non-polar PO matrix.
The most important feature of the invention is the use of a polar guest molecule
that can bond to the pre-intercalated clay layers and provide entangling possibility
for the main PO macromolecules. The process is sensitive, as insufficient amounts
of maleic anhydride (MAH) groups do not provide sufficient compatibilisation,
and too high concentration may lead to phase separation of the guest molecules
within the PO matrix, which in turn results in poor CPNC performance. Evidently,
as in any other phase separation process, this also depends on other factors than
MAH content, viz. molecular weight, temperature, pressure, stress field, etc.
2.3.6.1 Intercalation by Silylation

In the patent applications of 1992 MacRae Maxfield et al. [1995] introduced
traditional ‘sizing agents’ into nanotechnology. The aim was to obtain PA-based
CPNC by melt compounding. It was found that cation-exchanged MMT could
not be exfoliated during extrusion in a twin-screw extruder. However, the situation
improved when the organoclay was treated with a silane coupling agent. In the
intervening years better organoclays have been developed and today melt
compounding PA with cation-exchanged MMT can result in exfoliated CPNC.
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However, the observed enhancement of dispersion and resulting CPNC

performance by incorporation the sizing agents are valuable lessons for the many
difficult systems that remain.
The following procedure was described. A suspension of 5-15 wt% MMT in
water was heated to 80 °C in a high-speed mixer with (NaPO3)6 then an
ammonium salt (e.g., octadecyl-ammonium chloride) is added. The amine-
complexed clay was centrifuged, washed, dried, and ball milled to 100-mesh
powder. The powder was re-dried at 100-160 °C in vacuum for 8-24 h in the
presence of phosphorous pentoxide. Next, the intercalated clay was treated with
amino-ethyl amino-propyl trimethoxy silane in an organic solvent (e.g., dioxane,
DMSO, MEK). The modified clay (60 mmole of ammonium and 20 mmole of
silane per 100 g of clay) was compounded into a masterbatch using a TSE. The
masterbatch was finally diluted with PA-6 to mineral concentrations of 0.1, 0.05,
and 0.01 wt%.
The process was revised in the next patent [MacRae Maxfield et al., 1996]:
1. MMT (aspect ratio 15 ≤ p ≤ 300) was reacted with an organosilane,
organotitanate or organozirconate capable of forming covalent bonds with
the particles and either reacting with a polymer or at least miscible with the
polymerisation product. For example, a suspension of 5-15 wt% MMT in an
aqueous solution of sodium hexametaphosphate was heated at 50-90 °C. The
dispersion was combined with a solution of caprolactam-blocked isocyanato-
propyl triethoxy silane and 1-trimethoxysilyl-2-(m,p-di-chloro methyl)-phenyl-
ethane. The organosilane intercalated MMT was filtered, dried (at
60-160 °C for 8-24 h) and ground to about 100 mesh.
2. The intercalated MMT was combined with caprolactam and aminocaproic
acid having cation-exchange capabilities. The mixture was polymerised. In
the CPNC the amount of MMT varied from 0.1 to 10 wt% and the interlayer
spacing d001 ≥ 5 nm. The platelets were uniformly dispersed.
In 1998 Ogawa et al. [1998] described a general method of intercalation of layered
silicate (Na-magadiite). The process involved silylation of interlayer silanol groups
with organochlorosilanes with different functionality. The reaction created
organically modified surfaces where organic groups are covalently attached to
the clay surface. However, to start with, Na-magadiite was first ion exchanged
with dodecyl-trimethyl-ammonium (3MDDA). The resulting intercalated clay
(d 001 = 2.79 nm) was dispersed in a toluene solution of either
octyldimethylchlorosilane (C 8H 17 (CH 3 ) 2 SiCl (1)) or octyltrichlorosilane
(C8H17SiCl3 (2)), under a blanket of N2 for 48 h. The product was separated by
centrifugation, then washed with an acetone/water mixture and dried. During
the reaction de-intercalation of 3MDDA took place (evidenced by the absence of
N in elemental analysis). The basal spacing decreased to d001 = 2.33 and 2.18
nm, for (1) and (2) respectively. The amounts of the attached organosilyl groups
were determined to be 1.84 and 1.94 per 14SiO2 (molar ratio), respectively. The
two differently modified magadiites showed different adsorption behaviour. The
difference in the composition affected the reactivity, which in turn led to a different
level of the basal spacing (e.g., after absorption of n-octyl alcohol: d001 = 3.20
and 3.18 nm, respectively). After silylation the organosilyl groups formed
monolayers. When n-alkyl alcohols were introduced, they rearranged the
microstructure, forming a bilayer and expanding the interlamellar spaces.
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Jeong et al. [1998] and Hudson [1999] described preparing PO-based PNC
in three steps:
1. Functionalising MMT with an aminosilane.
2. Reacting the free amine with maleated PO (MW ≅ 20 kg/mol; ca. 1 wt%
MAH groups) either in solution (reaction time ca. 30 min) or in melt.
3. Dispersing the organomodified clay in a semicrystalline PO.
Cocrystallisation between the maleated and the semicrystalline PO is essential.
For example, the coupling reaction between MMT and amino ethyl-dimethyl
ethoxysilane was carried out for 2 to 4 h at T = 25-90 °C, in either ethanol and
water, or dimethyl acetamide. The monoalkoxy silane may either react with the
clay surface, self-condense to form dimer, or it may remain unreacted. Grafting
may lead to precipitation. The reaction produces ethanol, which has been detected.
Detection of the dimer by NMR is facile (resonance at 9.3 and 13.9 ppm). XRD
of the silane treated MMT demonstrated increased interlayer separation with
d001 = 2.4 to 7.3 nm. TEM showed the presence of many individual MMT-layers,
but in CPNC containing 15% clay, most were found in stacks of 2-4 layers ca.
1 μm long.
2.3.6.2 Intercalation Utilising Epoxy Compounds

Pinnavaia and his coworkers explored the use of epoxy compound as a second
intercalant for layered materials. As early as in 1994 [Wang and Pinnavaia, 1994;
1998a,b; Wang et al., 1996], delamination of organoclays in epoxy resin was
reported. The process involved heating an onium ion intercalated smectite with
epoxy at T = 200-300 °C. The work resulted in several patents [Pinnavaia and
Lan, 1998a,b,c; 2000a,b] and publications [Lan and Pinnavaia, 1994; Lan et al.,
1995; Massam et al., 1998] from the group. While most of this work was directed
towards production of thermoset CPNC, the possibility of using the two-step
intercalation method (involving cation-exchange and epoxidation) for the
manufacture of thermoplastic CPNC has also been suggested.
Giannelis and Messersmith [1996] used a similar approach. An organically
modified smectite (MMT-MT2EtOH; Cloisite® 30B) was dispersed in an epoxy
resin together with diglycidyl ether of bisphenol-A (DGEBA). The system was cured
in the presence of nadic methyl anhydride (NMA), and/or benzyl-dimethyl amine
(BDMA), and/or boron trifluoride monoethylamine (BTFA) at T = 100-200 °C.
Exfoliation of smectite was reported with interlayer spacings d001 ≥ 10 nm and
good wetting of the silicate surface by the epoxy. The curing involved reaction
between epoxy and the alkyl ammonium ions located in the galleries of the
organically modified clay. In other words, the reaction resulted in direct attachment
of the epoxy network to the silicate layers. The nanocomposite showed higher
dynamic storage modulus in the glassy region and very much higher in the rubbery
plateau region, when compared to the epoxy resin without clay. The patent focused
on the preparation of clay-epoxy nanocomposites.
In the year 2000, Ishida et al. [2000] proposed a more general approach to
intercalation of smectite clays. It involves the use of either epoxy or PDMS as a
‘swelling agent’ that increases the interlayer spacing of the cation-exchanged
smectites. Thus, Na-MMT was first intercalated by cation exchange reaction
with either ADA or with HDA. The products were labelled B12 and B16,
respectively. The epoxy derived from the DGEBA (Epon 825) is presented in
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Figure 5. Polymer (88 wt%), intercalated clay (10 wt%), and epoxy or PDMS
(2 wt%) were manually mixed for 30 min above either the Tg or Tm of the matrix
polymer. The XRD of B12 (no epoxy) showed the interlayer spacing,
d001 = 1.6 nm. Upon addition of epoxy the peak became wider and located at a
smaller diffraction angle, i.e., d001 increased to 2.3-1.9 nm. Thus, epoxy alone
does not exfoliate the onium-intercalated clay. For the CPNCs the percentage of
intercalation and/or exfoliation was calculated from XRD patterns as:
Exfoliation (%)
= 100×[1 - (clay peak area with epoxy)/(clay peak area without epoxy)]
The extent of exfoliation was found to increase with the mixing time, but the time
required for the completion of the process (from 4 to 120 min) depended on the type
of system. The extent of exfoliation may be related to the polymer solubility parameter,
δ, for epoxy and PDMS this is respectively, δ ≅ 9 and 8. Unfortunately, the authors
do not indicate the mechanism involved in the clay ‘swelling’ by either of these two
agents. The method was patented [Ishida, 2000].
2.3.6.3 Intercalation Utilising Organic Anions

As discussed in Section 2.2.4, there are three types of possible interactions that
may be used when preparing CPNC: exchangeable cations in the interlayers,
-OH groups on the silicate surface, and exchangeable anionic groups at the clay
platelet edges. Only recently have the latter groups been targeted for the second
step of smectite intercalation. Thus, natural or synthetic clay was first intercalated
with a quaternary ammonium ion, and then treated with negatively charged
organic molecules able to react with the edge cations. In recent patents from SCP
0.1 to 1.0 wt% (on dry weight of clay) of a high charge density anionic polymer
such as a polyacrylate has been used [Powell, 2001a,b]. The clay edge treatment
with polyacrylate was carried out before that with a quaternary ammonium ion.
In a continuation of the SCP technology (see Section 4.3), polyacrylate was added
to an aqueous slurry of MMT, which then was subjected to high shear in a Manton-
Gaulin mill. After shearing the clay was treated with a branched chain quaternary
ammonium ion. According to the author, the polymer became strongly attached
to the clay edges, making them strongly anionic. In the subsequent treatment an
alkyl quaternary ammonium cation not only reacted with the clay-surface anionic
charges, but also with the edges, which resulted in uniform, hydrophobic coating,
improved dispersability in the plastic matrix of the nanocomposite, and improved
properties.
In the patent example, PA-66 was melt compounded in a TSE with dry, doubly
intercalated MMT. The latter was prepared as described above, with dimethyl
hydrogenated tallow -2-ethyl hexyl ammonium methyl-sulfate (2MHTL8),
described in a prior patent from SCP [Dennis, 1998]. Polyacrylate (e.g., Alcogum
SL-76 or SL-78) was applied at a concentration of about 0.5 wt% by weight of
the dry clay. The slurry was dewatered, dried and ground. The extrudates were
subjected to wide angle XRD – total exfoliation was observed in CPNC with
clay content of ≤5 wt%.
2.3.6.4 Intercalation Utilising Macrocyclic Oligomers (Cyclomers)

The two-step intercalation process was used to produce CPNC with
polycarbonates, polyesters or polyphenylene ethers as the matrix polymer. The
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first step was the customary onium ion exchange, the second incorporation of
macrocyclic oligomers of these polymers [Takekoshi et al., 1996]. As in many
prior patents, the onium ion could be either ammonium, phosphonium or
sulfonium type. For example, MMT (CEC = 1.19 meq/g) was first intercalated
with dodecylammonium chloride or N-hexadecyl pyridinium chloride. Next, the
organoclay was mixed with a macrocyclic oligomer of terephthalic acid-co-
ethylene-co-butylene glycols, dried under a vacuum and then placed in an oil
bath at 190 °C. Finally, dioctyl tin dioctoxide was added to polymerise the
oligomer. The melt became viscous in about 15 s and the resulting solid polymer
composition comprised exfoliated MMT.
2.3.7 Intercalation by Inorganic Intercalants

There is a large body of literature dedicated to the physicochemical modification
of clays for use as catalysts or catalyst supports [see for example Pullukat and
Shinomoto, 2001; Wypart et al., 2002; Sun et al., 2002]. During the last few
years there has been an effort to use the insight gained into the chemistry of clays
for the production of inorganically intercalated clays. It is expected that these
new intercalated clays will have much greater thermal stability than the currently
used ammonium-intercalated systems.
During intercalation with inorganic intercalants pillared structures are formed
between clay layers. Cations of Al, Zr, Be, Cr, Fe, Ni, Nb, Ta, Ho, and others
have been used individually or in mixtures. Since the intercalated clays are
subjected to calcination at T ≅ 600 °C and are mainly used in catalysis, high
temperature stability has been essential [Mitchell, 1990]. However, even in
catalysis this technology is new and (the starting material being a natural product)
the reproducibility of created structures is poor. The use of inorganically-
intercalated clays for PNC is in statu nascendi.
Hydrothermally stable porous structures were prepared by intercalating a
smectite clay (e.g., MMT) with aluminium and rare earth salts, then calcination
at T < 760 °C [McCauley, 1989]. The pillars were formed of Al and rare earth
element oxides. They expanded the silica plates to an interlayer spacing of
1-5 nm. In 1979 Vaughan et al. [1979] dispersed smectite clay in an aqueous
solution of aluminium chlorohydroxide (AlCl2OH) and mixed the suspension
for about one hour at about 70 °C. The reacted clay was recovered and heated at
T = 200-700 °C to form solid pillars between the clay layers of 0.9-1.8 nm height.
Addition of ZrOCl2 increased the interlayer spacing to 2.2 nm. The pillars
collapsed when heated to T > 650 °C. Katdare et al. [2000] reported that
Na-MMT dispersed in water was mixed with AlCl2OH and subjected to ultrasonic
agitation at 50 kHz for 20 min. After washing, the intercalated clay was calcined
at 500 °C. Surprisingly, the XRD scan did not show any peak within the expected
range of 2θ, which may indicate total exfoliation. This is promising news –
hopefully, after some ‘compatibilisation’ step, these exfoliated individual clay
platelets may be incorporated into a polymeric matrix.
A Dow patent [Nichols and Chou, 1999] is the only one that professes to
produce inorganically intercalated clays for the manufacture of CPNC. The
intercalation involves organic and inorganic intercalants:
1. The clays of interest include MMT, nontronite, beidellite, hectorite, saponite,
magadiite and vermiculite, double or mixed hydroxides, viz.
Mg 6 Al 3.4 (OH) 18.8 (CO 3 )1.7H 2 O, chlorides, viz. ReCl 3 and FeOCl,
140
chalcogenides: TiS2, MoS2, and MoS3; cyanides, e.g., Ni(CN)2; and oxides
H2Si2O5, V5O13, HTiNbO5, Cr0.5V0.5S2, W0.2V2.807, Cr3O8,MoO3(OH)2,
VOPO4-2H2O, CaPO4CH3-H2O, MnHAsO4-H2O, Ag6Mo10O33, etc.
2. The organic intercalant may be a water soluble polymer (e.g., PVAl, PEG,
carboxymethyl cellulose, PAA, P4VP); a reactive organosilane compound, a
cationic surface active agent such as quaternary ammonium salt having C12
to C18 moieties. The preferred quaternary ammonium cations may have such
groups as: octadecyl trimethyl, dioctadecyl dimethyl, hexadecyl trimethyl,
dihexadecyl dimethyl, tetradecyl trimethyl and ditetradecyl dimethyl.
3. The inorganic intercalant can be an inorganic polymer obtained by
hydrolysing a metallic alcoholate: Si(OR)4, Al(OR)3, Ge(OR)4, Si(OC2H5)4,
Si(OCH3)4, Ge(OC3H7), Ge(OC2H5)4, etc. The colloidal particles include the
hydrolysed and dehydrated forms, e.g., Si(OH)4 or SiO2, Sb2O3, Fe2O3, Al2O3,
TiO2, ZrO2 and SnO2, etc. The size of the colloidal particle should be about
12 nm. It is preferable to modify the multilayered material with a metallic
alcoholate, e.g., Ti(OR)4, Zr(OR)4, PO(OR)3, B(OR)3 and the like alone or
in combination, with Ti(OC3H7)4, Zr(OC3H7)4, PO(OCH3)3, PO(OC2H5)3,
B(OCH3)3, B(OC2H5)3. Metallic chlorides such as TiCl4, metallic oxychlorides
such as ZrCOCl2, and nitrate chloride can also be used.
4. The polymeric matrix can be thermoplastic, thermoset or elastomeric. The
specifically named polymers include PO (e.g., PP, HDPE, LLDPE, ultra low
density PE (ULDPE), EPR, EPDM, ethylene-acrylate acid copolymer (EAA),
EVAc), PEST, PA, PC, acrylics (viz. PMMA, methylmethacrylate-butadiene-
styrene terpolymer (MBS)), styrenics (e.g., PS, styrene-butadiene rubber (SBR),
high impact PS (HIPS), styrene-acrylonitrile copolymer (SAN), styrene-
butadiene-styrene terpolymer (SBS)), TPU, etc.
Prior to intercalating the clay is swollen in an aqueous (e.g., H2O with methanol
or butanol) or an organic liquid (e.g., DMF, DMSO, hydrocarbons, halogenated
hydrocarbons, benzene, xylene, cyclohexane, toluene, mineral liquids and oils).
For example, a mixture of swollen clay and the polymerisable inorganic intercalant
can be contacted with a hydrolysing agent for the polymerisable intercalant to
form the inorganic polymer. In general, hydrolysis is conducted at T > 70 °C.
Following intercalation, the clay is centrifuged and dried at 50-80 °C. The
intercalant may optionally be calcined at T = 450-550 °C. Intercalation increases
the original interlamellar gallery height of ≤ 0.4 to about 0.5 to 60 nm. Next, the
intercalated, layered material can be dispersed in a monomer, which when
polymerised would form the polymer matrix. Alternatively, it can be incorporated
in the molten or dissolved polymer.
Melt blending is the preferred method for preparing CPNC of a thermoplastic
polymer. Typically, the polymer is melted and combined with the desired amount
of the intercalated clay using an extruder, a Banbury or Brabender mixer, a
continuous mixer, etc. Melt blending is carried out in the presence of an inert
gas, such as argon, nitrogen or neon. Alternatively, the polymer may be dry mixed
with the intercalant, then heated in a mixer and subjected to a shear sufficient to
form the desired composite. Sufficient exfoliation is defined as when ≥ 80 wt%
of the clay platelets (aspect ratio p = 10-2000) are individually and uniformly
dispersed in the polymeric matrix.
The patent does not provide any example of CPNC preparation with a specific
polymer and there are no numerical values of performance. The claims are very
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broad, naming virtually any polymer, viz. a thermoset (e.g., phenolics, epoxy,
urethane or urea resin), or thermoplastic polymer (including PO, PC, TPU,
styrenics) or a vulcanisable or thermoplastic rubber (e.g., EPR, PU). Similarly,
the description of the performance is quite generous. The unnamed CPNCs showed
excellent balance of properties, viz. superior heat, chemical or ignition resistance,
barrier to diffusion of polar liquids and gases, yield strength in the presence of
polar solvents such as water, methanol, ethanol and the like, stiffness and
dimensional stability. They are useful in diverse applications viz. in business
equipment, computer housings, transport (automotive and aircraft), electronic,
packaging, building and construction industry, etc.
Bora et al. [2000] developed another method for the manufacture of
intercalated, thermally stable organoclay. Since the metal complexes with organic
ligands show good thermal stability, the authors expected that MMT intercalated
with an appropriate metal complex might show superior thermal stability to that
of onium cations. The aim of the work was to intercalate MMT with bulky,
three-dimensional cationic metal complexes with ligand X. Two were selected:
• Ni-CX1 ≡ [Ni{di-2-aminoethyl amine}2]Cl2 and
• Ni-CX2 ≡ [Ni{2,2´:6´,2´´-ter-pyridine}2](ClO4)2.
Na-MMT was converted to Ni-MMT by adding NiCl2 to an aqueous suspension of
Na-MMT (CEC = 1.14 meq/g). The Ni-MMT could also be complexed with
CX1 or CX2, but the structure was different from that obtained by ion exchange
between Na-MMT and either Ni-CX1 or Ni-CX2. This reaction was carried out
by adding Ni-complexes to an aqueous suspension of Na-MMT and allowing
the reaction to proceed for 0.5 h, e.g.:
Na-MMT + Ni-CX12+ → [Ni-CX1]-MMT + Na+
The product was separated, washed and then dried at 50 ± 5 °C in an air oven.
Analysis of the dried samples indicated that complexes were adsorbed by MMT
up to about 0.57 meq/g, i.e., up to stoichiometry. Oriented samples on glass
slides were dried at room temperature, 100, 150, 200, 250, 300, 350 and 400 °C
for about 1 h. XRD of [Ni-CX1]-MMT showed that on heating d001 decreased
from 1.45 at 50 °C to 1.35 nm at 250 °C. However, XRD of [Ni-CX2]-MMT
showed d001 = 1.94 at 50 °C, decreasing to 1.90 nm at about 350 °C. Accordingly,
the FTIR spectra showed characteristic bands of these complexes up to about
250 and 350 °C, respectively. Thus, the thermal stability of MMT intercalated
with Ni-CX1 and Ni-CX2 were found to be about 50 and 150 °C higher compared
to that of their metal complex salts.
The difference between Ni-CX1 and Ni-CX2 is noteworthy. In the former the
ligand is aliphatic, in the other it is aromatic. Ligands with aromatic rings in the
main chain show higher thermal stability than the aliphatic. This general
observation was confirmed by results for the free complexes and their MMT
salts. Furthermore, the interlayer spacing of [Ni-CX1]-MMT was significantly
smaller than that for [Ni-CX2]-MMT. This may be due to π-interactions between
the oxygen on MMT and the aromatic rings of Ni-CX2.
2.3.8 Melt Intercalation

In a sense, melt intercalation is a misnomer – in reality the goal of the process is
not so much intercalation as exfoliation of layered inorganic material in a molten
142
polymer. However, since melt exfoliation is rarely achieved, there is some rationale
for the term.
Melt intercalation is the preferred method for the preparation of CPNC with
thermoplastic matrix polymers. Usually, the polymer is melted and compounded
with intercalated clay using an extruder, an internal mixer, a kinetic-energy mixer,
etc. Compounding is carried out in the presence of an inert gas, e.g., N2.
Alternatively, the polymer is first mixed with a compatibiliser (e.g., its
functionalised homologue) then compounded with intercalated clay. Industrially,
CPNC is considered to be exfoliated when ≥ 80 wt% of clay layers (aspect ratio
p = 10-2000) are uniformly dispersed in the polymeric matrix in the form of
stacks comprising not more than two platelets.
It is remarkable that macromolecules with significantly larger radius of
gyration than the interlamellar gallery height:
1 /2
rg2 > d001 − 0.96
are able to diffuse into the galleries. Evidently, the process will take place only if
it leads to a decrease of the free energy (ΔG), i.e.:
ΔGintercalation = ΔH - TΔS < 0 (15)
The enthalpic (ΔH) contribution usually comes from the chemical interaction
between clay and the intercalating compound, whereas the entropic one (ΔS)
usually comes from the ‘randomisation’ of the macromolecular segments
placement, e.g., diffusion into spaces devoid of macromolecular presence.
However, the conformational energy loss caused by chain stretching from the
random coil configuration into elongated structures inside the galleys, and
associated with this the topographical and energetic constraints (e.g., caused by
adsorption of the macromolecules on the clay surface) hinders the diffusion.
Thus, it is expected that for successful melt intercalation there must be an enthalpic
driving force for the functionalised macromolecules. Furthermore, the interlayer
spacing should be large, at least the same order of magnitude as the diameter of
the macromolecular Gaussian coil, and sufficient time must be provided for the
diffusion process to reach the centre of the stacked platelets. Two relations can
be used as guides:
1. The self-diffusion coefficient, Ds ∝ 1/Mn2.
2. The distance travelled by the diffusing macromolecules is proportional to
the square root of the diffusion time, viz. ldiff ∝ t1/2.
In practice numerous factors influence the process, affecting the validity of these
simple relations.
The melt intercalation process can readily be divided into static and dynamic.
Usually, the static process takes place under vacuum at temperatures at least 50 °C
above the transition temperature (Tg or Tm) in the absence of mixing, thus often
it is also called melt annealing. Dynamic melt intercalation is more-or-less a
standard compounding operation, performed in an extruder, internal mixer and
similar processing equipment.
2.3.8.1 Quiescent (or Static) Melt Intercalation

There is no commercially viable process that would start with dry, unaltered clay
powder and thermoplastics melt and produce exfoliated CPNC. For example,
143
attempts at a solventless intercalation of Na-MMT or Li-MMT with PEG or PS

failed [Vaia et al., 1993]. However, PS was intercalated with an organoclay
(Na-MMT ion-exchanged with alkylammonium chloride) by mixing the two
powders, pressing the mixture into a pellet, and heating the pellet in a vacuum at
165 °C. XRD showed that PS increased the interlayer spacing by about 0.7 nm,
which corresponds to a monolayer of stretched PS macromolecule. Interestingly,
the intercalated PS had no Tg within the temperature range from 50 to 150 °C.
The lack of chemical bonding was demonstrated by dissolving/dispersing the
CPNC in toluene and quantitatively extracting the PS.
For PEG the static intercalation (heating the polymer/Na-MMT mixture at 80 °C)
was slow, requiring from 2 to 6 h. The achieved final interlayer spacing was modest,
d001 = 1.77 nm [Vaia et al., 1995a]. The method failed for PS – it was found that prior
to melt intercalation the MMT had to be modified by treatment with dimethyl tallow
organosilicate that expanded the interlamellar gallery to at least 0.7 nm. Furthermore,
the process led to intercalation, but not to exfoliation. PDMS-base CPNC was prepared
by ultrasonication of organoclay (MMT-2M2HTA) with silanol-terminated-PDMS.
The system was crosslinked using a mixture of tetraethyl orthosilicate (TEOS) and tin
2-ethyl hexanoate. Exfoliation was facilitated by the presence of water at a concentration
corresponding to about a monolayer on the clay surface [Burnside and Giannelis,
1995; 2000]. In the latter publication exfoliation in the crosslinked PDMS/dimethyl-
ditallow-MMT system was confirmed, but only intercalation (d001 increased from 2.5
to 3.9 nm) was obtained when a copolymer, poly(dimethyl siloxane-co-diphenyl
siloxane), with 14-18 mol% of diphenyl, was used instead of PDMS. Furthermore, not
even intercalation was achieved for either polymer with Na-MMT.
In another study, organoclay was prepared by reacting, e.g., Na-MMT with
2M2ODA [Vaia et al., 1994] or Li fluorohectorite (FH) with ODA [Vaia et al.,
1995b]. In the latter study, 25 mg of organoclay was mixed with 75 mg of PS and
formed into pellet, which in turn was heated at T > Tg(PS) ≅ 100 °C. Melt
intercalation took place in a quiescent system as a function of the annealing
temperature (Ta = 155-180 °C), annealing time (ta ≤ 400 min), and molecular weight
of the intercalating PS (MW = 30-300 kg/mol). The extent of intercalation was
determined from XRD. Thus the interlayer spacing of organoclay (d001 = 2.13 nm)
during annealing with PS (having MW = 30 kg/mol) progressively increased to
d001 = 3.13 nm. The amount of polymer (Q) that diffused into the interlamellar
galleries over time (t) followed the dependence:
∑ (4 / α ) exp{−( D / a )α }
∞
2
Q(t ) / Q∞ = 1 − m mt (16)
m −1
where: αm is the m-th positive root of the Bessel zeroth-order function, and D/a2 is the
effective diffusion rate. Its temperature dependence was found to follow the Arrhenius
equation with the activation energy ∂ln(D/a2)/∂(1/T) = Ea ≅ 166±12 kJ/mol. The
molecular weight dependence was found to follow the dependence: (D/a2) ∝ 1/MW1.6.
The authors observed that intercalation by PS of commercial interest
(MW = 300 kg/mol) at T = 250 °C should take about 10 min. The melt annealing
would not result in exfoliation. There is no information about how the terminal
interlayer spacing depends on the molecular weight of the intercalating polymer.
In the following contribution by the same authors [Vaia et al., 1996] the
quiescent melt intercalation was conducted not only with PS (PS30 and PS400
with MW = 30 and 400 kg/mol, respectively) but also with poly(3-bromo styrene)
144
(PS3Br; MW = 55 kg/mol). The microstructure of the organoclay/polymer systems

was examined by XRD and high-resolution transmission electron microscopy
(HRTEM). In contrast to the averaging of XRD, HRTEM provides information
on local structure, spatial distribution of structural elements and defects.
When PS30 was used, the same interlayer expansion was observed as that
reported earlier, viz. d001 = 2.13 increasing to 3.13 nm. The HRTEM showed the
presence of ordered clay microstructures similar to that observed for non-
intercalated (by PS) organoclays, but slightly expanded. The publication in part
answers the earlier question as to whether the final interlayer spacing depends
on the polymer molecular weight. Partial intercalation by PS400 resulted in
similarly ordered structure as that observed for PS30, but the intercalated regions
expanded more, viz. the measured interlamellar spacing of 2-3 nm, compared to
2.17 determined for PS30. Since the unperturbed radius of gyration for PS30 and
PS400 coils is: <r2g>1/2 ≅ 5 and 18 nm, respectively, in neither case would the
interlayer spacing accommodate the Gaussian coil in 3D.
Intercalation by PS400 was only partial. The HRTEM micrographs showed
domains of intercalated and of non-intercalated (by PS) clay platelets with diameter
ranging from 0.05 to 0.5 μm formed by stacks of 50 to 100 parallel platelets. In
the intercalated and non-intercalated domains the number of layers in the stack
was similar – intercalation by PS just pushed the layers further apart. On the
basis of the HRTEM information it was concluded that polymer intercalation
occurs as a front that diffuses into organoclay interlamellar galleries from the
external edges. The non-intercalated (by PS) domains were more prevalent towards
the centre of the stack. Structural defects in the clay crystalline structure and
irregularities in the layer stacking have been observed.
In contrast with the PS-intercalated layered stacks, intercalation with PS3Br
resulted in exfoliation, evidenced by the lack of a well-defined XRD peak as well
as by the HRTEM micrographs. Evidently, the presence of -Br brings about
stronger interaction between the intercalated clay and the polymer than that
existing between clay and PS. Since the clay was intercalated with the primary
octadecyl ammonium, interaction between -Br and either C18-NH3+ or with -OH
groups at the platelets edges is possible. As observed under HRTEM, individual
platelets were intermixed with small stacks of 10 to 20 platelets with the interlayer
spacing ranging from 2.1 to 6.0 nm. The heterogeneous microstructure indicates
that the formation of these systems occurs by a more complex process than simple
sequential intercalation of individual layers starting from the surface of the primary
particle. The clay crystalline structure may contain defects or chemical
inhomogeneities that facilitate polymer transport or result in enhanced polymer-
silicate interaction. Long-range electrostatic forces tend to maintain layer stacks.
However, exfoliation most likely takes place layer-by-layer from the limits of the
original organoclay stack.
The earlier studies of PS/organoclay [Vaia et al., 1993] led to the conclusion
that PS macromolecules form monolayers inside the organoclay galleries. This
significantly changes the chain dynamics, e.g., resulting in absence of Tg for PS
within the expected range of 50-150 °C. Evidently, the presence of the onium
compound in the galleries must have influenced the macromolecular behaviour,
but the effects of 2D steric restriction must have also affected the chain dynamics.
Krishnamoorti et al. [1996] melt intercalated lightly deuterated PEG
(Mw = 180 kg/mol, Mw/Mn = 1.2) into Li-FH. The system was probed using
thermally stimulated current (TSC), XRD, DSC, SANS and solid-state NMR.
145
PEG chains were confined to 0.8 nm galleries. The 2H-NMR spectra were obtained
at the same temperatures for the bulk and the intercalated d-PEG. As the
temperature increased from 220 toward 250-270 K, a central peak of the
intercalated d-PEG developed earlier and became narrow. Thus, the enhanced
local chain dynamics of the intercalated d-PEG at low T may have resulted from
the absence of chain entanglements. However, within the high T-range
(T = 320-340 K), the intercalated d-PEG showed a broad base structure, whereas
the bulk d-PEG had a single narrow signal, indicating that the silicate layers
restrict macromolecular chain motion. Intercalation into the narrow interlamellar
space with height of 0.8 nm must have engendered interactions (hydrogen
bonding?) between the PEG segments and the platelet surface. Furthermore, the
narrow space between the clay layers topologically restricted the d-PEG chains.
The DSC experiments on an intercalated CPNC indicated the absence of any
thermal transitions of PEG; Tg or Tm. However, TSC suggested that the transition,
which in bulk PEG takes place at about Tg = -55 °C, upon intercalation increased
to Tg ≅ 60 °C. The TSC peak for the intercalated system was broad and shallow,
indicating a low level of molecular cooperativity near Tg.
The most comprehensive studies of the quiescent intercalation of organoclay
by molten polymers included: several intercalating organic cations, synthetic and
mineral clay, polymers (different chemically and with different molecular weight)
and annealing temperature [Vaia, 1995; Vaia and Giannelis, 1997a,b]. The
material characteristics are given in Table 18.
Table 18 Material characteristics for quiescent melt intercalation

[Vaia and Giannelis, 1997b]
Component Code Characteristics
Clays F Li+-fluorohectorite; CEC = 1.5, a = 0.39, Corning Inc.

S Li+-saponite; CEC = 1.0, a = 0.58, Southern Clay
M Products
Na+-MMT; CEC = 0.8, a = 0.72, Swy-1, U. Missouri,
Source Clay Repository
Ammonium 2C18 Dimethyl dioctadecyl ammonium bromide (2M2ODA)

salts Q18 Tri-methyl octadecyl ammonium bromide (3MODA)
Cn n-Alkyl-ammonium chlorides (CnH2n+1NH3+Cl-, with n =
6, 9-16, and 18)
Polymers PS30 Polystyrene; Mw = 30, Mw/Mn = 1.06, Tg = 96 °C

PS90 Polystyrene; Mw = 90, Mw/Mn = 1.06, Tg = 100 °C
PS400 Polystyrene; Mw = 400, Mw/Mn = 1.06, Tg = 100 °C
PS3Br Poly-3-bromo styrene; Mw = 55, Mw/Mn = 2, Tg = 113 °C
PVCH Poly(vinyl cyclohexane); Mw = 97, Tg = 120 °C
PVP Poly(2-vinylpyridine); Mw = 150, Mw/Mn = 2.1,
Tg = 104 °C
Notes: CEC = cation exchange capacity (meq/g)

a = clay surface area per cation (nm2)
Mw = weight-average molecular weight (kg/mol)
Tg = glass transition temperature (°C)
146
As before, dry organosilicate (25 mg) and polymer powder (75 mg) were
mechanically mixed and formed into a pellet using a hydraulic press at a pressure
of 70 MPa. Melt intercalation was carried out by annealing the pellet in vacuum
at T > Tg. Usually the samples were annealed to equilibrium, indicated by no
further changes in the X-ray diffraction pattern. The work brought out several
important observations:
1. Of the three clays the largest value of d001 was systematically observed for F
and the smallest for M, having, respectively, the highest and the lowest CEC
value. Note also that for the three clays there is a difference in the distribution
of the anionic charge on the silicate surface. The increased localisation of
surface charge for tetrahedrally-substituted S does not appear to affect CPNC
formation when compared to the more dispersed surface charge of
octahedrally-substituted M.
2. Li+-fluorohectorite (FH, clay F) was intercalated with the primary ODA (F18)
and subsequently annealed with each of the three PS. XRD showed intercalation
with d001 = 3.11 nm. However, while the intercalation for PS30 was achieved
after annealing for less than 6 h at 160 °C, to intercalate with PS90 took 24 h,
and PS400 more than 48 h. Since the XRD peak was quite similar for the three
polymers it was concluded that the kinetics of intercalation are strongly affected
by the polymer molecular weight, but that the structure of CPNC prepared
under quiescent conditions is independent of it.
3. The ammonium salt used in the cation exchange may have an important
effect on intercalation by molten polymer. Two aspects are worth stressing:
a. At T = 160 °C PS30 was unable to diffuse into the interlamellar galleries
of the F-clay intercalated with alkyl-ammonium chlorides having n ≤ 12.
Intercalation with alkyl ammonium with n = 6 to 12 engendered the
same initial expansion of the interlayer spacing, viz. d001 ≅ 1.8 nm (see
also Figure 23), but apparently alkyls with n < 12 do not sufficiently
shield the hydrophilic clay surface to assure PS interpenetration.
Annealing with PS30 at T = 180 °C expanded even F8 to the maximum
spacing d001 ≅ 3.1 nm, i.e., increasing the gallery height by about 1.1 nm.
This maximum value was found to be independent of the alkyl cation,
of the annealing temperature, and of the PS molecular weight.
b. The difference between primary and quaternary ammonium cations
can be evaluated by comparing the intercalation of PS30 into FC18
(primary) with that into FQ18 (secondary) and F2C18 (quaternary).
For the three compositions the interlayer spacing was found to be,
respectively, d001 ≅ 3.11, 3.64 and 3.80 nm. Thus, all three cations
facilitated the secondary intercalation by PS, but different types of
ammonium cation did influence the final gallery height. The difference
could originate in the difference in the ionic interaction strength for the
primary, secondary and quaternary onium ions as well as in the size of
the quaternary group.
4. Melt intercalation also depends on the chemical nature of the intercalating
macromolecules. Thus, in this series of styrene-derivative polymers with
M2C18 the interlayer spacing increased with the relative acid/base character
and the side-group polarisability in the order: poly(vinyl cyclohexane) (PVCH)
<< PS < PS3Br < PVP, giving d001 = 2.38, 3.20, 3.34 and 3.38 nm, respectively.
Thus, secondary intercalation was observed for all polymers, except PVCH.
147
On the other hand, none of the polymers intercalated F2C18, leaving the
initial (after cation exchange) spacing, d001 = 3.80 nm, unchanged. It is
noteworthy that the latter spacing is larger than that observed for doubly
intercalated MMT.
5. The kinetics of secondary intercalation under quiescent conditions inversely
depend on the molecular weight:Mmw , where the exponent m = 1.6 to 2.0
(exponent m = 2 is expected for pure chain reptation at T - Tg = constant).
Such dependence suggests that secondary intercalation is related to the self-
diffusion process. In the series of polymers: PS, PS3Br and PVP, even after
taking into account the differences in MW, intercalation for PS required
annealing for about 4 h, whereas that for the other two polymers for more
than 24 h. This again agrees with the self-diffusion behaviour theory, viz. the
stronger the interchain interactions the smaller the self-diffusion coefficient
[Kausch and Tirrell, 1989].
The question that remained unanswered is whether exfoliation in a quiescent
melt intercalation process is possible at all. Via and Giannelis [1997b] considered
exfoliation to be kinetically-limited, i.e., that transport of the clay platelets to
effect exfoliation would take a prohibitively long time, hence external forces are
needed (shear flow, ultrasonication, etc.). This idea found support in the work
published three years later [Huang et al., 2000] which focused on the preparation
of CPNC with PC as the matrix. The organoclay was MMT cation exchanged
with 2M2TA. The secondary intercalation was performed using either a polymer
(PC; Mw = 25 kg/mol) or a cyclic carbonate oligomer (OCC; Mw = 2 kg/mol).
The quiescent samples were prepared either in solution or in the melt. Thus,
0.5 g of organoclay was added to a solution of 10 g of either OCC or PC in
50 ml of CH2Cl2. After 5 min at room temperature, the solvent was removed
under vacuum and the residue was dried in the vacuum oven at 50 °C overnight.
As before, 10 g of either OCC or PC was mixed with 0.5 g of organoclay, pressed
into pellets with a hydraulic press and heated to 180 °C in a vacuum oven for 1 h
followed by heating at 240 °C for 15 min.
XRD showed that solution or melt intercalation with PC produced the basal
spacing d001 = 2.47 nm, virtually identical to that of organoclay. Several hours of
mixing would be required to increase the interlayer to d001 = 3.27 nm. Intercalation
with OCC was more successful as it caused the interlayer spacing to rapidly
increase to d001 = 3.62 nm. Thus, as was the case with styrene-derivative polymers,
here also the difference between the oligo- and poly-carbonate amounted to the
kinetics of intercalation. The difference in chain structure (cyclic versus linear)
may have also contributed to the intercalate formation. Next, the melt intercalated
(with OCC) organoclay was added to an internal mixer and processed at 100 rpm
at 180 °C for 1 h, then at 240 °C for 10 min, causing ring-opening polymerisation.
XRD of the material showed no peak and TEM revealed that a partially exfoliated
structure was obtained. However, when PC was similarly mixed, only an
intercalated system was obtained.
In conclusion, there is still no clear answer to the question as to whether
exfoliation in a quiescent melt intercalation process is possible. In the case of a
PC/organoclay system the initial spacing was small, which indicated an absence
of PC in the interlamellar galleries, hence exfoliation would not be expected. For
the OCC/organoclay system two elements worked in favour: (1) to start with,
much larger interlayer spacing, and (2) polymerisation that engendered
148
macromolecular coil formation that expanded the interlayer space the same way
as reported for the reactive intercalation of PA-6 (see Figure 25).
As will be shown in Section 3.1, the free energy of mixing as a function of the
interlamellar separation height may have a local minimum, thus intercalation
but not exfoliation is the thermodynamically favoured state. Fundamentally, flow
(energy) should help, but the magnitude of the imposed stresses must be
comparable to the attraction forces between clay platelets which hyperbolically
decrease with the interlamellar gallery height (see Figure 18). Thus, the shear
stress of about 1 kPa would not be sufficient to significantly affect the interlamellar
spacing from 2 nm, but conceivably so from 4 nm.
2.3.8.2 Dynamic Melt Intercalation

The terms ‘intercalation’ and ‘exfoliation’ refer to the degrees of dispersion of
layered silicates in a matrix. For maximisation of the filler effects on CPNC
performance (e.g., such as the barrier properties or the tensile/compressive
modulus) the maximum degree of dispersion is desired. Thus, intercalation is
only an intermediate step that is expected eventually to result in exfoliation – the
main goal of CPNC manufacturing. Hence, melt intercalation is a process that
either was designed to lead to intermediate products (for example, to study the
effects of different process parameters) or that failed to achieve the principal
objective – exfoliation.
It was pointed out by Lan et al. [2000] that melt exfoliation by polar, water-
soluble monomers, oligomers or polymers may take place in the presence of at
least 10 wt% H2O. The process may increase the interlamellar spacing all the
way to total exfoliation once a minimum interlamellar gallery space is created by
an exchange reaction of Na-MMT with organic cations. Similarly, melt exfoliation
of a neutral P4VP was found feasible if an acidic clay or suitably modified clay
was used as the inorganic component.
Dynamic intercalation and exfoliation of hydrophilic polymers (e.g., PEG,
EVAc, PVP, etc.) was mentioned earlier in Section 2.3.5.2. Further details will be
discussed in Section 4. Here only melt intercalation in hydrophobic systems will
be considered.
2.3.8.2.1 Melt Mixing

Melt intercalation is part of polymer mixing and compounding operations. This
laminar flow, in which the streamlines are smooth, comprises two types of flow:
dispersive (or intensive), which involves the application of stresses that break
domains of the dispersed phase to the desired size, and distributive (or extensive)
that involves homogenisation of a fluid, accomplished by the application of strain.
Melt intercalation is mainly concerned with dispersive aspects, but homogeneous
distribution of intercalated platelets or tactoids must also be achieved.
Virtually all the dispersive mixers (see the following Section) employ the shear
flow field that contains the vorticity stress components causing rotation of the
flow elements. This causes the aggregates to be repetitively stretched and
compressed. The process is inefficient, requiring the use of large amounts of
energy for little effect. Better efficiency can be achieved in the extensional flow
field, but generation of these flows is more difficult [Utracki and Shi, 2002; Utracki
and Luciani, 2000]. There is no theory capable of describing the dispersive
processes in viscoelastic media, or even one that provides explanation for the
149
divergent observations. The complexity of the problem involves three-

dimensionality, free surface, and non-stationary flow leading to complex
constitutive equations. The role of melt elasticity is not well understood and the
aspect of nonlinear viscoelastic behaviour in complex flow is mostly unknown.
An elongational flow field exists anywhere where the streamlines are not
parallel. This type of deformation is quite common during processing, viz. in
fibre spinning, film blowing, blow moulding, biaxial and uniaxial stretching and
similar operations carried out downstream from the die. However, these operations
have little to do with mixing. Nevertheless, the extensional flow field has been
used to generate orientation either in homopolymers or in filled or reinforced
systems. Convergent flow results in high fibre alignment in the flow direction,
whereas diverging flow causes the fibres to align 90° to the major flow direction.
Shearing reduces the alignment. Progress in the fundamental understanding of
microrheology led to designing a fully adjustable extensional flow mixer (EFM)
and its dynamic version, the DEFM, now available on the market [Song, 2000].
The use of an EFM for dispersing nanoparticles in polymeric matrix has been
successful in several research laboratories.
Mixing provides enhanced spatial homogeneity of a system, but assessment
of the quality of a mixture is difficult and time consuming. In a binary mixture of
A and B, the local concentration (in weight fraction) can be expressed as: a(x) +
b(x) = 1 (where x denotes vectorial location). Similarly, the sum of the average
compositions: aav + bav = 1. For such a system, the mixedness can be described by
the binary frequency function. For fine dispersions, variance of the composition
(σ2a), and the intensity of segregation (Is), may be defined as [Tucker, 1991]:
[
σ 2a = a( x ) − aav ]
2
and I s = σ 2a / aav bav (17)
2.3.8.2.2 Mixing Equipment

As summarised in Table 19, the melt mixers are either batch or continuous type.
The former require lower investment cost, but are more labour-intensive, have
low output and poor batch-to-batch reproducibility. Recent developments in
process control and automation have eliminated some of these disadvantages.
Continuous melt mixers comprise: extruders, continuous shaft mixers and
speciality machines. Several overviews of melt mixing are available, viz. [Utracki
and Shi, 2002; Tucker, 1991; Manas-Zloczower and Tadmor, 1994; Rauwendaal,
1998], etc.
Batch mixing is not efficient for handling large capacities, but it is well suited
for short-runs, e.g., for the manufacture of colour-concentrate masterbatches, or
products that have to have tailored identity. Because of the high stresses, an
internal mixer can complete a cycle in minutes. The residence time, shear,
temperature and, frequently, pressure may be controlled. These processing
parameters may be of critical importance while compounding heat-sensitive
materials or dispersing nanofillers. The most popular batch-type mixers are the
laboratory type manufactured by, e.g., Brabender or Haake, and their homologues
on the larger scale manufactured by, e.g., Banbury or Moriyama as dispersion
mixers.
The most serious drawback of the laboratory internal mixers is the heat
conduction by the mixing shafts. The mixer chamber is only heated from the
outside and the shafts conduct the heat away from the molten polymer.
150
Table 19 Melt mixing machines [Utracki and Shi, 2002]
Machine N P RTD Feeding* Dispersive Distributive
Powder Filler Sticky as such with as such with
additions additions
Internal mixer
Batch + - - + + + + +
Continuous 0 - - + + + + +
SSE + + - 0 - - - 0 - 0
TSE - CORI ++ 0 + + + 0 + + 0 +
TSE - ICRR + + + + 0 + + + - 0
TSE - CRNI + - - + + + - 0 - 0
Special
Pin-barrel + 0 0 0 - + + +
Kokneader 0 - + + + + + +
Planetary gear - - + 0 - - ++ 0
Disk + + + 0 0 - 0 + 0 +
Symbols: N - high screw speed, P - pressure generation, RTD - residence time distribution.
* Capability to be fed with difficult material, distributive and dispersive mixing without and with extra mixing elements or devices
CORI - co-rotating intermeshing
ICRR - intermeshing counter-rotating
CRNI - counter-rotating non-intermeshing
Evaluating symbols: + means good, 0 means acceptable, and - means poor
151
During mixing at relatively low temperatures and relatively high rotational speed
of the mixing shafts, a dynamic equilibrium may be reached, i.e., the heat from
the outside heaters is transferred to the melt, then to shafts that conduct it to the
internal drive system of the mixer. The dynamic equilibrium means that the higher
temperature is at the chamber wall and lower on the shafts’ surface. The difference,
ΔTchamber, of these two temperatures depends on the temperature difference between
that desired within the mixer and the ambient, the heat conductivity of the mixed
compound and shaft material, on screw speed, etc. Under the conditions securing
a rapid exchange of material within the mixer chamber, good mixing may reduce
ΔTchamber. However, while compounding the engineering or speciality polymers
with high Tg or Tm, the temperature drop across the chamber was determined to
be as large as ΔTchamber ≈ 100 °C.
Continuous mixing involves the continuous loading and unloading of
components. When properly performed, mixing decreases the compositional
variations to the desired level. Continuous operations have the advantage of
providing a stable process. The power consumption is usually lower than in batch
mixing. The stresses are imposed systematically, either in the shear or in the
shear-and-elongation mode of deformation. In spite of high capital costs and
complex mixing, continuous mixing is easy to justify on the basis of the production
volume (mixers with throughputs of up to 80 ton/h are available) and quality.
The continuous mixers make it possible to control: the feed rate, screw speed
and temperature, as well as the discharge orifice setting and temperature, but the
accessible range of residence times is small.
Extrusion is one of the most important forming methods in polymer processing.
Virtually all polymers go through an extruder at least once, viz. compounding
and pelletising reactor powders. The extruders are classified according to the
principal element of their construction, as:
• Single-, twin-, and multi-screw extruders.
• Single-, twin-, and multi-shaft compounders.
• Gear or disk extruders, e.g., Maxwell Melt-elasticity Extruder, Tadmor’s Disk
Extruder.
• Special extruders, e.g., Gelimat, Patfoort, etc.
Single-screw extruders (SSE) are relatively inexpensive machines for small or
medium size production lines. They are difficult to scale-up, notoriously poor
mixers with broad residence time distribution (excepting the case of plug flow of
compositions with the yield stress) and relatively long residence time. Over the
years, SSEs have been made more versatile by the introduction of special mixing
screws, by using add-on mixing devices, by utilisation of two or more extruders
operating in tandem, etc. The SSE operates under fully flooded conditions, thus
the quality and throughput depend on the screw speed, and to a lesser extent, on
feed. A summary of performance criteria of SSE and TSE is presented in Table 20.
Mechanically, a major difference between SSEs and TSEs is the type of
transport that takes place within the extruder; in the former it is drag-induced
(frictional drag in the solid conveying zone and viscous drag in the melt conveying
zone). There are many materials with unfavourable frictional properties that
pose severe feeding problems. In intermeshing TSEs the transport is by positive
displacement. Its degree depends on how well the flight of one screw closes the
opposing channel of the other screw. The most positive displacement is obtained
152
Table 20 Summary of the differences between SSEs and TSEs

Function SSE TSE
Degree of channel Fully filled Partially filled

fill
Throughput (Q) is Screw speed, N Feed rate

determined by:
Total strain Independent of Q and N Dependent on Q
Shear strain Low High, controllable
Material transport By friction (drag flow) Positive conveying
Material flow path Smooth, regular thinning Tortuous, diverse
Heat transport Ineffective Effective
Liquid and powder Present problems Do not present problems

additives
High viscosity Impossible to disperse Can be dispersed

additives
Mixing capability Poor Good, adjustable
Extruder length for Long Very short

melting
Extruder length for Long Short

mixing
Advantages Easy to make, High flexibility (modular

inexpensive, theory of its design), effective feeding,
operation well developed, devolatilisation, mixing,
lot of experience reactive processing
Disadvantages Lack of flexibility, Difficult to manufacture, cost

difficult feeding, up to 10× that of SSE, early
ineffective devolatiliser stage of theoretical analysis,
and mixer, not suitable narrow residence time
for reactive processing, distribution, requires accurate
low stress and strain feeders
in a closely intermeshing, counter-rotating geometry. In SSEs the velocity profiles

are well defined and fairly easy to describe, while in a TSE the flow is considerably
more complex, which results in several advantages, viz. good mixing and heat
transfer, large melting capacity, good devolatilisation capacity and control over
the stock temperatures. However, the theory of TSE is not nearly as well developed
as that of SSE.
153
By contrast with the SSE, the TSE operates with partially filled screws. The
polymer from a feeder is transported toward the pressure zone, usually created
by a flow restrictor, e.g., a left-handed or reverse screw element. Under the pressure
the resin pellets are compressed into a solid plug, which fractures and melts
mainly by friction between its fragments and the wall. Thus, melting in a TSE is
more efficient than that in a SSE – its length can be as short as less than one
screw diameter, L ≤ D. There is evidence that melting in a TSE affects the
generation of polymer blend morphology differently to that in a SSE. The modular
design of screws and barrel is universally accepted. Many TSE manufacturers
still insist that to control the dispersive-to-distributive mixing ratio simply the
width of the mixing block should be used – a set of narrower blocks results in
more distributive, and less dispersive mixing and vice versa.
As shown in Table 21, seven types of TSE are possible; of these three (marked
in bold below) are the most popular in the plastics industry:
I. 1A, screw: L-open & C-closed, discs: L& C-open (CORI - the most popular).
II. 1B, L & C-open (rare)
III. 1C, L & C-open (rare)
IV. 2A, L & C-closed (ICRR)
V. 2B, L & C-open
VI. 2B, L-open & C-closed (rare)
VII. 2C, L & C-open (CRNI)
For many years, CORI has been the compounder of choice. Its advantage arises
from the movement of the intermeshing surfaces in opposite directions, thus the
melt free surface is continuously renewed and the screws clean each other. In
addition, since at the intermeshing the material passes from one screw to the
other (change of the drag direction) there is low probability that the material
would go through the gap. Thus, there is no calendering pressure that may cause
the screws to bend. As a consequence, CORI has been able to operate at higher
screw speeds with longer barrel than ICRR, which is considered advantageous
especially for reactive processing. However, during the last ten years or so, several
manufacturers of these two types of extruders have demonstrated that in unbiased
tests ICRR may equal or even outperform CORI as far as the compound quality
and the throughputs are concerned. Even at lower screw speed ICRR frequently
showed better performance than CORI. This resulted in renewed interest in
redesigning ICRR, e.g., providing it with higher screw speeds and longer barrels.
Table 21 TSEs are classified into three categories

Screw rotation Intermeshing Confinement
1. Co-rotating A. Intermeshed a. Lengthwise closed or open

(L-closed or open)
2. Counter-rotating B. Tangential b. Crosswise closed or open

(C-closed or open)
C. Separated
154
Originally ICRR was developed as a positive displacement screw pump for viscous
fluids. This is the only TSE type that is fully, axially and radially, closed. The
extrusion speed depends on the intermeshing geometry and the screw speed. The
fully intermeshing ICRR has a narrower distribution of residence times and better
precision in controlling rapid reactions between liquid reagent and molten polymer
than a CORI. The low speed ICRRs have been used for PVC compounding and
forming. At higher screw separations and speeds, the machines can be used for
the incorporation of high viscosity toughening elastomer. To make ICRR fully
competitive with the more popular CORI the calendering gap between screws
was widened, reducing the high stresses and increasing the intensity of shearing
between the screws and the barrel. For some applications, ICRR offers the unique
advantage of a strong extensional flow field, able to disperse high viscosity
ingredients in a low viscosity matrix. A summary of the relative merits of CORI
and ICRR is given in Table 22.
In CRNI the material flow is based on a drag, not positive pumping. There is a
low shear stress field, responsible for the absence of dispersive mixing. However, the
interchange of material between the screws provides good distributive mixing. The
chemical reaction proceeds on the continuously renewed surfaces, related to
reorientation of the laminar flow patterns and the total strain. CRNI is well suited
for the polymerisation of miscible, low viscosity systems. The main advantage of
CRNI is a long enough residence time, sufficient to complete slow processes. CRNI
can offer larger outputs, and more interchange of material between the two screws
than the other types of TSEs. These machines are frequently used for the preparation
of composites with fibrous fillers. It is noteworthy that the closer the clearances and
intermeshing the more rapid the build-up of pressure, the narrower the lands and the
larger the clearances between screws, the greater the longitudinal mixing.
Within a TSE the shear and extensional stresses are generated by interactions
between two screws. The stress magnitude depends on the relative direction of the
screw rotation (co- or counter-rotating), shapes of the screw elements, the degree
to which they intermesh, and the rotational speed of the screws. The modular
design of a TSE makes it possible to adjust the relative magnitude of the distributive
and dispersive mixing. The TSE performs a series of different functions. There is a
continuous pressure toward bigger machines with higher ‘free volume’, with longer
barrels and higher screw speeds. CORI with L/D = 100, D ≤ 455 mm and screw
speeds of up to 2500 rpm are commercially available [Sakai, 2002].
Recently Nanocor published a CORI screw design for the manufacturing of
CPNC with PO as the matrix [Qian et al., 2001]. A Leistritz TSE with D = 27 mm
and L/D = 36 was used at 300-500 rpm and T = 170 to 190 °C (see Figure 30 and
Table 23) [Nanocor Technical Services Group, 2001]. Two vents at 13D and
24D were used. The melt exfoliation involved a two-step process:
1. Preparation of masterbatch containing 50-60 wt% of organoclay a
compatibiliser and matrix polymer (e.g., PP-MA and PP), and
2. Dilution to the desired clay content (e.g., 2-7 wt%).
Alternatively, a single-pass procedure can be used replacing the first vent with a
side stuffer, through which the diluting quantity of matrix polymer is fed [Nanocor
Technical Services Group, 2001].
Besides the ‘classical’ extruders (SSE and TSE) there are several less well-
known compounders. Of these the planetary roller extruder is the oldest. Here,
six or more evenly spaced planetary screws revolve around the circumference of
155
Table 22 Advantages and disadvantages of CORI and ICRR type TSEs
156
Extruder Advantages Disadvantages
Co-rotating, • Self cleaning • Capital cost
intermeshing, CORI • Dispersive and distributive mixing in transverse and • Only residence times below about 10 min are
longitudinal direction economic
• Lower than in ICRR, uniform and controllable • Limited ranges of pressure and vacuum
stress are available
• Good control of resin degradability
• Local pressure control
• High screw speeds and throughputs
• Local high vacuum possibilities
• Double-walled barrel for rapid temperature changes
• High specific energy input possible
• Residence time up to one hour
Counter-rotating, • Self cleaning • Transverse mixing is moderate
intermeshing, ICRR • High dispersive mixing in the shear and extension • Longitudinal mixing is poor
• It can accommodate multi-lobal mixing elements of • Only residence times below 10 min are economic
the gear type with excellent dispersive mixing • Limited screw speed
capabilities • Capital cost
• It has better specific energy than CORI
• It has narrower residence time distribution than
CORI
• High local pressures possible
• High local vacuum possible
• Better devolatilisation capability than CORI
• High specific energy input possible
• Shorter screws than in co-rotating
• Easy separation of desired functions, viz. mixing,
devolatilisation, chemical reaction, compounding, etc.
Table 23 CORI TSE screw configuration for melt compounding of

CPNC [Qian et al., 2001]
No. of T Screw element Screw element function
elements (°C) code
2 180 GFA 2-30-90 Screw forward conveying
2 18 0 KB 5-2-30-30° Forward kneading block elements
2 18 0 KB 5-2-30-30° L Reverse kneading block elements
1 180 GFA 2-30-90 Screw forward conveying (atmospheric vent)
1 18 0 GFA 2-15-30 Screw forward conveying
1 180 GFA 2-40-90 Screw forward conveying (660 mm Hg
vacuum vent)
1 18 5 GFA 2-20-90 Screw forward conveying
Figure 30 Screw configuration for compounding PP-nanocomposites in a

CORI TSE with L/D = 36 [Nanocor Technical Services Group, 2001]
Reprinted with permission from AMCOL
157
the central or so-called ‘sun’ screw. The planetary screws intermesh with the sun
screw and the barrel. The planetary barrel section has helical grooves
corresponding to the helical flights on the planetary screws. This section is usually
a separate barrel with a flange-type connection to the feed barrel section. The
planetary roller extruders are mostly used for processing heat-sensitive
compounds, viz. rigid or plasticised PVC formulations.
More recent are the disk or screw-less extruders, based on the viscous drag
transport principle. To this category belong: stepped disk, drum, spiral Diskpack
extruders and many others. Diskpack has the inherent capability of performing
the elementary steps of plastics processing by combining differently shaped
rotating disks in a drum-like housing. Stationary channel blocks that cause the
material to transfer from one disk-gap to another provide the wiping action.
Melting, laminar mixing, venting, and the pumping functions are all separated.
Diskpack has been used for reactive processing, blending, compounding, mixing
and devolatilising [Tadmor et al., 1983].
In the early 1980s Carlew Chemicals developed Gelimat, later re-named
K-mixer (K- for the kinetic energy). This mixer uses a high-speed rotor with
staggered blades mounted on a horizontal shaft at different angles. The number
and position of the blades vary with the mixer size. The mixing is carried out at
the blade tip velocity of 30-45 m/s. There is no external heating – the kinetic
energy generated by the particles impacting on each other and the mixer elements
produces sufficient heat to flux the material within 8 to 150 s. Since polymers
have low thermal conductivity, by varying the initial particle size it is possible to
melt only the skin of a particle or engender uniform melting. Once the material
reaches the desired temperature, the infrared sensor activates the bottom doors
of the chamber. The discharged dough can either be fed to a short screw extruder
and pelletised, or be passed between rolls and diced. High mechanical properties
were obtained by compounding in Gelimat PP with non-intercalated mica flakes.
To improve the distributive mixing often a static mixer (SM) is used (see
Table 24). It operates on the principle of repetitive dividing of a flow channel
into at least two new channels, reorienting them by 90°, and dividing again during
laminar flow. Mixing by SM is related to the number of striations (Ns) generated
by a number of SM elements (ne) and the number of divisions (new channels)
engendered by each element (nc):
N s = ncn e (18)
The efficiency of a SM is determined by comparing:
1. The length-to-diameter ratio (L/D proportional to ne) required to produce
the same degree of homogeneity;
2. The associated pressure drop, ΔPrel;
3. The holdup volume, ΔVrel;
4. The relative dimensions of the device, Drel and Lrel.
The efficiency of a SM also depends on the type of liquid [La Mantia, 1996].
2.3.8.2.3 Mixing in an Extensional Flow Field

The mixers discussed so far employ mainly the shear stress field. However, it has
been shown that the extensional flow field is more efficient as far as the energy
consumption per unit strain is concerned, as well as the rate of dispersive and
158
Table 24 Comparison of the performance of different types of

static mixers [Rauwendaal, 1998]
Static Mixer L/D ΔPrel ΔVrel Drel Lrel
Koch SMX 9 1.0 1. 0 1.0 1.0
Koch SMXL 26 0.6 1. 8 0.8 2.4
Koch SMV 18 2. 3 4.6 1.3 2.7
Kenics 29 0. 6 1.9 0.8 2.7
Etoflo HV 32 0. 6 2. 0 0.8 2.7
Komax 38 2.1 8.9 1.3 5.4
Lightnin 100 2. 6 29.0 1.4 15.3
PMR 320 14.5 51 1 2.4 86.0
Toray 13 1.3 1. 9 1.1 1.6
N-Form 29 1.4 4. 5 1.1 3.6
Ross ISG 10 8.6 9. 6 2.1 2.3
distributive mixing [Utracki and Shi, 2002; Luciani and Utracki, 1996]. In
processing equipment extensional flow requires non-parallel flow lines. In a SSE
extensional flow is only present in specially designed mixing elements, in add-on
torpedoes or in the convergent flow into the die. In a TSE extensional flow takes
place within the kneading disks. However, even here only about 8% of mixing
energy is used to generate an extensional flow field – the rest being consumed by
shear. The extensional flow mixer (EFM) is the only device that deliberately utilises
the elongation flow for mixing.
The EFM is a fully adjustable, general-purpose, motionless mixer. The mixing
action is provided by the development of an extensional flow field through a
convergent-divergent (C-D) flow geometry. It is primarily a dispersive mixer that
should be attached to a pressure-generating device. It efficiently homogenises
different liquid systems, even those where the components’ viscosity ratios are
large. The mixer attached to a SSE provided comparable or better mixing than
two TSE machines from different manufacturers, equipped with high mixing
screw geometry. The C-D channels are of progressively increasing intensity, with
flow in the radial not axial direction. To reduce the pressure drop, and to prevent
blockage, slit restrictions are used [Nguyen and Utracki, 1995]. A more recent
patent describes modifications of the original EFM design as well as its dynamic
version, the Dynamic Extensional Flow Mixer (DEFM) [Utracki and Luciani,
1997]. EFM has been used for: polymer blending, incorporation of elastomers
into resins, and dispersion of high viscosity resins or ‘gel particles’ [Utracki and
Luciani, 2000; Luciani and Utracki, 1996] as well as for dispersing organoclays.
Recently, preliminary tests were conducted to evaluate the suitability of EFM
for CPNC manufacture. The tests were conducted using the available device,
159
optimised for melt blending not for dispersing nanosized solid particles.
Nevertheless the results in three different laboratories have been encouraging.
The tests were conducted attaching an EFM to a CORI by a gear pump [Garcia-
Rejon and Simard, 2002]. The modulus of the resulting CPNC (PET with 5 wt%
organoclay) was twice as large in the presence of an EFM than without it. CPNC
containing PP with maleated-PP and organoclay were compounded using either
a TSE + EFM or a SSE + EFM. In both cases the presence of an EFM resulted in
significantly better dispersion of the clay platelets, as shown in high resolution
TEM [Song, 2002].
2.3.8.2.4 Melt Intercalation in a PA Matrix

Most processes that are labelled as ‘melt intercalation’ start with pre-intercalated
clay. For example, Maxfield [1996] conducted melt intercalation in a TSE starting
with PA-6 pellets and MMT whose interlayer cations were replaced by 2M2ODA.
The process was facilitated by addition of a silane coupling agent that partially
replaced the onium cations. The use of organosilanes of the type: RnSiX4-n (n = 1-3,
with R = organic radical having C-Si link and X is hydrolysable alkoxy, acryloxy,
amino or halogen group) had been proposed more than a decade earlier [Eilliott
and Beall, 1989]. For example, Na-MMT (CEC ≥ 0.75 meq/g) was intercalated
with quaternary ammonium ion and treated with a ‘sizing agent’, used in
reinforced plastic manufacture [Plueddemann, 1982; Petrarch Systems, 1987],
e.g., methyl trimethoxy silane.
The ammonium-modified clay may be used to prepare PNC at T < 250 °C.
With the exception of some elastomers, there are few polymers that can be
processed at these temperatures. The thermal stability of ammonium-modified
clay systems may be improved by extracting an excess of the intercalating
ammonium salt and/or by reacting it with, e.g., epoxies [Ton-That, 2000]. In
several patents, ammonium, sulfonium and phosphonium salts are listed [Hauser,
1950; Finlayson and Mardis, 1983; Ellsworth, 1999]. Phosphonium-clay salts
were reported stable to 370 °C, but this increased thermal stability does not
seem to translate into better (mechanical) performance.
CPNCs formed by melt blending have been described by Christiani and
Maxfield [Christiani and Maxfield, 1998]. First MMT was intercalated using
dipentyl ammonium chloride. The authors claim that the MMT-ammonium
complex with secondary amine was more thermally stable (onset of decomposition
at T = 275 °C) than that with either tertiary or quaternary ones. The melt
intercalation of the onium complex with PA-6 was conducted using a Leistritz
TSE at T = 200-250 °C and a screw speed of 250 rpm. The extruder was fed by
a dry-blend of PA-6 pellets with w = 2.95 wt% of onium-clay dried powder.
There is no information on the degree of dispersion achieved, but the CPNC
showed improvement (values for neat PA-6 are given in parentheses) of tensile
modulus: E = 3.4 GPa (2.4); tensile strength: σ = 80 kPa (66); ultimate elongation:
ε = 44 % (26); and deflection temperature under load: DTUL = 72 °C (55).
Judging by these numbers, MMT was probably well intercalated, but not
exfoliated.
Liu et al. [1999] prepared CPNC by melt intercalating PA-6 with up to 10.5 wt%
of organoclay (MMT-ODA) in a slowly rotating (30 rpm) TSE at T = 180 to
220 °C. XRD of injection-moulded specimens indicated that during processing
the interlayer spacing increased from d001 = 1.55 to 3.68 nm. Furthermore, the
area under the XRD peak decreased after mixing hence some exfoliation probably
160
took place. The incorporation of clay affected the crystalline form of PA-6 –
whereas in neat polymer only the α-form was present, after compounding with
organoclay the γ-form was also found. A good set of properties was reported.
Dennis et al. [2000; 2001] carried out fundamental studies of melt intercalation
in a PA-6 (Mn = 30 kg/mol; MI = 12) matrix. In the study 5 wt% of Cloisite® 15A
(C15A; MMT-2M2HTA) or Cloisite® 30B (C30B; MMT-MT2EtOH) (organoclay
properties are listed in Table 16) were used. A SSE and several TSE machines
with different screw combinations were employed. The organoclay powder
(particle size d ≅ 8 μm) was dry-blended with the PA-6 pellets. The mineral content
in the CPNC generated from C30B and C15A was 3.7 and 3.1%, respectively.
However, since melt blending of PA-6 with C30B resulted in easy exfoliation, the
studies were conducted with C15A.
Experimental studies of melt intercalation were carried out using four extruder
types: SSE, CORI (low and medium shear stress screw configurations), ICRR
(low medium and high shear stress screw configurations), and CRNI (low medium
and high shear stress screw configurations). The effects of mixing were evaluated
by XRD, TEM and tensile tests. It was found that the XRD peak position did not
change much (d001 = 3.2-3.8 nm), but its intensity varied, indicating diversity of
the dispersions. TEM micrographs were used to quantify the degree of dispersion
(DD) by counting the number of clay platelets or their stacks in twelve, 25 ×
25 mm squares. Evidently, the higher the number the more dispersed is the CPNC.
The results of this evaluation are shown in Figure 31.
Clearly the data from different mixing devices can be approximated to r2 = 0.86
by a simple two parameter equation:
{
DD = 4.37 × exp 0.00972 × t }; R = 0.86 (19)
Figure 31 Degree of dispersion as a function of the average residence time, t , in

several types of TSE with screws: corotating intermeshed (CORI), intermeshed
counter-rotating (ICRR), counter-rotating non-intermeshed (CRNI). Data [Dennis
et al., 2000]. The broken line follows the dependence: DD = 4.37 exp{0.0097 t}
with the correlation coefficient, r = 0.86.
161
Better correlation may be found when not only t , but also the variance of the
residence time distribution (σ 2a ; see Equation 17) is considered [Dennis et al.,
2000]:
DD = −4.2 − 0.21t + 564σ 2a + 0.0017t 2 − 4100(σ 2a )2 ; R = 0.98 (20)

Thus, on face value, these results indicate that not the stress, but the residence
time and its distribution determine the degree of intercalation/exfoliation.
However, the experiments were conducted at a single throughput hence a single
volumetric flow rate. Thus, during these tests the residence time should be a
measure of relative strains. Furthermore, there is a correlation between the TSE
configuration, operational parameters and the residence time and its distribution
– the low-shear stress screw configuration is associated with shorter residence
time and narrower distribution. The authors remarked that in each of the TSEs
the best dispersion was obtained using medium intensity screws, and that the
best overall dispersion was obtained using low stress CRNI that provided long
residence time. It is noteworthy that for a given TSE type, the highest shear
intensity configuration did not give the best dispersion.
These observations support earlier remarks by Vaia [1995] regarding diffusion-
controlled intercalation. However, the shear stress during extrusion significantly
accelerated the intercalation processes. The shear field seems to remove individual
highly intercalated platelets from the top and bottom surface of the stacks, thus
facilitating macromolecular diffusion into the remaining galleries. The proposed
mechanisms present during the dynamic melt intercalation are:
1. Diffusion-controlled, sequential intercalation and peeling of platelets,
2. Shear-related breaking of organoclay particles, and
3. Peeling off of organoclay platelets, one at a time, from the top and bottom
layers of individual stacks.
The data on PA-6/Cloisite® do not support the particle breaking mechanism (2),
but at high enough stresses the clay aggregates or stacks must be subjected to
attrition. Such a mechanical dispersion by means of high energy shearing (e.g., in a
Gaulin mill) was described in several patents (mainly from SCP) [Knudson and
Jones, 1986; 1992a,b; Jordan, 1994; 1996; Dennis, 1998; Gonzales, 1998; Farrow,
1998; Powell, 2001a,b]. Since intercalation is diffusion controlled, reduction of
platelet diameter shortens the diffusion time.
The mechanical properties versus DD are shown in Figure 32. Judging by the
value of the correlation coefficient, r, a correlation exists for tensile modulus and
stress (r = 0.82 and 0.75, respectively), but not for the impact strength or
elongation at break (r = 0.16 and 0.07, respectively). Thus, modulus increased
linearly with DD from E = 2.7 for PA-6 to 4.0 GPa for CPNC. Note that the fully
exfoliated PA-6/Cloisite® 30B, system showed E = 4.4 GPa. The yield stress, σ,
depends on dispersion to a lesser degree, but clearly shows a positive effect,
while the remaining two parameters (elongation at break and notched Izod impact
strength at room temperature) are independent.
In a related paper, molecular weight effects on melt intercalation in
PA-6/organoclay systems were studied [Fornes et al., 2001]. Three PA-6 resins
were used with two levels of clay loading (see Table 25). The clay was Na-MMT
(CEC = 0.92 meq/g) intercalated by SCP with methyl-rapeseed-bis(hydroxy-ethyl)
ammonium chloride (MR2EtOH). Rapeseed is a natural product containing
162
Figure 32 Mechanical properties of PA-6/Cloisite® 15A as a function of the

degree of dispersion. Data [Dennis et al., 2001].
Table 25 Molecular weight of PA-6, MMT concentration, specific

particle dispersion and average residence time in the extruder
[Fornes et al., 2001]
Mn (kg/mol) C (wt%) ηo (kPas) Sp (1/μm2) Spcalc t (s) σa2
16.4 1.6 0.34 25.6 22.5 257 0.209
16.4 3.0 0.34 30.7 35.8 257 0.209
22.0 1.4 1.7 57.1 45.7 211 0.173
22.0 3.1 1. 7 67.4 61.8 211 0.173
29.3 1.6 2. 5 60.6 71.9 207 0.167
29.3 2.9 2.5 83.1 84.3 207 0.167
Note: C - clay content; Sp - specific platelets dispersion; Spcalc the values of Sp

calculated from Equation 21; t - the average residence time; σa2-variance of the
residence time distribution - the magnitude of the last two parameters was
computed from data shown in Figure 1 of the original paper
saturated and unsaturated C18 to C22 hydrocarbons. Melt intercalation was

performed using a CORI (D = 30.5 mm, L/D = 10). The screws were assembled
to achieve ‘an optimum level of shearing and residence time’ at T = 240 to 280 °C.
The CPNC specimens were injection moulded, and then characterised by XRD
and TEM, as well as tested for mechanical and rheological performance. The
163
degree of dispersion, DD, was determined in a similar way as described by Dennis

et al. [2001], but the specimen thickness was smaller, the electron beam voltage
was higher and the method of calculation was different, thus the new set of data
cannot be directly related to the old one. Furthermore, the organoclay used in
these studies was similar to Cloisite® 30B not Cloisite® 15A explored before,
thus the degree of exfoliation was much higher, especially for the high and medium
molecular weight PA-6.
Fornes et al. [2001] calculated the specific particle dispersion per square
micrometre of the surface of a CPNC specimen and 1 wt% of the inorganic
component: Sp = DD/C, where DD is expressed as the number of individual
platelets or short stacks (2-3 platelets) per 1 μm2, and C (wt%) is the concentration
of the inorganic part of the organoclay in the specimen. To extract the effect of
molecular weight on the melt intercalation process, the Sp data in Table 25 were
fitted to:
S p ≡ DD / C = a0 + a1 C + a2 log10 ( Mn ) (21)
The linear regression gave the correlation coefficient squared, r2 = 0.991, hence
the postulated dependence represents the reported data reasonably well. The
analysis gave the following parameter values: a0 = -231 ± 48, a1 = 9.5 ± 5.7, and
a2 = 196 ± 33. Note that since the equation parameters, a1 and a2 are positive the
specific degree of dispersion increases with clay content and the molecular weight
of the matrix, thus with the matrix viscosity. If the melt intercalation were diffusion
controlled, the value of the a2 parameter should be negative! Thus, the data
indicate that contrary to expectation, the higher the molecular weight of PA-6
the easier the dispersion. This conclusion is supported by the TEM micrographs
shown in Figure 4 of the original paper [Fornes et al., 2001]. The CPNC with
either high or medium MW PA-6 have homogeneously exfoliated structures with,
on average, 1.3 or 1.5 platelets per stack, whereas that with low MW polymer
has large residual stacks and 2.4 platelets per stack.
The positive effect of MW on the mechanical dispersion process is even more
striking when the differences in the residence time and the residence time
distribution are taken into account. Using the values listed in Table 25, DD was
computed from Equations 19 and 20. The results plotted versus MW showed a
strong negative effect of MW on DD:DD∝Mn-1.6, in agreement with the diffusion-
controlled mechanism. The only conclusion from these seemingly contradictory
observations is that during melt intercalation in a compounding machine two
simultaneous processes take place: thermodynamically-driven diffusion of
macromolecules into the interlamellar galleries, and mechanical peeling off of
platelets or short stacks in which the diffusion-controlled intercalation sufficiently
reduced the solid-solid interactions between the adjacent clay platelets. It is
noteworthy that the zero-shear viscosity of the three polyamides varies nearly by
a factor of 8, thus higher shear stresses are acting on weakened stacks in high
molecular weight matrix. Since the organoclay value, d001 = 1.8 nm is small, the
diffusion of macromolecules must rapidly expand it for the shear stresses to be
effective.
Cho and Paul [2001] used SSEs and TSEs to prepare CPNC with 5 wt% of
MMT-M2REtOH in PA-6 as a matrix. The residence time distributions for the
SSE and TSE were quite different, narrow with a peak at about 2.5 min for the
former and very broad with a peak at about 5 min for the latter, just opposite to
what one could expect for flow of polymer melt through SSE and TSE. This may
164
be caused by the plug flow of CPNC through SSE. XRD of the organoclay showed
a strong peak at d001 = 1.8 nm – compounding in a SSE reduced the peak to a
barely discernible shoulder, while that in a TSE pushed it to low angle values,
2θ < 2°, i.e., d001 > 4.4 nm. The presence of short stacks in both products indicated
that exfoliation was not complete. Improved mechanical properties were reported,
e.g., addition of 3.16 wt% of inorganic clay resulted in 38% higher modulus and
30% higher strength (than PA-6) keeping the Izod impact strength about the
same.
Intercalated and exfoliated CPNC of PA-6 with organoclay were prepared in a
TSE at T = 250 °C [Varlot et al., 2001]. The organoclay was Na-MMT cation-
exchanged with methyl octadecyl bis-2-hydroxyethyl ammonium methyl-sulfate
(MODA2EtOH) and dimethyl dioctadecyl ammonium chloride (2M2ODA), which
resulted in the interlayer spacing of d001 = 1.96 and 3.68 nm, respectively. After
compounding, the CPNC specimens were found, respectively, exfoliated and
intercalated into short stacks containing 2-4 MMT platelets. The nanocomposites
were anisotropic. The preferential orientation of the MMT platelets as determined
by SAXS was parallel to the flow direction during injection moulding. The orientation
of the MMT plates and the PA-6 lamellae is expected to play a major role in the
mechanical properties. In the CPNC the matrix crystallised preferentially in the
γ-form.
2.3.8.2.5 Melt Intercalation in PEG Matrix

In his doctoral thesis of 1995 Vaia [1995] described the preparation of polymer
electrolyte nanocomposites for batteries. Thus, PEG was melt intercalated into
Na-MMT or Li-MMT with CEC = 0.8 meq/g. The process was carried out by
grinding a mixture of, e.g., 28 wt% of PEG (MW = 100 kg/mol) with 72 wt%
Na-MMT, then compressing it into a sheet at 80 °C for up to 6 h. The final d001
spacing was 1.77 nm, the same as that obtained in the solution intercalation
method. Considering the high solid loading larger interlayer spacing could not
be expected. Judging by the cited patents from AMCOL, the intercalation process
is facilitated by the presence of water (from 6 to 10 wt%), and increasing the
PEG content may increase the interlayer spacing.
2.3.8.2.6 Melt Intercalation in PO Matrix

Development of CPNC with a PA as a matrix has been carried out since the late
1960s. Owing to the polar nature of these polymers and advances in the chemistry
of the ammonium ion, at present melt exfoliation in the PA-matrix is conducted
on an industrial scale. By contrast, the melt intercalation of clays in a PO-matrix
is at a relatively early stage of development. The information from the patent
literature will be discussed later. Here the focus will be on the more basic aspects
of PO-melt intercalation technology.
By contrast with PA or PEST, POs are nonpolar, nonreactive and sensitive to
thermomechanical oxidation on the tertiary carbon by the free radical mechanism.
The fundamental question remains whether it is at all possible for PO
macromolecules to diffuse into the hydrophilic, repulsive environment of the
clay interlamellar galleries.
As with PA, here also most of the work involves MMT modified with organic
compounds. Because of the difficulties encountered during polymerisation in the
presence of clay [Heinemann et al., 1999], melt intercalation is the preferred
165
technique. The large resin manufacturers are pursuing the development of the
polymerisation-intercalation method with moderate success.
During the last decade, PP technology underwent a dramatic evolution that
resulted in a rapid increase of PP application in various industries, including
transportation. Thus, it is of no surprise that PP-based CPNCs have been of interest
to researchers around the globe.
The early work on PO-based CPNC was published by the Toyota group. Its
strategy was based on a multistep intercalation:
1. Primary intercalation of clay by cation exchange with onium salt;
2. Secondary intercalation with a compatibiliser, e.g., PO macromolecules grafted
with a polar compound (such as MAH); and
3. Melt compounding with the matrix PO.
The two critical steps are the selection of the organic cation (able to react with
clay anions and interact with the compatibiliser), and selection of the polar
compatibiliser, which will react with organoclay and remain miscible with the
basic resin. Some success was also obtained by combining steps 2 and 3 into one,
by modifying the PO only slightly, and compounding it directly with organoclay
as a polar matrix.
In studies by Usuki et al. [1997] (which provided the basis for the first patents
in this field [Usuki et al., 1996; 1999]) Na-MMT (CEC = 1.19 meq/g) was
intercalated with 45.8 wt% of dimethyl distearyl ammonium chloride (2M2ODA),
which increased the MMT interlayer spacing to d001 ≅ 3.28 nm. Next, the
organoclay was suspended in toluene and blended at a weight ratio of 1:1 with
the compatibilising ‘main guest molecule’ (hydroxylated
oligo-olefin: OO-OH; e.g., hydrogenated polybutadiene with telechelic -OH
groups, Mw ≅ 3 kg/mol, Polytail H from Mitsubishi) then dried. The interlayer
spacing increased to d001 ≅ 3.87 nm, but when the ratio of OO-OH-to-organoclay
increased to 10 the XRD peak disappeared altogether, indicating that d001 ≥ 8.8 nm.
Still better results were obtained by either reducing the molecular weight of the
OO-OH compound, or by replacing the -OH groups by either -COOH, acid
anhydride or epoxy (Polytail EP from Mitsubishi Kagaku). Next, PP (Mw = 30 kg/mol)
was melt-compounded in an internal mixer at 220 °C with either: Na-MMT, the
MMT-2M2ODA organoclay or the exfoliated OO-OH/organoclay material. The
TEM images taken of these three compounds showed, respectively, a micron-level
dispersion, the presence of large stacks, and exfoliation with only short stacks.
Thus, good dispersion of clay platelets in molten PP was achieved when prior to
compounding the clay platelets were exfoliated by the combined effects of onium
ion and the OO-OH compatibiliser. The authors stressed good miscibility of the
MMT-2M2ODA organoclay with PO, e.g., PP, butyl rubber (BR), polyisoprene
(IR), polybutadiene, etc.
In another publication [Kato et al., 1997] two-step exfoliation was carried
out. Thus, Na-MMT was intercalated with octadecyl ammonium chloride (ODA),
which increased the MMT interlayer spacing to d001 = 2.17 nm. Melt blending it
with either maleated PP (PP-MA; Mw = 30 kg/mol, acid value = 52 mg KOH/g) or
hydroxylated PP (PP-OH; Mw = 20 kg/mol, OH value = 54 mg KOH/g) was carried
out in an internal mixer at 200 °C for 15 min, with the ingredient ratio changing
from 1:3 to 3:1. The interlayer spacing of CPNC containing 50 wt% of organoclay
was d001 = 3.82 and 4.40 nm for the PP-MA and PP-OH matrices, respectively.
However, for an organoclay concentration of 25 wt% d001 = 7.22 nm was
166
obtained. Note, that the PP-MA matrix had lower molecular weight than
commercially desirable, but still above the entanglement molecular weight:
(Mw > Me = 2.8 kg/mol [Porter, 1995]). Furthermore, under the same conditions
the same resin with lower acid value (PP-MA; Mw = 12 kg/mol, acid value = 7 mg
KOH/g) was unable to expand the organoclay spacing. The authors concluded
that to obtain intercalation one polar group per 25 PP mers is required.
Unfortunately, there is no explanation of the MAH group reaction(s) with the
organoclay – is it with the primary ammonium ion, with clay surface -OH groups,
or the surface cations at the platelet edges?
In the following publications from Toyota [Kawasumi et al., 1997; Hasegawa
et al., 1998] again a three-step melt intercalation was used. Thus, Na-MMT was
first intercalated with ca. 32 wt% ODA, which increased the interlayer spacing
from d001 = 1.2 to 2.2 nm. The same procedure was repeated with synthetic
fluoromica (FM) (Somasif ME100 from CO-OP Chem.). As the ‘main guest
molecule’ two grades of PP-MA were used (Yumex 1001 and 1010 from Sanyo,
with Mw = 40 and 30 kg/mol, acid number = 26 and 52 mg KOH/g, Tm = 154 and
145 °C, respectively). The powders of organoclay (7.3 wt%), PP (melt flow rate
MI = 16 g/min; 70.8 wt%) and Yumex (21.9 wt%) were dry-blended, then
compounded in a TSE at 210 °C. About 5 wt% of the clay (MMT or FM) was
incorporated. The miscibility of PP with PP-MA was examined at 200 °C by
means of an optical microscope – Yumex 1001 was found miscible while Yumex
1010 was immiscible. The degree of clay dispersion in injection-moulded
specimens was determined by XRD and TEM. It was found that compounding
organoclay with PP caused a reduction of the interlayer spacing, while that with
either PP-MA increased it to d001 = 5.9 and 6.4 nm for MMT and FM, respectively.
In three-component systems (organoclay/PP-MA/PP) a significant difference in
the degree of dispersion was observed for systems with Yumex 1001 and 1010.
In the first case, the miscibility of the PP/PP-MA blend resulted in a high degree
of dispersion (displayed in TEM micrographs), but with residual short stacks
detected as a shoulder on the XRD (d001 ≅ 3.3 nm). In the case of the immiscible
PP/Yumex 1010 system the XRD peaks indicated reduced interlayer spacing to
d001 ≅ 5.5 and 5.9 nm for MMT and FM, respectively. The authors stated that
there is ‘strong hydrogen bonding between the maleic anhydride groups and the
oxygen groups of the silicates’, suggesting that MAH groups react with the clay
surface -OH functionalities.
Evidently, preparation of CPNC with such non-polar polymers as PP requires
thermodynamic compatibilisation. The ‘compatibilising’ molecules (e.g., PP-MA)
must be selected considering several aspects:
1. Interaction with pre-intercalated clay;
2. Miscibility with the matrix polymer;
3. Ability to entangle with the matrix, and
4. The effects on the crystallinity of the matrix.
As Kawasumi et al. have shown [1997] the miscibility of PP-MA with PP is of
great importance. As expected, when the MAH content exceeds a critical acid
value (≤ 52 mg KOH/g) the immiscibility with PP results in a micron-size dispersion
of PP-MA/organoclay phase in PP. Thus, a high degree of maleation leads to
immiscibility and poor results. Similarly [Kato et al., 1997], when the degree of
maleation is too small, there is insufficient interaction with the organoclay and
167
again platelet dispersion is poor. However, miscibility depends on concentration,

temperature and pressure [Utracki and Kamal, 2002b]. Furthermore, the structure
of the copolymer is important. When maleation is conducted in the presence of a
relatively high concentration of free radicals, random grafting of individual MAH
groups onto PP short chains takes place. Grafting PP with a small amount of free
radicals in the presence of styrene may lead to high molecular weight PP with
few SMA-chains attached to it. Significant differences in the compatibilising
capabilities of these two types of PP-MAH compounds are to be expected. It is
noteworthy that the commercially available PP-MA compounds widely differ in
purity, polydispersity and type of grafting hence their performance in CPNCs
vary widely.
Hasegawa et al. [2000a] explored the earlier observation from the Toyota
laboratory that melt compounding of lightly maleated PO (compatibiliser not needed)
with pre-intercalated clay may lead to a high degree of dispersion. Thus, ca. 5 wt%
of organoclay (MMT-ODA) was melt-incorporated into each of the three, slightly
maleated POs: PP (Mw = 210 kg/mol; MI = 150 g/10 min; MAH = 0.2 wt%), PE
(MI = 2 g/10 min; MAH = 0.62 wt%), and EPR (Mw = 270 kg/mol; MI = 0.06 g/10 min;
MAH = 0.55 wt%). The blending was carried out at 200 °C in a TSE (D = 30 mm,
L/D = 45.5). Excellent dispersion of clay platelets was shown by XRD and TEM
(in decreasing order) for EPR, PP and PE. In the latter system residual short stacks
with d001 ≅ 3 nm were detected. The authors also showed that under the same
compounding conditions, non-maleated PO gave a coarse, ca. 1 μm in size,
dispersion of organoclay aggregates with d001 ≅ 2.2 nm.
Next, the effects of organoclay concentration on melt intercalation were
studied [Hasegawa et al., 2000b]. Again, Na-MMT (CEC = 1.19 meq/g) was
intercalated with ODA, which increased the interlayer spacing from d001 = 1.2 to
2.2 nm. The organoclay (2.1 to 5.3 wt%) was melt compounded with PP-MA
(Mw = 209 kg/mol; acid number = 2.1 mg KOH/g; MAH = 0.2 wt%) in a TSE at
200 °C. Good dispersion was obtained – the XRD spectra were free of d001 peaks,
but a small shoulder for the highest clay content indicated the presence of short
stacks. The tensile modulus increased linearly with clay content (by nearly a
factor of two), whereas the increase of tensile strength was more modest (from
21 to 25 MPa), stabilising at about 4 wt% clay loading. Compounding of
organoclay with non-maleated PP gave a coarse dispersion of organoclay
aggregates with unchanged interlayer spacing (d001 = 2.2 nm), higher modulus,
but lower elongation at break and strength than the neat resin.
A three-step procedure was successfully used for melt intercalation of PP (MI =
1.5 g/10 min) with PP-MA (MAH = 1 wt%, MI = 1.2 g/min) and MMT intercalated
with 2M2ODA [Zhang et al., 2000b]. Mixing PP/PP-MA (ratio 50:1) with
organoclay was carried out in a TSE at 200 °C. As a result, the interlayer spacing
of the organoclay (d001 = 1.74 to 3.6 nm) progressed towards exfoliation, leaving
only a small shoulder in the XRD spectrum (short stacks with d001 ≅ 3.4 nm).
Tensile and impact strength at T = 5 °C were determined (see Figure 33). Thus,
incorporation of organoclay increased the tensile strength from about 29 to
31 MPa. The effect of organoclay on impact strength is more difficult to judge,
as addition of 0.1 wt% organoclay increased it from 9 to 26 kJ/m2, whereas
further addition of organoclay erratically reduced it to 6 kJ/m2. One may suspect
that PP-crystallinity and/or PP/PP-MA miscibility plays a role. More recently, the
effects of additional shearing were investigated [Zhang et al., 2003]. During the
packing stage of injection moulding an oscillatory flow through the mould cavity
168
Figure 33 Tensile and impact strength (at 5 °C) versus organoclay content for
PP/PP-MA/organoclay [Zhang et al., 2000b].
was generated. The CPNC was partly intercalated – shearing improved the degree
and homogeneity of dispersion. However, this improvement was at a cost of
platelet orientation in the flow direction. Some bent MMT platelets were observed
under TEM. As a result the improvement of tensile strength was modest,
decreasing with clay loading from positive 19% to negative 19% for 1 and 10 wt%
of organoclay, respectively.
Several modifications of these procedures have been proposed. For example,
the interlayer spacing of an ammonium-intercalated MMT was expanded by
swelling with an organic solvent with boiling point: BP = 100-200 °C, viz. ethylene
glycol, naphtha or heptane [Wolf et al., 1999]. The swollen organoclay was then
compounded with PP in a TSE at 250 °C, replacing the solvent molecules by PP
segments and evacuating the solvent. The extent of dispersion is unknown, but
the authors reported absence of an XRD peak in the 2.0-4.0 nm range.
The aspect of the thermal stability of the organic cation used to intercalate
Na-MMT was also analysed [Lee et al., 2000a]. PP (Mw =278, Mn = 72 kg/mol),
PP-MA (Mn = 23 kg/mol, 2 wt% MAH) and organoclay (Cloisite® 20A or 30B,
i.e., MMT with 2M2HTA or MT2EtOH, respectively) were melt-mixed for 10 min
at 210 °C in an internal mixer at the weight ratio of about 70:22:8, respectively.
The XRD of the mixtures with C20A showed that the interlayer spacing increased
from that of organoclay (d001 = 2.47 nm) to 3.4 nm for C20A with PP-MA, and
to full exfoliation for the three-component CPNC. The opposite trend was seen
for mixtures with C30B. After compounding with PP-MA and/or with PP/PP-MA
the C30B interlayer spacing (d001 = 1.86 nm) was reduced to about 1.4 nm.
Furthermore, it was found that compounding under a blanket of N2 or in air
gave different results. The effect was also observed for binary PP mixtures with
organoclay (without PP-MA) where a change of the interlayer spacing was not
169
expected. The FTIR measurements indicated thermal desorption and

decomposition of organic ions in C30B. By contrast, C20A heated with PP retained
its relatively large spacing, which in the presence of PP-MA expanded all the way
to exfoliation. The C30B spacing is small to start with and upon heating it readily
collapses, preventing PP-MA diffusion into interlamellar space. This observation
is particularly interesting since C30B melt-exfoliated during melt compounding
with PA-6 in a TSE at T = 200-250 °C [Dennis et al., 2000]. Evidently PA chain
ends were able to react with the -OH groups of the intercalant either preventing
their decomposition or forming their own PA-clay bonds through amine or amide
groups.
Cloisite® C6A, C20A, C25A, and C30A (see Table 16) were also used with three
PP resins of different melt index (PP-L, MI = 820; PP-M, MI = 200; and PP-H,
MI = 60) and four PP-MA resins (unknown MW) containing 0.55, 1.1, 3 and
5 wt% MAH [Kim et al., 2000a]. First, PP-L was mixed with 5 wt% of organoclay
in an internal mixer at 200 °C and 20 rpm for 10 to 30 min. In systems containing
C20A (MMT-2M2HTA) the interlayer spacing increased by 0.73 nm, while for
the three other organoclays it decreased by 0.1 to 0.2 nm. However, since the
magnitude of the XRD peak decreased on mixing, some exfoliation may occur.
Next, three component mixtures: PP:PP-MA: Cloisite® = 80:15:5 wt%, were
prepared. The best results were obtained using PP-L and PP-MA containing the
lowest concentration (0.55 wt%) of MAH. Apparently, the phase separation at
higher MAH content interfered with exfoliation. In another report [Ryul et al.,
2001] PP-M with Cloisite ® C10A (2MBHTA) or C20A (2M2HTA) was
compounded in an internal mixer (T = 180 °C, 75 rpm, t = 20 min) equipped
with an ultrasonic wave generator. In this series of experiments the PP-MA was
replaced by styrene. The role of ultrasonics was to generate free radicals as well
as to help in breaking the organoclay stacks, thus facilitating intercalation. A high
degree of dispersion was obtained in the case of PP-M:styrene:C10A = 80:15:5 wt%;
for C20A the d001 peak shifted from 2.39 to 3.65 nm. Ultrasonics caused chain
scission of PP followed by copolymerisation with styrene.
The superiority of C20A (2M2HTA) over the other organoclays indicates that
the most favourable conditions for achieving a high degree of dispersion are:
1. A relatively large initial interlayer spacing of organoclay that makes diffusion
of the compatibilising molecules possible,
2. A relatively small area of the clay surface blocked by the intercalating ion,
3. Availability of sufficient concentration of -OH groups on the clay surface,
4. Chemical bonding between the compatibiliser reactive group (e.g., MAH)
and ≡Si-OH group,
5. Miscibility of the compatibiliser with the base resin, and
6. High enough molecular weight of the compatibiliser to obtain entanglement
with the matrix molecules.
The above observations are also valid for CPNC prepared with synthetic hectorite
(FM, Somasif ME100 from CO-OP Chem.) [Reichert et al., 2000]. First, the
synthetic clay (FM) was treated with protonated alkyl amines, viz. butyl (C4),
hexyl (C6), octyl (C8), dodecyl (C12), hexadecyl (C16) and octadecyl (ODA). The
primary ammonium ion intercalation resulted in expansion of the interlayer
spacing from 0.95 to 1.98 nm (see Figure 34). PP (Tm = 163 °C; MI = 3.2 g/10 min)
170
was compounded with 20 wt% of PP-MA (type E: Mw = 22.9 kg/mol, Mw/Mn = 2.6,
MAH = 2.9 wt% or type H: Mw = 32 kg/mol, Mw/Mn = 8, MAH = 4.2 wt%) and
0, 5 or 10 wt% of the organoclay in a CORI at 300 rpm and T = 190 to 230 °C.
Only C12, C16 and C18 amines produced organoclays (d001 ≥ 1.68 nm) that could
be dispersed in the compatibilised PO matrix. The interlayer spacing was found
to increase with MAH content, viz. 10 wt% of FM intercalated with either C16-
or C18-amine, when blended with 20 wt% PP-g-MA (type-H) and 70 wt% PP
gave the best performance, viz., increase of Young’s modulus by 129%, yield
stress increase by 32%, notched Izod impact strength decrease by 18% and
elongation at break decrease by 99%. XRD and TEM indicated that full
exfoliation was not achieved. The miscibility of PP-MA with PP was not examined.
Manias et al. [2001] reacted Na-MMT with either 2M2ODA or ODA
obtaining two organoclays. PP was grafted with ca. 0.5 wt% of p-methylstyrene
(PP-MS; Mw = 200 kg/mol), then the p-methyl group was converted into either
-(CH2)3-OH (PP-OH) or -CH2-maleic anhydride (PP-MA). A block copolymer
of PP with PMMA was also prepared (PP-b-PMMA; Mw = 15 kg/mol). CPNCs
were:
(i) Extruded at 180 °C using a SSE with residence time up to 10 min,
(ii) Compounded in an internal mixer at 170 to 180 °C for up to 20 min, or
(iii) Ultrasonicated in trichlorobenzene.
Figure 34 Synthetic clay (Somasif ME10) intercalated with salts of primary

amines, CnH2n+1NH2. The interlayer spacing (d001) and amine content (w) are
plotted as functions of the number of carbon atoms in the amine (n). The amount
of adsorbed amine and the stepwise increase of d001 may be approximated with the
linear dependence with the correlation coefficient, r = 0.980 and 0.996,
respectively. Data [Reichert et al., 2000].
171
According to XRD and TEM all three methods resulted in similarly structured
CPNC: intercalated tactoids and exfoliated platelets. Thus, reacting MMT-
2M2ODA with PP-MA resulted in expanded interlayer spacing from d001 = 2.4 to
3.0 nm, whereas mixing it with either PP-MS or PP-OH gave d001 = 3.4 nm. The
MMT-ODA was found to expand when blended with PP-b-PMMA from d001 = 2.2
to 3.2 nm. The short note does not contain either the postulated mechanism of
reaction between the functionalised PP and the organoclay or information about
how the chemical structure and blending time affected the exfoliation. It seems
that in the series of MMT-2M2ODA with grafted PP the interlayer expansion
was controlled by the presence of the styrenic group – the presence of MAH gave
lower expansion than that obtained from the non-polar -CH3 group. MMT-ODA
with PP-b-PMMA also showed a similarly modest expansion of the interlayer
space by Δd001 ≅ 1 nm.
Oya et al. [2000] examined the role of clay as well as a secondary intercalant
on the degree of dispersion and mechanical properties of CPNC with PP. Thus,
synthetic hectorite (FM), MMT and mica (MC) were intercalated with a
quaternary ammonium ion (2MHDODA) of the formula:
(CH3)2N+(C16H33)(C18H37). Next, the organoclay was dispersed in a toluene
solution of diacetone acrylamide (CH2=CHCONHC(CH3)2CH2COCH3; DAAM)
with a free radical AIBN initiator. After polymerisation of DAAM a solution of
PP-MA was added, the product was precipitated, washed, dried, and finally melt
compounded with PP. In parallel, CPNC was similarly prepared without DAAM.
In all cases only intercalation was obtained – the largest interlayer spacing (and
the overall best dispersion) was obtained for doubly intercalated FM prepared
with poly-DAAM. However, the best mechanical properties at 3 wt% of clay
loading were these of CPNC with MC. The authors speculated that the difference
originates in the relatively high modulus of MC pristine platelets. In conclusion,
mica may be a better nanofiller than FM, but the performance of CPNCs with
MMT was nearly as good. The additional polymerisation step did not result in
the expected improvement of dispersion and/or mechanical performance.
Intercalated nanocomposites of PP-MA with 2, 4 and 7.5 wt% clay were prepared
via melt extrusion at 200 °C in a TSE [Nam et al., 2001]. The organoclay was
synthesised by an ion exchange reaction between Na-MMT (CEC = 1.10 meq/g;
d001 = 2.31 nm after ion exchange) and ODA. The PP was modified by grafting
with 0.2% MAH (PP-MA; Mw = 195 kg/mol and Mw/Mn = 2.98). It was found
that the interlayer spacing (as measured by XRD) decreased with the clay
concentration (from d001 = 3.24 to 2.89 nm), while the thickness of the short clay
stacks increased (see Figure 35). The XRD and TEM data indicated that the
extent of exfoliation and/or stacking is controlled by the amount of clay. The
grafted MAH-groups in the PP-MA chains promoted interactions with the clay
particles by diffusion of PP chain into the space between the silicate galleries.
The authors focused on the effect of the organoclay on PP-MA crystallinity
and hierarchical structure formation. The hierarchical structure starts with the
intercalated clay spacing of 2¯3 nm, to crystalline lamellae thickness of 7-15 nm
and spherulitic texture of 10 μm diameter. Two important observations were
made. After crystallisation at 80 °C, the PP-MA formed a rod-like crystalline
texture of about 10 μm length consisting of an interfibrillar structure. The total
volume fraction of the crystalline phase was about constant, but with the increasing
clay content the γ-phase crystalline content increased from zero to 10.5%. The
formation of the γ-phase originates in the reduction of the PP-MA chain mobility
172
Figure 35 Interlayer spacing, d001, stack thickness, t, and its aspect ratio, p, in
PP-MA/stearyl ammonium-MMT. Data [Nam et al., 2001].
affected by the intercalation of PP chains into the interlamellar gallery space.

The orthorhombic unit cell of the γ-phase consisted of two parallel helices with an
inclination of 40° to the lamellar surface. The diffraction peak of the 130-plane of
the γ-phase appears at 2θ = 19.3°. The clay particles are located inbetween the
crystalline fibrils made of assembly of lamellae. Thus, even when the lamellar
parameters (thickness and spacing) remain about constant, the crystalline fibril
size and interstack correlation distance decrease with clay concentration. The
CPNC showed enhanced moduli (compared to the matrix) related to the clay
content and aspect ratio by the Halpin-Tsai relation.
The system: PP (Mw = 280 kg/mol) with PP-MA (Mw = 47 kg/mol; 2.5 wt%
MAH) and organoclay (ODA and n-decyl amine, treated with silane; d001 = 2.3 nm)
was melt-mixed in an internal mixer at 180 °C and 150 rpm [Marchand and
Jayaraman, 2001]. The aim was to maximise the degree of clay dispersion by
varying the PP-MA content (0 to 14 vol%) at a constant organoclay content of
1.8 vol%. The optimum concentration of PP-MA was found to be ca. 9-10 vol%.
Furthermore, it was reported that a higher degree of exfoliation was obtained
using ODA than its silane-treated homologue.
In a recent publication from NCL in Pune, a SSE (T = 160 to 200 °C, at
45 rpm) was used to melt-blend PP/PP-MA into organoclays [Kodgire et al., 2001;
Hambir et al., 2001; 2002]. The organoclays used in this study were Cloisite®
6A (2M2HTA; see Table 16), and Nanoclay (N1; Na-MMT with CEC = 1.35 meq/g
ion exchanged with ODA) from Nanocor Inc. The material characteristics are
shown in Table 26. The composition of the CPNC was: 84 wt% PP, 12 wt% PP-MA,
and 4 wt% organoclay. XRD of the Na-MMT gave the interlayer spacing d001 = 1.2 nm.
For the intercalated clays, Cloisite® 6A (C6A) and Nanoclay® ODA (N1),
respectively, three peaks: d001 = 1.2, 1.8 and 3.3 nm, and a single: d001 = 2.45 nm,
173
Table 26 Material characteristics for PP, PP-MA and organoclays

[Hambir et al., 2001]
Sample Sample Grade MW Supplier
code (kg/mole)
PP PP1 Vestolen 2000 164 Hüles, Germany
PP PP2 Koylene M0030 241 IPCL, India
PP PP3 Vestolen 7000 36 2 Hüles, Germany
Polybond PB PB 3150; 1 wt% grafted 188 BP Chem., USA

MAH
Vinbond VB VB 100; 0.65 wt% grafted 151 Vin Enterprises,

MAH India
Cloisite® 6A 47 wt% of 2M2HTA - Southern Clay

Products
Nanoclay N1 ODA - Nanocor
were observed. In the presence of C6A the XRD showed the presence of multiple
peaks, indicating non-uniform structure.
Melt-blending the two organoclays with PP and PP-MA (Polybond 3150 from
Uniroyal Chemical) resulted in a reduction of the XRD peaks’ intensity. This was
particularly evident with C6A; for N1 the interlayer spacing shifted to a higher
value (d001 = 2.7 nm), but the reduction of intensity was not as pronounced.
Thus, both systems did not exfoliate, but the degree of dispersion was better in the
presence of C6A. However, as data in Figure 36 and Table 26 indicate, it is N1 that
yields higher rigidity. The effect may originate in the different type and/different
content of the crystalline phase or the platelets’ aspect ratio. The performance of
PP was enhanced by incorporation of PP-MA and organoclay. About a 35%
increase in the tensile modulus and about a 10% increase in the tensile strength
were observed. The thermal decomposition temperature increased from 270 to
about 400 °C (for C6A). The most interesting observation is the dramatically
different large-scale morphology for PP and CPNC based on it; while PP3 crystallises
in well-known spherulites, the presence of PP-MA/organoclay (PP3/PB/6A) changed
it into a fibrillar structure. After prolonged crystallisation the fibres grow in length
and diameter, but do not revert to the spherulites. Furthermore, the PP/clay system
crystallises at temperatures higher by ca. 10 to 20 °C than neat PP, suggesting
strong nucleating capabilities of the organoclays.
In another study from the same laboratory [Hambir et al., 2002], three grades
of PP and two of PP-MA were used (see Table 26). Judging by XRD spectra, melt
intercalation with PB was superior to that of VB – evidently the acidity of the
latter graft copolymer was insufficient. The data also indicated that the use of
lower MW PP resulted in a higher degree of dispersion (judged by the reduction
of the peak areas).
Tethered PP/organoclay CPNCs were prepared via melt compounding in a
TSE at T = 180, 190, 200 and 190 °C (from hopper to die), at a screw speed of
174
Figure 36 Temperature dependence of the tensile storage modulus, E´, for PP

and PP/PP-MA/organoclay for: Cloisite® 6A and Nanocor N1. Data [Kodgire et
al., 2001].
180 rpm. For testing, dried pellets of the nanocomposite were injection-moulded
at 200 °C with a mould temperature of 30 °C [Liu and Wu, 2001]. The organoclay
was prepared from Na-MMT (CEC = 0.80 meq/g) by ion exchange reaction with
trimethyl hexadecyl ammonium bromide (3MHDA). In the presence of dibenzoyl
peroxide the product was compounded in an internal mixer for 60 min with glycidyl
methacrylate, at a weight ratio of 13:2. This epoxidised product (E-MMT) was
then compounded with PP. XRD of Na-MMT, 3MHDA and E-MMT gave the
following interlayer spacings: d001 = 1.24, 1.96 and 2.98 nm, respectively. XRD
of PP with 5 wt% of 3MHDA indicates that the d001 peak of the organoclay
remains at the same position, i.e., PP does not intercalate into the organoclay. By
contrast, XRD of PP with different loadings of E-MMT (1, 3, 5, and 7 wt%)
showed expansion of the interlayer spacing, viz. 4.92, 5.09, 4.61 and 4.75 nm,
respectively. Thus, E-MMT can lead to intercalation but not to exfoliation. The
mechanical properties of the CPNC improved with addition of organoclay,
increasing the storage modulus (by 40% at 7 wt% loading), not affecting the
impact strength and slightly reducing Tg. The addition of clay did not change the
crystal structure of PP, however silicate layers acted as nucleating agents, increasing
the crystallisation peak temperature of PP from Tc = 110.5 °C to about 120 °C.
Nanocor recently recommended CORI screw design for the manufacture of
CPNC with PO as a matrix [Qian et al., 2001]. A Leistritz TSE with D = 27 mm
and L/D = 36 was used at 300 to 500 rpm and T = 170 to 190 °C. Two vents at
13D and 24D were used. The recommended configuration is given in Table 23.
The process involves two-steps:
1. Preparation of masterbatch containing about 50 wt% of organoclay, a
compatibiliser (ca. 25 wt%), and a matrix polymer (e.g., PP-MA and PP).
2. Dilution to the desired clay content (e.g., 2 to 7 wt%).
175
The latter process may be carried out using either a TSE or a SSE [Cho et al., 2002].
For example, first, organoclay/PP/PP-MA masterbatch was prepared. It contained
50 wt% Nanomer® I.30P (MMT-ODA) with 25 wt% PP-MA and 25 wt% PP.
Next, dilution of the masterbatch with PP (to 6 wt% organoclay in the final
CPNC) was carried out in either a SSE (containing different mixing screws or
add-on mixers) or in a CORI. For comparison, PP nanocomposites were prepared
following a single-step procedure. Thus, PP, PP-MA and 6 wt% I.30P were
compounded in a CORI. The interlayer spacing of all six CPNC batches prepared
by different methods was small, viz. d001 = 2.7 to 2.8 nm. Thus, intercalation not
exfoliation was obtained. The mechanical properties of the neat resin, CPNC
prepared by dilution of the masterbatch either in a SSE or in a TSE, as well as of
CPNC prepared by direct compounding are presented in Table 27. CPNC prepared
by the two-step method showed slightly better performance than that prepared
by direct compounding in a TSE, but dilution in a TSE results in a marginally
better performance than that in any SSE configuration (independent of which
mixing unit was installed). The difference between the two-step and single-step
is most likely related to the difference in d001. The origin of the increased interlayer
spacing may be related to the total residence time of the CPNC subjected to melt
compounding. Since the stated aim of the process is exfoliation, more detailed
discussion can be found in Section 2.4 and Part 4.
By contrast with the customary use of ammonium-intercalated clays, Pozsgay
et al. [2001] treated Na-MMT with N-cetyl pyridinium chloride. Melt
compounding of this organoclay with PP in an internal mixer produced rather
disappointing results as the tensile strength of PP was found to decrease with the
organoclay loading (from 1 up to 10 wt% clay). The decrease superimposed on
data obtained for a PP mixture with neat Na-MMT, indicated a lack of miscibility
between PP and the cetyl C16H33-paraffin group of the intercalant.
As reported by Wang et al. [2001a], organoclay may also act as a compatibiliser in
polymer blends. The authors dispersed 10 wt% of Nanomer I.30 TC (MMT-ODA).
Comparing the binary blend PA-6/PP = 9/1 with the three-component system
PA-6/PP/I30 = 9/1/1 it was found that addition of organoclay significantly improved
the tensile properties, viz. modulus increased from 2.5 to 4.7 GPa, tensile strength
Table 27 Mechanical properties of PP nanocomposites

[Cho et al., 2002]
Material Process Nanomer® Flex Flex HDT d001 (nm)
I.30P (%) strength, σb modulus, Ef (°C)
(MPa) (GPa)
PP 6523 (neat 0 33.7 1.08 85 -

resin)
CPNC SSE 6 44.5 ± 0.5 1.71 ± 0.03 102 2.79 ± 0.01

dilution
CPNC TS E 6 45.9 1.81 104 2.8

dilution
CPNC Direct 6 43.8 1.57 100 2.7
176
from 65 to 73 MPa, but at a cost of impact strength, which decreased from 70 to

13 J/m. Compatibilisation of the blend by addition of PP-MA reduced the modulus
to 3.4 GPa, but slightly improved the strength and impact strength (to 75 MPa and
17 J/m, respectively). Evidently, in the four-component system PP-MA migrated to
the clay-PA-6 interface, thus its role as the blend compatibiliser was reduced.
The fundamental principle of additive incorporation into a multiphase polymeric
system is that it must be inserted into a specific phase – if in the blend one phase is
rigid and the other ductile, increasing the volume of each of these with the same
additive will have opposite effects. For example, it is known that incorporation of
PS into the rubbery phase of HIPS increases the ductility of the system, while
incorporation of glass fibre (GF) into PA-66 in its blend with ABS increases the
modulus [Utracki, 2002]. Obviously, the same principles are valid for CPNC with
polymer blend as a matrix. Recently two blends, PC/ABS and PA-6/ABS were
prepared by melt compounding with MMT-3MHDA [Wang et al., 2004]. The
TEM micrographs showed that in the former CPNC clay platelets dispersed in the
ABS phase, whereas in the latter system, they were dispersed mainly in the PA-6
phase. The dynamic self-organisation of organoclay was studied, but unfortunately
there is no information regarding the effect on performance.
Extensive studies on melt intercalation of PP were carried out by Ton-That et al.
[2002]. The authors focused on CPNC containing PP melt compounded in a TSE at
200 °C with 2 wt% of Cloisite® 15A and 4 wt% of a compatibiliser. Several commercial
PP-MA compounds, a PP-AA and an onium-terminated PP have been used as
compatibilisers. XRD spectra have shown that the interlayer spacing d001 ≤ 3.9 nm
was achieved. TEM confirmed this by displaying a number of short stacks along with
individual platelets dispersed in the matrix. The highest values of tensile modulus were
obtained for PP-MA with 0.5 wt% MAH and with PP-AA with 6 wt% acrylic acid.
To close this discussion on the melt intercalation of PP, it is necessary to stress
that in many reports all the observed differences in the performance of CPNC
and neat PP matrix resin are assigned to the more-or-less exfoliated clay. However,
the behaviour of this semicrystalline polymer strongly depends on crystallinity:
crystallographic form, type and size of crystal, total crystallinity, etc. Rare are
the publications that even consider these effects.
In 2001 Saujanya and Radhakrishnan published interesting work on the effects
of calcium phosphate (CaPO3) particles on the crystallinity of PP. The authors
prepared nanosized CaPO3 using an in situ deposition technique in the presence
of PEG or PEG/PVAc. The composite was prepared by grinding together 2, 5 or
10 wt% of CaPO3 with PP in an agate mortar and pestle. A small quantity of the
powder was isothermally crystallised on the microscope hot stage. The growth
of spherulites as well as the intensity (grey scale) of transmitted light in the cross-
polar mode was recorded.
The results were compared with those for PP containing conventionally
prepared CaPO3. Both filled PP as well as neat PP crystallised in the monoclinic
α-crystalline phase. However, as the size of CaPO3 particles (d) decreased, the
isothermal crystallisation rate increased dramatically – this is illustrated in
Figure 37 as a decrease of the crystallisation half-time (t1/2) versus 1/d. The overall
crystallisation rate (G) was found to follow the dependence: log G ∝ (1/d).
Similarly, the nucleation efficiency of CaPO3 particles was found to increase with
their inverse diameter, resulting in a decrease of the ultimate spherulite size and
enhanced optical transparency of the PP/nanoparticle composites. These results
were further confirmed by DSC analysis.
177
Figure 37 Crystallisation half-time versus reciprocal diameter of calcium

phosphate powder in PP. Data [Saujanya and Radhakrishnan, 2001].
The dependence of t1/2 versus 1/d presented in Figure 37 confirms that at the same
volume fraction the efficiency of a nucleating agent depends on its surface area.
The dependence is not linear, suggesting that as the particle size is reduced to
nanosize, additional factors start to play a role, viz. particle shape, aspect ratio,
curvature, increased proportion of the high energy surface atoms at a cost of the
shielded atoms in the interior, etc. The smallest CaPO3 particle with d = 7 nm (i.e.,
specific area, Asp = 69 m2/g) has a surface area one order of magnitude smaller than
MMT (Asp = 700-800 m2/g). However, it is organoclay not neat mineral that gets
incorporated into the PP matrix hence the shielding effect of the organic intercalant
plays an important role – often the clay surface is fully shielded from the matrix.
Another point that often escapes attention is the actual location of the
nanoreinforcing platelets in the semicrystalline polymer matrix. The
thermodynamics of crystallisation require that any foreign material should be
expelled from the growing crystal. Hence, the organoclay must be located mainly
in the non-crystalline part of the CPNC, in the liquid phase of PP at T > Tg ≅ 0 °C
or in the glassy part at lower temperatures. Since the crystallinity of PP in CPNC
may be as high as 68%, the clay concentration in the non-crystalline phase may
be three times higher than average. Owing to the crowding effect, the interlayer
spacing in this case may be reduced by a factor of up to 3. Thus, on the one hand
large effects of organoclay addition into a semi-crystalline matrix may not be as
significant as those in an amorphous one and on the other the mechanism of the
nanoclay nucleating activity should be taken into account.
The key information from the relatively large number of reports on melt
intercalation of PP/organoclay systems is summarised in Table 28. As far as the
tensile modulus is concerned, the data indicate that at low clay loading it increases
linearly with clay content. For exfoliated CPNC with PA-6 as the matrix the
dependence (up to 10 wt% of clay) may be expressed as:
E R ≡ E / Ematrix 1 + a0 w ; a0 = 0.2 (22)
where w is clay (inorganic part only) content.
178
Table 28 Summary of melt intercalation in PP matrix
Clay Intercalant Compatibiliser Polymer Process d001 (nm) Performance Ref.
Na-MMT 2M2ODA Hydroxylated PP 30 Internal mixer > 3.87 to Telechelic diol or PP-MA Maxfield et al.,
polybutadiene or kg/mol at 220 °C exfoliation should have good 1995,
PP-MA chemical affinity to Usuki et al., 1997
2M2ODA
Na-MMT ODA PP-MA; acid = 52; none Internal mixer 7.22 for 33 wt% Optimum when one polar Kato et al., 1997
or PP-OH; OH = at 200 °C of organoclay group per 25 PP-mers is
54 present
Na-MMT ODA PP-MA (Yumex PP TSE at 210 °C; 5.9 & 6.4 for Miscibility of the PP/PP- Kawasumi et al.,
or FM 1001, acid # 26) and injection MMT & FM MA blends is of critical 1997; Hasegawa
moulded importance eet al., 1998
MMT Aminosilane PP-MA, 1-5 wt% PP In xylene at 2.4 to 7.3 The key is bonding Hudson, 1999
H2NR1 MAH; Mn = 20 120 °C, or in through co-crystallisation
-SiR2R3R4 kg/mol melt between the grafted PP
and the main PP
MMT Ammonium Solvent with BP = PP TSE at 250 °C No XRD peak in Wolf et al., 1999
intercalated 100 – 200 °C (solvent the range 2.0-4.0
evaporation) nm
Na-MMT ODA PP + 0.2 wt% none TSE at 200 °C Exfoliation + Tensile modulus up by a Hasegawa et al.,
MAH; Mw = 210 shoulder factor of 1.9 (at 5% 2000a
kg/mol d001 ≅ 3.4 loading), tensile strength
up by 19%
179
180
Na-MMT ODA PP + 0.2 wt% none TSE at 200 °C Exfoliation + Relative tensile vs. T: E´ = Hasegawa et al.,
MAH; short stacks at 1.5 to 2.5 with max at T = 2000b
Mw = 210 kg/mol 5.3 wt% clay 50 °C. Note that Young’s
modulus E(PP) = 780,
E(PP-MA) = 429 MPa
Na-MMT 2M2ODA PP-MA; 1 wt% PP TSE at 200 °C Exfoliation + Tensile strength from 29 Zhang et al.,
MAH shoulder 3.4 to 31 MPa 2000b
Cloisite® 2M2HT PP-MA, 2 wt% PP Internal mixer Exfoliation at Good performance Lee et al., 2000a
C20A MAH at 210 °C 8% C20A
Cloisite® MT2EtOH PP-MA, 2 wt% PP Internal mixer 1.4 Bad performance – Lee et al., 2000a
C30B MAH at 210 °C composite
Cloisite® 2M2HT PP-MA, 0.55, 1.1, PP Internal mixer 3.2 at 5 wt% Best for low MW PP & Kim et al., 2000
C20A 3, 5 % MAH at 200 °C C20A the lowest MAH content
Cloisite® 2MHTEtOH PP-MA, 0.55, 1.1, PP Internal mixer 1.8 at 5 wt% Worst case Kim et al., 2000
C25A 3, 5 % MAH at 200 °C C25A
FM n-alkyl PP-MA, MAH = PP CORI, 300 Exfoliation? Young's up by 129%, Reichert et al.,
amines 2.9 wt% rpm, 190 to yield stress up by 32%, 2000
C4 – C18 5 & 230 °C Izod impact down by
10 wt% 18%, elongation down by
99%.
Na-MMT 2M2ODA PP-OH or PP-MA - SSE at 180 °C; Stacks (3.4 nm) Improved mechanical Manias et al., 2001
ultrasonics + platelets properties and reduced
(US) in solvent flammability
Na-MMT ODA PP-OH or PP-MA - SSE at 180 °C; Stacks at 3.2 + Improved mechanical Manias et al., 2001
US in solvent platelets properties and reduced
flammability
MMT, 2MHDODA Polyacrylamide + PP 2.3 to 3.8 At 3 wt% clay modulus Oya et al., 2000
FM, or PP-MA increased by 67%, TS by
mica 26%, Izod by 95%
Cloisite® 2MBHT Styrene PP Internal mixer Exfoliation? Ultrasonics caused Ryul et al., 2001
C10A at T = 180 °C copolymerisation of
+ US styrene
Cloisite® 2M2HT Styrene PP Internal mixer 3.65 Ultrasonics caused Ryul et al., 2001
C20A at T = 180 °C copolymerisation of
+ US styrene
Na-MMT ODA PP with 0.2% PP TSE at 200 °C Intercalation; PP-MA formed rod-like Nam et al., 2001
MAH 2.9 to 3.2 crystals; higher modulus
MMT ODA PP-MA, 2.5 wt% PP Internal mixer Intercalation Best results with ODA and Marchand and
MAH at 180 °C 10 wt% PP-MA Jayaraman, 2001
Cloisite® 2M2HT; 4 PP-MA Polybond PP SSE at 160 to 1.2 to 3.3 Better dispersion than for Kodgire et al.,
6A wt% 3150; 1 wt% 200 °C Nanoclay, but poorer 2001; Hambir et
MAH performance al., 2001; Hambir
et al., 2002
Nanoclay ODA; 4 wt% PP-MA Polybond PP SSE at 160 to 2.7 Higher modulus than with Kodgire et al.,
3150; 1 wt% 200 °C 6A (increased by 42%); 2001; Hambir et
MAH TS increased by 10% al., 2001; Hambir
et al., 2002
181
182
Na-MMT 3MHDA; Organoclay PP TSE at T = 180, 5.09 with Storage modulus up by Lui and Wu, 2001
5 wt% grafted with 190, 200 °C, epoxidised 40% (7 wt% loading),
glycidyl 180 rpm; IM organoclay same impact strength, Tg.
methacrylate Down Tc up by 10 °C
Nanomer® ODA; PP-MA PP CORI for master 2.7 to 2.8 Flex modulus up by 67%, Sakai, 2002; Cho
I.30P 6 wt% batch, then flex strength up by 36%, et al., 2002; Lan
either CORI or HDT up by 19 °C and Quiqan, 2000
SSE for diluting
to 6 wt%
Na-MMT N-cetyl None PP Internal mixer ? Tensile strength of PP Pozsgay et al.,
pyridinium down with organoclay 2001
loading
Nanomer ODA PP-MA; 1.5 to 5.8 PP/PA-6 TSE at T = 180- 3.7; organoclay Modulus increased by Wang et al., 2001a
I.30 TC wt% MAH 230 °C, 90 rpm as compatibiliser 36%, tensile strength by
15%, impact strength,
down 70 to 13 J/m.
Nanomer OD A PP-MA; 0.2 wt% TSE at 200 °C 3.03 at 4 % Okamoto et al.,
of MAH organoclay 2001
Cloisite 2M2HT; AA-g-PP PP 6100 TSE at 200 °C, 3.5 Improved: Flex strength: Ton-That et al.,
15A 2 wt% (Polybond 1001), 200 rpm 13%, modulus: 22%; 2002
4 wt% tensile strength: 1%;
modulus: 15%, Izod: 45%
Cloisite 2M2HT; MA-g-PP PP 6100 TSE at 200 °C, 3.5 Improved: Flex strength Ton-That et al.,
15A 2 wt% (Polybond 3150), 200 rpm 16%, modulus 32%; 2002
4 wt% tensile strength 3%;
modulus 9%, Izod 25%
As discussed in Section 3.5.1 (Micromechanics of CPNC), well-dispersed CPNC

with PP as the matrix follow the same dependence. This is quite remarkable
since the parameter ao is a measure of the hydrodynamic volume which depends
on the aspect ratio – for hard spheres the Einstein prediction is ao ≈ 0.005 (for
poorly dispersed organoclays the constant ao ≈ 0.07). Thus, the observed
dependence indicates that in these solid CPNCs the aspect ratio of clay platelets
is p ≈ 277. In short, at least as far as tensile modulus is concerned, one can get
similarly high performance form the PP/clay system as that of the renowned
PA-6/clay.
As evident from this discussion, PP is the principal polyolefin of interest.
Numerous patents and research publications on CPNC with PO as the matrix
usually mention other polymers, but the cited examples invariably focus on PP.
One of the exceptions is a publication by Wang et al. [2001b], who prepared
LLDPE-based CPNC using MAH grafted LLDPE (PE-MA) and one of four
organoclays, viz. Cloisite® 20A (2M2HTA), and synthesised alkyl ammonium-
MMT (CEC = 1.19 meq/g) with alkyls: dodecyl, hexadecyl or octadecyl
(respectively C12M, C16M, ODAM). The interlayer spacings of C20A, C12M,
C16M, and ODAM were determined by XRD as d001 = 2.47, 1.36, 1.79 and
1.85 nm, respectively. Two types of PE-MA were used, one a direct product of
MAH grafting on LLDPE, and the second obtained by mixing neat LLDPE with
PE-MA (0.85 wt% MAH). The CPNC were prepared by melt compounding in
an internal mixer at 140 °C and 60 rpm.
The XRD scans at 2θ = 2 to 10°, for CPNCs with 5 wt% of either C20A or
ODAM did not show a d001 peak indicating exfoliation – confirmed by TEM.
For the two other organoclays there was a significant reduction of the peak area
– only a trace of a peak was observed for C16M and a weak one for C12M.
Thus, for exfoliation of alkyl ammonium-MMT in an LLDPE matrix at least
C16-alkyl chain in the organoclay is required. The authors also determined that
the critical level of MAH grafted onto LLDPE is 0.1 wt% – below this level even
C20A or ODAM could not be exfoliated.
Several publications report that full exfoliation in PE/clay CPNC has been
achieved. However, these were prepared by polymerisation of ethylene in the
presence of organoclay. The encountered problem is that the system is not
thermodynamically stable, and during the subsequent processing the platelets
reaggregate, reducing the interlayer spacing and the performance.
2.3.9 Temperature and Pressure Effects on Interlamellar Spacing

The ‘standard’ intercalation procedure (e.g., by ammonium salts) is carried out
under mild conditions, viz. ambient pressure, P = 0.1 MPa, and T = 20-80 °C.
However, melt exfoliation of CPNC may involve much more severe treatment.
There is little information in the literature as to how T and P affect the interlayer
spacing. What is available, seems to be system-specific.
For example, the temperature effects on the interlayer spacing were found to
depend on the onium ion and (to a lesser extent) on the type of clay. In Figure 38
variation of the interlayer spacing, d001, as a function of T is presented for
ammonium salt intercalated magadiite (a) and beidellite (b); circles represent
tetradecyl ammonium-tetradecyl amine complex (C14H29N+H3× C14H29NH2),
while triangles represent dimethyl ditetradecyl ammonium [(CH3)2N+(C14H29)2].
Magadiite is a layered sodium silicate: Na2Si14O29.9H2O. Evidently, the interlayer
spacing variations with temperature depend on the ammonium radical, and to a
183
Figure 38 Interlayer spacing, d001, as a function of temperature for (a)

magadiite and (b) beidellite intercalated with salts of tetradecyl ammonium-
tetradecyl amine (C14; circles) or dimethyl ditetradecyl ammonium (2(C1C14);
squares; open squares show values after cooling). Data [de Siquira et al., 1999].
184
lesser extend on the type of clay [de Siquira et al., 1999]. The authors explained
the observed changes in the interlayer spacing as caused by molecular
rearrangement of the ammonium radicals, melting of the n-paraffin groups, or
changes of hydration.
Information on the effects of pressure (P) is even more difficult to find.
However, there are indications that with increasing P the interlamellar gallery
height decreases. High-resolution data were obtained using time-of-flight neutron
diffraction of hydrated Ca- and Na-smectite and vermiculite [de Siquira et al.,
1999]. The measurements were conducted in a special Ti/Zr cell that could
withstand simultaneously T ≤ 350 °C and P ≤ 200 MPa.
The data are presented in Figure 39. One of the more interesting conclusions
from that work was that the interlayer water is denser than that in the bulk: ρinterlayer
= 1.06 versus ρ bulk = 0.874 g/ml. In other words, there is a reduction of free
volume in the vicinity of the clay particle surface. If so, the compressibility should
also be reduced. The transitionless reduction of the interlayer spacing of Ca-smectite
gives the isothermal volumetric compressibility of the hydrated clay: κ = 4.8-10-5
MPa-1, to be compared with bulk water compressibility of κ = 4.5-10-4 MPa-1 – a
reduction by a factor of 9.
2.3.10 Layered Nanofillers, other than Montmorillonite

Excepting the patents that list a plethora of diverse layered nanofillers, the majority
of published research on CPNC and all the industrial activities focus on swellable
smectite clays, such as natural montmorillonite or synthetic hectorite (quite similar
to MMT). However, the properties of polymer/clay nanocomposites do depend
on the kind of layered material that has been used. Thus, it is advisable to consider
the possibilities of CPNC formation with clays other than MMT.
Figure 39 Pressure dependence of d-spacing for calcium- and sodium-smectite

and vermiculite. Data [de Sequira et al., 1999].
185
2.3.10.1 Kaolinite
The structural formula for kaolinite is A14Si4Ol0(OH)8, and it is a 1:1 type clay,
hence different from the commonly used 2:1 type smectites. Its lattice consists of
one sheet of tetrahedrally coordinated SiO4 and one sheet of octahedrally
coordinated AlO2(OH)4. Kaolinite has a low value of CEC = 0.02-0.04 meq/g
and large aspect ratio. In neat kaolinite the adjacent cells are spaced about 0.71 nm
across the (001) plane. A layer of -OH covers the octahedral sheet forming strong
hydrogen bonds between the layers, hence only a limited number of polar guest
species, viz. N-methyl formamide (NMF) or dimethyl sulfoxide (DMSO), can be
introduced. However, once the layers are separated, the -OH functionality may
be used for hydrogen bonding with some polymers. Thus, kaolinite has quite a
different structure than MMT, viz. one side of the interlayer space is covered
with hydroxyl groups of the AlO2(OH)4 octahedral sheets and the other side is
covered by oxygen atoms of the SiO4 tetrahedra. As a result, CPNC with kaolinite
are expected to exhibit different behaviour from those with MMT. In 1996 Tunney
and Detellier provided an overview of the earlier work.
The first incorporation of a polymer into kaolinite was reported in the early
1990s. In a series of publications Sugahara and his colleagues [Sugahara et al.,
1992] intercalated kaolinite with monomeric acrylonitrile, acrylamide or
vinylpyrrolidone then induced thermal polymerisation. However, this method
did not provide a means for controlling the molecular weight and its distribution.
The first direct intercalation of kaolinite with macromolecules took place more
recently [Tunney and Detellier, 1996]. The motivation for this work was a search
for anisotropic ionic conductivity. In other layered materials two-dimensional
confinement of PEG provided the desirable performance. In other words, here
total exfoliation was neither expected nor desired. The applied method consisted
of two steps:
1. Intercalation of kaolinite with a solvent, and
2. Compounding the intercalated kaolinite with a polymer, which progressively
displaced the solvent molecules in the interlamellar galleries.
The authors have shown that it is possible to prepare two distinct ethylene glycol
phases of kaolinite, with d001 = 0.94 and 1.08 nm. The former intercalate had the
ethylene glycol unit covalently bound to the interlayer aluminol surface, while
the other had a more weakly bound intercalated phase.
The logical next step was to intercalate larger oxyethylene-based molecules
into kaolinite. Thus, first DMSO or NMF was used to intercalate kaolinite, and
then PEG-3400 or PEG-1000 displaced the low molecular weight intercalant.
This was accomplished by heating PEG with ca. 17 wt% DMSO-intercalated
kaolinite in a round-bottom flask for 9 days at T = 155 °C. The product was
purified and dried in an oven at 100 °C for 3 days. Elemental analysis: carbon
7.90%; hydrogen 2.63%. XRD gave d001 = 1.112 ± 0.004 nm. The calcination
weight loss was 29.1%.
Several samples were prepared from combinations of clay, intercalating
solvents and melt-intercalating PEG resins. Their interlayer expansion was
comparable, ranging from d001 = 1.085 to 1.119 nm, i.e., providing an interlamellar
space of Δd001 ≅ 0.37-0.41 nm. This indicates that the intercalated oxyethylene
units are arranged in a flattened monolayer conformation. It is noteworthy that
intercalation, using PEG-1000 dissolved in either water or 1,4-dioxane, was
186
unsuccessful. The success of the intercalation by the melt method could be due to
a strong concentration effect of the polymer and lower stabilisation energy of
polymer segments.
Larger interlayer expansion was obtained by reacting kaolinite with phenyl-
phosphonic acid (PPA) in a water/acetone (1:1) solution at 95 ± 5 °C for up to
19 days [Guimarães et al., 1998]. The topotactic reaction was stoichiometric,
viz.:
Al2Si2O5(OH)4 + 4 H2O3PPH → Al2Si2O5(OH)(HO3PPH)3×2H2O + 3H2O
As a result of reaction the interlayer spacing increased from that of kaolinite
(d001 = 0.716 nm) to the spacing of the kaolinite phenyl-phosphonate (KPP):
d001 = 1.502 to 1.645 nm, i.e., providing an interlamellar space of Δd001 ≅ 0.786-
0.929 nm. The analysis suggested that phenyl-phosphonate groups were grafted
to the kaolinite platelets. The materials were stable up to ca. 450 °C.
In another report [Guimarães et al., 1999] hydrated kaolinite phenyl-
phosphonate (KPP-hyd) was reacted with hexylamine. The reaction produced a
stable light-yellow compound (KPP-hex). XRD gave d001 = 1.636 nm, consistent
with the size of the intercalating hexylamine. The thermal analyses showed that
at T ≅ 230 °C hexylamine molecules decomposed, but the resulting KPP remained
stable up to 498 °C, at which temperature the grafted phenyl phosphonate started
to decompose and dehydroxylation of kaolinite takes place.
In 1999 Gardolinski et al. [1999] intercalated kaolinite in two steps, first
reacting it at 60 °C with an aqueous solution of DMSO. After washing and
characterisation, the resulting complex: Al 2 Si 2 O 5 (OH) 4 (DMSO) 0.4 was
stoichiometrically reacted at RT with N-methyl-2-pyrrolidone (NMP). The product
was Al2Si2O5(OH)4(NMP)n (where n = 0.39 ± 0.02). XRD gave d001 = 1.231 nm,
i.e., an expansion of 0.11 nm over the DSMO complex. The presence of NMP
molecules in the interlamellar space resulted in a notable enhancement of the
thermal stability – while the DMSO-complex decomposes at 175 °C, the NMP
complex remains stable up to 431 °C.
In the next publication from this group, first kaolinite was reacted with DMSO,
producing a kaolinite-DMSO complex. The complex was subsequently reacted with
either PEG or bacterial polyhydroxybutyrate (PHB) in the molten state at 130 or
180 °C, respectively [Gardolinski et al., 2000]. The displacement of DMSO molecules
took several days – highly ordered polymer/kaolinite CPNC was obtained. In the
interlamellar galleries of kaolinite, PEG macromolecules formed a polymeric
monolayer. The characteristics of the kaolinite-complexes are listed in Table 29.
As mentioned above, Sugahara and his colleagues synthesised several kaolinite-
polymer compounds (viz. kaolinite-PAN, kaolinite-PAAM, or kaolinite-P4VP)
by first intercalating kaolinite with the appropriate monomers and then
polymerised by thermal treatment. The serious drawback of this procedure is the
lack of control of the degree of polymerisation of the resulting polymers.
Recognising the problem, the authors developed an alternative intercalation
method [Komori et al., 1999b]. The publication is particularly valuable as that
the authors also reported the unsuccessful attempts. The process resembles the
‘common solvent method’ discussed in the next Chapter. Thus, pre-intercalated
kaolinite at room temperature is dispersed in a polymer solution. For example
when kaolinite-ammonium acetate was used as the intermediate for the
intercalation of P4VP (Mw = 10 kg/mol) dissolved in water, the displacement was
187
Table 29 Characteristics of intercalated kaolinite

[Gardolinski et al., 2000]
Intercalant Content d001 (nm) Δd001 (nm) Decomposition-T
(wt%) (°C)
(nil) (nil) 0.716 0 (450)
DMSO 8.8 1.121 0.404 175
PEG 28.9 1.116 0.399 349
PHB 15.5 1.170 0.453 309
not successful, leading to de-intercalation of ammonium acetate. However, when

kaolinite-methanol (K-MeOH) was used as the intermediate and methanol as
the solvent for P4VP, the 24 h long polymer infusion increased the interlayer
spacing. The product was centrifuged and yellowish white powders were obtained
without washing. K-MeOH was also used to intercalate such organic species as
alkylamines, p-nitroaniline, and ε-caprolactam.
XRD of kaolinite, K-MeOH and kaolinite-P4VP determined that d001 = 0.72,
1.11 and 1.24 nm, respectively. Elementary analysis showed that the number of
P4VP mers per kaolinite unit was 1.9, hence the formula:
[Al 2Si 2O5(OH) 4]×(C6H9NO)1.9. The complex kaolinite-P4VP can easily be
destroyed by washing with ethanol or water – P4VP could be removed after a
few minutes of washing. The authors determined that out of the 1.9 mers per
unit cell, about 1.1 are adsorbed on the stack surface with only 0.8 mers in the
interlayer space, i.e., twice as much as is obtained by in situ polymerisation
(0.4 P4VP mers per kaolinite-unit cell).
Komori et al. [2000] reported a partial methoxylation of -OH groups in a
kaolinite. Kaolinite-NMF complex (d001 = 1.08 nm) was dispersed in methanol
and mixed for a day. After centrifugation, the complex was redispersed and the
procedure repeated seven times. The final, wet K-MeOH complex (d001 = 1.11 nm)
was separated and dried in air to convert it into methoxylated compound
(K-OMe; d001 = 0.86 nm). The amount of methoxy groups was determined by
analysis. The results can be written as Al2Si2O5(OH)4-x(OCH3)x with x ≅ 0.36.
The authors stressed that even when methanol can readily be removed from the
K-MeOH complex, methoxy groups are more stable, e.g., they and water
molecules remain in the interlayer space of kaolinite after air drying.
The next publication from the group focused on the usefulness of K-OMe as an
intermediate for the preparation of CPNC with PA-6 as the matrix [Itagaki et al.,
2001]. A two-stage process was used, first preparing kaolinite-PA-6 intercalation
compound, using a kaolinite-6-amino-hexanoic acid (AHA) as a precursor, then
kaolinite-PA-6 was melt compounded with PA-6 (commercial 1015B grade from
Ube Industries Co.). The compounding was carried out using a TSE at 240 °C and
300 rpm. XRD gave d001 = 1.15 nm indicating that the layered structure of kaolinite
was not exfoliated. For comparison, PA-6 was also compounded without clay
(PA-6(extruded)) and with unmodified kaolinite (PA-6/kaolinite). The PA-6/MMT
commercial 1015C2 grade from Ube was used as a reference. The properties of
these CPNCs are listed in Table 30. The relative properties of the last two
188
Table 30 Mechanical properties of kaolinite-PA-6 type

nanocomposites [Itagaki et al., 2001]
Material Clay Tensile Tensile Notched Izod
content strength, σb modulus, E impact strength,
(wt%) (MPa) (GPa) NIRT (J/m)
PA-6 (neat) 0 74.0 1.13 27.8
PA-6 (extruded) 0 72.7 1.16 34.5
Kaolinite-PA-6 1.42 79.2 1.29 27.7
PA-6/kaolinite-AHA 1.48 77.0 1.25 21.6
PA-6/kaolinite-PA-6 1.38 80.4 1.33 27.7
PA-6/MMT 1.80 89.1 1.36 25.4
compositions in the table are of interest. Taking into account different clay loadings,
the performance ratio of PA-6/kaolinite-PA-6 to that of PA-6/MMT (per 1 wt% of
clay) is: 1.18, 1.28, and 1.2, for the tensile strength, tensile modulus and impact
strength, respectively. Evidently, the properties are not proportional to the clay
content, thus the performance ratios showing about 20% better performance for
CPNC with kaolinite than with MMT may not be correct. However, it is intriguing
that kaolinite with only slightly expanded interlayer spacing offers at least
comparable performance to that of commercial-grade CPNC with exfoliated
MMT. Since kaolinite in the PA-6/kaolinite-PA-6 material is not exfoliated, the
enhancement of properties must be related to the surface effects. The surface of
kaolinite particles is covered by -OH groups, which interact with PA-6 via
hydrogen bonding. The particle size of kaolinite is larger than that of MMT,
which might also contribute to the enhanced properties.
2.3.10.2 Micas and Synthetic Micas

The composition and polymorphism of micas vary considerably (see Section 2.2.2).
There are 34 phyllosilicate minerals with a layered or platy texture that are
classified as micas. The commercially important micas are muscovite and
phlogopite. Mica sheets are transparent to opaque, resilient, reflective, refractive,
dielectric, chemically inert, insulating, lightweight and hydrophilic. Mica is also
stable when exposed to electricity, light, moisture and extreme temperatures. It
has been fabricated into parts for electronic and electrical equipment.
Micas have a 2:1 sheet structure, similar to MMT, but the maximum charge
deficit is in the tetrahedral layers and contains K+ that is held tenaciously in the
interlayer space. The XRD basal spacing d001 ≅ 1.0 nm is broad and skewed
toward wider spacings. The illite’s CEC = 0.2-0.3 meq/g of dry clay. Since the
natural mica sheet diameter can be almost as large as one metre (e.g., in Calcutta
– nowadays Kolkata – museum), the numerical value of the aspect ratio is
ridiculously large. The intercalation strategies for micas and smectites are the
same. Exfoliated mica sheets in polymeric matrix with aspect ratio of p > 1,200 have
been reported [Yano et al., 1993; 1997].
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The early work on mica/polymer systems was aimed at improving the

performance of mica for electrical applications. For example, in 1981 Ishizaka
and Fujii patented composites comprising an organosiloxane resin, mica and
acid phosphates, suitable for use in the manufacture of mica products with superior
mechanical strength, electrical characteristics, water resistance and heat resistance.
Synthetic micas are also available, e.g., Barasym SMM-100, a muscovite-
type; mica-montmorillonite with CEC = 0.7 meq/g or Somasif ME100, a
fluoromica (or fluorohectorite) with CEC = 0.7-0.8 meq/g and d001 = 0.95 nm.
By contrast with natural micas the synthetic ones have been reported as having
low aspect ratio, thus inefficient for improving the barrier or mechanical
properties. However, it may be that the low aspect ratio is not inherent, but
rather caused by mechanical attrition during compounding in molten polymer.
Micas: ‘DM clean A’ from Topy Ind. Co. have CEC = 1.19 meq/g and a high
aspect ratio of p = 1230. The chemistry of mica was discussed in Section 3.4.
Yano et al. [1993] prepared CPNC with polyimide (PI) as matrix in which
2 wt% of one of the four clays (hectorite, saponite, MMT and synthetic mica)
was dispersed. The clays had CEC = 0.55, 1.00, 1.19 and 1.19 meq/g, and aspect
ratio: p ≅ 46, 165, 218, and 1,230, respectively. They were intercalated with
DDA, filtered, washed and freeze-dried. The interlayer spacing was: d001 ≅ 1.5
(hectorite), and 1.8 nm for the three other clays. To prepare PI/clay films, 2.49 wt %
of organoclay was dispersed in dimethyl-acetamide and vigorously stirred for
3 h at 90 °C, diamino diphenyl ether was added and the mixture was stirred at
30 °C for 30 min, then pyromellitic dianhydride was introduced and the mixture
stirred for an additional 6 h. The resulting solution was spread on a glass plate,
solvent was evaporated off for 2 days then the film was heated at 100 °C for 1 h,
at 150 °C for 1 h, and at 300 °C for 2 h under N2. A 60 μm thick film of
polyimide with 2 wt% of clay was obtained. The XRD spectra showed that
CPNC with MMT and synthetic mica had no peaks indicating exfoliation, this
was confirmed by TEM. XRD of PI with either hectorite or saponite showed
peaks at d001 = 1.5 nm, but smaller in intensity than those in the respective
organoclays. This implies that roughly one layer of organic molecules exists in
the interlamellar space. TEM of CPNC with saponite showed dispersion of
individual platelets with a small number of tactoids. In the PI/hectorite system
most clay formed aggregates. This difference in dispersability goes in the reverse
direction to the aspect ratio, hence it is either the CEC or, more probably, the
chemical reactivity of these clays that leads to these effects.
It is to be expected that the higher the aspect ratio and degree of dispersion,
the higher the PI properties. This indeed is the case as far as water vapour
permeability is concerned (see Figure 40). Two elements account for the reduction
of permeability (see also Part 5.3): dispersion of high aspect ratio of oriented
platelets and reduction of the free volume. The relative permeability coefficient
(PR) (see Figure 41) is given by:
PR = P/P0 = d/d´ = [1 + pφ/2]-1 (23)
where φ is the volume fraction of the platelets, P is the permeability coefficient at
platelet content φ, P0 is that at φ = 0 and p = L/W is the aspect ratio. The relation
was derived assuming perfect alignment of individual clay platelets – if for a
given system this assumption is not obeyed, the aspect ratio necessary to fit such
data will be a projection of the true aspect ratio on a plane perpendicular to the
190
flux direction. As shown in Figure 40, the permeability reduction (at constant
concentration of clay in PI matrix) is fully accounted for by the clay platelets’
aspect ratio. Furthermore, addition of 2 wt% of synthetic mica reduced the PI
thermal expansion coefficient at 100 °C by 40%. Smaller factors were obtained
for the other clays with smaller aspect ratio.
The same intercalation method was successfully used for Na-MMT and
synthetic fluoromica (FM, Somasif ME-110 from CO-OP Chem. Co.) [Kawasumi
et al., 1997; Hasegawa et al., 1998]. First the clays were intercalated with ODA,
then organoclay powder (7.3 wt%), PP (melt flow rate = 16 g/min; 70.8 wt%)
Figure 40 Relative permeability of polyimide containing 2 wt% of clays versus

aspect ratio [Yano et al., 1997]. The line was calculated from Equation 23.
Figure 41 Tortuosity model: d = film thickness; d´ = tortuous path of diffusing

molecules; L and W are platelet diameter and thickness, respectively, hence the
aspect ratio p = L/W.
191
and PP-MA (21.9 wt%) were dry-blended, then compounded in a TSE at 210 °C,
incorporating about 5 wt% of clay (MMT or fluoromica). It was shown that
compounding organoclay with PP caused a reduction of the interlayer spacing,
while in the presence of PP-MA it increased to d001 = 5.9 and 6.4 nm for MMT
and FM, respectively. In other words, neither one of these two clays was exfoliated,
but the degree of dispersion was higher for the system with FM. The authors
presented a strong case for the critical importance of PP/PP-MA blend miscibility
– well dispersed clay platelets were evident in TEM micrographs for miscible
systems, with a shoulder on the XRD spectrum indicating the presence of tightly
spaced short stacks.
In 1998 Katahira et al. [1998a,b,c,d] published a series of articles on the use
of mica for the production of PA-6-based PNC. Thus, purified Na-mica flakes
were dispersed in hexanoic acid-ω-ammonium phosphate, prepared by treating
ε-caprolactam with phosphoric acid. The intercalation was rapid even at 20 °C,
but the exchange of Na+ was accelerated by heating to T > 60 °C. The monomer-
intercalated mica showed d001 = 1.47 nm. During polymerisation (under low or
high pressure) the mica exfoliated. Owing to the high dispersion of high aspect
ratio clay platelets excellent amelioration of the bending strength and modulus
were obtained for the CPNC. Thus, the formation of CPNC consisted of three
steps:
1. Protonation of ε-caprolactam by phosphoric acid,
2. Intercalation of mica by ion exchange of Na+ with protonated lactam,
3. Polymerisation at T ≥ 260 °C which expanded the interlamellar spacing all
the way to exfoliation.
Badesha et al. [1998] prepared CPNC with fluoroelastomer matrix and dispersed
in it mica-type clay (SCPX-984 from SCP). The aspect ratio of mica platelets
ranged from p = 50 to 1000. The clay was first intercalated with 2M2ODA. The
fluoroelastomers of interest were copolymers and terpolymers of vinylidene
fluoride, hexafluoropropylene, and tetrafluoroethylene, known commercially as
Viton, Fluorel, Aflas, Tecnoflon, etc. These may be cured with, e.g., a bisphenol
and organophosphonium salt (accelerator). Other additives, such as colouring
agents, processing aids, conductive fillers, initiators and accelerators may also be
added. The intercalated mica could be dispersed in the matrix by compounding,
e.g., milling prior to curing. During compounding the fluoroelastomer chains
penetrate the organophilic clay, causing each platelet to be surrounded by polymer,
hence exfoliating. The exfoliated nanocomposite may be formed with or without
going through the intermediate stage of intercalation. An example describes
addition of 10 phr of organoclay to 100 parts of Fluorel, and then milling the
compound for 15 min on a two-roll rubber mill with a tight nip at 27 to 38 °C.
XRD indicated that no intercalation had taken place. However, when the milling
temperature was increased to 50 °C, the interlayer spacing increased to d001 = 3.3 nm
– hence intercalation. However, at still higher milling temperature, T = 66 °C,
fully exfoliated CPNC was produced.
Zilg et al. [1999a] investigated the correlations between the polymer
composition, type of clay, its concentration and mechanical properties. The matrix
was based on diglycidyl ether of bisphenol-A (DGEBA) cured with
hexahydrophthalic anhydride. Three types of clay were used:
1. Synthetic fluoromica (FM; Somasif ME 100 from CO-OP Chem.),
192
2. Purified Na-MMT (particle diameter 15 μm, BET surface area 25 m2/g from
Südchemie AG) and
3. Synthetic hectorite (FH; Optigel SH from Südchemie AG).
The clays were made organophilic by ion exchange with various alkyl ammonium
ions: dodecylamine (DDA), N,N-dimethyl didodecyl amine (2M2DDA),
N,N,N-trimethyl dodecyl ammonium chloride (3MDDA), N-methyl dodecyl
N,N-bis(2-hydroxyethyl)-ammonium chloride (MD2EtOH; AKZO Ethoquad
C12), 12-aminododecanoic acid (ADA), a,x-bis(aminopropyl)-terminated
oligo(propylene oxide), known as Jeffamine of the D series (JAD 130, 300, 500,
800), N,N,N,N-dimethyl dioctadecyl ammonium chloride (2M2ODA) and
N,N,N,N-dimethyl benzyl-octadecyl ammonium chloride (2MBODA). Upon
intercalation the interlayer spacing of FM increased in the expected sequence,
e.g., after ion exchange with MD2EtOH the neat clay spacing of d001 = 0.94
increased to 1.74 nm, and then upon matrix polymerisation to d001 = 6.79 nm.
The authors reported that (at 5 wt% of clay content) FM was difficult to disperse
beyond short stacks. Easier to disperse (but still in form of short, intercalated
stacks) was MMT, while FH exfoliated quite readily.
Enhanced toughness was associated with the formation of dispersed
anisotropic laminated nanoparticles consisting of intercalated silicates. The
authors confirmed the earlier report from Pinnavaia’s laboratory that d001 spacing
increases with the onium salt alkyl chain length, and that primary amines increase
the interlayer spacing more than the quaternary ones. During curing, the former
most likely reacted with epoxy which the latter were unable to do. With 10 wt%
of the ammonium salt used on the silicates, not all were properly intercalated,
i.e., XRD showed a diffraction peak indicating intercalation. On the other hand
(e.g., for FH intercalated with 2MBODA) TEM micrographs showed randomly
dispersed individual platelets, suggesting exfoliation. An interesting observation
came from comparing the spacings calculated from XRD and AFM micrographs,
viz. 6.8 and 11 nm, respectively. The explanation offered is that the individual
clay platelets are quite flexible and bend under the force of the AFM test tip.
The mechanical properties of four series of epoxy-based CPNCs are
summarised in Figure 42. Surprisingly, there is little improvement of properties
by 2MBODA intercalation – the tensile strength of neat MMT or FH is higher
(mid-concentrations) than that after intercalation. The best fracture toughness
was reported for FM and MMT, intercalated or not.
In another publication from the same laboratory [Zilg et al., 1999b], CPNCs
based on a PU matrix were prepared by dispersing synthetic fluoromica (FM;
Somasif ME100 from CO-OP Chem. Co.). The clay was manufactured by heating
Na2SiF6 with talc. The FM lamellae consist of a sheet of octahedral alumina
sandwiched in between two sheets of tetrahedral fluorosilica. Because in the
octahedral sheet Mg2+ ions substituted for some Al3+ ones, the lamellae are
anionically charged. Similarly, like MMT, FM behaves as a weak silicilic acid, with
Na+ as counterions in the interlamellar gallery. During dispersion, the fairly large
FM particles of average diameter around 5,000 nm (aspect ratio p ≤ 5,000) were
broken down into anisotropic nanoparticles resembling short fibres of 500 nm
length and 20 to 50 nm diameter, thus the effective aspect ratio (peff) for the clay
was only peff ≅ 20 to 50. Two series of CPNC samples were prepared, with non-
intercalated and with intercalated FM. In the latter case, FM was intercalated with
2MBODA (Ethoquad C12) in aqueous medium. Dry, intercalated FM was dispersed
193
Figure 42 Mechanical properties of four series of epoxy-based CPNC: MMT - not

intercalated purified bentonite; MMT/B - MMT intercalated with N,N,N,N-dimethyl
benzyl octadecyl ammonium chloride (2MBODA); FM/B - fluoromica intercalated
with 2MBODA; H - not intercalated hectorite; H/B - hectorite intercalated with
2MBODA. Data [Zilg et al., 1999a].
in trihydroxy-terminated oligo(propylene glycol) with Mn = 3.8 kg/mol, which,

after high shear mixing was cured with diisocyanatophenyl methane, accelerated
with 0.6 wt% N,N-dimethyl-benzylamine at 80 °C. According to XRD, the
interlayer spacing of neat FM (d001 = 0.9 nm) increased in the CPNC to 8.8 nm.
194
The clay lamellae were well dispersed within the matrix, but without full
exfoliation. The mechanical behaviour of the two series of PU/FM nanocomposites
is presented in Figure 43. Intercalation significantly improved the tensile strength
(by 60-240%) and elongation at break (by 130-400%), but it had a negative effect
on modulus. The CPNC seems to have clay platelets bonded to PU. In conclusion,
dispersion of intercalated synthetic fluoromica in a polyurethane matrix results in
the formation of intercalated (not exfoliated) structures that offer significant
improvement of mechanical properties (in comparison to neat PU).
An interesting use of PA-6-based CPNC was reported by Cheng et al. [2000].
The authors found significant differences in the suitability of PA-6 and its CPNC for
the preparation of microporous membranes. While neat PA-6 generated asymmetric
membranes with tight skin and a porous sublayer, the intercalated mica/PA-6 system
(PA-6/mica nanocomposites, M1030D from Unitika; Mn = 15 kg/mol, MI = 19)
produced skinless microporous membrane with an open, bicontinuous structure
that could easily be adjusted. Hence, while PA-6 produced membrane useless for
microfiltration, the mica-filled CPNC engendered perfectly adjustable, useful
products.
To close this discussion on CPNCs with non-MMT layered nanofillers, the
use of layered double hydroxides (LDH) should be mentioned. A recent review
described the synthesis and characterisation of these materials [Leroux and Besse,
2001]. The LDH ideal structural formula is:
[MIIxMIII1-x(OH)2]intra[Am-x/m·nH2O]inter
where MII and MIII are metal cations, A is the anion, and intra and inter denote
the intralayer domain and the interlayer space, respectively. The structure consists
of edge-sharing M(OH)6 octahedra. Partial MII to MIII substitution induces a positive
charge for the layers, balanced with the presence of the interlayer anions. LDH are
Figure 43 Mechanical behaviour of PU/FM and PU/FM-2MBODA

nanocomposites. (Full symbols – PU/FM, i.e., with non-intercalated clay; open
symbols – PU with FM-2MBODA (Ethoquad C12)). Data [Zilg et al., 1999b].
195
often prepared via coprecipitation using MII and MIII salts at constant pH, mostly
basic conditions. Their charge density is significantly higher than that of Na-MMT,
viz. 0.25 to 0.40 nm2/charge versus 0.70 nm2/charge for the latter. Correspondingly,
the CEC for the LDH material ranges from 0.6 to 4.8 meq/g, whereas that for
Na-MMT is about 1 meq/g. A lower CEC makes exfoliation easier.
There are three principal methods of LDH intercalation:
(a) Using such monomers as aniline, pyrrole, ω-aminoacid, methyl methacrylate,
vinylbenzene sulfonate, vinylpyrrolidone, vinyl acetate, etc.;
(b) Direct intercalation of extended polymer chains in the host lattice, for
example, PEG/MoO3, poly(p-phenylene)/molybdenum bronze, PANI/MoS2,
or PEG/NbSe2. Sometimes, a two-step intercalation (as for MMT) may have
to be used;
(c) Transformation of the host material into a colloid and precipitation in the
presence of the polymer.
Thus, numerous methods for the preparation of LDH/polymer systems have been
used, viz. coprecipitation, exchange, in situ polymerisation, two-step surfactant-
mediated incorporation, hydrothermal treatment, reconstruction, or restacking.
The latter method, effective via the exfoliation of the LDH layers, appears to be
more appropriate for the capture of monomers. Examples of polymer/LDH
systems are given in Table 31.
These multicomponent systems are thermally more stable than the pristine
inorganic compounds, leading, for example, to potential applications in flame
retardant composites. A large variety of LDH/polymer systems may be tailored
considering the highly tunable interlayer composition coupled to the choice of the
organic moiety. DNA may be stabilised in the interlayer space of (Mg2AlNO3) as a
gene reservoir. Some of the intercalated polymers present excellent physical
properties such as conductive properties (PANI), insulation (PS), or ion-gate
properties (polypyrrole (PPY)), but are difficult to process because of a lack of
mechanical strength. Numerous studies have focused on the use of conductive
polymers as capacitor, rechargeable battery materials or in electrochromic windows.
Hsueh and Chen [2003] prepared LDH (by co-precipitation in NaOH solution
of Mg(NO3)2·with Al(NO3)3), with polyimide (PI) and epoxy matrix, respectively.
According to TEM and XRD, in both nanocomposites the LDH were exfoliated.
In parallel, the mechanical performance of these systems was enhanced. In CPNC
with a PI matrix the elongation at break (εb) and maximum tensile strength (σy)
were obtained at ca. 4 and 5 wt% organoclay loading, respectively. Similarly, for
CPNC with epoxy matrix εb reached maximum at about 3 wt%, while σy
continuously increased up to the highest organoclay concentration of 7 wt%.
For both systems the tensile modulus and thermal decomposition temperature
also increased, while the thermal expansion coefficient decreased with LDH
loading. The fine dispersion of the inorganic component was illustrated by
photographs, which showed that in the whole range of LDH concentration the
epoxy nanocomposites remain transparent.
While exfoliation of any layered nanofiller is easier in a matrix with polar
groups, dispersion of clay or LDH in non-polar polymers is difficult. For these
reason two publication from B. Qu laboratories are of particular interest [Chen
and Qu, 2003; Chen et al., 2004]. The first describes exfoliation of Mg3Al(OH)8-
(C12H25SO4), or MgAl-LDH for short, by intercalation with PE-g-MAH in a
solution of xylene under reflux.
196
Table 31 Examples of polymeric nanocomposites based on layered

double hydroxide (LDH) [Leroux and Besse, 2001]
Polymer LDH Method* d
(nm)
PANI Cu0.66Cr0.33(OH)2(terephthalate)0.17·nH2O a 1.33
PANI Cu0.66Al0.33(OH)2(hexacyanoferrate)0.17·nH2O a 1.35
PVAl Ca0.66Al0.33(OH)2(OH)-0.33·H2O a 1.8
Poly(α, Mg0.74Al0.26(OH)2(CO3)2-0.13(NO3)-0.006·0.32H2O a, b 0.90
β-aspartate)
PSS Mg0.66Al0.33(OH)2(CO3)2-0.17·nH2O cop 2.08

Zn0.75Al0.25(OH)2(CO3)2-0.13·nH2O
PSS Zn0.75Al0.25(OH)2(CO3)2-0.13·nH2O co p 2.16
2-
PS Mg0.66Al0.33(OH)2(terephthalate) ·0.17·nH2O
0.17
a 2.32
PAA, PVS Mg0.66Al0.33(OH)2(CO3)2-0.17·0.17·nH2O cop 1.20,
1.31
PAA, PVS Zn0.75Al0.25(OH)2(CO3)2-0.13·nH2O co p 1.24,
1.33
PVS Co0.75Al0.25(OH)2(OH)-0.13·nH2O cop 1.33
PAA, PVS, PSS Ca0.66Al0.33(OH)2(CO3)2-0.17·nH2O cop 1.24,
1.31,
1.96
Polyacrylate Mg0.66Al0.33(OH)2(NO3)-0.33·nH2O a 1.34
Polyacrylate Ni0.7 Fe0.3(OH)2·nH2O b 1.26
PSS Zn0.66Al0.33(OH)2(Cl)-0.33·0.63H2O a-c 1.56,
2.12,
1.98
PEG Cu0.66Cr0.33(OH)2(Cl)-0.33·1.14H2O b 3.01
PEG/alkenyl Cu0.66Cr0.33(OH)2(Cl)-0.33·1.14H2O b 3.74
sulfonic acid
PANI sulfonate Cu0.66Cr0.33(OH)2(dodecylsulfate)-0.33·nH2O a 1.42
Notes: PANI = polyaniline, PVAl = poly(vinyl alcohol), PSS = poly(styrene
sulfonate), PS = Polystyrene, PAA = poly(acrylic acid), PVS = poly(vinyl
sulfonate), and PEG = poly(ethylene glycol)
*Methods a, b, c are described in the text, while cop indicates a templating
reaction, during polymer coprecipitation with a [Mg2Al] or [Zn3Al] LDH material
[Oriakhi et al., 1996]
197
The platelets of LDH were about 0.48 nm thick and ca. 70 nm in diameter. The
nanocomposites containing 5 wt% LDH had a higher decomposition temperature
(by ca. 60 °C), and greater thermal stability than PE-g-MA. In the second
publication Zn3Al(OH)8(C12H25SO4), or ZnAl-LDH for short, was prepared by
spontaneous self-assembly in an aqueous solution of Zn(NO3)2, Al(NO3)3, and
C 12H 25SO 4Na at pH ≅ 10. As before, the exfoliation of ZnAl-LDH was
accomplished by refluxing its suspension in a xylene solution of (unmodified!)
LLDPE for 24 h. The exfoliated nanocomposites contained up to 20 wt% of
ZnAl-LDH. Better thermal stability was observed. The method is expected to be
applicable to other polymers, viz. PP, PS, rubbers, and the polar ones.
Another interesting layered material is Zr(HPO 4) 2·H 2O, α-zirconium
phosphate (α-ZrP). Clearfield et al., synthesised it in 1964 and for years studied
its ion exchange ability [Clearfield et al., 1969; 1972]. In comparison to MMT
the α-ZrP has higher charge (CEC = 2), smaller interlayer spacing (d001 = 0.76 nm),
and it can be prepared with a desired aspect ratio (at least 100) and particle size
distribution. Crystalline α-ZrP has the layers formed by Zr and O atoms of the
phosphate groups, with one -OH group pointing into the interlamellar galleries.
More recently, to study the interrelations between CPNC structure and
performance, the team prepared the first nanocomposites with exfoliated α-ZrP
in epoxy [Sue et al., 2004]. Thus, α-ZrP was synthesised, intercalated with
monoamine-terminated polyether (Jeffamine M715), and then 1.9 vol% of the
intercalated α-ZrP was incorporated into DGEBA. According to TEM, XRD
and the optical transparency of the cured nanocomposites, full exfoliation was
achieved. The influence of hydrogen-bonded α-ZrP intercalate on the mechanical
properties of epoxy was investigated. The volume percentages of the specimen
components were: α-ZrP = 1.9, Jeffamine = 18.7 and DGEBA + curing agent =
79.4 vol%. Thus the cured specimen contained a large amount of the plastifying
intercalant: CH3O(CH2CH2O)14CH2CH2NH2. The rubbery plateau modulus of
the nanocomposite was about 4.5 times higher than that of the matrix. Upon the
addition of 1.9 vol% α-ZrP, the tensile modulus increased by 50%, and the yield
strength improved by 10%, but the elongation at break was drastically reduced.
However, the mode-I critical stress intensity factor, KIC, indicated that the fracture
toughness is not significantly affected by the addition of the intercalated nanofiller
– the epoxy resins are inherently brittle and/or notch-sensitive.
Nanocomposites of PA with up to 65 wt% of hydroxyapatite have been
prepared for use as a load-bearing bioactive material for bone repair or substitution
[Jie et al., 2003].
2.3.11 Summary of the Intercalation Methods

Clay intercalation for use as rheological additives, catalyst supports or
nanoreinforcements has been practiced for nearly 70 years. The initial applications
were for aqueous systems, and then for organic ones (e.g., thickening of oils or
greases). Intercalation for the preparation of CPNC is more recent, but the old
technology (developed for the greases) dominates the market. The developments
are summarised in Table 32.
198
Table 32 Summary of intercalation methods

Clay Intercalant d-spacing (nm) Comments
MMT None; (CEC = 1.0 to 1.2 0.96 Dry clay
meq/g)
MMT Water 1.3 Ambient humidity
MMT Ethylene glycol or sorbitol 1.7 Thickener
Clays with CEC CH3(CH2)n NH4+ cations 1.3-2.2 Spacing depends on
= 0.8 to 1.5 CEC and on n
meq/g (stepwise)
Clays Phosphonium or (as above) Alternatives to
sulfonium salts with ammonium; in aq.
aliphatic or aromatic or organic solvent
radicals
Clays Onium salt + organosilane ? Rheological
(CEC ≥ 0.75) additive
Na-MMT Aq. solution of ⇒ exfoliation Organic solvent
MB2HTA-chloride thickener
Na-MMT Aq. solution of hydroxy- ⇒ exfoliation Thickening of
polyoxy-ethylene-tri-alkyl- highly polar
ammonium chloride organic solvents
MMT Aq. solution of PVAl ≈ 2.0 PVAc 88%
hydrolysed
Na-MMT Aq. solution of ω-amino- ⇒ exfoliation For PA-based
C12-18 acid onium ion, viz. CPNC (Toyota)
H3N+C12 H24 COOH and
H3N+C12 H25 with
caprolactam
MMT ODA-, 2MODA, ⇒ exfoliation For PA-based
2M2ODA cation, and CPNC
aminoethyl aminopropyl (AlliedSignal)
trimethoxysilane
Na-MMT + Liquid polybutadiene ⇒ exfoliation For rubber-based
aqueous HCl (PBD) CPNC (Toyota)
Na-MMT (CEC Aq. 2M2ODA chloride, ⇒ exfoliation For rubber-based
= 1.2 meq/g) then toluene solution of CPNC (Toyota)
end-hydroxylated PBD
Na-MMT (CEC Aq. chloride melt- ⇒ exfoliation For rubber-based
= 1.2 meq/g) compounding with low- CPNC (Toyota)
MW PP-MA
199
Table 32 Continued
Clay Intercalant d-spacing (nm) Comments
A layered Hydrolysed alcoholates: ⇒ exfoliation For PO-based
material, e.g., Si(OR)4, Al(OR)3, CPNC (Dow)
MMT Ge(OR)4, Si(OC2H5)4,
Si(OCH3)4, Ge(OC3H7)4,
Ge(OC2H5)4
Clay filler Amino-functional silane + ⇒ exfoliation For PO-based
carboxylated or maleated CPNC
semicrystalline PO
Acidified clay; Lewis bases, esp. primary ⇒ exfoliation Tested for epoxy-
H+MMT amines and PU-based
CPNCs
Synthetic Aq. solution of Intercalation 2 weeks
smectite ethylenediamine + polyol, intercalation for
then oleophilic solution of fire-resistant clays
triethyl phosphate (TEP)
MMT Aq. solution of PVP (at 1.5-11.0; 3-4.5 Thickener or for
least 10% of water is is optimum drug-delivery
needed)
MMT Polar, water soluble ⇒ exfoliation For CPNC as well
compounds
Smectite Aq. solution of AlCl2(OH) 2-6 (rigid) For catalyst support
+ ZrOCl2
MMT Waterless PEG in 2-6 h 1.77
Organoclay Monomer or polymer ⇒ exfoliation For PA-type
Inorganic Inorganic polymer having 1.5-6.1 For TS, TP or

layered materials colloidal particles, e.g., rubber-based
hydrolysable metallic CPNC
alcoholates
200
Exfoliation of Clays
2.4
The high surface-to-volume ratio of nanoparticles leads to a high reinforcement

efficiency. Thus, CPNCs with well dispersed platelets at a low clay loading of 2
to 5 wt% show highly increased modulus, yield strength, DTUL as well as reduced
flame propagation and permeability. In the crystallisable polymer matrix, the
clay platelets (if not totally covered by the intercalant organic tails) promote
faster crystallisation and higher levels of crystallinity, which results in improved
solvent and moisture resistance, but reduced impact strength. The presence of
clay may result in modification of the crystalline structure of the matrix polymer
(e.g., α to γ transformation in PA-6), which may promote enhancement of the
performance characteristics.
Owing to the nature of the nanoscale reinforcement, the CPNC may be treated
as an improved grade of a homopolymer, hence it may be used as a replacement
for its matrix polymer in diverse multicomponent polymeric systems, viz. blends,
composites or foams. For example, Akkapeddi in 2000 reported using CPNC
for making either short or long glass fibre (GF) reinforced composites, getting
good processability (e.g., fast moulding cycle), low density, further improvements
of modulus, strength, moisture resistance, permeation barrier, etc. The materials
were aimed at automotive parts (viz. fuel system components, fuel tanks, door
and rear quarter panels, consoles, door panels, pillars, under hood components),
packaging (containers, films for food and electronics packaging), appliances,
building & construction, electrical & electronic, lawn & garden, power tool
applications, etc.
There are four basic structures for polymer/clay mixtures:
1. Conventional clay-filled composite with micron-sized aggregates of clay
particles.
2. Nanocomposites with intercalated clay.
3. Exfoliated nanocomposites with locally ordered structure, where the ordering
is imposed by flow and concentration, φ > φmax.
4. Exfoliated nanocomposites with disordered structure, φ < φmax.
Not all performance characteristics depend to the same degree on exfoliation.
However, as Kojima et al. [1993] have shown (see Table 33), the benefits increase
with the degree of dispersion. Thus, the goal of CPNC technology is to achieve
the highest possible degree of clay exfoliation, i.e., the best dispersion and
distribution in a polymeric matrix.
Exfoliation is the last step in the preparation of CPNC. The methods for
achieving it can be discussed under three titles:
201
Table 33 Effect of the degree of dispersion on performance. Data

[Kojima et al., 1993]
Material Clay E σ NIRT HDT (°C)
(wt%) (GPa) (MPa) (kJ/m2)
PA-6 0 1.1 69 2.3 65
Intercalated 5 1.0 61 2.2 89
Exfoliated 4.2 2.1 107 2.8 14 5
Notes: E is tensile modulus; σ is yield stress; NIRT is notched Izod impact

strength at room temperature; HDT is heat deflection temperature
1. Polymerisation in the presence of organoclay.

2. Melt compounding a polymer with a suitable organoclay complex.
3. Other exfoliation methods:
• Combining the organoclays with latex.
• Ultrasonic exfoliating of organoclay particles in a low MW polar liquid.
• Others, viz. sol¯gel templating, co-precipitation, etc.
In Part 4 of this book the patent literature on CPNC is summarised, first with
thermoplastic polymer matrices, then with those of thermosets and elastomers.
Since the maximum performance is achieved when clay is exfoliated, the
exfoliation methods are discussed there in depth. For this reason, this chapter on
the basic elements of CPNC technology will focus on the general aspects of
exfoliation technology.
2.4.1 Principles
The layered inorganic materials that are to be used as nanofillers, e.g., natural or
synthetic clays, have strong ionic and van der Waals interactions and small
interlamellar spacing, much too small for allowing organic molecules, monomers,
oligomers or polymers, to diffuse into. Expansion of the interlayer spacing to
total exfoliation is accomplished in several steps.
Since clays are strongly hydrophilic, the first step is suspending them in an
aqueous medium. Few types of hydrophilic, highly polar, low MW polymers
(viz. PEG or P2VP) may be used to exfoliate directly such a swollen clay. For the
great majority of CPNCs with hydrophobic polymeric matrices the swollen clay
must be intercalated with one or two intercalants (e.g., onium salt and silane or
an epoxy compound). The hydrophobic monomers and polymers require that
the nanofiller is pre-intercalated, and often compatibilised.
The following four pathways have been distinguished [Usuki, 2001]:
1. Hydrophilic matrix with strong polar groups, e.g., P2VP or PEG:
water hydrophilic polymer
clay swollen clay CPNC
water polar organic

clay swollen clay CPNC
202
2a. Hydrophobic matrix with strong polar groups, e.g., PA or PEST:

intercalant(s) monomer
clay intercalated clay
polymerisation
expanded clay CPNC
2b. Hydrophobic matrix with strong polar groups, e.g., PA:
intercalant(s)
clay intercalated clay
compounding
+ polar polymer CPNC
3. Hydrophobic non-polar matrix, e.g., PP:
intercalant(s)
clay intercalated clay + compatibiliser
compounding
+ non-polar polymer CPNC
The difficulty in achieving exfoliation increases in the sequence from pathways 1
to 3. The key to good performance is on the one hand obtaining initial expansion
of the interlayer galleries for penetration by monomer(s) or polymer, and on the
other good thermodynamic miscibility between the preintercalated clay platelets
and the polymeric matrix. In the case of the reactive exfoliation processes
(pathways 1 and 2a) an important additional condition is that the polymerisation
inside the gallery is at least as fast as that outside it. When this condition is not
met, the polymer formed outside the interlamellar galleries may hinder expansion
of the interlayer space, leading to intercalation but not exfoliation. It is noteworthy
that the clay and the intercalating onium salt often affect the polymerisation rate
– one must ascertain that these effects are positive, i.e., that these catalyse the
reaction. Another often forgotten requirement is the stability of the clay-matrix
bond. The CPNC must survive the forming stage! There are very few polymers
that can be processed below 200 °C. Above this temperature the ammonium
intercalants (especially quaternary) are not thermally stable (especially in the
presence of oxygen and shear field). Reaggregation of clay platelets (that were
exfoliated during in situ polymerisation) during melt processing of CPNC has
been reported.
As the listed pathways indicate, either a single one- or a two-step sequential
intercalation-cum-compatibilisation may be required. Thus, the pathways focus
on the chemical aspects of intercalation. Unspecified in these are the contributions
of physics: the thermodynamics that controls the phase behaviour as well as P
and T effects on the interlayer spacing, molecular diffusion, flow which introduces
dispersive forces, radiation-absorption which may accelerate the exfoliation
process under the influence of, e.g., ultrasonics, etc.
Pathway 1 has been presented in sufficient detail in Section 2.3.5.2, hence
there is no need to discuss it again. Pathway 2a is pertinent to virtually any
polymeric nanocomposite, with thermoplastic, thermoset or elastomeric matrix
hence a brief description of these systems will be given. Finally, pathways 2b and
3 belong to the most important mechanical exfoliation methods and need more
detailed analysis.
203
2.4.2 Polymerisation in the Presence of Organoclay

Several different methods have been explored to prepare CPNC by chemical reactions.
Following Usuki’s suggestions [Usuki, 2001], one may categorise them as:
1. Monomer intercalation – viz. preparation of PA-6 nanocomposites.
2. Monomer modification – viz. preparation of acrylic-based nanocomposites.
3. Non-reactive intercalated clays – viz. preparation of styrenic-type CPNC.
4. Co-vulcanisation – viz. preparation of NBR-based nanocomposites.
5. Common solvent method, frequently used to prepare PI-based CPNC.
6. Others.
In the methods 1 and 2 the clay is intercalated with a compound that subsequently
enters the polymerisation reaction – polycondensation in method 1, and radical
polymerisation in method 2. Thus, as a result of either of these two processes
end-tethered CPNC is obtained.
2.4.2.1 Monomer Intercalation – PA-6 Nanocomposites

Preparation of CPNC via in situ polymerisation was used at the Toyota Institute
for the first nanocomposites with PA-6 as matrix. The process involved three
steps [Deguchi et al., 1992]:
1. Intercalation of Na-MMT with ω-amino dodecanoic acid chloride in water
– the interlayer spacing increased from d001 = 0.96 (dry) to 1.3 (wet) to 1.8
nm (intercalated).
2. Mixing the intercalated clay with ε-caprolactam and water at the ratio of
1:9:9 - the interlayer distance further increased to d001 = 3.87 nm. At this
stage, a catalyst and an activator were added.
3. Polymerisation at 100 and 250 °C for 48 h followed by TSE extrusion. A
high level of exfoliation was obtained, with rare short stacks containing two-
to-three clay platelets evident in TEM micrographs.
The following year, Usuki et al. [1993a] found that clay, intercalated with
ω-amino dodecanoic acid can be swollen by molten ε-caprolactam (30 to 98 wt%).
Polymerisation under nitrogen at 250 to 270 °C for 48 h resulted in well-dispersed
silicate layers in a PA-6 matrix. The TEM images showed single platelets even in
CPNC containing 31 wt% MMT. At 2 wt% of organoclay loading, the modulus
increased to 1.5 times that of PA-6, the heat distortion temperature increased
from 75 to 140 °C, and the moisture permeability was reduced by 50%. At the
same time the density increased from 1140 to 1150 kg/m3, i.e., by a theoretically
predictable 0.88% [Ube Industries, Ltd., 2000]. The method was reported
economic, efficiently producing a PNC with any PA matrix, having a wide viscosity
range for all processing operations. The material had good mechanical properties,
heat resistance, improved dye affinity and whitening resistance during stretching.
When discussing exfoliation it is important to pay attention to clay
concentration and the aspect ratio, p. During shear flow platelets rotate and the
maximum packing volume fraction of such ‘encompassed volume’ spheres is
φmax = 0.62. It can be shown that for such platelets:
φmax = 0.93/p (24)
When: φ > φmax the platelets cannot rotate and have to locally align. In this case
the distance between them can be calculated from geometry as:
204
d001 = (hclay ρclay / ρ polymer )(100 / wlocal − 1) + hclay ≈ + a0 + a1 / w (25)
where hclay is the platelet thickness, ρclay and ρpolymer are densities, and wlocal is the
local clay concentration (in wt%), a 0 and a 1 are corresponding equation
parameters.
Owing to the tendency of the clay platelets to align parallel to each other in
local stacks, the clay concentration within the stack is not known, hence the
parameters in Equation 25 cannot be calculated from first principles. However,
since it can be assumed that the concentration within stacks is proportional to the
average, global concentration: wlocal ∝ w (wt%), d 001 should be inversely
proportional to the clay content. Thus, for organoclays with large aspect ratio
the formation of local stacks takes place at low concentration, and the interlayer
spacing may be small, not because of a lack of exfoliation, but due to the crowding
effects. It is worth noting that at φ > φmax the interlayer thickness is independent
of the aspect ratio – p only dictates the concentration at which the local stacking
starts.
Okada and Usuki [1995] published data on the interlayer spacing in PA-6/clay,
measured by XRD and TEM. Using Equation 25 the maximum packing for free
platelet rotation is predicted for organoclay content below 1.13 wt%. From the
relation, at a clay content of 2 wt% the interlayer spacing d001 is 44.2 nm (see
Figure 44). Evidently, starting with ω-aminoacid end-tethered CPNC were
produced.
Emulsion polymerisation was used to prepare CPNCs with PMMA as a matrix
[Choo and Jang, 1996]. Thus, MMA was polymerised in the presence of Na-
Figure 44 Basal spacing in CPNC versus organoclay content as measured by XRD

and TEM. The organoclay was MMT intercalated with ω-dodecyl acid:
NH2(CH2)11COOH and ε-caprolactam . Data [Okada and Usuki, 1995]. The line
indicates Equation 25 dependence with a0 = 1.37; a1 = 0.856; and the correlation
coefficient r = 0.991.
205
MMT. The intercalating PMMA macromolecules were found oriented parallel

to the clay lamellae. The interlayer distance decreased with MMT loading from
d001 =1.73 nm at 10 phr to 1.28 at 50 phr (33 wt%). Both the thermal stability
(char formation on decomposition) and tensile properties were enhanced. The
system was not end-tethered, but the ion-dipole interactions were strong enough
to be the driving force for the introduction of MMA monomer into the
interlamellar galleries and bonding of the PMMA molecules to clay surfaces.
This work was extended to the emulsion copolymerisation of ABS in the
presence of clay [Jang et al., 2001]. The clay content varied from 10 to 50 phr
and correspondingly the interlayer spacing changed from d001 = 1.75 to 1.56 nm.
Thus, it seems that the process results in expansion of Na-MMT particles (ca.
500 nm diameter) by monomer intercalation. In either case clay was not exfoliated.
Similar results were obtained by adding an aqueous dispersion of Na-MMT to
SBR latex, then coagulating the emulsion, washing, drying and curing [Zhang et
al., 2000b]. Clay ‘bundles’ 4 to 10 nm thick and about 200 to 300 nm long were
observed, thus intercalation not exfoliation was obtained.
Better results for MMT exfoliation in PMMA matrix were obtained using the
monomer modification method, described in Section 4.2.2.2. Exfoliation was
also obtained using a polar intercalant-compatibiliser, e.g., PCL [Kim et al.,
2001a]. The other approach is based on clay intercalation with a compound that
chemically participates in the subsequent polymerisation.
Full exfoliation was reported for a PE/MMT system prepared by Ziegler-Natta
polymerisation of ethylene in the presence of organoclay [Jin et al., 2002]. The
latter was Cloisite® 30B (MMT with MT2EtOH) treated with TiCl4 to affix the
catalyst to the intercalant –OH group. As was expected, polymerisation in the
presence of Na-MMT had little effect on the clay interlayer spacing. The authors
processed the exfoliated polymerisation product by compression moulding or TSE
extrusion. The processing resulted in a partial re-aggregation of MMT platelets
with d001 ≅ 1.4 nm. The extent of re-aggregation depended on the processing
conditions – it was slight for compression moulding, but quite pronounced for
extrusion.
The polymerisation route was also selected by Alexandre et al. [2002a,b].
Thus PE was polymerised in the presence of either MMT or hectorite. The clays
were first treated with trimethyl aluminium-depleted methyl aluminoxane, and
then a Ti-based constrained geometry catalyst and monomer were incorporated.
The tensile properties of the resulting CPNC were poor and essentially independent
of the nature and content of the silicate. When hydrogen was used to control the
molecular weight of PE the tensile modulus was significantly increased (from
0.69 to 2.48 GPa for PE and PE with 11.4 wt% clay), but at a cost of a dramatic
reduction of the strain at break (from 244 to 3%, respectively). Clay exfoliation
in the reaction products was confirmed by XRD and TEM. However, as it has
been reported before, during melt processing of the CPNC the interlayer spacing
partially collapsed. Evidently, the system is thermodynamically unstable and the
strong solid-solid interaction between clay platelets drives the phase separation.
2.4.2.2 Monomer Modification – Acrylic-Based Nanocomposites

Usuki et al. [1995] introduced the term ‘monomer modification’ to indicate that
the organoclay was intercalated with a reactive compound, which subsequently
participates in polymerisation. One may presuppose that preparation of PA-6/clay
CPNC (which starts with ω-amino dodecanoic acid) also belongs to this category.
206
However, while PA polycondensation results in a single attachment of a

macromolecule to a clay platelet, the monomer modification strategy results in a
copolymerisation of the reactive monomers, one type of these being ionically
bonded to clay. Thus, the resulting copolymer may have numerous molecular
units bonded to the clay surface. Monomer modification will usually start with
intercalation of clay using molecules that have at least one group capable of
reacting with other monomer(s), forming a multitethered, exfoliated CPNC.
This approach has been used for the preparation of PMMA/organoclay [Biasci
et al., 1994]. The organoclay was MMT intercalated with quaternary ammonium:
either 2-(N-methyl-N,N-diethyl ammonium iodide)-ethylacrylate (QD1) or with
2-(N-butyl-N,N-diethyl ammonium bromide)-ethylacrylate (QD4) – owing to
the bulkiness of the intercalating molecules only up to 58% of the clay active
sites were exchanged. The radical copolymerisation of MMA with the intercalated
clay was carried out either in bulk or in acetonitrile at 60 °C. As a result of
intercalation and subsequent polymerisation the interlayer spacing increased to
d001 = 1.45 to 1.78 nm, respectively. The length of MMA sequence in the formed
copolymers was 3.5 and 1.1 to 8.2, after bulk and solution reaction, respectively.
Apparently, bridging the interlamellar gallery by the macromolecular chain
prevented exfoliation. When the sequence was reversed (intercalating Na-MMT
with MMA/QD1 or MMA/QD4 copolymers) the interlayer spacing increased to
d001 = 2.96 nm and thermal stability was enhanced.
Usuki et al. [1995] prepared CPNC by first copolymerising ethyl acrylate
(90 mol% of EA: CH 2 =CHCOOC 2 H 5 ), acrylic acid (10 mol% of AA:
CH2=CHCOOH), and a quaternary ammonium salt of dimethyl aminopropyl
acrylamide: Q = (CH2=CHCOOCH2CH2CH2N+(CH3)2C3H7)Cl– (0.12, 36, 56, and
0.89 mol%). Next, the copolymer was mixed with an aqueous suspension of
Na-MMT to induce intercalation. Four CPNCs were prepared with a clay content
of 1, 3, 5, and 8 wt%. CPNCs with MMT ≥ 3 wt% showed high viscosity and
yield stress. In comparison to the neat copolymer, incorporation of the end-tethered
clay increased viscosity by 4 to 6 orders of magnitude. The CPNCs were used for
the preparation of transparent films (crosslinked with melamine). Gas permeability
through the film followed Equation 23, with p ≅ 100 (see Figure 45).
Heinemann et al. [1999] prepared PO-based PNCs starting with hectorite
intercalated with dimethyl benzyl stearyl ammonium chloride (2MBODA), having
d001 = 1.96 nm. When HDPE was polymerised in the presence of the intercalated
clay, the XRD peak shifted to d001 = 1.40 nm. Best results were obtained for
LLDPE-type ethylene-octene copolymers. The authors reported superior
performance of the reactively prepared CPNCs over that prepared by melt
compounding. However, the intercalated clay was found to interfere with the
metallocene catalysts and the processing of these CPNCs resulted in re-aggregation
of the clay platelets.
A bulk polymerisation method was used to prepare PS-based PNC [Fu and
Qutubuddin, 2000; 2001], starting with MMT intercalated by dimethyl
vinylbenzyl dodecyl ammonium chloride (2MVBDDA). Owing to good miscibility
of 2MVBDDA with styrene, a uniform dispersion of platelets was obtained.
Polymerisation for 48 h at 60 °C resulted in exfoliation. At 7.6 wt% of clay, the
modulus of the PNC was about 70% higher than that of PS.
MMT was intercalated with either oligo (n = 25)-ethylene-glycol diethyl methyl
ammonium chloride (SPN) or with methyl-trioctyl ammonium chloride (STN).
The organoclays were dispersed in either MMA or styrene by ultrasonication for
207
Figure 45 Oxygen permeability through crosslinked acrylic film versus clay

content. The line was calculated from Equation 23 with p = 100 . Data [Usuki et
al., 1995].
7 h then radically polymerised. For comparison, PMMA and PS were also

synthesised in the presence of the quaternary amines [Okamoto et al., 2000;
2001b,c]. In the earlier publication, polymerisation of the CPNCs systematically
resulted in decreased interlayer spacing, viz.:
1. MMA/STN; before polymerisation d001 = 2.96 - after 2.66 nm.
2. MMA/SPN; before polymerisation fully exfoliated - after a shoulder at
4.55 nm.
3. Styrene/SPN; before polymerisation nearly totally exfoliated with only a small
shoulder at d001 = 3.65 - after a large peak at 3.65 nm.
This behaviour suggests a thermodynamically driven phase separation. The
dynamic mechanical temperature scans indicated only a minor change in the
storage modulus. In the latter publication only the SPN organoclay was used.
Polymerisation of the MMA/SPN system was carried out as in the earlier
publication, but in the presence of small amount of polar comonomer, viz.
N,N-dimethyl aminopropyl acrylamide (PAA), N,N-dimethyl aminoethyl
acrylamide (AEA) or acrylamide (AA). The radical polymerisation resulted in
exfoliation. The storage modulus versus T scan indicated a significant increase,
viz. from 1 to 3 GPa.
Similarly good exfoliation was reported for PS/organoclay systems [Zhang et
al., 2003]. The authors used one non-reactive intercalant (3MHDA) and three
reactive ones, each containing one methacryloyloxy and two methyl groups, and
in addition either a benzyl, octyl or hexadecyl group. Na-MMT was pre-
intercalated with each of these, and then dispersed in styrene. The suspension
was transformed into oil-phase for γ-ray initiated suspension polymerisation. At
5 wt% organoclay loading, exfoliation was obtained for all three reactive
organoclays, while only intercalation occurred with the MMT-3MHDA.
208
Soap-free emulsion polymerisation of MMA was used to prepare exfoliated

CPNC with PMMA as a matrix [Choi et al., 2001]. Thus, the reaction was carried
out in two steps. In the initial step, Na-MMT was dispersed in water with 25%
(of the total amount) of MMA and 2-acryl-amido-2-methyl-1-propane sulfonic
acid (AMPS). The ratio of MMT/AMPS varied from 8 to 67. AMPS played a
triple role as a surfactant, intercalating agent and coreactant. In the second step,
the remaining monomer was used to complete the reaction. XRD and TEM
showed that the PNCs containing up to 10 wt% of Na-MMT were exfoliated.
Surprisingly at 10 wt% of Na-MMT the exfoliation occurred after 10 min of
reaction. The molecular weight of PMMA in PNC slightly decreased with the
AMPS content, while the glass transition temperature (Tg) and storage modulus
(E´) significantly increased.
2.4.2.3 Non-Reactive Intercalated Clays

Translucent acrylic nanocomposites were recently described [Dietsche et al., 1999;
2000]. The CPNC was prepared by polymerisation of methyl methacrylate-
dodecyl methacrylate copolymer in the presence of 2-10 wt% bentonite
intercalated with N,N,N,N-dimethyl dioctadecyl ammonium (2M2ODA).
Addition of n-dodecyl methacrylate improved interactions and accounted for the
improved stiffness-to-toughness balance, higher Tg and thermal stability, in
comparison to the corresponding copolymer. Evidently, this polymerisation
strategy does not create covalent bonding between clay and the acrylic matrix.
The only bonding that could take place is by cocrystallisation of the C12 paraffinic
chains.
Recent patents from Eastman [Barbee and Matayabas, 2000; Matayabas et
al., 2000] described PET-based CPNC with enhanced barrier properties. Thus,
MMT was intercalated (with a quaternary onium salt) and then treated with a
secondary intercalant, e.g., PEG, PCL or vitamin E. The organoclay (d001 = 2.2 to
4.2 nm) was incorporated into PET either by polycondensation or melt
compounding, followed by solid-state polymerisation. TEM showed mostly
individual platelets with only few tactoids and aggregates.
PC-based CPNC was prepared starting with PC-cyclomer and MMT
intercalated with dimethyl ditallow ammonium cation (2M2TA; B34 from Rheox,
Inc.; d001 = 2.47 nm) well washed with water/ethanol to remove excess quaternary
ammonium salt [Huang et al., 2000]. Cyclic oligomers of PC have lower solution
and melt viscosities (compared to the corresponding polymer), thus the
intercalation process is significantly easier. For example, the organoclay was
dispersed in CH2Cl2 and mixed with either PC or PC-cyclomer. After 5 min of
mixing with PC, the basal reflection was identical to that of B34. By contrast,
intercalation with PC-cyclomer was quick, increasing d001 to 3.62 nm. The
enhanced intercalation rate may be related not only to the lower viscosity, hence
enhanced diffusivity of the cyclomer, but possibly to the difference in molecular
architecture as well, the absence of end groups and the intermolecular interactions
between the cyclomer and the clay surface.
Similar differences between the intercalation processes of PC and PC-cyclomer
were observed during melt processing. After 24 h of melt annealing with PC d001
= 3.27 nm was obtained – the same as obtained by intercalation from solution.
By contrast, melt annealing with PC-cyclomer readily resulted in d001 = 3.8 nm.
Furthermore, when a mixture was compounded in an internal mixer for 1 h at
180 °C, an exfoliation was achieved. Subsequently, raising the temperature to
209
240 °C for 10 min, caused ring-opening polymerisation, converting the cyclomer

to linear PC (MW = 40 kg/mol). TEM showed the presence of individual layers
as well as tactoids consisting of 3 to 5 platelets. Thus, again partially exfoliated
CPNC was obtained without covalent bonding between the clay and the matrix.
2.4.2.4 Co-Vulcanisation
Toyota was the first to develop a process for producing polyolefin (PO)-based
CPNC [Usuki et al., 1989]. However, the patent claims extend to ‘vinyl-based
polymeric compound, a thermosetting resin and a rubber’. Ammonium salt having
a terminal vinyl group was used to intercalate MMT. The product was mixed
with a vinyl-based monomer and/or oligomer, e.g., ethylene, propylene, butadiene,
methylmethacrylate, styrene, etc. The mixture could be polymerised either in
bulk, suspension or in solution reaction, by a radical, cationic, anionic,
coordination or condensation mechanism. Polymerisation took place within the
interlayer space, expanding the interlayer distance to d001 > 3.0 nm.
However, to prepare exfoliated CPNC with a rubber, first MMT was reacted
with low molecular weight liquid rubber. For example, in an aqueous solution of
DMSO a liquid acrylic rubber (amino-terminated butadiene-acrylonitrile rubber
(ATBN), MW = 3400, 16.5% AN), HCl, and Na-MMT (clay platelet thickness
= 1.0 nm, p = 1000, CEC = 1.19 meq/g) were dispersed. The reaction product
was filtered and dried. Pulse NMR indicated that a strong bond was formed
between MMT and ATBN, with ca. 20% of the rubber molecules restricted near
the interface. XRD indicated that the (001) peak of MMT had disappeared,
d001 > 8.8 nm, and the MMT platelets were uniformly dispersed in the matrix.
Next, the complex (containing 32.5 wt% of MMT) was cooled with liquid N2,
crushed by a hammer mill and mixed with NBR (AN = 33%). The blends
(containing 5 or 10 wt% MMT) were vulcanised with sulfur. Superior
performance in tensile, dynamic viscoelastic, and swelling tests were observed.
A similar method has been used to prepare ATBN-intercalated MMT,
subsequently mixed with NBR and vulcanised [Kojima et al., 1993a]. TEM of
the resulting CPNC showed intercalated, well-dispersed short stacks of MMT
dispersed in the matrix. The permeability reduction for H2 and H2O through the
CPNC (containing 3.6 wt% of MMT) when compared to a standard rubber
with 10 vol% of carbon black was reduced by 37 and 26%, respectively.
2.4.2.5 Common Solvent Method – Polyimide Based Nanocomposites

Yano et al. [1993; 1997] discovered that organoclay intercalated by ion exchange
with dodecyl ammonium chloride (DDA), could be homogeneously dispersed
in N,N-dimethyl acetamide (DMAc). Thus, to prepare PI/clay films, organoclay
was dispersed in DMAc, then diamino diphenyl ether, pyromellitic dianhydride
was added and the solution stirred for 6 h. The film was cast from a
homogeneous mixture of organoclay and polyamic acid, and was heated at
300 °C to polymerise. With 2 wt% of clay the water and CO2 permeability
decreased to 50%. XRD and TEM showed that the CPNC was exfoliated [Lan
and Pinnavaia, 1994].
As an extension of this procedure, nematic liquid crystal (LC) with (up to
2 wt%) MMT was prepared [Kawasumi et al., 1998]. Thus, MMT was
intercalated with a variety of ammonium cations, including 4-cyano-(4´-biphenyl-
oxy)-undecyl ammonium salt, which showed enhanced miscibility to the LC.
210
The intercalated clay was than dispersed in dimethyl formamide (DMF) and the
LC was added. The solvent was slowly evaporated at 50 °C under vacuum, while
stirring. When the clay had good affinity for LC, the system was homogeneously
dispersed. The CPNC exhibited a bi-stable and reversible electrooptical effect
between a light scattering state and transparent state, which could be selected by
changing the frequency and voltage of the applied electric field.
In 1999 Yang et al., further examined the common solvent method for the
preparation of CPNC with PI as matrix. The work focused on the influence of
the intercalation agents upon dispersability of organoclay in a selected solvent
(DMAc) as well as that in PI. First, Na-MMT was intercalated with either amino
acids, primary aliphatic amines or quaternary ammonium salt, viz.: (1)
p-aminobenzoic acid (ArNCO), (2) ethanolamine (HONH), (3) N,N-dimethyl
aminoethyl methacrylate (DMAEM), (4) dodecylamine (12CNH), (5) 1-hexadecyl
amine (16CNH), (6) hexadecyl-trimethyl amine (3MHDA) and (7)
6-aminohexanoic acid (6NCO). The interlayer spacing of the organoclays
increased from d001 = 1.26 nm (Na-MMT) to, respectively, 1.27, 1.29, 2.16,
2.87, 3.70, 4.05, and 4.96 nm. However, the dispersability did not follow the
same order – the best dispersability in DMAc and PI was observed for the
intercalants 1, 2, 5 and 7, the worst for 3 and 6. Evidently, the dispersability
depends on the type of functional groups present in the solvent or PI and the
bulky group of the intercalation agent. Thus, one can disperse clay aggregates
(or tactoids) well without exfoliation, but the CPNC properties depend on the
homogeneous dispersion of MMT platelets.
The organosoluble PI was based on pyromellitic dianhydride (PMDA) and
4,4´-diamino-3,3´-dimethyl-diphenyl methane (MMDA). The organoclay was
added to DMAc and agitated for 3 h at 90 °C before adding it to MMDA solution
in DMA, which was followed by addition of PMDA. The mixture reacted at
room temperature for 6 h then it was cast on a glass and heated at 100 °C for
6 h, 150 °C for 4 h and 270 °C for 2 h under N2 to obtain MMT/PI hybrids.
The properties of the final product greatly depended on the degree of
dispersion. Only when the MMT was well dispersed did the CPNC show good
performance, e.g., simultaneous high strength and toughness, improved thermal
stability, decreased thermal expansion coefficient, retention of the solubility of
the polyimide matrix and high optical transparency. The chemical structure of
an intercalation agent imposes great influence on the dispersion of MMT. MMT
modified with 1-hexadecyl amine (HDA) showed the best dispersion behaviour
and the best set of properties.
Tyan et al. [1999a,b] observed that imidisation of polyamic acid (PAmA) is
accelerated by the presence of organoclay. The organoclay was prepared by
intercalating Na-MMT (CEC = 0.764 meq/g) with p-phenylene diamine. During
the intercalation only one amine group was converted into a cation (–NH3+).
The other -NH2 group was able to react with the dianhydride end group of
PAA when these molecules diffused into interlayer galleries. PAA was synthesised
by dissolving 4,4´-oxydianiline (ODAn) and pyromellitic dianhydride (PMDA),
in DMAc at 25 °C under N2. To a viscous PAmA solution a suspension of
organoclay in DMAc was added then mixed to obtain PAA/organoclay/DMAc.
During the reaction, the intercalant became an integral part of the PI molecules,
making these nanocomposite more thermally stable and mechanically stronger.
The spin-coated films containing 0, 2, 5 or 7 phr of organoclay were dried then
heated at 150, 200, 230 and 250 °C. XRD indicated that the interlayer spacing
211
of organoclay was d001 = 1.549 nm, but all PAA/organoclay systems were
exfoliated. In the presence of organoclay the imidisation temperature and the
imidisation time were reduced. For example, the imidisation temperature was
reduced from 300 to 250 °C, while at 250 °C the reaction time was reduced to
15 min (for 7 phr of organoclay). Initially, the reaction followed the first-order
kinetics:
ln(1-p) = -kt (26)
where p is the extent of reaction at a reaction temperature T, k is the rate constant
and t is the reaction time. The temperature effects were well-described by the
Arrhenius dependence:
k = A exp{-Ea/RT} (27)
where A is the pre-exponential factor, R is the gas constant, and Ea is the activation
energy (see Figure 46).
In the next paper 4,4´-oxydianiline (ODAn) was used as an intercalant [Tyan
et al., 2000]. After drying in a vacuum oven at 80 °C TGA indicated the presence
of 5.41 wt% structural water and 29.0% of the intercalant. The interlayer
spacing of the organoclay was d001 = 1.5 nm. PAmA was prepared by dissolving
ODAn in DMAc under N2 then adding 3,3´-4,4´-benzophenone tetracarboxylic
dianhydride (BTDA). The system was stirred for 1 h, which produced a viscous
PAmA solution to which different quantities of organoclay suspension in DMAc
were added (to yield 0, 1, 2, 3, 5, and 7 wt% of organoclay in the product),
and then mixed for 12 h. The organoclay-PAmA suspension was cast, and then
solvent was removed under vacuum at 30 °C over 48 h. Imidisation was carried
out in an air circulation oven at 100, 150, 200, and 300 °C for 1 h and then at
400 °C for 5 min. In the final product full exfoliation was obtained. The
Figure 46 Arrhenius plot of the imidisation rate constant for 0, 2, 5 and 7 phr of
organoclay in the CPNC. Parameters of the Arrhenius equation are listed. Data
[Tyan et al., 1999a,b].
212
modulus, the maximum stress and the elongation at break of these CPNCs are
increased with organoclay content – see Figure 47.
CPNC with PI as a matrix has also been produced starting with MMT
(CEC = 1.15 meq/g) intercalated with N-hexadecane pyridinium chloride (HP-MMT)
[Gu and Chang, 2001]. PAA was prepared in a THF/MeOH solution, dissolving
in it at room temperature first ODAn then pyromellitic dianhydride (PMDA)
and mixing the resulting solution for 3 h. Then a solution of triethylamine (Et3A)
was added and the process took another 3 h of stirring to complete. Next, to a
stirred viscous pale-yellow solution a suspension of HP-MMT was added at 30 °C.
After 6 h of stirring, the solution was coated on a glass plate to a thickness of
250 μm. The film was dried at 25 °C for 30 min, 40 °C for 30 min, and 80 °C for
2 h, and then cured at 150, 200, and 300 °C under N2 to produce a transparent
PI-based CPNC film with a thickness of 26 ± 2 μm. Results showed that the
organoclay was fully exfoliated in the polymer matrix, had high modulus
(2.38 GPa), tensile strength (110 MPa), elongation at break (11%), and low
coefficient of thermal expansion (35%, compared to 100% for neat PI).
In the next paper from the group, the same HP-MMT was used to prepare
CPNC with PI as a matrix using two methods [Gu et al., 2001]:
1. Blending a DMAc solution of ODAn with the organoclay dispersion in DMAc
before adding PMDA; and
2. Blending a DMAc solution of PAmA with the organoclay dispersion in DMAc.
Compositions containing 1, 3, 5 and 10 wt% of organoclay were prepared – the
interlayer spacing was: d001 = 2.2 to 1.4 nm, respectively. Tensile, thermal, dielectric
and water absorption properties of these CPNCs were studied. The properties
depended on the clay type, clay concentration, and the method of preparation.
The best performance was obtained using 3 wt% HP-MMT prepared by the
Figure 47 Mechanical properties (tensile modulus, E; tensile strength, σ; and

elongation at break, ε) of PI with MMT-ODA. Data [Tyan et al., 2000]. The three
functions are well approximated by straight lines – their parameters are given.
213
second method: tensile strength = 110 MPa, tensile modulus = 2.35 GPa,
elongation at break = 14.5%.
Delozier et al. [2002] used several methods to prepare PI-based CPNC, with
MMT that was intercalated with a long chain aliphatic quaternary ammonium
cation. The methods included:
1. Mixing the organoclay into a high molecular weight poly(amide acid) solution;
2. Mixing as in (1), followed by sonication; and
3. In situ preparation, starting with dispersion of organoclay in N-methyl-2-
pyrrolidinone (NMP), then addition of 4,4´-oxydianiline (ODAn) and
3,3´,4,4´-benzophenone tetracarboxylic dianhydride (BTDA) to prepare high
molecular weight poly(amide acid). The imidisation step involved a high-
temperature treatment (i.e., 1 h each at 100, 200 and 300 °C in air or N2).
The best results were obtained using the latter approach - the specimen obtained
using the other methods had aggregated clay particles that caused film failure in
tensile tests (stress concentration). However, high shear mixing using a
homogeniser improved intercalation and exfoliation, but the films were extremely
brittle making mechanical properties impossible to measure.
The CPNCs that contained 3-8 wt% of organoclay, were characterised by DSC,
TGA, TEM, XRD and thin film tensile properties. After thermal treatment of amide
acid films that caused imidisation, the films with clay were darker than those without
and the interlayer spacing was reduced. During imidisation at T = 200 to 300 °C
thermal degradation of the quaternary ammonium took place. The effect was less
pronounced when imidisation was carried out under N2. The degree of dispersion
was assessed from TEM micrographs. There is evidence that in the in situ prepared
CPNC exfoliation dominates. The exfoliated particles were 200¯700 nm long and
1¯10 nm thick. However, XRD analysis indicated that the interlayer spacing was
about constant, d001 = 1.34 nm - the peak intensity increased with clay content. It
is noteworthy that this spacing is closer to that known for Na-MMT than for the
organoclay (d001 = 2.37 nm). The polyimide/organoclay hybrid films exhibited
higher room temperature tensile moduli, but lower strength and elongation to
break than the control films. The Tg for the neat ODAn¯BTDA system was 283 °C
and remained constant within 4 °C for the hybrid films. At 5 to 8 wt% of clay the
temperature for 5% weight loss was ca. 517 °C.
Chang et al. [2001b,c] studied the preparation of CPNC in polybenzoxazole
(PBO) matrix. The common solvent method was chosen with DMAc as the solvent.
MMT (CEC = 1.19 meq/g) was intercalated with primary hexadecyl ammonium
salt (MMT-HDA). Polyamic acid (PAmA) was synthesised in DMAc, then the
suspension of MMT-HDA in DMAc was added. The solution was cast, solvent
was evaporated at 50 °C and the films, 10-15 μm thick, were thermally treated.
The conversion to PI was carried out at 300 °C for 1 h under N2. The final conversion
to PBO was accomplished at 550 °C. CPNCs with 0, 1, 2, 4 and 8 wt% of organoclay
were prepared. Good exfoliation in systems containing up to 4 wt% MMT-HDA
was found, although short stacks were visible in TEM micrographs. The specimens
were thermally stable up to 611 °C, retaining about 75% of weight at 900 °C
– clay presence hardly affected these properties. However, the tensile strength was
doubled for 4 wt% loading and modulus increased by 37%.
A one-step method for the solution preparation of PI nanocomposites was
also proposed [Huang et al., 2001a,b]. First, MMT was intercalated with primary
(dodecyl or hexadecyl, DDA or HDA, respectively) or quaternary (trimethyl
214
hexadecyl, 3MHDA) ammonium ions. The organoclay was then dispersed in

m-cresol by mixing and ultrasonication for 1 h at 100 °C. To the suspension the
reactants (diphenyl ether-tetracarboxylic anhydride and diamino dimethyl
diphenyl methane) were added. The reaction was conducted at room temperature
for 2 h, and at 180 °C for 3 h. The solution was cast, then heated stepwise at 70,
120, 200 and 270 °C for a total of 22 h. The interlayer spacing of MMT
(d001 = 1.3 nm) increased upon intercalation to 1.75, 3.37 and 4.01, for DDA,
HDA and 3MHDA, respectively. Nanocomposites comprising: 0, 2, 3.2, 5, 10
and 20 wt% of MMT were prepared with MMT-3MHDA. Fully exfoliated
CPNCs were obtained only for 2 and 3.2 wt% of clay. The mechanical properties
linearly increased with clay content up to 5 wt%. In the full range of investigated
compositions the decomposition temperature increased from 518 to 524 °C, while
Tg(PI) = 286 °C increased by 4 °C and the coefficient of thermal expansion (CTE)
hyperbolically decreased following the dependence:
CTE = a0 + a1/(a2 + w) (28)
The PI data for MMT content (w) versus CTE followed the dependence with
a0 = 30.0 ± 4.0; a1 = 203.9 ± 78.5; a2 = 5.19 ± 1.59; and standard deviation
σ = 1.85, correlation coefficient squared r 2 = 0.9995 and coefficient of
determination (CD) = 0.988 (see Figure 48).
Delozier et al. [2003] investigated the influence of the cation exchange capacity
(CEC = 0.63 to 1.11 meq/g) on the degree of exfoliation in a PI matrix. To adjust the
CEC the Na-MMT was ion-exchanged with 1N LiCl, then centrifuged and placed in
an air circulating oven at T = 120 to 170 °C for 24 h – the higher the temperature,
the lower the resulting CEC. Next, the treated clay was intercalated with an aromatic
primary di-ammonium compound: 1, 5-di(3-amino-phenoxy)-3-oxapentane (BAOD).
CPNC with polyamic acid was prepared in NMP (16% solids) at room temperature,
under N2 in 24 h. The solution was cast, dried, then cured at T ≤ 300 °C. The first
series of specimens was prepared with clays having different CEC, but at a constant
Figure 48 Coefficient of thermal dispersion of PI containing 0-20 wt% of MMT.

Data [Huang et al., 2001a,b]. The broken line follows Equation 28.
215
clay loading of 3 wt%. XRD showed the presence of a peak for all specimen with
corresponding values of d001 = 1.20 to 1.31 nm, with the largest value for CEC
≅ 0.7 meq/g. However, TEM showed a random dispersion of individual clay platelets
and short stacks. Using these selected clays, the second series of specimens was
prepared with clay loading of up to 8 wt%. A small enhancement of the tensile
modulus was accompanied by reduction of strength and elongation at break. TGA
showed a significant increase of thermal stability.
Better dispersion was obtained by dispersing MMT-DDA in a NPM solution of
photosensitive polyamic acid (PAA) [Hsu et al., 2003]. The latter was prepared by
polymerising pyromellitic dianhydride, oxydiphthalic anhydride, and oxydianiline.
The photosensitive formulations contained 2,3,4-tris(1-oxo-2-diazonaphthoquinone-
5-sulfonyloxy)-benzophenone as the photosensitiser and 3 wt% organoclay. The
films were transparent and tough. XRD and TEM indicated exfoliation before
and after thermal imidization. The thermal expansion coefficient was 23% lower
than that of film that did not contain the organoclay. The tensile modulus increased
by 14%, while the strength and elongation at break decreased by 15 and 33%,
respectively.
An intrinsically photosensitive PI/MMT system was prepared by solution
polymerisation at 180 °C of 4,40-diamino-3,30-dimethyldiphenylmethane
(MMDA) with benzophenone-3,30,4,40-tetracarboxylic dianhydride (BTDA) and
isoquinoline in the presence of MMT-HDA [Liang et al., 2004]. The solution
was either cast or spin coated, devolatilised and imidized at T ≤ 280 °C. XRD
and TEM indicated exfoliation in the full range of MMT concentrations. Excellent
mechanical properties were obtained – in the full range of MMT content (0 to
3 wt%) the modulus, tensile strength and elongation at break increased by 211,
48 and 11%, respectively. At the same time the thermal expansion coefficient
was reduced by up to ca. 32%, and Tg increased by 6 °C. While the addition of
organoclay did not affect the inherent PI solubility, the presence of MMT
significantly reduced the rate of solvent absorption. Finally, the photolithographic
properties of PI remained unaffected by the clay presence, but only for
concentrations up to 2 wt%.
Polybenzoxazines are thermoset phenolic resins developed to overcome the
shortcomings of the novolacs and resoles. They show excellent properties, viz.
heat resistance, good electrical properties, flame retardance, dimensional stability,
toughness, stable dielectric constant, and low moisture absorption - all these at
relatively low cost. They can be synthesised from inexpensive raw materials,
cured without strong acid or base catalyst, and do not release by-products during
polymerisation, thus they are attractive candidates for many applications [Riess
et al., 1985].
Agag and Takeichi [2000] prepared CPNC of polybenzoxazine (PBOa) by
first intercalating Na-MMT with octyl (OA), dodecyl (DDA) or stearyl (ODA)
ammonium chloride, then mechanically mixing with different amounts of a
PBOa precursor, bifunctional bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl)
isopropane (B-a). The ring opening polymerisation of pristine B-a started at
223 °C, while in the presence of organoclay at T = 177 to 190 °C. According to
XRD, the MMT intercalated with either DDA or ODA became totally exfoliated
in the product. Viscoelastic measurements showed that the Tgs of the CPNCs
were higher than that of neat PBOa. Increased storage modulus, decomposition
temperatures and thermal stability were also noted. However, as the authors
216
remarked, the method was difficult because of the high viscosity of the monomer
and the small difference between its gelation temperature and the melting point.
More recently, several types of CPNCs with PBOa as a matrix have been
prepared [Takeichi et al., 2002]. The authors described the effects of the
preparation method and that of type and content of organoclay on the CPNC
properties. Two monomers were used: B-a and monofunctional 3-phenyl-3,
4-dihydro-2H-1,3-benzoxazine (P-a). These produced crosslinked PB-a and linear
PP-a matrix, respectively. Na-MMT (CEC = 1.19 meq/g) was intercalated with
ammonium salts of such amines as tyramine, 2-phenyl-ethyl amine, aminolauric
acid, and DDA.
The nanocomposites were prepared either by melt or solution method. The
melt method involved incorporating organoclay into B-a or P-a above its melting
point (Tm = 100 and 60 °C, respectively). The solution method involved dispersing
the organoclay in a solvent NMP or tetrahydrofuran (THF) at 80 °C for 1¯2 h
and then blending with either B-a or P-a at 80 °C for 3 h. The blends were cast
on glass plate, dried at 60 °C for 16 h, then cured at 100, 150, 200 and 240 °C
for 1 h each. Good dispersion was obtained in NMP, but poor in THF. The
CPNCs were transparent, red-wine coloured with thickness ranging from 0.2 to
0.4 mm.
The intercalation increased the interlayer spacing, from d001 = 1.24 nm of
Na-MMT only to ≤ 1.83 nm. Thus, it is remarkable that using either method a
high degree of exfoliation in the cured nanocomposites was obtained. Evidently,
changing the solvent, concentration and procedure affected the result, viz. when
THF was used, a small XRD peak remained indicating intercalated clay, but
when NMP was used total exfoliation was achieved. As before, increasing the
organoclay concentration reduced the level of platelet dispersion. The effect of
clay addition on P-a was much larger than on B-a. The smaller P-a molecules
penetrated into the clay galleries more easily and the number in contact with the
catalytic clay surface should be larger than with the bigger B-a molecules. The
melt method also resulted in exfoliated structures [Agag and Takeichi, 2000].
DSC showed that the incorporation of any type of organoclay lowered the
curing temperature. The effect was particularly large for a small amount of
organoclay - addition of 5 wt% reduced the onset curing temperature by ca.
50 °C, suggesting a catalytic effect of the organoclay on ring opening
polymerisation. A plot of Tg versus clay content showed a maximum at about
4 wt%, with all the CPNC values higher than that of neat resins. As evidenced
by TGA, an addition of organoclay improved the thermal stability – the best
results were obtained for MMT intercalated with tyramine (p-ethyl-amine phenol).
In summary, the work on PBOa-type CPNCs illustrates the importance of
miscibility and chemistry on the exfoliation process. Even when the organoclay
had small expansion of the interlamellar galleries (Δd001 ≤ 0.59 nm), but was well
dispersed in a solvent and/or monomer, good exfoliation was achieved after curing.
As in thermoplastic systems, here also the best results were obtained when the
matrix polymer was chemically bound to clay by reactive intercalant (tyramine).
High energy shearing may help, but it does not replace good thermodynamics
and chemistry of the system.
The common solvent method has also been used to prepare POSS-type
nanocomposites in PI matrix [Tsai and Whang, 2001a]. The polyimide/
polysilsesquioxane-like (PI/PSSQ-like) films had 3D structure with linear PI blocks
217
and a crosslinked PSSQ-like structure. The system showed higher thermal stability
and char yields than pure PI from 4,4´-diamino-diphenyl ether and
3,3´-oxydiphthalic anhydride (ODPA). In a series of X-PIS films (PI modified
with p-amino-phenyl tri-methoxysilane (APTS), where X is the molecular weight
of each PI block), decreasing the PI block length enhanced the storage modulus,
tensile modulus, and Tg but reduced the α-relaxation damping peak intensity,
density and elongation. The change in the moduli and Tg may be caused by an
increase in the crosslinking density and rigidity of the network. The changes in
the peak intensity and density may be caused by increased free volume or the PI
interblock separation and decreases in the interblock PI chain interaction. The
decrease in elongation is related to increased rigidity. The activation energy of
the α-transition depended on the length of the PI block. A maximum value was
reached for the chain length of 10 kg/mol because of two opposing factors:
crosslinking density and free volume.
In a series of X-PIS-y-PTS (X-PIS modified with phenyl trimethoxysilane (PTS),
where y is the weight-ratio percentage of PTS to APTS-polyamic acid) films with
a constant PI block length, the storage modulus, tensile modulus, Tg, density,
and α-relaxation damping peak intensity decrease with the PTS content. This
could be because of the increase of the PSSQ-like domain size with the PTS content,
which leads to the introduction of more free volume or interblock separation
and to a decrease in the interblock chain interaction force.
2.4.2.6 Other Methods – Epoxy-Based Nanocomposites

CPNCs with thermoset matrix were already considered in the preceding section
where the common solvent methods were discussed. However, owing to the
specificity of the epoxy systems it seems desirable to summarise specifically the
work carried out on their synthesis. A short review on these systems was recently
published [Wang et al., 2000a]. As these authors remarked, the strategy for the
preparation of epoxy-based CPNC depends on whether the cured system is glassy
(with Epon 826) or elastomeric (with Epon 828 – see Figure 5). In the first case,
it was advantageous to disperse organoclay in epoxy overnight at 50 °C before
adding the curing agent. In the second case, organoclay should be added directly
to a mixture of epoxy with a curing agent. Kornmann, in his doctoral thesis of
2001 offers an overview of nanocomposites technology with a special emphasis
on the preparation of CPNC with epoxy resin matrix.
Pinnavaia et al., explored the use of epoxy compounds as the second intercalant of
layered materials. As early as in 1994 [Wang and Pinnavaia, 1994; 1998a,b], exfoliation
of organoclays in a glassy epoxy resin was reported. The process involved heating pre-
intercalated smectite with epoxy resin at T = 200-300 °C. Synthetic Na+-magadiite
was intercalated with a series of ammonium ions, viz. CH3(CH2)17NH3-n+(CH3)n,
where n = 0-3, by ion-exchange reaction in the presence of neutral amine [Wang et
al., 1996]. For primary amine (ODA or C18; n = 0) the interlayer spacing, d001 =
3.82 nm, was found consistent with the structure of onium ions and neutral amine
inclined at an angle of about 65°. As the number of methyl groups increased from n
= 1 to 2 and 3, d001 decreased to 3.74, 3.20 and 3.41 nm, respectively. Epon 828 was
used along with Jeffamine (PPG-bis(2-aminopropyl ether)) as the curing agent. The
desired amount of organomagadiite was added to the mixture and stirred for 60
min, degassed and cured at 75 °C for 3 h and at 125 °C for a different length of time.
When that time exceeded 5 min, even for systems with 15 wt% organoclay, full
exfoliation was recorded. In the cured epoxy matrix good exfoliation was obtained
218
for magadiite intercalated with either the primary or secondary onium ions (n = 0 or
1). In the case of higher amines (n = 2 or 3) XRD indicated an interlayer spacing of
d001 = 7.82 and 4.10 nm, respectively. The observed strong effects of the intercalant
structure was interpreted as due to the high acidity of ODA, which is reduced by the
presence of methyl groups, especially when n = 2 or 3. The acidity is responsible for
the intercalant’s catalytic effects on the curing reaction within the interlamellar galleries,
which lead to exfoliation. Good enhancement of the tensile strength was reported.
The enhancement was shown to depend on the degree of exfoliation, e.g., at 10 wt%
of clay the tensile strength increased by a factor of 4.8, 3.5, and 2.3 for the exfoliated,
ordered exfoliated and intercalated systems, respectively (n = 1-3). The transparency
and high barrier properties makes these CPNCs attractive as packaging materials
and protective films.
The early work resulted in several patents [Pinnavaia and Lan, 1998a,b]. The
authors observed that the extent of epoxy resin diffusion into the interlamellar
galleries depends on the hydrophobicity controlled by the chain length of the
alkylammonium cations. Thus, to start with Na-MMT was cation exchanged
with alkylammonium cations with different alkyl chain length (CnH2n+1, where
n = 4, 8, 10, 12, 16 or 18). Equivalent amounts of the epoxy resin (Epon 828
27.5 wt %) and the polyether-amine (72.5 wt %) were mixed at 75 °C for 30 min,
then 10 wt% of the organoclay was added, mixed and cured. The XRD results
indicated that the clays with alkyl chain length n ≥ 10 were exfoliated. The
mechanical performance was significantly enhanced by exfoliation.
In later patents [Pinnavaia and Lan, 1998c; 2000a,b], Na-MMT was treated
with HCl to prepare protonated clay, H-MMT (d001 = 1.05 nm). Next, polyether-
amine was added to the aqueous suspension and stirred at room temperature for
6 h (d001 = 4.6 nm). After evaporation of the suspending medium the gel of
intercalated clay was mixed with Epon 828. The XRD pattern showed absence
of the clay diffraction peaks, suggesting exfoliation. The tensile strength and
modulus were superior in comparison to CPNC prepared with alkylammonium
cation intercalated clay (see Figure 49). However, it is worth stressing that the
presence of ≥ 5 wt% MMT reduced the heat of reaction [Butzloff et al., 2001].
Exfoliation was observed only at a MMT concentration below 2.5 wt% – above
this limit the system was progressively less exfoliated and more intercalated.
Intercalated CPNCs in glassy epoxy resin were obtained by dispersing
Nanomer I.28E (MMT-3MODA) into Epon 825 at 65 °C, degassing and curing
with a stoichiometric amount of Jeffamine D400 at 65 °C for 15 min [Zerda and
Lesser, 2001]. The XRD data indicated that the interlayer spacing of organoclay,
d001 = 2.28 nm, increased during pre-swelling in Epon to 3.42 nm, then shrank
during curing to 3.21 nm. The tensile modulus increased from 2.8 GPa for neat
resin to 3.2 GPa at 12.5 wt% of clay. However, the tensile stress was reduced
from 70 to 46 MPa. For the middle range of organoclay concentration (2.5 to 10
wt%) the fracture energy nearly doubled. The results are understandable
considering the presence of large scale (10-30 μm) aggregates, evident in SEM
micrographs. The measured fracture energy release rate (G1C) was shown to
depend on the generated surface area, as measured by AFM.
Lü et al. [2001] studied the dispersability of MMT intercalated with either
CH3(CH2)17NH3+- (ODA) or CH3(CH2)17N(CH3)3+ (3MODA) in epoxy resin,
which was a reaction product of the diglycidyl ether of bisphenol-A (DGEBA;
MW = 380 g/mol) with p,p´diaminodiphenylmethane (DDM) or methyl-
tetrahydrophthalic anhydride (MeTHPA). The CPNC was prepared in two steps:
219
1. Dispersing organoclay in DGEBA (either directly at 70-80 °C for 20-60 min,

or in chloroform at room temperature for 60 min), and
2. Incorporation of the curing agent followed by degassing, casting and curing.
The products have been studied using XRD and DSC.
Dispersing the organoclays into epoxy increased the interlayer spacing from
d001 = 2.4 to 3.7 nm, indicating enhanced intercalation. The two mixing procedures
gave equivalent results. Using DDM as a curing agent, full exfoliation was rapidly
achieved for MMT intercalated with the primary amine (ODA), but not when
MMT was intercalated with the quaternary onium (3MODA) - evidently, the
quaternary ammonium ion does not have the catalytic activity observed for ODA.
However, anhydride curing with MeTHPA resulted in exfoliation of either
organoclay. As the authors remarked, it is important that the exfoliation time is
shorter than the gel time – in the studied systems both these processes required
nearly the same time, viz. at 80, 100, 120 and 150 °C the exfoliation time (as
observed by XRD) was 60, 15, 8 and 5 min, respectively. Furthermore, the
exfoliation must take place before the extragallery epoxy matrix reaches its gel
point. The factors facilitating the curing inside the interlamellar gallery space
enhance the exfoliation.
Nanomer 1.30E (MMT-ODA) was dispersed in a matrix obtained by curing
Epon 828 with m-phenylene diamine (MPDA) by stirring and sonication for
about 30 min and degassing under vacuum [Chin et al., 2001]. To the mixture 5,
14.5 or 25 phr of MPDA was added at 60 °C, the mixture was heated for 2 h at
80 °C and for 2 h at 135 °C. The structural evolution in the CPNC was examined
by time-dependent small-angle X-ray scattering (SAXS) using synchrotron
radiation. A conventional XRD, AFM and DSC were used to probe the static
structure and the reaction kinetics. The interlayer spacing of the Nanomer 1.30E
Figure 49 Tensile strength and tensile modulus of epoxy-based CPNC. The

subscript ‘H’ indicates a new method of intercalation that starts with protonated
H-MMT; ‘18’ indicates systems where clay was intercalated with C18 H37 NH3+
cation. Data from [Pinnavaia and Lan, 1998c; 2000a,b].
220
was d001 = 2.3 nm, increasing upon dispersion in Epon to 3.9 nm. Addition of the
curing agent and heating for 2 h at 80 °C did not change the latter spacing.
Heating the mixture at 135 °C for additional time caused progressive expansion
of the interlamellar space toward exfoliation: d001 ≥ 20 nm. The latter spacing
was observed for less than an equimolar amount of the curing agent and clay
concentration up to 5 wt% (for 20 wt% clay d001 = 8.3 nm). When Epon was
cured with more than equimolar MPDA, exfoliation was suppressed – high curing
agent concentrations seem to favour extragallery crosslinking. Exfoliation was
obtained for the amount of curing agent ranging from zero to less than its
stoichiometric amount. The time-dependent SAXS measurements indicated that
exfoliation proceeded by progressive delamination of the stacks.
While most authors prepare CPNC with epoxy (DGEBA cured with acid
anhydride) matrix using either MMT-ODA or MMT-3MODA, recently MMT
pre-intercalated with an ‘alkyl ammonium salt with hydroxyethyl groups’ was
used [Zhang et al., 2004]. According to TEM, at 3 wt% of organoclay loading
only intercalated stacks with d001 ≅ 5.5 nm were obtained. However, in spite of a
lack of exfoliation, excellent performance was obtained: impact strength increased
by around 85%, tensile strength by 22%, storage tensile modulus (at T < Tg) by
33% and Tg increased by ca. 14 °C.
A new approach to clay exfoliation in epoxy matrix involves the use of
aromatic amine hardener as the clay intercalant, dispersing such organoclay in
epoxy, and then curing the system [Ma et al., 2004]. For example, m-xylylene-
diamine (m-C6H4(CH2-NH2)2 or MXD for short) was acidified and used to
pre-intercalate Na-MMT. The epoxy (DGEBA) was added to the desired quantity
of purified organoclay suspension, and after stirring the mixture was dried. Finally,
CPNC was obtained by curing the mixture with a stoichiometric amount of
4-aminophenyl sulfone (DDS). Within 2θ = 1 to 9o XRD did not show any peak
that may have indicated exfoliation. However, TEM showed the presence of
randomly dispersed, ca. 3 nm thick clay platelets, possibly bridged by acidified
MXD. The authors speculated that the disorderly exfoliated structure originated
from the large crosslinked epoxy molecules connected to the clay platelet via the
MXD hardener-intercalant. No information on performance of this CPNC was
given.
Kornmann et al. [2001] studied the effect of the cation-exchange capacities
(CEC) on the formation of CPNC in epoxy matrix. Two MMTs with CEC = 0.94
and 1.4 meq/g (MMT09 and MMT14, respectively) were intercalated with ODA.
Epon 828 and a polyoxyalkylene diamine curing agent (Jeffamine D-230) were
used. First, the epoxy was mixed with the desired amount of organoclay at 75 °C
for several hours, and then a stoichiometric amount of Jeffamine was added. The
mixture was outgassed under vacuum, poured into a mould, then cured for 3 h at
75 °C and post-cured for 12 h at 110 °C. The dispersion was studied using XRD,
SEM and TEM. The interlamellar spacing of the two clays increased from
d001 = 0.97 for MMT09 to 1.72 nm for organophilic MMT09-ODA, and from
d001 = 1.21 for MMT14 to 2.14 nm for the MMT14-ODA. Surprisingly, swelling
the former organoclay in Epon resulted in exfoliation (d001 > 8.8 nm), whereas the
latter slowly intercalated to reach d001 = 3.47 nm after 24 h. The high surface
energy of MMT is known to attract polar species such as epoxy molecules hence
they diffuse into the interlamellar galleries. If these are able to polymerise, the next
molecules are able to diffuse into the interlamellar galleries causing exfoliation,
hence self-polymerisation of epoxy in MMT09-ODA may be postulated. Within
221
MMT14-ODA there is a significantly larger amount of the intercalant present,

leaving less space for the Epon molecules to diffuse into, and probably less
opportunity to contact the ammonium group. It is expected that curing the already
exfoliated mixtures of Epon with MMT09-ODA will result in exfoliated CPNC.
However, exfoliation (as defined by the absence of a 001 peak in XRD spectra)
was also achieved in systems comprising MMT14-ODA.
Although XRD showed exfoliation, TEM indicated that clay platelets formed
stacks with interlamellar spacing of 11 and 9 nm for MMT09 and MMT14,
respectively. Furthermore, a XRD peak at 2 θ = 20° that corresponds to
crystallographic planes 110 and 020 of the clay, was observed and its intensity
increased with the clay content. Its presence demonstrates that the XRD analysis
is sufficiently sensitive to detect the presence of the clay in the nanocomposite
and to quantify it. SEM was also used to investigate dispersion of MMT14 in the
nano and micro-composites. The latter system was prepared by dispersing the
non-intercalated clay in the matrix. Here XRD showed two peaks: a broad one
at d001 = 1.4 nm and a sharp one at 0.97 nm. For both systems clay aggregates
were observed, albeit significantly smaller in the (supposedly) exfoliated nano -
than in the microcomposite (ca. 10 μm particles).
Recently, high performance epoxy-nanocomposites were prepared by dispersing
synthetic sodium fluorohectorite (FH; Somasif ME-100; CEC = 1.0 meq/g) in a
matrix composed of tetraglycidyl 4,4´-diaminodiphenyl methane (TGDDM) cured
with 4,4´-diamino diphenyl sulfone (DDS) [Kornmann et al., 2002]. The FH was
intercalated using one of the following compounds: ODA, 1-methyl-2-norstearyl-
3-stearinoacid-amidoethyl-dihydro-imidazolinium metho-sulfate (W75),
hydroxyethyldihydro-imidazolinium chloride (HEODI), and ricinyl-dihydro-
imidazolinium chloride (RDI). ODA is known to produce organoclays that can be
exfoliated during curing of epoxy systems, while the dihydro-imidazolines are known
to impart good thermal stability. The matrix was N,N,N´,N´-tetraglycidyl 4,4´-
diamino-diphenyl methane (TGDDM) cured with 4,4'-diamino-diphenyl sulfone
(DDS). The influence of the intercalants on curing reactions, the morphology, matrix
Tg and the mechanical properties was investigated. TGDDM epoxy resin was heated
to 100 °C under vacuum in a high shear mixer then an organoclay was added and
the mixture was mixed for 3.5 h. Next, the temperature was increased to 140 °C
and a stoichiometric amount of the DDS was added, mixed for 30 min and then
poured into a mould. Curing was performed in several steps, e.g., 2 h at 140 °C +
2 h at 177 °C + 7 h at 200 °C.
DSC studies of the curing reaction indicate that FH has no influence on
TGDDM polymerisation – the reaction with or without the clay had the
exothermic peak at Tpeak = 316 °C. However, 10 wt% of FH-W75, FH-HEODI
or FH-RDI reduced the exothermal peak by 6 ºC and with 10 wt% of FH-ODA,
by 11 °C. Thus, the intercalants do catalyse curing, but the dihydro imidazolines
are not as effective as the ODA ions. This suggests that FH-ODA would produce
the best exfoliation, if not for the thermal decomposition of ammonium ions
which starts near 200 °C.
The interlayer spacing of intercalated FH and that of cured epoxy
nanocomposites is presented in Table 34. Intercalation expands the interlamellar
gallery by Δd001 = 0.96 to 2.26 nm. Once the organoclays are dispersed in the
epoxy matrix, the gallery increases for FH-ODA, FH-HEODI and FH-RDI
whereas it decreases for FH-W75. In the latter case the TGDDM and the DDS
were not able to diffuse between the layers, the polymerisation took place outside
222
Table 34 Organic content and interlamellar spacing of cured epoxy

nanocomposites. Data [Kornmann et al., 2002]
Materials Intercalant as % of Interlamellar spacing d001 (nm)
clay CEC a
In organoclay In epoxy
FH - 0.94 -
FH-ODA 99 1.9 4.0
FH-W75 67 3.2 2.5
b
FH-HEODI 90 2.2 4.1
c
FH-RDI 110 2.5 7.5
Notes:
a
At 5 wt% clay, cured as indicated in the text
b
In ordered places
c
Irregular distribution
the interlamellar galleries, compressing them by Δd001 = 0.7 nm. Apparently, FH-
W75 is immiscible with some components of the epoxy matrix. At least part of
the reason for immiscibility is that only partial ion exchange took place during
intercalation. None of the nanocomposites produced contained fully exfoliated
clay. TEM confirmed the interlayer spacing deduced from the XRD data – indeed,
the largest average spacing was observed for FH-RDI, but some nonintercalated
platelets were also visible. The SEM micrographs also indicated the presence of
clay aggregates, particularly bad (some as large as 20 to 30 μm) for FH-W75 and
FH-ODA. This is an important observation! Without the evidence of SEM one
would concentrate the interpretation of data on the nanometre-scale morphology,
whereas for a number of performance characteristics (for example the impact
properties) the micron-scale aggregates may be more important.
The tensile properties of the nanocomposites were examined. The clay
concentration effect on the tensile modulus is shown in Figure 50. The results for
FH-W75 are clearly the worst, falling even below the microcomposites with
nonintercalated FH. Of the remaining three systems, the best is the one with FH-
RDI and the worst with FH-ODA – here at last the expected correlation with the
degree of platelet dispersion is observed. The fracture energy for all the intercalated
systems was found to be higher than that for the microcomposite with FH, but
again the data for FH-W75 were the lowest and these of FH-RDI the highest. At
5 vol% clay loading the fracture energy was nearly twice as large as that for the
neat matrix resin.
Epoxy resins are inherently brittle and several methods have been used to
improve toughness without loss of stiffness. Since CPNC with an epoxy matrix
frequently show improved modulus and reduced ductility, a growing number of
publications have appeared, trying to solve this problem. Thus, for example,
Ratna et al., 2003 used a combination of linear (DGEBA) and 11-arm star
branched epoxy to prepare CPNC with 5 wt% of MMT-ODA. A high degree of
intercalation was obtained. In spite of the phase separation between the two
epoxies, good performance was reported, viz. enhancement (in comparison to
223
Figure 50 Tensile modulus versus fluorohectorite (ME-100) content in high

temperature epoxy systems. Data [Kornmann et al., 2002]. For explanation of the
Figure legend see text.
cured DGEBA) of flexural strength and modulus by 21 and 26%, respectively,

and impact strength by 114%.
Fröhlich et al. [2003] toughened their epoxy (hexahydrophthalic acid
anhydride-cured DGEBA) with PPG-PEG liquid rubber treated with methyl
stearate. Up to 15 wt% organoclay (synthetic fluorohectorite pre-intercalated
with MDD2EtOH) was dispersed as short stacks with d001 = 2.94 nm. The thermal,
and mechanical properties were determined. Addition of the additives reduced
the modulus and improved the toughness. In parallel, the yield strength, and Tg
also decreased. At a later date the same epoxy system was reinforced by a diversity
of layered silicates intercalated with phenolic alkyl imidazoline amide cations
[Fröhlich et al., 2004]. Natural and synthetic clays (bentonite and fluorohectorite,
respectively) were pre-intercalated and used at loadings of up to 10 wt%. For
comparison, the same epoxy was prepared with talc as well. Intercalation
expanded the interlayer spacing to about d001 = 3.3 to 3.7 nm, but dispersing it in
epoxy slightly reduced the gallery height (by ca. 0.3 nm). The mechanical
performance of the samples with organoclay was quite similar to that of the talc-
filled composite. The poor performance of organoclay-filled CPNC seems to have
been caused by immiscibility between the organoclay tails and the matrix.
2.4.2.7 Other Methods – PU-Based Nanocomposites

Polyurethanes (PU) have been mixed with nanosize particles for a number of
decades. Carbon black, metal and silica particles have been used. Three examples
selected from between many will be mentioned.
2.4.2.7.1 Metal Particles

PU was dissolved in dimethyl acetamide and a solution of metal ions (iron, cobalt,
nickel and copper) was added [Chen et al., 1996]. The metal ions were reduced
224
by sodium borohydride under mild conditions into amorphous fine powders.

Polar polymer and low metal concentration favour smaller particles. The polymer
chains prohibited excessive aggregation of the metal atoms and had a protective
effect on the fine metal powders. An energy disperse X-ray spectrometer connected
with TEM proved that the dispersed particles were metal clusters with the sizes
ranging from 10 to 150 nm.
2.4.2.7.2 Silica
A series of PU nanocomposites was prepared with 0-50 wt% of silica, having a
particle size of about 12 nm [Havni and Petrovic, 1998]. SEM showed regular
distribution and small spacing between neighbouring particles at all
concentrations. For all samples XRD showed a single broad maximum at about
6° and a shoulder at 20°. The Tg of PU increased with the silica concentration. A
parallel series of PU filled with micron size silica had higher density, hardness
and modulus than nanosilica filled systems, but the tensile strength and elongation
at break were dramatically better for the latter systems. Composites with nanosilica
were clear and transparent while those with micron size silica were opaque.
Petroviç et al. [2000] prepared PU nanocomposites by dispersing amorphous
SiO2 particles (average diameter 12 nm) in MEK. Next, PPG was added, MEK
was removed, MDI added and the system was cured at 100 °C for 16 h. The final
concentration of SiO2 was up to 50 wt%. Properties of these nanocomposites
were compared to those of microcomposites containing crystalline SiO2 with an
average particle diameter of 1.4 μm. The nanocomposites showed 3-fold higher
tensile strength and elongation at break, but lower modulus and hardness.
The sol-gel process has also been used to generate nanosized silica particles
within a PU matrix [Goda and Frank, 1997]. At lower concentration the silica
penetrated the hard segment domains of PU, at higher it disrupted its ordered
structure.
2.4.2.7.3 Cadmium Sulfide Particles (CdS)

Nano-CdS particles were prepared by reverse micellisation [Hirai et al., 1999].
They were dispersed into PU, by surface-modification with 4-hydroxythiophenol
or 2-mercaptoethanol, followed by polyaddition of ethylene glycol with toluene-
2,4-diisocyanate. The resulting CdS-PU powder could be dissolved in organic
solvents such as DMF to make nanoCdS/PU transparent films that showed
quantum-size effects. These were used for photocatalytic generation of hydrogen.
2.4.2.7.4 Organoclays
Several already cited broad patents on CPNCs have stated that the invented
technology is also applicable to PU [Usuki et al., 1989; Nichols and Chou, 1999,
Beall et al., 1996a; 1999b]. One of these general patents was granted to Pinnavaia
and Lan [2000a,b]. However, the cited examples are only for epoxy-based CPNC.
The patent information will be discussed later on in this book.
PUs are prepared by the reaction of isocyanate and polyols:
HO-R-OH + OCN-R´-NCO → -(-CO-NH-R´-NH-CO-O-R-O-)n-
The polyol component -R- usually contains a base, such as a secondary or tertiary
amine. Therefore, these may react with the protons within the clay interlamellar
gallery enhancing the intercalation.
225
Wang and Pinnavaia [1998b] prepared thermoset PU-based CPNC by curing

a PU network in the presence of MMT intercalated with C12H25NH3+ or
C18H37NH3+ (Nanocor C12A and C18A, respectively). The organoclays were
solvated in one of several polyols commonly used in PU synthesis, viz. ethylene
glycol (EG), polyethylene glycol (PEG), polypropylene glycol (PPG), and glycerol
propoxylates (Voranols). The solvation could be carried out at room temperature,
but it was more rapid at higher temperatures, say T = 50 °C for 12 h. The d001
-spacing depended mainly on the chain length of the onium ion. As shown in
Table 35, the observed values of interlayer spacing agree with calculations (dcalc).
Initially, the onium ion paraffin tails in the non-solvated clay are oriented parallel
to the clay platelets, as judged by the values d001 = 2.22 and 2.30 nm, then they
reorient from this position to optimise solvation by polyol. PU-based PNCs were
formed by adding a methylene diphenyl diisocyanate prepolymer (MDDP; MW
= 1050; functionality = 2.0) to a mixture of organoclay and Voranol V230-238.
Before use, the polyol was degassed under vacuum at 100 °C for 6 h. The
diisocyanate was added and the mixture was stirred at 70 °C for 15 min before
degassing at 95 °C under vacuum. The mixture that contained ≤ 10 wt% of
organoclay was pourable. The bubble-free mixture was poured into a mould for
curing at 95 °C for 10 h under N2.
The alkylammonium-exchanged ions of the intercalated clay were considered
to react with isocyanate and were counted as contributors to the polymerisation
stoichiometry; hence the amount of V230-238 was reduced accordingly. No
catalyst was used. During curing at 95 °C the interlayer spacing increased with
time from d001 = 3.74 to 5.08 nm. The presence of the Braggs reflections indicated
that the clay layers formed large tactoids. However, the distance between the
nanolayers was in the range where matrix reinforcement could be expected.
Inorganic fillers are commonly used in PU to reduce formulation cost and to
increase stiffness, but the improvements in modulus are compromised by a loss
Table 35 Basal spacing of MMT intercalated with alkylammonium

salt then solvated with polyols. Data [Wang and Pinnavaia, 1998]
Organo- Intercalated/solvated Calc-
clay ulated
Cloisite® Air- Glycol PEG300 PPG2000 V230- V230- V230- dcalc

type dried (62)b (300)b (2000)b 238a 112a 056a
(700)b (1500) (3000)b
b
d001 (nm)
C12A 2.22 3.39 3.20 3.31 3.23 3.29 3.29 3.10
C18A 2.30 3.67 3.66 3.78 3.74 3.71 3.80 3.87
Notes:
a
Glycerol propoxylate (Voranol from Dow);
b
Molecular weight of polyols;
c
Calculated basal spacing for a vertical orientation of the onium paraffin tails
226
of elastic properties. By contrast, PU-based CPNC exhibits improvement of

toughness, as well as of modulus. An illustration of the mechanical behaviour is
shown in Figure 51. The tensile strength, tensile modulus, and strain-at-break
versus organoclay concentration are plotted for PU prepared from V230-238,
MDDP and MMT intercalated with ODA (C18A). Evidently, incorporation of
nanoclay both strengthened and toughened the elastomeric matrix in comparison
with the neat polymer. Even when the clay platelets are in the form of intercalated
tactoids, they strengthen, stiffen and toughen the matrix. At an organoclay loading
of 10 wt% the values of all three functions at least doubled. It is noteworthy that
the PU-based nanocomposites retained high optical transparency.
Chen et al. [1999b] prepared CPNC with PU as the matrix going through a
stage of polycaprolactone-based nanocomposite as an intermediary. Thus, first
Na-MMT in aqueous solution was intercalated with 12-aminolauric acid. The
adduct was collected, washed, dried, ground and screened through a 325-mesh
sieve. Next, the organoclay was dispersed in ε-caprolactone which subsequently
was polymerised for 3 h at 170 °C while stirring. PU was prepared in two steps:
1. Mixing 4,4´-diphenyl-methane diisocyanate (MDI), polycaprolactone diol
and DMF for 2 h at 70 °C, then reacting the mixture with 1,4-butanediol for
30 min.
2. The PCL-based PNC was added and the combined mixture was allowed to
react for 30 min.
The prepolymer solution was spread, dried under vacuum and cured at 80 °C for
10 h. XRD showed that the clay was exfoliated and that the reaction product
comprised crystalline PCL.
Thus, the prepared CPNC was a complex system with segmented PU forming
the matrix chemically bonded to the randomly dispersed PCL-based exfoliated
nanocomposites. Size exclusion chromatography (SEC) or gel permeation
chromatography (GPC) indicated that the Mn of PCL was only 3.62 kg/mol, and
Figure 51 Mechanical behaviour versus organoclay content of PU-based CPNC.

Data [Wang and Pinnavaia, 1998b].
227
that in PU, Mn decreased with the content of PCL-based nanocomposite, from

Mn = 52 to 13 kg/mol. The miscibility of the PU/PCL-clay blend was not studied.
The mechanical properties versus clay content plot showed a surprising behaviour
(see Figure 52). For example, in tensile tests the tensile strength increased linearly
with clay content, but the elongation at break went through a sharp maximum at
0.74 wt% clay. In the lap-joint shear strength tests (ASTM D1002) the modulus
increased linearly with clay content while the strength went through a local
maximum at a clay content of 1.3 wt%.
CPNC were prepared by dispersing synthetic fluoromica (FM; Somasif ME100;
aspect ratio p ≤ 5,000) in a PU matrix [Zilg et al., 1999b]. The ME-100 behaves
as a weak silicilic acid, with Na+ as counterions in the interlamellar gallery. FM
was intercalated in aqueous solution with methyl-dodecyl bis(hydroxyethyl)-
ammonium chloride (MDD2EtOH; Ethoquad C12). After drying it was dispersed
in trihydroxy-terminated oligo(propylene glycol) having Mn = 3.8 kg/mol, then
reacted with diisocyanato-phenyl methane catalysed with N,N-dimethyl-
benzylamine (NNDB) at 80 °C. The reaction rate was slightly slowed by the
presence of organoclay. At 10 wt% clay loading the CPNC was not exfoliated,
but d001 increased from 0.9 (dry ME-100) to 8.8 nm. Evidently, the intercalant
and polyol diffused into ME-100 interlamellar galleries. TEM showed that the
intercalated clay formed stacks, 500 nm in length and 20 to 50 nm in thickness.
The stacks were well dispersed within the PU matrix. As shown in Figure 53, the
tensile strength and elongation at break increased with the organoclay content.
However, a less satisfactory correlation was reported for the tensile modulus and
the Shore-A hardness – the data were scattered.
PU-based CPNC were prepared starting with Na-MMT (CEC = 0.76 meq/g)
which was intercalated (3 h stirring in aqueous suspension at 60 °C) with either
12-aminolauric acid (ADA) or benzidine (BZD), forming the complexes: MMT-
Figure 52 Tensile (ASTM D412) and lap-joint strength (ASTM D1002) test data
for PU containing dispersed PCL-based CPNC. Data [Chen et al., 1999b].
228
Figure 53 PU-based CPNC – tensile strength and elongation at break versus

fluoromica clay content. Data [Zilg et al., 1999b].
ADA and MMT-BZD, respectively [Chen et al., 2000]. The intercalated clay was
washed, dried under vacuum at 80 °C for 12 h, then ground and screened through
a 325-mesh sieve. In a parallel operation, MDI and polytetramethylene glycol
(PTMG) at a molar ratio of 2:1 were dissolved in DMF and heated to 90 °C for 2.5
h to form a prepolymer. To the prepolymer 1,4-butanediol was added with rapid
mixing at 90 °C for 10 min. Next, an appropriate amount of organoclay (to give 1,
3 or 5 wt% of organoclay in CPNC) was dispersed in 10 ml of DMF, added to the
prepolymer mixture and the reaction was allowed to proceed to completion in 3 h
at room temperature under mixing. The final concentration of PU in DMF was 30
wt%. After removing DMF at 80 °C and degassing the mixture an elastic film was
obtained.
XRD of MMT-ADA and MMT-BZD gave d001 = 1.7 and 1.54 nm, respectively.
The difference was attributed to the size of the intercalant molecule. The PU-based
PNCs prepared with 1, 3 and 5 wt% MMT-ADA, as well as with 1 and 3 wt%
MMT-BZD were all exfoliated. This conclusion was supported by TEM
micrographs – randomly placed, about 1 nm thick layers of organoclay were
observed. However, the PNC with 5 wt% MMT-BZD had a broad peak of
d001 = 2.47 nm indicating intercalation.
The molecular weight of PU in neat resin and in CPNC prepared in the presence
of MMT-ADA or MMT-BZD was Mn ≅ 11 kg/mol. Similarly, for all seven samples
the glass transition temperature was -58 ≤ Tg ≤ -59 °C. Also, as expected, the
water absorption was found to vary from 1.3 to 1.7 wt%. Surprisingly, TGA
analysis of PU-based CPNC containing MMT-ADA showed that it started to
degrade faster than neat PU. This may be due to the presence of extra ADA
unattached either to clay or to PU. However, at higher temperatures (T > 350 °C)
the PU/clay nanocomposite displayed higher thermal resistance than that of PU.
The stability of the MMT-BZD/PU system was better than that with MMT-ADA.
229
The mechanical properties of the PU-based PNC are shown in Figure 54. Addition
of MMT-ADA only slightly improved the tensile strength and elongation at break
over that of neat PU. However, the effect of MMT-BZD was quite significant –
improvement of the tensile strength by a factor of 2.0 and the elongation at break by
a factor of 2.8. The large contrast between the effects of MMT-ADA and MMT-
BZD was explained by the interactions between the intercalant, clay and PU matrix.
ADA has one terminal -NH2 group that might form a complex with Na-MMT and
still be able to react with a -NCO to form urea. BZD had two terminal -NH2 groups
that can participate in these interactions/reactions. Therefore, ADA can form linear
chains while BZD a crosslinked one. Schematics of these interactions/reactions are
presented in Figure 55, which illustrates the molecular structure in PU-based PNC
formed in the presence of (a) MMT-ADA and (b) MMT-BZD.
Ma et al. [2001] prepared elastomeric PU based nanocomposite starting with
MMT (CEC = 0.9-1.0 meq/g, with particle size of about 40-70 μm) intercalated
with trimethyl hexadecyl-ammonium chloride (3MHDA). Three types of polyol
of different MW and functionalities were used: PPG1, and PPG2 having Mn =1
and 2 kg/mol, respectively, and glycerol propoxylate (GPO3, with Mn = 3 kg/
mol). Dry organoclay was dispersed in GPO3 for 2 h. The degassed dispersion
was mixed with the PU prepolymer, prepared by reacting PPG1 and PPG2 with
toluene diisocyanate (TDI) at 80 °C. The mixture was cured at 80-90 °C for 2 h.
CPNCs containing either PPG1 or PPG2 were also prepared. The XRD data
indicated that MMT was intercalated with the interlayer spacing d001 ≤ 4.6 nm.
The tensile strength and elongation at break reached maximum values at ca.
8 wt% clay. The maximum improvement of the tensile strength and elongation
at break was by a factor of 2 and 5, respectively (based on neat PU). TGA showed
that the temperature for the maximum thermal decomposition increased from Td
= 377 (PU) to 385 °C. The best properties were observed for CPNC comprising
GPO3. Nanocomposites prepared by first dispersing the organoclay in low MW
polyol had better mechanical properties than those prepared by dispersing
organoclay in high MW polyol.
In 2001 Hu et al., reported a similar degree of dispersion. The authors first
expanded the interlayer spacing of MMT-3MHDA in PEG and then added TDI
and caused polymerisation. The reported interlayer spacing was: for MMT
d001 = 1.26; for organoclay 1.96; and for CPNC with (10 wt% organoclay)
d001 ≤ 4.85 nm. In accord with these observations, only intercalation could be
expected in systems containing clay intercalated with quaternary ammonium ions.
An interesting strategy has been used by Yao et al. [2002]. Different
amounts of Na-MMT (from Nanocor) were mixed with modified polyether
polyol (MPP) at 50 °C for 72 h. The mixture was then blended with a known
amount of modified 4,4´-diphenylmethylate diisocyanate (M-MDI) and moulded,
curing it at 78 °C for 168 h. Thus, MPP was used as an intercalating agent that
expanded the interlamellar galleries from Δd001 = 0.14 to 0.64 nm – evidently,
only a moderate level of intercalation was achieved. It was observed that with an
increasing amount of clay the heat of reaction was reduced. The reduction was
ascribed to immobilisation of MPP that intercalated the clay, being strongly
bonded to the solid surface.
In spite of the low degree of dispersion, the CPNC showed significant improvement
of the tensile strength and strain at break, increasing with the amount of clay. At a clay
loading of 21.5 wt%, tensile strength increased by ca. 44% and the strain at break by
20%. The storage modulus at T < Tg of the soft segments increased by 350%.
230
Figure 54 Mechanical behaviour of PU-based CPNC containing MMT intercalated

either with 12-aminolauric acid (ADA) or with benzidine (BZD) [Chen et al.,
2000].
Figure 55 Schematic representation of the molecular structure in PU-based CPNC

formed in the presence of (a) ADA-MMT and (b) BZD-MMT.
Reproduced from Chen et al., 2000, with permission from Elsevier.
231
The thermal conductivity initially decreased with clay loading (by ca. 10% for
17% clay) then returned to the original level.
MMT is known to be hygroscopic and, as TGA experiments indicate, it may
contain a significant amount of adsorbed and chemically bound water [Ogawa
et al., 1992; Menéndez et al., 1993]. The -NCO groups readily react with water,
for example, and 1.0 g of water will consume 18.0 g of toluene-diisocyanate
(TDI). Cloisite® 10A (MMT-2MBHT) was de-watered by dispersing it in toluene
followed by azeotropic distillation for 6 h [Zhang et al., 2003]. Next, the
dehydrated organoclay was dispersed in PEG, reacted with TDI at 80 °C for 4 h,
and then cured at 90 °C for 15 h under vacuum – the clay concentration ranged
from 0 to 7 wt%. The authors reported that only about 4.1% of the organoclay
-OH groups were able to react with -NCO groups of TDI, hence grafting the PU
matrix directly to the clay surface. The reaction was detected by FTIR. XRD of
Cloisite® 10A and the CPNC gave d001 values of about 2.3 and 3.5 nm, respectively.
In spite of the lack of exfoliation the mechanical properties were found to be
greatly improved, viz. the dynamic tensile modulus, E, increased by a factor of
10, the tensile strength and the elongation at break by about 160%. These
improvements in the intercalated systems are clear evidence of the benefits of
direct matrix-filler bonding.
2.4.3 Melt Exfoliation

Melt blending is the preferred method for preparing CPNC with a thermoplastic
polymer matrix. Typically, the polymer is melted and combined with the desired
amount of the intercalated clay in an extruder, internal, kinetic energy or a
continuous mixer. Melt blending is carried out in the presence of an inert gas,
such as argon, neon or nitrogen. Alternatively, the polymer may be dry mixed
with the intercalant, then heated in a mixer and subjected to a shear sufficient to
form the desired degree of dispersion. While total exfoliation can be achieved for
some diluted systems, the industrial standard requires that ≥ 80 wt% of the clay
platelets (aspect ratio p = 10 to 1500) are individually and uniformly dispersed
in the polymeric matrix, with the rest forming short stacks.
There are several advantages of the melt versus the reactive exfoliation method.
The process is more economic, it is closer to the ultimate product manufacturer,
hence it is better suited for rapid changes of formulation, it is more versatile
offering ready adaptability, it involves more participants with the technical know-
how (hence it offers more rapid penetration of the industry), and finally it does
not require that a big polymer production line is dedicated to developing a material
with uncertain application and hesitant market.
As discussed in Section 2.3.8, the beginning of melt exfoliation started with the
quiescent, diffusion-controlled melt intercalation process. For example, Vaia et al.
[Vaia et al., 1993; Vaia and Giannelis, 1997b] prepared PS-based CPNC by such
a static melt processing method.
Melt exfoliation of clay in PDMS matrix was pioneered by Burnside and
Giannelis [1995; 2000]. Na-MMT was first intercalated with dimethyl ditallow
ammonium bromide (2M2TA), and then dispersed in the matrix by sonication.
Similarly, silicone rubber-type CPNCs were prepared by melt intercalation [Wang
et al., 1998]. In this work Na-MMT was intercalated with trimethyl hexadecyl-
ammonium bromide (3MHDA). The CPNCs with ≤ 20 phr of organoclay (≤ 9
wt% of clay) were prepared by mechanical mixing. The resulting nanocomposites,
232
characterised by XRD, TEM and TGA, were reported intercalated with d001 =
3.71 nm. Thus, the ordered organosilicate structure of clay was still present in
the CPNC, forming stacks that were ca. 50 nm thick and uniformly dispersed in
the silicone rubber matrix. The mechanical properties and thermal stability of
the hybrids were very close to those of aerosilica-filled silicone rubber. Melt
intercalation/exfoliation of hydrophilic polymers, such as P4VP, PEG or PVAl is
relatively easy. The strategies used have been described in Section 2.3.5.2.
More recently, Zanetti et al. [2000a,b] described the melt exfoliation of
fluorohectorite (fluoromica, FM) in a PVAc matrix. The melt-produced CPNCs
show a similar set of properties as those obtained by the reactive route, viz.
superior heat, chemical or ignition resistance, barrier to diffusion of gases and
polar liquids such as water, methanol, ethanol etc., yield strength, stiffness and
dimensional stability. These CPNCs may be useful in diverse applications viz. in
business equipment, computer housings, transport (automotive and aircraft, viz.
in under the hood and exterior body trim applications), electronic, packaging,
building and construction industry, etc.
However, this method is at an early stage of development with numerous
unanswered questions still remaining. A consensus emerges that the clay platelets,
e.g., individual lamellae of MMT, should be treated as any other structural plates,
with their own value of mechanical performance characteristics, e.g., modulus,
maximum strain at break, etc. There is TEM evidence that in shear the clay
platelets tend to bend. The work on FM showed extensive reduction of the aspect
ratio, but it is not known whether the phenomenon is general and which
mechanism controls the attrition.
2.4.3.1 PA-Based CPNCs

Maxfield et al., from AlliedSignal (now Honeywell) [1995; 1996; Christiani and
Maxfield, 1998] were the first to propose melt exfoliation in a PA-6 matrix. The
aim was to produce PA-based CPNC with advantageous performance, without
infringing on the Toyota reactive exfoliation method. The method comprises
three steps:
1. Treating an aqueous suspension of clay (the preferred platelet diameter is
15 ≤ D ≤ 300 nm) with peptising Na6P6O18 at 50-90 °C, and then with
organosilanes (e.g., aminoethyl aminopropyl trimethoxysilane),
organotitanates or organozirconates. The process increases the interlayer
spacing to d001 ≥ 5 nm. The authors suggested that to facilitate intercalation
the size of clay particles may be reduced, or the mixture may be exposed to
heat, ultrasonic cavitation, microwaves, etc. The complexes of organosilanes,
organotitanates and/or organozirconates (with or without onium salt)
improved the thermal stability at T > 300 °C.
2. Saturating the dried clay (interlayer spacing d001 ≥ 1.5 nm) with a monomer,
e.g., ε-caprolactam, (the patent claims are broad, stretching to ‘one or more
thermosetting and/or thermoplastic polymers or rubbers’) then polymerising
it, which increases the interlayer spacing to d001 ≥ 5 nm.
3. Compounding the modified clay at T ≥ Tm with matrix polymer until the
desired level of exfoliation is reached. The authors emphasised the formation
of γ-phase crystalline PA-6 by compounding with clay.
233
Melt compounding was also used by Liu et al. [1999] to prepare PA-6/organoclay
PNC. First, Na-MMT was intercalated with octadecyl ammonium chloride
(ODA), which increased d001 from 0.98 to 1.55 nm. Next, PA-6 was dry blended
with ≤ 17 wt% of the organoclay, then melt-compounded in a TSE and injection
moulded. Melt blending increased the interlayer spacing to d001 = 3.68 nm and
reduced XRD peak intensity, indicating a partial exfoliation. Similar results were
claimed by the RTP Co. for melt compounded PA-6 [Dahman, 2000]. In the
latter study various organoclays were used at different concentrations. Melt
exfoliation was carried out in a TSE.
As described in Section 2.3.8.2.4, Dennis et al. [2000; 2001] reported that melt
blending of PA-6 with Cloisite® 30B (2M2EtOH) resulted in exfoliation, thus the
fundamental studies on the intercalation processes were conducted with PA-6/Cloisite®
15A (2M2HTA) as a model system. The work has shown that at least for this
organoclay/polymer system, intercalation depends solely on the residence time and
the residence time distribution inside the processing equipment.
The observed difference in the ability of Cloisite® 30B and Cloisite® 15A
organoclays from SCP to exfoliate demonstrated the importance of the chemical
treatment of the clay, which controls the clay/polymer interactions. As shown in
Table 16 the exfoliating Cloisite®-30B (methyl-tallow-bis-2-hydroxyethyl) differs
from the intercalating Cloisite® 15A (bis-methyl-bis-hydrogenated tallow) on three
accounts:
1. It contains one (non-hydrogenated) tallow group versus two hydrogenated
in C15A,
2. It contains two hydroxyethyl groups versus two methyl groups of C15A and
3. It has lower substitution of organic ions (0.9 for C30B versus 1.25 meq/g for
C15A).
In short, C30B has a lower density of the organic intercalant within the interlamellar
galleries than C15A and at the same time it has higher polarity, which originates
from two -OH groups and unsaturation of the tallow group. Thus, Cloisite® 30B
has stronger attraction for PA molecules causing them to diffuse into galleries, and
more space for them to do so.
In another publication from the same laboratory an experimental organoclay
SCPX-2004 was used [Cho et al., 2000; Cho and Paul, 2001]. This new organoclay
is a close cousin of Cloisite® 30B – in SCPX-2004 the tallow is replaced with
rapeseed, which contains ca. 95% of C22 alkyl chain with single unsaturation at
C13 (erucyl). In both cases the same Na-MMT was used with CEC = 0.91 meq/g.
SCPX-2004 has been successfully used for exfoliation via direct melt compounding
of PA-6 (Mn = 29.3 kg/mol) with 0-20 wt% of the organoclay, using either a TSE
or a SSE at 240 °C. The extruded pellets were injection moulded into standard
test mould. For the SCPX organoclay, XRD gave the interlayer spacing
d001 = 1.8 nm. CPNC (with 5 wt% clay) was prepared either in a TSE or a SSE;
the former process engendered full exfoliation, while the latter only a partial
exfoliation, but large domains of unaltered organoclay remained. TEM confirmed
these observations. The individual layers were found aligned along the flow axis.
The average clay platelet thickness and length were determined as approximately
3 and 120 nm, respectively. At a clay content of 3.16 wt% it produced a respectable
modulus (3.7 GPa versus 2.7 GPa for neat PA-6 and 4.3 GPa for PA-6/C30B)
and excellent elongation at break (38% versus 40% for neat PA-6 and 10% for
PA-6/C30B).
234
TGA showed that due to the degradation of the quaternary alkylammonium,

the nanocomposites had lower stability than neat PA-6. A series of CPNC with
5 wt% clay were prepared varying temperature (T = 230-280 °C) and screw
speed (N = 80-280 rpm) in the TSE. Their mechanical properties were also given.
To detect tendencies, the published data were fitted to a linear relation:
Y = a 0 + a1 T + a 2 N (29)
where Y is any of the four variables listed in Table 36, N is screw speed, and a1
and a2 are equation parameters. Evidently, there is no correlation between the
two compounding variables and impact strength as well as elongation at break.
These properties may be more related to the crystallinity of the specimens than
the process variables. However, there is strong correlation for the modulus
(r2 = 0.9999) and the yield stress (r2 = 0.9998). Increasing the compounding
temperature and screw speed results in higher modulus. One may speculate that
the degree of platelet dispersion also increases. For yield strength the coefficient
a1 < 0, hence an increase of T reduces the yield strength. Most likely, thermal
decomposition of the SCPX quaternary alkylammonium weakens the bonding
between dispersed clay platelets and the matrix (see also Figure 32).
Cho and Paul also plotted the relative strength, modulus and elongation at
break versus the mineral clay content using data from four sources: their own
laboratory and from the literature [Christiani and Maxfield, 1998; Liu et al.,
1999; Okada et al., 1988; Okada and Usuki, 1995]. Three of the CPNCs were
prepared by melt compounding, whereas the fourth one was prepared by the in
situ reactive exfoliation method. Cloisite® 30B gave slightly higher modulus and
strength than SCPX, but the latter was far superior as far as the elongation at
break is concerned. The plots indicated a good linear increase of the relative
Table 36 Statistical analysis of CPNC performance versus

compounding conditions. Data [Cho and Paul, 2001]
Variables Izod impact Tensile Yield Elongation
strength modulus, E strength, σY at break, εb
(J/m) (GPa) (MPa) (%)
Standard 4.2889 0.0656 2.0258 5.4628

deviation
R-squared, r2 0.9961 0.9999 0.9998 0.9901
Coefficient of 0.3287 0.6832 0.6792 0.0556

determination
Range of values 38 - 47 3.66 - 3.85 81.1 - 87.6 29 - 38
Parameter value 37.2 ± 3.39 ± 91.0 ± 40.6 ±

a0 = 27.7 0.42 13.1 32.2
Parameter value 0.003 ± 0.00059 ± –0.054 ± –0.03 ± 0.14

a1 = 0.110 0.0016 0.052
Parameter value 0.030 ± 0.00095 ± 0.026 ± 0.010 ±

a2 = 0.030 0.00046 0.014 0.039
235
modulus with clay content, a similar increase of the tensile strength and poorly
correlating decrease of the elongation at break. The authors also reported a
synergistic effect on tensile strength and modulus when the exfoliated
nanocomposite was used as the matrix for a glass fibre reinforced composite.
Work from the same laboratory by Fornes et al. [2001] indicated that during
melt intercalation two processes simultaneously take place: thermodynamically-
driven diffusion of macromolecules into the interlamellar galleries, and mechanical
peeling off of platelets or short stacks. If during the former process the diffusion-
controlled intercalation sufficiently reduced the solid-solid interactions between
the adjacent platelets, the latter process may lead to exfoliation. It is noteworthy
that the minimum interlayer thickness of the organoclay needed for the PA-6
macromolecules to diffuse into is relatively small, d001 = 1.8 nm. However, the
chemical character of the intercalated onium cation, hence miscibility with PA-6,
is important as the diffusion of PA-6 molecules expands the interlamellar gallery
height at least by a factor of two. The stress field present during the compounding
also seems essential for efficient exfoliation.
The next contribution from this group was analysis of the behaviour of a
series of CPNCs with PA-6 as the matrix and containing up to 4.5 wt% of
organoclay [Fornes et al., 2004]. Three types of organoclays with quaternary
ammonium ions were tested. These were MMT-type, intercalated with: tetramethyl
(4MA), trimethyl hydrogenated-tallow (3MHTA), or dimethyl di(hydrogenated-
tallow) (2M2HTA). The nanocomposites were prepared by melt compounding
in a TSE. XRD and TEM demonstrated that the degree of dispersion increased
from 4MA (the worst) to 3MHTA. The modulus and yield strength increased in
the same order, while the elongation at break showed the opposite trend. These
results indicate that for melt intercalation by PA-6, a minimum interlayer spacing
is required – the minimum being located between d001 = 1.36 and 1.80 nm,
measured for MMT-4MA and MMT-3MHTA, respectively. The second important
information concerns the interaction between the PA-6 macromolecules and the
organoclay – in spite of larger initial interlayer spacing (d001 = 2.42 nm) MMT-
2M2HT did not disperse as well as MMT-3MHTA. Evidently, a more thorough
covering of clay platelet in MMT-2M2HTA by immiscible (with PA-6) long alkyl
tails than that produced by MMT-3MHTA is to blame. Partial access of the clay
surface to PA-6 chain-ends provides compatibilisation, similar to that provided
by PO-MAH in CPNC with PO as the matrix.
Exfoliated CPNC was obtained by melt compounding PA-6 with doubly-
intercalated MMT [Liu et al., 2003]. Thus, MMT was first intercalated with
3MHDA, and then with the diglycidyl ether of bisphenol A. A high level of clay
dispersion was achieved up to 5.6 wt% of inorganic content. At this loading the
mechanical properties (with reference to neat PA-6) increased by: tensile modulus
112%, tensile strength at yield 71%, flexural modulus 89%, flexural strength
54%, impact strength 34%, etc. In parallel, the HDT of PA-6 of 62 °C increased
to 157 °C.
Hasegawa et al. [2003] described quite a revolutionary method for the
production of PA-based nanocomposites. Thus, PA-6 was compounded in a TSE
with an aqueous suspension of Na-MMT (2 wt% solids). During compounding
the water was removed by vacuum-aided devolatilisation. The PA-matrix was
not hydrolysed. According to OM and TEM the clay platelets were exfoliated
and dispersed homogeneously. The tensile and flexural moduli of the CPNC were
28 and 14% higher than those of neat PA-6, respectively. Similarly, the tensile
236
and flexural strengths were higher by 28 and 12%, respectively. The Izod impact
strength of the new nanocomposites was 12% lower compared to PA-6 and HDT
increased from 75 °C for the neat resin to 102 °C. Gas permeability was 31%
lower than that of neat PA-6. In short, the properties of the new PA-6/MMT
nanocomposites were comparable to those of commercial CPNC from Ube (see
Table 62), prepared by compounding PA-6 with 2 wt% MMT-ADA organoclay.
CPNCs with PA-66 as a matrix were prepared in a high strain rate TSE [Nair
et al., 2002]. The final composition contained 1 to 15 wt% of unidentified
organoclay from SCP. While no details on the compounding protocol were given,
the strategy adopted by the group involves:
1. The use of organoclay suitable for melt compounding.
2. Preparation of a concentrate by compounding the organoclay with the matrix
resin in a TSE.
3. Using a continuous or batch mixer, dilute the concentrate to the final
composition and pelletise.
4. Adjust the MW of PA by solid-state polycondensation.
5. Form final object by injection moulding, extrusion, etc.
The processing conditions are not critical, but moderation is recommended – the
process must provide sufficient residence time at sufficient shear stress at a
temperature near to the Tm of the matrix resin. According to the authors, the
variables that mostly affect the dispersion are: screw design, rotational speed,
throughput rate and the feeding method.
The cited publication focused on the fracture mechanics study of PA-66
with different types of layered silicate having nanoscale (fully dispersed) or
multiscale (mixed nanoscale/microscale) structure. Independently of the structure
and concentration, the fracture toughness was proportional to the size of the
crack-tip plastic zone at fracture. At low clay concentration, the toughening
effects in CPNC increased with exfoliation and strong clay/matrix interactions.
However, at high clay concentrations, where the initiation toughness was low,
no significant effect of these microstructural factors was observed – the
composites with mixed nanoscale/microscale particulates exhibited the best
toughness. In the latter systems high initiation toughening from the nanoclay
was combined with high propagation resistance from the micron sized particles.
The organoclays seem to influence shear flow at the crack tip, thus playing an
important role in the toughening mechanism.
Incarnato et al. [2003] melt compounded a commercial ADS copolyamide with
up to 9 wt% Cloisite® 30B. The specimens showed mixed intercalated/exfoliated
clay dispersion with altered matrix crystalline morphology, e.g., high content of
the γ-crystalline phase, and reduced crystallisation temperature.
2.4.3.2 PO-Based CPNCs

Plastics comprise over 15 wt% of an automobile weight. Owing to its low price
and good performance the share of PP is expanding – it already constitutes 68%
in an Opel Astra. Incorporation of 4 wt% of exfoliated clay should improve the
flexural strength of PP by ≥ 50%, the modulus by at least 35%, and HDT by
≥ 32 °C, while maintaining the ductility to 10 °C. This makes the development
of PP-based nanocomposites commercially important. Serious efforts toward melt
237
exfoliation of layered materials in PP have been carried out in Japan, North

America and Europe. Since most of these efforts lead to intercalation, in part
they have already been discussed in Section 2.3.8.2.
Usuki et al. [1997] described an early, simple route to PO-based CPNC. First,
Na-MMT was cation-exchanged with dimethyl distearyl ammonium chloride
(2M2ODA, clay content = 52.8 wt%, d001 ≅ 3.3 nm). Next, an olefin oligomer with
telechelic -OH groups (a diol, carbon number = 150 to 200) was dissolved in toluene,
and different quantities of 2M2ODA were added to it. After evaporation of toluene,
the d001 of the doubly intercalated MMT-2M2ODA/PO was found to depend on the
diol-to-2M2ODA ratio: for the ratios 1:1, 3:1 and 5:1 the XRD peak position did
not change, giving d001 ≅ 4.4 nm, indicative of the presence of short stacks, but when
the ratio was 10:1 a full exfoliation was obtained. Finally, 5 wt% of MMT-
2M2ODA/PO (diol-to-2M2ODA = 1:1) was compounded with PP in an internal
mixer at 220 °C until the torque reached a plateau (ca. 5 min). XRD and TEM
showed that in the resulting CPNC the clay was exfoliated and uniformly dispersed.
It is noteworthy that in the absence of diol, organoclay dispersed only into micron-
size aggregates. The authors concluded that the oligomeric or telechelic diol has
good chemical affinity to 2M2ODA, so it can be inserted into the interlamellar space
in the presence of toluene. After evaporation of toluene, the -OH groups hydrogen
bond with MMT. The presence of oligomer increased the interlayer spacing enough
for the PP macromolecule to diffuse into the predominantly hydrocarbon filled
interlamellar galleries, eventually exfoliating the organoclay. The short note does
not report on the performance of these systems, but since the hydrophobic organoclay
is dispersed in PP without covalent bonding between these two or efficient
entanglement formation, one would not expect strength to be improved.
Another report from the Toyota laboratory also describes melt-intercalation of
doubly intercalated clay in PP [Usuki et al., 1999]. MMT was intercalated with a
primary ammonium salt (ODA), and then dispersed in a toluene solution of end-
hydroxylated PBD or maleated-PP. The complex was well-dried, added to molten
PP at 200 °C and mixed for 30 min. The interlayer spacing of the product was d001
= 3.82 nm. However, as reported by Kato et al. [1997], adequate exfoliation can
only be obtained by melt compounding when the acid value of the MA-PP is
reasonably high. Thus, MMT-ODA (d001 = 2.17 nm) was melt blended with PP-
MA in an internal mixer at 200 °C for 15 min. For the PP-to-organoclay ratio
= 3:1, d001 = 7.22 nm was found, indicating advanced intercalation. The authors
concluded that one polar group per 25 PP-mers is required to achieve exfoliation.
In 1997 Kawasumi et al. [1997] described another version of the process.
Thus, PP-based CPNC was prepared by compounding PP, PP-MA, and either
MMT (CEC = 1.19 meq/g) or fluoromica (FM) intercalated with stearyl
ammonium chloride (ODA). Two types of PP-MA were used: Yumex 1001 and
Yumex 1010 from Sanyo Chem., with Mw = 40 and 30 kg/mol, acid number 26
and 52 mg KOH/g, Tm = 154 and 145 °C, respectively. Intercalation of MMT
increased the interlayer spacing from d001 = 1.2 to 2.2 nm (inorganic content
67.4 to 68.4 wt%). Similarly, nearly quantitative intercalation of ODA in FM
was achieved (d001 = 2.2 nm; inorganic content 68.8 to 70.8 wt%. Exfoliation
was carried out by first dry blending the three ingredients, and then compounding
them in a TSE at T = 210 °C. The dried pellets were injection-moulded.
Miscibility of the PP/PP-MA blends was evaluated using an optical microscope.
Phase separation was observed in PP/ Yumex 1010 blends, while PP/ Yumex 1001
mixtures were miscible. Evidently, miscibility of PP/PP-MA depends on the relative
238
concentration of ingredients and temperature, but mainly on the concentration of

MAH in PP-MA. Yumex 1010 contains 52 mmole of KOH/g of polar MAH groups
that tend to form their own phase. In consequence, a relatively strong XRD peak
was observed for the PP/Yumex 1010 systems (d001 = 5.9 nm), indicating lack of
exfoliation. By contrast, the XRD of PP/Yumex 1001 exhibited a relatively small
and highly reduced peak indicating a high degree of exfoliation with only few
short stacks present. TEM confirmed these results.
In compositions containing PP with either MMT-ODA- or FM-ODA, but
without PP-MA compatibiliser, the clay formed particles several hundred
micrometres in size. Thus, these materials should be considered to be conventional
mineral-filled composites. Evidently, addition of compatibilising PP-MA is
essential if exfoliation is to take place. Thus, the polar molecules, viz. telechelic
diol or PP-MA, must first intercalate into the interlamellar space. The driving
force of this secondary intercalation originates from the hydrogen bonding
between the polar groups of the compatibiliser (-OH, MAH or -COOH) and the
clay surface =Si=O, ≡Si-OH or the intercalant =NH groups. As the interlayer
spacing of the clay increases, the solid-solid interactions between the layers are
reduced. Under the influence of a strong shear field the doubly intercalated clay
disperses in the PP matrix. However, when the doubly intercalated clay is
immiscible with the matrix, phase separation occurs and the clay concentrates in
domains where exfoliation is unable to take place.
Another modification of these methods was published by Hasegawa et al. [2000a].
Thus, MMT-ODA was compounded with three slightly maleated polyolefins, viz.
PP (Mw = 210 kg/mol; MI = 150 g/10 min; MAH = 0.2 wt%), PE (MI = 2 g/10 min;
MAH = 0.62 wt%), and EPR (M w = 270 kg/mol; MI = 0.06 g/10 min;
MAH = 0.55 wt%). The blending was carried out at 200 °C in a TSE (D = 30 mm,
L/D = 45.5). Excellent dispersion of clay platelets was shown by XRD and TEM (in
decreasing order) for EPR, PP and PE. In the latter system short stacks with
d001 ≅ 3 nm were visible.
Similarly, Okamoto et al. [2001a] prepared CPNC using organoclay (MMT-
ODA from Nanocor Inc.) and PP-MA (from Exxon Chem.; Mw = 195 kg/mol,
Mw/Mn = 2.98; 0.2 wt% of MAH; Tm = 141 °C). Introduction of such a small
amount of MAH was enough to obtain sufficient interaction between the PP
matrix and the organoclay. Three CPNCs with MMT contents of 2, 4 and 7.5 wt%
were prepared at 200 °C in a TSE (TEX30α-45.5BW from JSW). The extruded
and pelletised strands were moulded into ca. 2 mm sheets. The interlayer spacing
of the organoclay, d001 = 2.31 nm increased to 3.24, 3.03 and 2.89 at the three
clay concentrations, respectively. At the same time TEM microscopy showed a
fine dispersion of the clay platelets, with about 150 nm in length and about 5 nm
in thickness. The XRD diffraction peaks most likely resulted from short stacks
comprising 2-3 platelets.
The effects of organoclay concentration on melt intercalation were also
investigated [2000b]. Thus, MMT-ODA was melt compounded with PP-MA. Good
dispersion was obtained - XRD spectra were free of d001 peaks, but a small shoulder
for the highest clay content indicated the presence of short stacks. Apparently, the
chemical similarity of the paraffinic intercalant to PP matrix and the PP-MA
compatibiliser improved the degree of exfoliation, albeit by a small amount.
Another approach to the double intercalation strategy for the preparation of
PO-based CPNC was proposed by Hudson [1999] and by Jeong et al. [1998].
The three steps are:
239
1. Functionalising MMT with an aminosilane.

2. Reacting the free amine with maleated PO (MW ≅ 20 kg/mol; about 1 wt%
MAH) either in solution or in melt.
3. Dispersing the organomodified clay in a semicrystalline PO.
XRD of the silane treated MMT demonstrated an increase in interlayer separation
with d001 = 2.4 to 7.3 nm. TEM showed the presence of many individual MMT-
platelets, but in CPNC containing 15% clay most were in stacks of 2-4 layers,
ca. 1 μm long. Co-crystallisation between the maleated and the semi-crystalline
PO is essential to provide a mechanism of stress transfer between the matrix and
clay particles.
Serrano et al. [1998] patented CPNC that comprised 40-99.95 wt% EVAl
and more than 2 wt% of exfoliated MMT. No onium ion or silane coupling
agent was required, provided that water-soluble intercalants were used, e.g., P2VP
or PVAl. These hydrogen-bonded to the platelet surface, covering the Na+ and
thus shielding the EVAl from its degrading influence. For example, MMT was
compounded in a TSE with an intercalant at T = Tm + 50 °C. The CPNCs could
be used as external, heat-resistant body parts for the automotive industry; for
tyre cords; food wrapping with enhanced gas barrier properties; electrical
components; food-grade drink containers, etc.
The process for preparation of exfoliated PO nanocomposites developed in
Nanocor laboratories involves the use of proprietary organoclays, I.30P and I.31PS
(containing a silane coupling agent) [Lan and Quian, 2000; Nanocor’s Technical
Service Group, 2001, Nanocor Technical data sheets, 2001]. The process involves
addition of 2-5 wt% of PP-MA which acts as a compatibiliser between 2-6 wt%
of organoclay and PP. The compounding was carried out in a Leistritz CORI
TSE with L/D = 36. The screw configuration is shown in Figure 30. The
compounding temperature (including the devolatilisation zone) was 180 °C,
increasing progressively to 190 °C at the die. Two approaches were examined. In
the first a masterbatch that containing 50-60 wt% of organoclay was prepared,
then diluted to the final composition of 2-6 wt% organoclay. In the second, the
final composition was compounded directly. In both cases a high degree of
exfoliation was obtained, although some short stacks were evident on the TEM
micrographs. Good properties were reported, viz. tensile strength increased by 8
or 15%, tensile modulus increased by 29 or 28%, flexural strength increased by
18 or 22%, etc., for direct (single pass) compounding, and the two-step process,
respectively. These values were calculated from the authors’ data for CPNC with
4 wt% organoclay. They seem to be short of the expected benchmark set by the
automotive industry. There is quite a bit of data scattering. Within the experimental
error the single pass provides as good CPNC as the one involving masterbatch.
One of the reasons may be matrix degradation – since PP is prone to
thermomechanical chain scission, two passes through an extruder are expected
to engender more damage.
Polypropylene-based CPNCs were also prepared by melt intercalation with
two organoclays, three PP-MA containing 1.5 to 5.8 wt% MAH and a PA-6
resin [Wang et al., 2001a]. The two organoclays were MMT-ODA (Nanomer
I.30 TC) and Cloisite ® 20A (C20A; MMT-2M2HTA from SCP). The
compounding was carried out in an intermeshing, CORI TSE (Leistritz ZSE-27;
L/D = 40) operating at T = 180 to 230 °C and at screw speed N = 100 to 200 rpm.
To achieve better dispersion, PP-MA was mixed with C20A, then PP was added
and compounded to make PP/PP-MA/C20A nanocomposites.
240
Since PA-6 has Tm ≅ 219 °C, I.30 with better thermal stability than C20A
was chosen for the preparation of CPNC with PP/PA-6 blend. The compounding
sequence was altered, first blending PP with PP-MA, and then adding I.30 at 100
rpm. PA-6 was incorporated using two procedures:
1. Two-step process where first PA-6, PP-MA, and I.30 were mixed, then PP
was added;
2. Three-step process, where first PP-MA was mixed with I.30, then with PA-6,
and finally with PP.
As summarised in Table 37 the compounding resulted in intercalation. The
presence of PA-6 did not increase the d001 value, but reduced the intensity of the
XRD diffraction peak, indicating a higher degree of exfoliation.
The molecular weight and MAH content of the compatibilising PP-MA strongly
affect the nanostructure and the properties of PP nanocomposites. PP-MA with a
lower molecular weight and a high MA content leads to better dispersion, but
reduces the mechanical performance. Similarly, addition of PA-6 increases the
interlayer spacing, but reduces the tensile strength. Addition of a high molecular
weight PP-MA with lower MAH content may improve both stiffness and
toughness, but improvements are limited viz. 14% for tensile strength, 49% in
Table 37 Interlayer spacing in PP/PP-MA/clay and PP/PP-MA/

PA-6/clay nanocomposites. Data [Wang et al., 2001a]
Material d001 (nm)
Cloisite® 20A 2.3
PP + 5 wt% Cloisite® 20A 2.48
PP-MA (1.5 wt% MAH) + 25 wt% Cloisite® 20A 2.9
PP-MA (2.5 wt% MAH) + 25 wt% Cloisite® 20A 3.0

®
PP-MA (5.8 wt% MAH) + 25 wt% Cloisite 20A 3.7
PP + 15 wt% PP-MA (1.5 wt% MAH) 3.0

+ 5 wt% Cloisite® 20A
PP + 15 wt% PP-MA (2.5 wt% MAH) 2.9

PP + 15 wt% PP-MA (5.8 wt% MAH) 3.6

Nanomer I.30 TC 2.3
PA-6 + 5 wt% Nanomer I.30 TC 3.71
PP + 15 wt% PP-MA (1.5 wt% MAH) 2.85

+ 5 wt% Nanomer I.30 TC
PP + 5 wt% PP-MA (1.5 wt% MAH) 3.7

+ 5 wt% Nanomer I.30 TC + 10 wt% PA-6
241
tensile modulus and 30% in Izod impact strength. The best overall performance
was obtained from the system: PP + 15 wt% PP-MA (1.5 wt% MAH) + 5 wt%
Cloisite® 20A.
Following the successful direct melt exfoliation of Na-MMT in a PA-6 matrix
by Hasegawa et al. [2003] the method was extended to a Na-MMT/PP system
[Kato et al., 2003]. A TSE with D = 32 mm, and L/D = 77 was used at T = 200
to 220 °C and screw speed of 300 rpm, with residence time of ca. 6 min. The
barrel was divided into three functional sections: (1). mixing, (2). exfoliation,
and (3). devolatilisation. Into section (1), first PP and PP-MAH were fed from
the main hopper to be melt compounded with Na-MMT (fed a bit downstream).
Into section (2) ca. 10% of water was injected (at the processing temperatures
the saturated vapour pressure is 1.5 to 2.3 MPa) to expand the interlayer spacing
of Na-MMT, and facilitate reactions between MAH and the clay surface. In
section (3) a two-stage devolatilisation was carried out. As a result, the clay was
uniformly dispersed as either exfoliated platelets or intercalated short stacks.
The mechanical properties of these nanocomposites were nearly the same as those
of conventional CPNC prepared by compounding with organoclay, for example,
the flexural modulus of the new CPNC was 2.76 versus 2.88 GPa.
2.4.3.3 PCL-Based CPNCs

With the growing concern for recycling industrial and municipal waste,
biodegradable polymers and their nanocomposites are becoming increasingly
attractive [Akovali et al., 1998]. As discussed in Section 5.4.2, polylactic acid
(PLA) has been selected by Toyota for progressive replacement of PP composites
in automotive applications. Poly-ε-caprolactam (PCL) is another biodegradable
aliphatic polyester with good potential for the consumer market. However,
performance of both these resins, PLA and PCL, should be enhanced by
incorporation of exfoliated clay platelets.
In a series of papers from Mons-Hainaut the focus has been placed on the
development of a melt compounding process for the preparation of CPNC with
PCL as the matrix, which would show significant improvement of mechanical
properties at low clay loading [Pantoustier et al., 2001; Lepoittevin et al., 2002a].
Thus, commercial PCL (Mn = 49, Mw = 69 kg/mol) was mixed with several clays:
(C1) Na+-MMT;
(C2) MMT¯DDA;
(C3) MMT-ODA;
(C4) MMT-2M2ODA (Cloisite®25A); and
(C5) MMT-MHT2EtOH (Cloisite®30B).
The mixing was carried out in a two-roll mill at 130 °C for 10 min, followed by
compression moulding into 3 mm thick specimens. Compositions containing 1,
3, 5 and 10 wt% of MMT were prepared.
The interlayer spacing of the neat organoclays (after dispersing 3 wt% in
PLC) was: d001 = 1.21/1.23; 1.38/1.37; 1.87/2.56; 2.9/3.6; and 1.84/3.1 nm, for
C1 to C5, respectively. Evidently, Na+-MMT and MMT¯DDA did not intercalate,
whereas modest intercalation was obtained for the remaining organoclays, where
the diffusion of PCL macromolecules increased the interlamellar galleries by Δd001
= 0.69, 0.7 and 1.26 nm, respectively. A summary of the mechanical performance
is displayed in Figure 56. Except for the modulus, the best performance from between
the six materials is that of neat matrix, PCL.
242
Figure 56 Tensile properties of polycaprolactam (PCL) and its mixtures containing

3 wt% of MMT in the form of organoclays C1 to C5 – see text. The vertical
broken lines are drawn to help judge the magnitude of the property change in
maximum stress at break, tensile modulus and the maximum strain at break. Data
[Pantoustier et al., 2001].
A partial explanation for the poor mechanical performance can be found in the
reduction of crystallinity. To compensate for it a higher clay loading is required.
Thus, CPNC with up to 10 wt% MMT were prepared with C4 and C5 organoclays
[Lepoittevin et al., 2002a,b]. The highest tensile modulus was obtained for 10 wt%
C5 (increase by a factor of 1.85), but the material became brittle (7% elongation
at break). A better balance of properties was obtained for a 5 wt% C5 loading,
viz. modulus increased by 45% and the elongation at break, εb = 560%. The
CPNC also showed improved thermal stability and flame resistance.
Lepoittevin et al. [2002b] also prepared CPNC with PCL as the matrix via in
situ intercalative ring-opening polymerisation of ε-caprolactone catalysed by
dibutyl-tin dimethoxide, Bu2Sn(MeO)2. For comparison, 1, 3, 5, and 10 wt % of
C1, C4 and C5 organoclays were incorporated. The C1 and C4 content had no
effect on the PCL molecular weight (Mn = 14 to 24 kg/mol), but as C5 content
increased, the Mn was found to decrease, probably due to chain transfer by the
intercalant’s –OH groups. The polymerisation resulted in a modest intercalation
of C1 (d001 increased from 1.2 to 1.63 nm for the 3 wt% in PCL matrix); in
intercalation of C4 (d001 increased from 1.86 to 2.68 nm); and in nearly full
exfoliation of C5, confirmed by TEM. TGA showed better thermal stability for
the exfoliated than for the intercalated CPNC, both exceeding the degradation
temperature of neat PCL.
Tortora et al. [2002] also used the polycondensation route, but starting with
MMT pre-intercalated with ω-amino dodecyl acid, 0 to 44 wt% of MMT-ADA.
According to XRD exfoliation was achieved for CPNC with up to 16 wt% clay.
243
Incorporation of clay slightly reduced the Tm (from 62 to 57 °C), but significantly

reduced the matrix crystallinity as well as the onset of degradation temperature:
Td = 382 (for PCL) to 188 °C (for CPNC with 44 wt% clay). The reduction
could in part be explained by the decrease of the matrix molecular weight with
increasing organoclay content (from Mn = 11.6 to 6.5 kg/mol). The permeability
of dichloromethane or water vapours through these CPNCs was also significantly
reduced.
The same method was used to prepare CPNCs of PCL polymerised in the
presence of up to 44 wt% of MMT-ADA [Pucciariello et al., 2004]. As the
organoclay content increased the molecular weight decreased, viz. Mn from 11.6
to 6.5 and Mw from 14.9 to 7.8 kg/mol. According to XRD the nanocomposites
with low organoclay content (6 and 18 wt%) were exfoliated, whereas those
containing 22, 30 or 44 wt% were only intercalated. In parallel with the interlayer
spacing there was a significant difference in thermal behaviour – the CPNC with
exfoliated structures showed an increase of Tc, Tm and the heats of transition,
whereas the intercalated ones showed the reverse trend – these thermal properties
decreased with organoclay content. Surprisingly, as the clay content increased
the crystallisation rate decreased, but the PCL morphology remained spherulitic.
Since clay platelets act as nucleating agents, the slower crystallisation most likely
resulted from hindrance of molecular motion in the progressively more and more
crowded interlamellar galleries.
In related work, PCL was polymerised in the presence of 3 wt% of
co-intercalated MMT [Gorrasi et al., 2004]. The co-intercalants were:
(CH3)2(CH2CH2OH)(C16H33)N+ Cl– or 2MEtOHHDA, and (CH3)3(C16H33)N+
Cl– or 3MHDA. The co-intercalation was carried out with the ratio of these two
ammonium salts ranging from 0 to 25, 50, 75, and 100%. Similarly, as in the
preceding communication, the PCL molecular weight decreased with
2MEtOHHDA (i.e., -OH group) content (the clay loading being constant) from
Mn = 56 to 28 kg/mol. According to XRD, only the CPNC with more than 50%
2MEtOHHDA were exfoliated, confirming the importance of good bonding
between clay and matrix. The tensile modulus increased with the organoclay
hydroxyl group content to about 9-fold of the value for neat PCL. Furthermore,
as the –OH group content increased, so did the grafting density of PCL to clay,
and as a consequence the gas and vapour diffusion (e.g., dichloromethane or
water) were reduced.
Considering on the one hand the relative ease of producing exfoliated CPNC
with PCL, and on the other hand its miscibility with several commercially
important resins (e.g., SAN, ABS, PVC, CPE, PEST, PEMA, etc.), it is only natural
that this CPNC would be used as a vehicle for nanoreinforcing PCL-miscible
polymer blends [Choe et al., 2002]. To ascertain system miscibility, 20 to 40 wt%
of PCL (MW = 10 to 100 kg/mol) with well dispersed organoclay has been used.
The preferred clay is MMT pre-intercalated with
CH 3 (CH 2 ) 17 N + (HOCH 2 CH 2 ) 2 CH 3 Cl - , acidified CH 3 (CH 2 ) n -NH 2 or
CH3(CH2)nNHR ( where n = 8 to 18, and R is a hydrocarbon). As the cited
examples show, melt compounding at T ≤ 140 °C for the required time (e.g.,
20 min!) results in exfoliation, whereas melt compounding at T > 140 °C results
in intercalation with d001 < 4 nm. Compounding in a single step involves
simultaneously mixing organoclay with PCL and a miscible resin. Compounding
in two steps involves first, the preparation of organoclay concentrate (≤ 30 wt%)
in PCL, and subsequently diluting it with the selected blend component (e.g.,
244
PVC, SAN or ABS). It was found that incorporation of organoclay improved

mechanical properties (tensile modulus increased by 350%) and heat deflection
temperature (by 50 °C). With these advantages, CPNC may replace the
conventional ABS resin and its blends with PVC, for example, in electronic housing
applications.
To prepare CPNC of SAN, Lee and Kim [2004] dispersed Na-MMT in
caprolactam, polymerised the suspension, and then melt compounded the product
with SAN. Surprisingly, XRD indicated full exfoliation within the PCL domains,
while Tg showed good miscibility between PCL and SAN. The stress-strain curves
from the tensile tests at room temperature indicated significant improvement of
the stress and elongation at break.
2.4.3.4 Other Systems

Melt compounding is becoming a method of choice for CPNCs with a variety of
polymeric matrices. The method has not been successful in the case of a PS matrix
[Tanoue et al., 2003]. The authors compounded three grades of PS with Cloisite®
10A under diverse processing conditions. The interlayer spacing versus residence
time in the TSE initially slightly increased to decrease at longer times toward the
value of non-intercalated MMT. The reason for this behaviour was a rapid
thermomechanical decomposition of organoclay by the Hofmann elimination
mechanism, followed by chain scission of PS. Better results could be obtained
using MMT pre-intercalated with either imidazolium cations [Wang et al., 2003],
or with ammonium-ion terminated oligostyrene [Su et al., 2004]. Owing to the
higher decomposition temperature, and good miscibility with the matrix, a
satisfactory dispersion of clay platelets has been obtained.
Intercalated CPNC with PMMA as the matrix were prepared by melt mixing
with 10 wt% of commercial organoclays, viz. Cloisite® -10A, -20A, -25A and
–30B [Kumar et al., 2003]. The interlayer spacing of the organoclays was found
to increase by 0.7 to 1.4 nm. The glass-transition temperature of these CPNC
was lower than that of neat PMMA by ca. 10 °C.
Melt compounding was also used to disperse 1 to 10 wt% of Cloisite® 30B in
an epoxy matrix [Yasmin et al., 2003]. Thus, a three-roll mill was used at 60 °C
to exfoliate the clay. The tensile stress-strain curves indicated that as the organoclay
loading increased the modulus increased as well (by 67% at 10% loading), but
the strain at break decreased (by a factor of ca. 5.7). Incomplete degassing, leaving
voids in the specimen was most likely responsible for these modest improvements.
However, since the method does not require solvent it is environmentally-friendly
and worth pursuing.
2.4.4 Functional CPNC

The previous examples described CPNC prepared as structural materials, with
improved strength, modulus, and/or high barrier properties. However, the methods
are quite general, applicable to other materials, designed to perform specific
functions. A few examples will be mentioned.
2.4.4.1 Liquid Crystal/Clay Composite (LCC)

Kawasumi et al. [1998] prepared nematic liquid crystal (LC) with up to 2 wt%
of MMT. First, the clay was intercalated with a variety of ammonium cations,
245
including primary and quaternary alkyl (C8, C12, C18, etc.) as well as primary
and tertiary amines with biphenyl groups, e.g., 4-cyano-(4´-biphenyl-oxy)-undecyl
ammonium salt, that showed good miscibility with LC. MMT intercalation was
conducted in aqueous medium at 50 °C stirring the suspension for 3 h, washing
the precipitate with ethanol and freeze-drying it. The interlayer spacing varied
with the intercalant from d001 = 1.37 to 3.28 nm. Next, the organoclay (0.2 to 2
wt% in the final composition) was dispersed in DMF or dimethyl acetamide
(DMAc) and the LC was added. The solution was spin-coated on slide glass,
DMF slowly evaporated at 50 °C, and then under vacuum. When the clay had
good affinity for LC, the system was homogeneous. The CPNC exhibited bistable
and reversible electrooptical effects between a light scattering and transparent
state that could be selected by changing the frequency and voltage of applied
electric fields. To activate transparency a 50 ms electrical field (60 Hz, 100 V)
application was required. To induce opacity a 50 ms high frequency field (1.5
kHz, 100 V) was needed. When the field was switched off the transparency (in
the first case) or opacity (in the second) remained. The memory effect is related
to the orientation of clay particles caused by application of the low frequency
field and randomisation by the high frequency one. This new CPNC is a potential
candidate for light controlling glasses, high information display devices (that do
not require active addressing devices), erasable optical storage devices, etc.
2.4.4.2 Biodegradable CPNC with Polylactic Acid (PLA)

Lactic acid (LA), a colourless liquid with chemical formula CH3CHOHCOOH
was identified by Carl W. Scheele in 1780. It exists in two optically active forms,
dextro- and laevo-, often designated as D-lactic acid and L-lactic acid. Ordinary
(or racemic) lactic acid is optically inactive. Pharmaceutical and food industries
prefer the L-lactic acid and lactates since the human body does not metabolise
the D-form. Lactic acid has been produced by fermentation controlled by specific
bacteria, using sugar as the starting raw material.
While LA can be synthesised, its commercial production is based on
fermentation. The starting material is usually starch from any plant (e.g., corn,
potatoes or sweet potatoes). In the first step, starch is recovered from plant material
and enzymatically converted to glucose, which in turn is fermented by
microorganisms (e.g., Lactobacillus amylovorus) to PLA [Yan et al., 2001]. For
high productivity the fermentation requires immobilisation of the bacteria and a
complex mixture of nutrients.
Carothers in 1932 produced a low molecular weight polylactic acid (PLA) by
heating lactic acid under vacuum. Following this discovery DuPont manufactured
medical grade sutures, implants and packaging for controlled drug release
applications. Today the two principal routes to PLA are:
1. Direct condensation followed by chain coupling, and
2. Ring-opening polymerisation of lactide(s).
In the first process the polycondensation water is removed by azeotropic
distillation and high vacuum – the approach used by Carothers (nowadays by
Mitsui Toatsu Chem.) to produce a low to intermediate MW polymer. This product
may be used directly, or if high MW is required, it can be chemically coupled
using isocyanates, epoxies, anhydrides, carbodiimides, ortho-esters, etc. The
second process also starts with polycondensation of LA under mild conditions,
246
to produce a low MW intermediary PLA, which in turn can be catalytically

converted to cyclic dimer – the lactide. The latter has three forms that can be
separated by distillation: L-, D-, and DL- or meso- [Kõhn et al., 2003]. The ring
opening polymerisation of the lactide leads to a wide range of molecular weights.
Several manufacturers supply PLA, viz. Galactic, Mitsui Toatsu Chem., Mitsubishi
Plastics, Inc. (‘Ecoloju’ Biodegradable Plastic Films and Sheets), Shimadzu,
Trespaphan-Celanese AG (biaxially oriented PLA, BOPLA), and Cargill Dow
Polymers. The latter company announced a major expansion aimed primarily at
the fibre and nonwovens market.
Typical properties of PLA are listed in Table 38. L-PLA shows better mechanical
properties than meso-PLA. The former properties are comparable to these of typical
commodity resins, viz. PP, PS or PVC. The main problem is the relatively low Tg
and crystallinity. In consequence, PLA has a tendency to permanently deform under
stress at T > 50 °C. It is expected that incorporating nanoclays may solve both
problems. Solution crystallised PLA was shown to reach over 80% crystallinity
[Fischer et al., 1973]. Another problem – the relatively high density of PLA – may
be eliminated by microfoaming a properly formulated CPNC.
Table 38 Physical properties of polylactic acid (PLA)

Property Typical values
Molecular weight (kg/mol) 100 to 300
Glass transition temperature, Tg (ºC) 55-70
Melting temperature, Tm (ºC) 130-215
Heat of melting, ΔHm (J/g) 8.1-93.1
Crystallinity, X (%) 10-4 0
Surface energy (dynes) 38
Solubility parameter, δ ( J / mL ) 19-20.5
Density, ρ (kg/m3) 1.25
Melt flow rate, MFR (g/10 min) 2-2 0
Permeability of O2 & CO2 (f mol/m s Pa) 4.25 & 23.2
Tensile modulus, E (GPa) (orientational effects) 1.9-4.1
Yield strength, L-PLA/meso-PLA, σy (MPa) 70/53
Strength at break, L-PLA/meso-PLA, σB (MPa) 66/44
Flexural strength, L-PLA/meso-PLA, I (MPa) 119/88
Elongation at break, εB (%) 100-180
Notched Izod impact strength, L-PLA/meso-PLA, (J/m) 66/18
Vicat, L-PLA/meso-PLA, (°C) 165/52
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In 1998 Rhone-Poulenc obtained a US patent for nanocomposites prepared

by dissolving polyethylene glycol- and/or polypropylene glycol-polylactic acid
copolymers in an organic solvent followed by adding it to an aqueous suspension
of clay [Spenleuhauer et al., 1998]. CPNC could be recovered by precipitation
(without additional colloidal protective agents) or by microfluidisation and solvent
evaporation.
Also in 1998, Toyota established the Biotechnology & Afforestation Business
Department. The group, elevated to the level of an independent business division,
actively promotes business activities in forestation, agriculture and other fields
contributing to the solution of such problems as food shortages and environmental
degradation. In 2001, Toyota jointly with Mitsui & Co., Ltd started a joint venture
in Indonesia. The aim is to produce ca. 100 kton/year of sweet potatoes from
6,000 ha dedicated farmland for the production of PLA and animal feed.
Production will start in early 2004. The PLA plant will be built next to the animal
feed processing plant. In the meantime there is serious ongoing research and
engineering design effort for the manufacture of lactic acid, its polymerisation
into PLA, and upgrading the performance of the latter by means of CPNC
technology. The main concerns are heat resistance, mechanical performance and
durability. Toyota believes that upgraded PLA can be used to replace PP fabrics
and mouldings in automobile interior parts, such as seat mouldings, interior
door finish, pillar garnish, etc. Some of these parts were already introduced in a
concept car presented at the 2002 motor shows.
CPNCs with PLA as a matrix can be prepared either by polymerisation in the
presence of organoclay (e.g., by the monomer intercalation method) or by melt
compounding. Ray et al. [2002a] selected the latter route. PLA (D-enantiomer
content of 1.1-1.7 wt%) was vacuum dried, and dry blended with MMT-ODA.
The inorganic content varied from 2 to 4.8 wt%. The effect of a compatibiliser,
a low molecular weight o-PCL (α,ω-hydroxy-terminated with Mw = 2 kg/mol),
was also studied. The mixtures were melt-compounded in a TSE at 190 °C.
XRD and TEM provided evidence of intercalation but not exfoliation. As a
result of melt-compounding the interlayer spacing of MMT-ODA, d001 = 2.31 nm,
increased to higher values, dependent on the clay content, viz. d001 = 3.10 (for
2 wt%) and 2.89 nm (for 4.8 wt%). Incorporation of the compatibiliser did not
change the XRD peak position, but it increased its intensity. The number of clay
platelets per stack was calculated as 10 to 13. Good bonding between the clay
platelets and the matrix was evidenced by melt rheology – the low frequency
storage modulus strongly increased with the organoclay content. The degree of
crystallinity of PLA was determined as 36% – incorporation of either organoclay
or PCL increased it to ca. 50%. However, the latter additive simultaneously
decreased the Tg by about 5 °C. The two additives also had opposite effects on
the storage modulus – the clay increased it, the compatibiliser decreased its value.
Interesting and unexpected results were obtained by burning the CPNC. The
resulting cinder was a highly porous, ‘house of cards’, a sort of ceramic foam,
with density, ρ = 0.187 g/ml. Since the BET surface area of MMT is 780 m2/g and
that of the ceramic foam is 31 m2/g, the reduction is about 25-fold [Ray et al.,
2002b]. XRD indicated that the sintered material had amorphous structure.
A more detailed study of the effect of clay on PLA crystallinity was published
separately [Ray et al., 2002c]. In this case, instead of MMT-ODA + PCL
compatibiliser, a fluoromica (FM; CEC = 1.2 meq/g; p ≈ 250) pre-intercalated
with methyl coco-alkyl bis(2-hydroxyethyl)-ammonium ion (MC2EtOH) was
248
used. Melt compounding of PLA with 4 wt% of this organoclay was carried out
in a TSE at 210 °C. Compounding increased d001 from 2.1 to 3.1 nm, but it
reduced the PLA Mw from 177 to 150 kg/mol. The effect of the organoclay on
crystallinity was quite modest, viz. the degree of crystallinity increased by ca.
4%, Tg decreased by 4 °C, Tm was unchanged and Tc increased by 28 °C. However,
at the same time the improvement of the mechanical properties of PLA was
significant – flex modulus, storage modulus and flex strength at 25 °C all increased
by: 26, 25 and 9%, respectively. Surprisingly, incorporation of the organoclay
accelerated the rate of PLA biodegradability by ca. 60%.
In the fourth paper of this series [Ray et al., 2003], PLA was melt compounded
in a TSE at 210 °C with 4, 5 or 7 wt% of organoclay. The latter was MMT (CEC
= 0.9 meq/g; p ≈ 100), pre-intercalated with trimethyl octadecyl ammonium
(3MODA). Melt compounding only slightly reduced the Mw of the PLA matrix
(from 177 to 165 kg/mol), and virtually did not affect Tg and Tm. The strongest
increase of the PLA degree of crystallinity was for 4 wt% clay loading – an increase
from 36 to 65%. At the higher organoclay contents the crystallinity decreased to
56 and 54%, respectively.
Again, these nanocomposites were only intercalated. While the interlayer
spacing of organoclay was d001 = 1.93 nm, incorporation into PLA melt at the
level of 4, 5 and 7 wt% organoclay increased this value to 3.05, 2.7 and 2.8 nm,
respectively. The data also indicate that here the number of platelets in a short
stack was about 4. Nevertheless, the improvement of the mechanical properties
(see Figure 57) was quite impressive – note that the tensile strength and the
elongation at break go through a local maximum at about 4 wt%. On the other
hand, the Young’s modulus and the heat distortion temperature linearly increase
with the clay content in the whole range of compositions. In Figure 58 the relative
oxygen permeability is shown versus organoclay content. The experimental data
Figure 57 Mechanical properties of a PLA/MMT-3MODA system as functions of

the organoclay content. The data points are experimental [Ray et al., 2003], the
lines have been included to guide the eye.
249
Figure 58 Relative oxygen permeability of a PLA/MMT-3MODA system as a

function of organoclay content. The calculated dependence suggests low a clay
platelet aspect ratio of p = 24 or their misalignment. Data [Ray et al., 2003].
follow Equation 23 with the aspect ratio, p = 24. Since the average number of
platelets in the stack is about 4, and the interlayer spacing is about 3 nm, the
effective length of the stack is 288 nm – to be compared with the estimate by the
authors of approximate platelet diameter, D ≈ 200 nm.
As has been noted before, incorporation of MMT enhanced the
biodegradability of PLA. It is interesting that the enhancement is not observed
during an initial period (30 < ti < 50 days). Afterwards, without the organoclay
the biodegradation proceeds at a slow rate, whereas in its presence it is
dramatically increased – all specimens decomposed in 60 days. Since the
biodegradation proceeds by hydrolysis of the ester linkages, one may speculate
that the difference is related to the size of the PLA crystals, as well as the presence
of ≡Si-OH hydroxyl groups. The melt flow behaviour of these systems strongly
suggests that these groups react with PLA, causing end tethering. However, such
a non-catalysed reaction is slow and numerous ≡Si-OH groups are most likely
left behind.
Paper 5 of this series examines the influence of different organoclays on the
performance of PLA nanocomposites [Ray et al., 2003b]. At a constant loading
of 4 wt%, the best performance was obtained using synthetic fluoromica (FM)
pre-intercalated with methyl di-polyethylene glycol coco ammonium ion: the
flexural modulus increased by 26%, strength by 9%, HDT increase by 17 °C,
and O2 permeability was reduced by a factor of 2.8. Furthermore, biodegradability
of this system was twice as rapid as that of neat PLA. The final contribution in
this series [Ray and Okamoto, 2003] focused on the flow and foamability of
PLA containing up to 7 wt% of MMT-ODA. Non-linear viscoelastic behaviour
was observed in dynamic, steady state and extensional flow fields. High quality
foams with bubble size of 2.59 ± 0.55 μm were produced.
250
Recently, fundamental studies on the crystalline and supermolecular structures

of CPNC with PLA as matrix were carried out [Pluta et al., 2002]. The specimens
were prepared by melt compounding in an internal mixer (at 60 rpm and 180 °C
for 10 min). Thus PLA (MW = 166 kg/mol; 4.1 mol% D-lactide) was mixed with
0.3 wt % Ultranox 626 stabiliser and 3 wt% (inorganic content) of a nanofiller.
As the latter, either Na-MMT (CEC = 0.92 meq/g; p = 250 to 500; d001 = 1.22 nm)
or MMT intercalated with MHT2EtOH from SCP were used. The compounds
were compression moulded at 185 °C into 0.5 mm thick sheets. Three solidification
procedures were used: quenching, annealing of the quenched sample at 120 °C,
and crystallisation from the melt at 120 °C for 3 h. XRD showed that melt-
compounding MHT2EtOH with PLA resulted in intercalated CPNC – the
interlayer spacing increased from 2.1 to 3.14 nm. By contrast, Na-MMT only
formed a microdispersion in PLA matrix. Microscopic observations of the
specimen structures are summarised in Table 39. The authors noted that in the
nanocomposites the clay short stacks were incorporated into the interlamellar
and/or intralamellar regions. The data are a bit disappointing as the nanofiller
had negligible effects on the Tg as well as on crystallinity. However, it was found
that during melt compounding with clay or organoclay PLA degraded less than
without it, viz.: decrease of Mn for PLA, NC and MC was 41.2, 19.6 and 22.1%,
Table 39 Morphology of PLA and its micro- and nano-composites.

Data [Pluta et al., 2002]
Material Code* Crystallinity** Tg T1 Tm Δ Hm
(°C) (°C) (°C) (J/g)
PLA PLA(Q) Amorphous 58.4 108.3 129.6 3.6
PLA(A) Thin spherulites 58.4 125.4 153.7 42.3
PLA(C) Spherulites 52.9 124.0 154.1 52.6

D ≈ 330 μm
PLA + 3 wt% NC(Q) Amorphous 58.0 113.7 130.9 1.0

MHT2EtOH
NC(A) Thin spherulites 58.2 121.9 152.7 38.7
NC(C) Spherulites 54.9 124.0 154.3 49.0

D ≈ 200 μm
PLA + 3 wt% MC(Q) Amorphous 58.5 110.6 130.0 1.6

Na-MMT
MC(A) Thin spherulites 58.8 124.3 153.1 39.5
MC(C) Spherulites 54.1 124.0 154.3 51.6

D ≈ 150 μm
Notes:
* Q = quenched, A = sample Q annealed at 120 °C, C = crystallized from melt
at 120 °C for 3 h
** D = spherulite diameter, Tg is the glass-transition temperature, T1 is the onset
temperature for cold crystallisation and Tm is the melting temperature
251
respectively. The processability of these compositions was comparable to that of

the neat PLA. An improvement of the CPNC thermal stability under oxidative
conditions was also noted.
CPNC based on polycaprolactone (PCL) were prepared by melt mixing [Di et
al., 2003]. The exfoliation of Cloisite® 30B was achieved for an organoclay loading
below 10 wt%. In parallel with the degree of dispersion was the increase of the
PCL crystallisation temperature. A significant enhancement in mechanical
properties and thermal stability was reported.
For packaging applications, Paul et al. [Paul et al., 2003] studied the
preparation and properties of CPNC with plasticised PLA. To make these systems
competitive with the standard packaging resins (viz. PE or PP) such PLA properties
as thermal stability and gas barrier properties should be enhanced. Thus PLA
(Mw = 155 kg/mol) was plasticised with PEG (Mw = 1 kg/mol; 5, 10 or 20 wt%)
and melt-compounded with a nanofiller (1 to 10 wt% of clay) in the presence of
0.3 wt% of Ultranox® 626 stabiliser. Four Cloisite‚s from SCP were used: Na-MMT,
C25A, C20A and C30B (see Table 16). The compounding was done in an internal
mixer at 180 °C and 20 rpm for 4 min, then at 60 rpm for 3 min. The compound
was pressed into 3 mm thick sheets. According to XRD, at a loading of 3 wt% of
these four nanofillers, only intercalation was obtained. The interlayer spacings
increased from d001(Na+) = 1.21 to 1.77 nm, d001(C25A) = 2.04 to 3.24 nm,
d001(C20A) = 2.36 to 3.65 nm, and d001(C30B) = 1.84 to 3.80 nm. The intercalation
process was complicated by two secondary intercalants, PLA and PEG. Intercalation
of Na-MMT was most likely done by PEG, but in the case of organoclays both
partake in the process. Plasticisation reduced the Tg from 55 to 15 ± 1 °C, and
slightly increased the Tm from 167 to 170 ± 1 °C, i.e., the nanofillers have been
found unable to affect the PLA transition temperatures. On the other hand, the
decomposition temperature was significantly increased, e.g., addition of 3 wt% of
C30B increased it by 40 °C. The flammability was also suppressed. The mechanical
properties were not reported.
Bionolle, a commercial biodegradable polybutylenesuccinate (PBS) was used
as CPNC matrix for a series of organoclays [Someya et al., 2004]. The latter were
based on MMT pre-intercalated with primary and tertiary ammonium cations
(e.g., DDA, ODA, ADA, N-lauryldiethanolamine, and 1-[N,N-bis(2-hydroxyethyl)
amino]-2-propanol). MMT-ODA provided CPNC with the largest interlayer
spacing, d001 = 3.27 nm, but even in this case the improvement of mechanical
performance was relatively minor, for example, at 3 wt% clay loading tensile
modulus increased by 40% while strength decreased by 9%. A similar enhancement
of rigidity and reduction of strength was reported by Okamoto et al. [2003] for
CPNC with PBS as matrix – only intercalation was achieved.
Several other water-soluble polymers have been proposed for biodegradable
applications of CPNC, viz. PVAl, EVAl, PEG or PCL. While melt blending resulted
in intercalation, the reactive route leads to exfoliated CPNC [Pramanik, et al.,
2001; 2002; Kwiatkowski and Whittaker, 2001; Pantoustier et al., 2002].
However, none of these materials has been as intensely promoted as the CPNC
with MMT and PLA.
2.4.4.3 Poly(N-Vinyl Carbazole)/MMT

Polymerisation of purified N-vinyl carbazole (NVC) was conducted in the presence
of dehydrated MMT either in bulk, just above Tm = 64 °C, or in benzene solution at
252
50 °C [Biswas and Ray, 1998]. Both methods resulted in a similar conversion versus
time plot. The cationic polymerisation at 50 °C was catalysed by MMT. First, the
NVC was adsorbed by the MMT surface, forming a complex either with the
counterion or with metal oxide impurities in MMT (e.g., Fe2O3), which resulted in
electron transfer that initiated polymerisation. Up to 10 wt% of poly-N-vinyl carbazole
(same as poly-9-vinyl carbazole, PVK) was retained by MMT after extraction by
benzene, indicating the presence of end-tethered macromolecules. XRD showed that
as a result of polymerisation the characteristic MMT diffraction peak (d001 = 0.99 nm)
was significantly reduced in intensity and a new one (d001 = 1.46 nm) appeared. The
latter indicated intercalation, but judging by its low intensity, probably some
exfoliation took place. Considering the high concentration of MMT in these systems
(≤ 43 wt%) exfoliation was not to be expected. Incorporation of MMT significantly
improved the thermal stability; whereas PVK totally decomposes at 700 °C, the CPNC
lost only 12.2 wt% at 683 °C. However, the most astonishing result of the process
was the increase of DC conductivity by 10 orders of magnitude: from 10-16 to 10-6
S/cm, and doping may increase it even further.
In the subsequent paper the authors discussed polymerisation of NVC in the
presence of FeCl3-impregnated MMT [Ray and Biswas, 1999]. XRD displayed
only one d001 = 0.98 nm peak, thus the MMT-FeCl3 complex was not intercalated
during polymerisation. TEM showed the clay particles to be in the range 30-
40 nm. However, the DC conductivity of the CPNC was in the range 3.1 x 10-5 S/cm
at 5.9 wt% of FeCl3, dependent on the FeCl3 loading. In this context it may be
interesting to note that polymerisation on the surface of nanoparticles can be
used for the preparation of self-assembled monolayers. For example, brush-type
core-shell macromolecular structures were polymerised on the surface of Au
particles with diameter d = 2-5 nm by means of surface-initiated living cationic
polymerisation of 2-oxazolines [Jordan et al., 2001].
In 2002 Suh and Park prepared CPNC with MMT-ODA dispersed in a PVK
(Mw = 100 kg/mol) matrix. Three organoclays were prepared, containing 0, 50,
75 and 100% of intercalant per 100% of the clay’s CEC. Dissolving PVK in
chlorobenzene, and then adding a suspension of 1 wt% organoclay resulted in
CPNC. XRD of the organoclay indicated that the interlayer spacing increased
with ODA content from d001 = 1.25, 1.72, 1.77 and 1.89 nm, for 0, 50, 75 and
100% CEC, respectively. The spacing in dry, cast films of PVK/MMT-ODA also
depended on the ODA content. Evidently, for 0% (neat MMT) a non-intercalated,
simple, filled system was obtained. Intercalated CPNC were obtained for
compositions containing 75 and 100% CEC of ODA. However, the system
containing a low density of the intercalant in organoclay, PVK/MMT-50%ODA
was found exfoliated. This, seemingly surprising observation is in excellent
agreement with thermodynamic theories discussed in Section 3.15.
Yu et al. [2004] prepared a series of CPNCs by dispersing an organoclay in
NVC, and then UV-photoinitiating in situ polymerisation with triarylsulfonium
salt as the initiator. The organoclay was Na-MMT pre-intercalated with acidified
diallyl amine: (CH2=CH-CH2)2NH2+ Cl–. The final CPNC contained 0 to 1 wt%
of clay. Within this range of composition, Mn decreased from 2273 to 1438 g/mol,
while Tg increased from ca. 48 to 78 °C. This Tg increase is intriguing, considering
the low clay loading, poor exfoliation, and the low and decreasing (with clay
content) molecular weight of the matrix (note that Tg decreases with Mn as:
Tg = Tg∞ - A/Mn).
253
2.4.4.4 Polydiacetylene
An attempt was made to intercalate MMT, vermiculite or mica with diamine-
diacetylene (DADA), monoamine-diacetylene (MADA), or ω-aminoacid-diacetylene
(AADA), then polymerise these using 60Co irradiation [Srikhirin et al., 1998]. For
this purpose, 14-amino-10,12-tetradiynoic acid and 10,12-docosadiyndiamine
(diacetylenic diamine), were synthesised. The approach was to intercalate the clays
with a cationically terminated diacetylene monomer by cation exchange. The
intercalation was carried out by mixing the clay with diacetylene ammonium salt
solution in 10% EtOH/water for up to seven days at 70 °C. XRD and FTIR
confirmed the intercalation. The interlayer spacing of the intercalate decreased
with the number of washings, e.g., from d001 = 4.5 to 3.7 nm. The interlayer spacing
and polymerisability of the intercalated diacetylene were found to depend on the
molecular length, the CEC of the clay, the type of diacetylene molecule, and the
solvent treatment.
Polymerisation of a diacetylene may occur when the monomer has proper
packing in the solid state. The polymerisation results in a conjugated backbone,
providing π-electron delocalisation along the backbone which gives polydiacetylenes
their unique electrical and optical properties. The polymerisation of the intercalated
diacetylene should result in growth of the polydiacetylene chain along the interlayer
gallery. However, packing of the intercalated monomers controls the reactivity of
the diacetylene/clay complex. Since the intercalated DADA/MMT, AADA/MMT
and AADA/vermiculite lie flat on the clay surface they lack the proper geometry to
be polymerised. The intercalated MADA/vermiculite and MADA/MMT are tilted
with respect to the clay surface, but polymerisation was only observed in
MADA/vermiculite where the intercalated diacetylene has proper packing geometry
and monomer density (smaller area per intercalated molecule).
The conductivity of I2-doped polyaniline (PANI) approaches that of Cu, but
the polymer is brittle and sensitive to humidity and oxygen. Recently MMT was
intercalated with aniline hydrochloride, and then aniline was electropolymerised,
increasing the interlayer spacing to d 001 = 1.47 nm [Feng et al., 2001].
Unfortunately, the note did not report data on the stability and conductivity of
this potentially interesting material.
2.4.4.5 Clay-Functional Organic Molecules

The intercalation of indigo blue into clay is credited for the preservation of vivid
colours in Maya’s frescos.
Several patents from AMCOL (e.g., [Beall et al., 1999b]) describe the direct
intercalation of clay with organic molecules having functional properties, e.g.,
fungicides, pesticides, insecticides, acaricides and other agricultural or medically
active compounds. These systems were prepared by dispersing clay in an aqueous
medium, followed by adding a solution of a functional compound. The latter
must have a polar moiety, e.g., carboxylic acid, ester, amide, aldehyde, ketone,
sulfur-oxygen or phosphorus-oxygen moiety, cyano, or a nitro moiety. Judging
by XRD diffraction the compounds intercalated into the interlayer galleries. In
some cases strong ionic bonding was obtained, in others (viz. the pesticide
trifluralin) the bonding was of the physical adsorption type, allowing the
compound to be fully released from the interlamellar space.
There is another group of compounds of industrial interest: molecules with
specific functionalities, e.g., catalysis, photoluminescence, photochromism, optical
254
nonlinearity, etc. Using such molecules as intercalants may impose molecular

ordering that enhances the performance. Furthermore, intercalation often results
in improved thermal and oxidative stability caused by reduced thermal motion
and/or reduced oxygen diffusivity.
Recently [Kim et al., 2001] nanocomposites of organic laser dye-hectorite
complexes were prepared. Thus, nanocomposites of hectorite (CEC = 0.44 meq/g)
with 7-diethylamino-4-methyl coumarin dye were produced. By alternate
adsorption of positively charged polyelectrolyte and a negatively charged hectorite/
coumarin complex, a multilayered film was fabricated. The coumarin was acidified
and then intercalated into hectorite by the ion exchange reaction. The original
interlayer spacing of hectorite (d001 = 0.98 nm) slowly increased with coumarin
content up to the total exchange of inorganic cations (from 1.34 to 1.39 nm),
then more rapidly up to 2.22 nm at a coumarin loading of 20.4 wt% (252% of
the CEC). This suggested different packing of coumarin molecules within the
interlayer galleries – a flat monolayer below 100% CEC and a tilted monolayer
above. As a consequence, CPNC films with high molecular order and thermal
stability were prepared for photonic applications. A multilayered composite film
showed a linear increase in the absorption and in the fluorescence intensity with
the number of deposited layers. Other photofunctional chromophores and
fluorophores with a high degree of molecular orientation order and enhanced
electrooptical properties can be prepared. By adjusting the intercalant-clay
interactions the quantum efficiency of fluorescence can be adjusted. Molecular
dynamic simulation of the adsorption of methylene blue by MMT, beidellite and
muscovite has been carried out, predicting d001 = 1.23 to 1.57 nm [Yu et al.,
2000b].
CPNC have been prepared by polymerising 2-ethynyl pyridine within MMT
[Liu et al., 2001]. Intercalation was carried out in benzene, by first dispersing in
it dehydrated Ca2+-MMT (CEC = 1.20 meq/g), adding 2-ethynylpyridine (2-EPy)
and then stirring the mixture at 65 ± 3 °C for 24 h. Initially, the suspension was
red. The colour darkened gradually to reach dark brown colour when the reaction
was terminated. Thus, 2-EPy polymerised spontaneously within the interlayer
galleries. The complex was centrifuged and washed several times with benzene
then dried. Up to 21.3 wt% of 2-EPy was adsorbed, increasing the interlayer
spacing up to d001 = 1.64 nm, consistent with the van der Waals dimension of a
pyridine ring (0.66 nm). Thus, the polyacetylene macromolecules are flat on the
MMT surface with pyridine rings tilted with respect to the surface.
2.4.4.6 Super-Absorbent CPNC

MMT was dispersed in an aqueous solution of Na-acrylic acid, N,N´-methylene-
bis-acrylamide (crosslinker) and K2S2O8 (free radical initiator) [Lin et al., 2001].
The reaction (4 h at 60-70 °C) resulted in a slightly yellow powder. The water
absorbency (Q) strongly depended on the crosslinker concentration (e.g., 1.1 at
0.05% to 0.7 kg/g at 0.13%), MMT content (maximum Q was found at 30 wt%
MMT), and the degree of neutralisation. Interlayer spacing has not been measured.
2.4.4.7 Emulsion Polymerisation of CPNC

The preferred methods for the preparation of PS-based CPNCs are emulsion,
solution or bulk (co-) polymerisation that start with organoclay dispersed in a
monomer phase. Since clay intercalation is usually in water, emulsion
255
polymerisation is an obvious choice. However, when the hydrophobicity induced

by intercalation is insufficient, the clay will not be transferred to the monomer
phase, leading to a limited improvement of the resulting polymer properties. For
example, SBR-based PNC was prepared by emulsion polymerisation in the
presence of onium-intercalated MMT. The PNCs showed superior barrier and
mechanical properties [Elspass et al., 1997; 1999]. SAN-based PNCs [Noh and
Lee, 1999] were prepared by emulsion or solution polymerisation.
Thermogravimetric analysis showed that at 500 °C the amount of remaining
residue was: 5 wt% of SAN, 20 wt% of solution-type PNC and 70 wt% of
emulsion-type. There is a detailed discussion on the dispersion of organoclays
during emulsion or suspension polymerisation in Section 4.1.4.1.
256
Introduction
Part 3
Fundamental Aspects
Thermodynamics
3.1
Thermodynamics
Nanostructures are intermediate in size between molecular and micron-size

structures. They contain a countable number of atoms and thus resemble
molecules. Their small size and structure result in strong interactions and high
surface-to-volume ratio. Nanostructures may show specific electronic and
magnetic characteristics, often dominated by the quantum effects. Their properties
depend upon the size, the shape and arrangement of the atoms; for example,
substitution of Mg for Al in the octahedral layer of smectites is essential for
intercalation and exfoliation in a polymeric matrix. Thus, there is a need to
develop new fundamental tools capable of describing and predicting properties
of the nanoscale structures.
3.1.1 Glass Transition in Thin Films

As the size of the particles decreases, the transition temperatures change as well.
For example, the melting point of bulk PE is about Tm ≅ 400 K, but the Tm of its
nanosized particles with diameter of 5 and 13 nm is 218 and 266 K, respectively.
Similar reductions were reported for the glass transition temperatures (Tg) of
thin film. In the latter case, three types of behaviour were distinguished:
(1) for thin films grafted to a solid substrate,
(2) for supported films, and
(3) for unsupported films [Forrest and Dalnoki-Veress, 2001].
The two latter cases are under active investigation at present.
1. For type (1) the Tg depends on the degree of molecular bonding and it may
either decrease or increase with decrease of film thickness.
2. For type (2) there is a reduction of Tg with reduction of film thickness that
seems to be independent of molecular weight. An empirical relation was
derived:
Tg = Tgb ⎡1 − ( a / h) ⎤
δ
(30)
⎢⎣ ⎥⎦
where Tgb is the glass transition of the bulk phase, h is the film thickness,
and a and δ are empirical parameters which depend on the system, viz. for
PS a = 3.2 nm and δ = 1.8; for PMMA a = 0.35 nm and δ = 0.8. It was
reported that the behaviour was independent (or nearly so) of the substrate.
A mechanism that may explain such Tg behaviour is the presence of a thin
surface layer having high molecular mobility and higher free volume fraction
than that in the bulk [Forrest and Dalnoki-Veress, 2001]. The thermodynamic
analysis of the surface/interface energy indicated that there are two basic
mechanisms responsible for the minimisation of the surface energy: high
257
concentration of highly mobile chain ends and migration toward the surface
of low molecular weight components (low MW fractions and additives)
[Helfand and Tagami, 1971; 1972].
Recently, Monte-Carlo (MC) simulation was used to study the behaviour of
thin polymeric films. As shown in Figure 59, the computations gave results
closely resembling the experimental results. Furthermore, it was found that
the thin films have a fluid-like interfacial region where mobility is considerably
higher than in the bulk film [Jain and de Pablo, 2002]. The computed results
indicated that it is not an effect of different skin composition, but rather the
chain conformation. In agreement with Helfand and Tagami calculations,
near the surface MC simulations predicted high concentration of chain ends
and reduced density. In this region the linear macromolecules have non-
Gaussian coil configuration.
3. For type (3) the Tg depends on both film thickness and weight-average
molecular weight (Mw). The reduction of Tg is significantly more pronounced
than in type (2). For high Mw the following dependence was found to describe
the behaviour:
Tg − Tg* = b ln(Mw / Mw* ) × (h − h* ) (31)
where symbols with asterisk (*) are reference variables.
For PS: b = 0.70 ± 0.02 K/nm, Mw* = 69 ± 4 kg/mol, h* = 10.3 ± 0.1 nm, and
Tg* = 423 ± 2 K. The dependence is illustrated in Figure 60.
Chow [2002] proposed the glass transition theory for unsupported, nanoscale
polymeric films with thickness < 100 nm. The theory is based on the Gibbs and
DiMarzio time-independent theory that Tg is related to the loss of configurational
entropy of a liquid during the cooling experiment. The entropy in turn can be
related to the free volume fluctuations, which depend on the temperature and
film thickness. The Langevin equation was used to derive the following
dependence:
[ ⎧
]
2θ ⎫
[ ] ( )
ln Tg (h, N ) / Tg∞ = − k B N / 2 N o ΔC p ⋅ exp ⎨− (h / ho ) ⋅ N o / N ⎬
⎩ ⎭
(32)
where Tg and Tg∞ are the polymer glass transition temperature in the film and in
the bulk, respectively; h and ho are the film thickness and its critical value equal
to the radius of gyration; kB is the Boltzmann constant; N and No are the number
of statistical segments in a polymer and in a reference state; ΔCp is heat capacity.
The exponent θ = 0.7 was determined for polystyrene. The relation predicts that
the Tg of low molecular weight polymer thin films has higher value than that of
high molecular weight. This unexpected result is confirmed by experiments and
the empirical dependence is illustrated in Figure 60. The author also derived an
expression predicting variation of Tg with the strength of the polymer-substrate
interactions. For low (or absent) interactions the dependence for free film was
recovered; hence Tg(film) < Tg(bulk). For strongly interacting systems the Tg in
thin film was predicted to have a higher value than that observed for the bulk
polymer: Tg(film) > Tg(bulk).
Another type of nanosized particles with unexpected Tg behaviour was recently
described [Mi et al., 2002]. The authors prepared single-macromolecular coil
size globules of polyacrylamide (PAAM; Mw = 5,000 to 6,000 kg/mol) by
atomisation spraying of a dilute polymer solution, followed by drying. Thermal
analysis showed that the globules had a higher Tg than that of the same bulk
258
Thermodynamics
Figure 59 Glass transition temperature for thin, supported PS films. Line

represents experimental data, points computed as Tg* ≡ k B Tg ε −1 (where kB is the
Boltzmann constant and e is the nearest-neighbour interaction energy – see text).
Figure 60 Glass transition temperature for thin, freestanding PS films. Lines

computed from Equation 31 for the indicated molecular weights.
259
polymer, viz. 205 versus 193 °C, respectively. The explanation offered is based
on the configurational entropy of a single macromolecule in the bulk and in the
globular state. The analysis indicated that polymer chains in the latter state should
have Tg higher by a few percent (absolute T-scale), e.g., by ca. 10 °C, which
indeed was observed. However, this analysis neglects the surface energy difference
(which acts in the opposite direction), as well as the interaction of the globule
with the substrate (which tends to increase Tg).
In conclusion, three factors have been identified as affecting the glass transition:
molecular weight (MW), film thickness (h), and the interactions between film
and the substrate (χ). The theory predicts that high molecular weight polymer
diffusing into narrow interlamellar galleries will have high mobility under the
condition of poor interaction with the clay, but poor interactions means absence
of the driving force for diffusion. On the other hand, strong interactions means
good ‘motivation’ for the macromolecules to diffuse, bind with the clay substrate
and ‘solidify’ into a layer of adsorbed macromolecules with low segmental
mobility.
3.1.2 Nanothermodynamics
In the early 1960s Hill noted that the equilibrium thermodynamic properties of
sufficiently small systems differ from those predicted by the classical
thermodynamics of large systems [Hill, 1994]. More recently, the field was
renamed nanothermodynamics [Hill, 2001a; 2001b]. Originally, the treatment
considered homogeneous, small systems, such as individual macromolecules or
colloidal particles, each composed of n-elements. For n → ∞ the macroscopic
properties are recovered. However, when n is small there are at least two significant
contributions to the energetic state of such a system, the first depends on the
surface energies, and the second on the entropy related to the dynamic state of
the particles. For example, a single platelet of MMT, owing to its thickness
(0.96 nm) and large aspect ratio, has a specific surface area of ca. 800 m2/g, and
about 36% of its atoms are on the surface. Considering the high surface energy
of solids (e.g., surface energy of freshly cleaved mica is γ = 4,500 mN/m) the
surface effects are expected to dominate the thermodynamic state of nanoparticles.
Since in most systems the miscibility and phase equilibria are determined by a
fine balance of small energetic and configurational contributions, the surface
effects are expected to influence them, and thus to be critical for the performance
of CPNC.
For the principle of nanothermodynamics to apply to a macroscopic system,
it must be visualised as an ensemble of small subsystems (or aggregates)
independent of each other. The number of elements n in each aggregate does not
have to be the same. A good example is a semicrystalline substance having
numerous small crystals of various sizes that contain n molecules. The substance
may show size-related effects, e.g., of the melting point, width of the melting
transition, heat capacity, glass transition temperature, etc. Other examples are
provided in recent publications on statistical thermodynamics of metastable
droplets [Hill and Chamberlin, 1998], on ferromagnetism [Chamberlin, 2000]
or on phonon scattering by the boundary of nanocrystals [Shrivastava, 2002]. In
the latter paper it was shown that the specific heat of crystalline materials depends
on particle size.
One of Gibbs contributions to the equilibrium thermodynamics was addition
of the chemical potential to the basic energy-heat-work equation. This
260
Thermodynamics
concentration-dependent contribution is essential for understanding and

computing diverse thermodynamic properties, viz. chemical reactions, phase
separation, gas solubility, osmotic pressure, etc. In a sense, incorporation of the
nanoscale effects into the thermodynamics is the next step in generalisation of
the thermodynamic behaviour. Thus, Hill formally wrote the total (subscript ‘t’)
energy of a macrosystem as:
dEt = TdSt − PdVt + ∑ μ dN

i
i i, t + edn
(33)
e ≡ (∂Et / ∂n) St, Vt, Ni ,t
where T is temperature, P is pressure, V is volume, S is the entropy, μi is the
chemical potential and Ni is the number of molecules of species ‘i’. The last term
in this dependence, edn originates from the extra contribution of the small system.
In Hill’s concept, any macroscopic system may be described in terms of
contribution from all elements, viz.: Xt º nX, where X = E, S, V, Ni, with n being
an extensive variable. The variable e is a sort of chemical potential of the whole
ensemble, i.e., a ‘subdivision potential’ that varies with T, P and μi:
de = − SdT + VdP − ∑ N dμ i i
i (34)
− S = (∂e / ∂T ) P, μ ; V = (∂e / ∂P)T, μ ; Ni = (∂e / ∂μ i )T, P, μ
i i j
The nanothermodynamic properties usually differ in different ‘environments’.

For example, a rigid incompressible aggregate of n = 102 or 103 spherical molecules
in a constant temperature bath may be considered as having two ‘environmental
variables’, n and T. The aggregate entropy can be computed considering the
translational, rotational and vibrational motions of the molecules. However, one
may ‘construct’ such an aggregate considering that the constant-temperature bath
contains individual molecules with chemical potential, μ. Depending on the value
of μ the molecules will form an aggregate containing n´ molecules, hence now
the ‘environmental variables’ are μ and T. One may choose a value of μ that will
result in n = n´. However, the calculated entropy for the first case (n, T) will be
smaller than that for the second (μ, T). The reason for the discrepancy is the
presence of fluctuations in the second case that cannot be directly incorporated
in the first case. However, as the aggregate approaches macroscopic size, i.e.,
when n → ∞, this entropy difference will disappear or in other words, when an
ensemble contains only one aggregate, the ‘classical’ macroscopic equilibrium
thermodynamics is recovered.
Hill considered four sets of ‘environments’: (N, V, T); (N, P, T); (μ, V, T); and
(μ, P, T). For example, the ‘subdivision potential – e’ of a one-component small
system in the four sets of variables was computed.
1. Environmental Variables N, V, T:
From the partition function:
Q( N , V , T ) = ∑ exp{− E ( N , V ) / kT}
i
i (35)
the following relationships are derived:
− kT ln Q = E − TS = − PV + μN + e
(36)
− d ( kT ln Q) = − SdT − PdV + μdN
261
2. Environmental Variables N, P, T:
Δ( N , P, T ) = ∑ j, V
{ }
exp − E j ( N , V ) / kT exp{− PV / kT } (37)

− kT ln Δ = E − TS + PV = μN + e
(38)
− d ( kT ln Δ ) = − SdT − VdP + μdN
3. Environmental Variables μ, V, T:
Ξ (μ, V , T ) = ∑ j, N
{ }
exp − E j ( N , V ) / kT exp{− Nμ / kT } (39)
− kT ln Ξ = E − TS − μN = − PV + e
(40)
− d ( kT ln Ξ ) = − SdT − PdV − Ndμ
4. Environmental Variables μ, P, T:
ϒ ( μ , P, T) = ∑ j, N, V
{ }
exp − E j ( N , V ) / kT exp{Nμ / kT } exp{− PV / kT } (41)
− kT ln ϒ = E − TS + PV − μN = e
(42)
− d ( kT ln ϒ ) = − SdT + VdP − Ndμ = de
The latter case is particularly important since here the system is ‘completely open’
and all environmental variables are intensive. Note that the three variables: μ, P
and T cannot all be independent in a macroscopic system but they can in a small
system. In nanosystems these intensive variables determine the mean size N (an
extensive variable). This type of system is found in biology, in bulk magnetic
materials, a Gibbs surface excess resulting from an adsorbent molecule at the
end of a one-dimensional lattice gas, or metastable supersaturated gaseous states
near the gas-liquid transition point.
Recently, this treatment was extended to one-dimensional adsorption of gas
[Hill, 2001a; 2002b]. Consider a surface of B adsorbent, with molecules
independent of each other, from each of which a chain of M binding sites extends
vertically. B and M are both very large. The B molecules, at T and μ, go on and
off the sites. There is an interaction energy (w) between any two adsorbed
molecules on nearest-neighbour sites of a chain. Also, there is an interaction
energy w′ between an adsorbent molecule and an adsorbed molecule that occupies
the first site of the chain. The mean number of adsorbed molecules per chain is
denoted N ex and typically its magnitude is of the order of 1 to 10. For B surface
excesses (small system) free energy is:
E = TS + μN ex B + eB
(43)
(
dE = TdS + μd N ex B + edB )
So far, nanothermodynamics have not been applied to PNC.
262
Thermodynamics
3.1.3 Vaia’s Lattice Model for Organoclay Intercalation by Molten

Polymer
3.1.3.1 Introduction
In his PhD thesis of 1995 Vaia used a lattice model to describe the thermodynamic
behaviour of CPNC comprising organically modified layered silicates, e.g., mica
or MMT (the work was published two years later [Vaia and Giannelis, 1997a;
1997b]). Initially, the interlayer galleries are occupied by hydrated alkali metal
cations, which during intercalation are exchanged for organic ones – most often
quaternary alkylammonium ones. Because of the negative charge on the silicate
surface and crowding of intercalant groups, the alkyl tail of the alkylammonium
molecule projects away from the surface. However, as the data in Figure 23
demonstrate, the expansion of the interlamellar gallery proceeds step-wise, at
lower efficiency than would be expected from fully stretched hydrocarbon chains.
At the processing temperature of CPNC, Tprocess ≥ 150 °C, the interlayer
structure is expected to be disordered with a density comparable to that of liquid
alkanes. Preparation of CPNC involves the formation of nanostructures where
the matrix molecules (monomers, macromers or cyclomers introduced during
the reactive process or macromolecules incorporated during melt compounding)
diffuse into the interlayer galleries, either as a result of static annealing, dynamic
mixing or both. Polymer diffusion into galleries expands the silicate layers.
Depending on the degree of penetration and resulting interlayer spacing, either
intercalated or exfoliated nanocomposites are obtained. Their structure depends
on the length, density and type of intercalant, on the type, molecular weight and
structure of the polymer, on the concentration of the pre-intercalated clay, as
well as the polymer-clay and polymer-intercalant interactions.
Vaia modelled CPNC as two parallel platelets pre-intercalated with short
chains tethered to the clay surface, and then dispersed in an infinite sea of molten
polymer (infinitely diluted system). During the second stage of the intercalation
the macromolecules diffuse into the interlamellar galleries. Within these galleries
the polymer forms a dilute solution with intercalant molecules. The basic
assumptions are that the system is incompressible, has constant polymer density,
and the intercalant is end-tethered. Furthermore, it was assumed that the
interactions that account for the miscibility/immiscibility of polymer/organoclay
systems are polymer-intercalant and polymer-clay type – the clay-clay interactions
and their variation with the gallery height were neglected. The final state of the
intercalation is given by the equilibrium thermodynamics. The author assumed
that the interlamellar gallery height does not exceed the full extension of the
intercalant chains on both gallery surfaces, thus the model accounts only for the
initial intercalation of organoclay by molten polymer. A thermodynamic
description takes into account the entropy-related configurations of the
constituents and the interactions between them. The external forces (e.g., shearing)
are not considered.
Derivation starts with the assumption that the macroscopic thermodynamic
description of the system is obtained considering a single sandwich of the organoclay
clay (having infinite breadth and width and the initial separation h0) embedded in
molten polymer. As the macromolecules diffuse into the gallery, the interlamellar
spacing increases to h. The Helmholtz free energy change, ΔF, associated with the
interlayer expansion from ho to h, is given by the internal energy change (associated
263
with intermolecular interactions), ΔE, and the combinatorial entropy change

(associated with configurational changes of the constituents), ΔS:
ΔF ≡ F(h) − F(ho ) = ΔE − TΔS (44)
where T is the absolute temperature. Accordingly, the negative value, ΔF < 0,
would indicate that, from the equilibrium thermodynamics point of view, the
interlayer expansion is favourable. The average interlayer volume fraction, ϕ̂ i ,
of the end-tethered intercalant chains (ϕˆ 2 = ho / h) and the intercalated polymer
(ϕˆ 1 = 1 − ϕˆ 2 ) are expressed in terms of gallery height, h. The end-tethered
intercalant molecules can only reach the distance h∞ of fully extended alkyl chain
length, thus uniform mixing will not be possible when the interlayer height exceeds
its double size, h > 2h∞. Therefore, the mean-field approximation is only valid
for ϕˆ 1 ≤ 1 − (ho / 2h∞ ) .
3.1.3.2 Entropic Contributions

There are three contributions to the configurational entropy, ΔS: (1) from changes
associated with the intercalated clay, (2) from the diffusing polymer and (3) from
the intercalant molecules. During polymer diffusion into the interlamellar galleries
the clay platelets are pushed apart, but their translational entropy is relatively
small and Vaia considered this contribution negligible. For the polymer, the
configurational entropy arises from changes of the macromolecular confinement,
from its unperturbed random coil structure in the melt to a solution with the
intercalant molecules within the gallery; hence there is a loss of the macromolecular
configurational entropy. By contrast, the tethered intercalant chains gain
configurational freedom (thus entropy) as the gallery height increases. Thus, ΔS
has an entropy loss associated with confining the macromolecules and the entropy
gain of the tethered intercalant during the gallery height increase from h0 to h:
ΔS = ΔS polymer + ΔSintercalant (45)
For thermodynamically favourable intercalation of organoclay by polymer the
Helmholtz free energy should be negative hence the favourable entropic
contribution, ΔS, should be positive.
The entropic contribution per interlayer volume (superscript ‘v’) of a
macromolecule diffusing into the interlayer gallery was expressed in terms of the
Dolan and Edward’s theory for confined random-flight polymer chains with
excluded volume:
ΔS polymer
v
(
/ R = −(ϕˆ 1a1 / ν1 h) π 2 a1 / 6h + u 3 / m1 ) (46)
where v1, al, and m1 are the molar volume per segment, the segment length, and
degree of polymerisation of the polymer, respectively. Excluded volume is included
in the dimensionless parameter, u. Since all the parameters in Equation 46 are
positive, the entropic contribution of the polymer diffusing into clay gallery is
negative hence it hinders the intercalation process. Using estimated numerical
values of parameters (see Table 40) the entropic effect per surface area, ΔSA/R,
was computed.
To express the second contribution, ΔSintercalant, the authors used the Huggins-
Flory lattice model for polymer solutions. The original relations were modified
to account for the restricted freedom of the end-tethered alkyls and the influence
of the silicate surface on their conformation. The entropy change per interlayer
volume was expressed in terms of the increased layer separation from h0 to h:
264
Thermodynamics
Table 40 Parameters used for computing the thermodynamic

properties. Data [Vaia, 1995]
Parameter Symbol Value
Polymer segment length a1 2.5a2
Polymer molar volume v1 3v2

-1/2
Excluded volume um1 0.8
Intercalant (ODA) C18H37-NH3+ m2 = 9.5
Intercalant segment length (nm) a2 0.25
Intercalant molar volume (ml) v2 33
Initial gallery height (nm) h0 1.3
Final gallery height (nm) 2h∞ = 2a2m2 4.75
ΔSivntercalant / R = (ϕˆ 2 / v2 )(ψ s − ψ so ) ln c − (ϕˆ 1 / m1 v1 ) ln ϕˆ 1 ≅ (ϕˆ 2 / v2 )(ψ s − ψ so ) ln c

with ψ ≅ (a / h) cos 2 (πh / 2h )
s 2 ∞
(47)
where νi, mi, and ϕi are the molar volume per segment, the number of segments per
chain, and the interlayer volume fraction, respectively. The statistical surface
fractions of interlayer sites near the surface that are occupied by the tethered chains
are expressed as: ψs ≡ ψs (h); ψso ≡ ψsh0 ≥ ψs h ≥ h0). The statistical surface factor, c,
accounts for the inaccessibility of sites on the far side of the surface (c = 0.75 for z
= 4, decreasing to 0.5 for z → ∞, where z is the lattice coordination number).
Finally, a2 is the intercalant segment length of the tethered chain and R is the gas
constant. Since ln c < 0, Equation 47 predicts that the entropic contribution of
the intercalant is positive, thus favourable for intercalation.
The parameters of the configurational entropy that originates from the
polymer, intercalant and their sum are listed in Table 40; the computed
dependencies are presented in Figure 61. Evidently, the loss of polymer entropy
during its diffusion into a gallery is partially compensated by the configurational
gains of the intercalant molecules. While initially there is a possibility of a small
increase of the interlayer spacing (by 0 < h - ho < 0.8 nm sufficient to accommodate
1 to 2 macromolecules) any larger expansion is forbidden by a rapid decrease of
the total entropic change. Thus, in the absence of favourable energetic interactions
any further polymer diffusion into the interlamellar galleries is not possible.
As it will be evident from the experimental data presented in Section 4, many
CPNC prepared by the melt or reactive intercalation method (e.g., in PS or PO
matrix), show increased interlayer spacing, Δd001, by about 0.35 to 0.75 nm,
which corresponds to single or two macromolecular layers inside the interlamellar
gallery. On the basis of Vaia’s entropic calculation one may postulate that in
these systems the energetic contribution to the thermodynamics is negligibly small.
265
Figure 61 Changes of entropy during diffusion of macromolecules into

interlamellar galleries. Initially, the positive contribution from the intercalant
compensates for the negative one from polymer. After expansion by ca. 0.8 nm, the
entropic contribution becomes negative and, in the absence of negative enthalpic
contribution, the diffusion is expected to stop. After [Vaia, 1995].
3.1.3.3 Interactions
Vaia assumed that the energetic contributions originate in interactions between
the three components of the system: the silicate, s, the tethered intercalant, a,
and the polymer, p. Furthermore, the total change of the internal energy is taken
as a sum of the energy change associated with each pairwise interaction, εjk, with
the number of contacts expressed by the contact area. The pairwise interaction
energy per contact was expressed in terms of the cohesive or interfacial energy
per lattice site. Thus, the internal energy change of the system upon polymer
intercalation is:
(
ΔE = Aspf ε sp + Aapf ε ap + Asaf − Asai ε sa)
where A jkf and A ijk is
the total area of contact between components j-k for the final
(f) and the initial (i) system, respectively. The dependence was simplified assuming
that initially all the lattice sites within the interlayer gallery are occupied by
tethered intercalant chain segments, thus
Asp = Asaf − Asai
The next step in the derivation was a bit arbitrary, using van Opstal et al. [1991]
expression for the internal energy change per interlayer volume that takes place
during intercalation:
Δeν = ϕˆ 1ϕˆ 2 Δε =
(
2ϕˆ 1ϕˆ 2 ε sp, sa / ho + ε ap / r2 ) (48)
[
1 − ϕˆ 2 1 − (r1 / r2 ) − (r1 / ho ) ]
266
Thermodynamics
where Δε is the effective interaction energy per interlayer volume and ri is the
radius of the interaction surface, related to the molar volume and segment length
by the simple dependence: ri2 = ν i / πN A ai (where NA is Avogadro’s number). The
change in interactions at the interlayer surface was written as εsp, sa = εsp – εsa. To
encourage intercalation by diffusion of macromolecules the energetic contribution,
Δev, thus the numerator in Equation 48, should be negative. Evidently, this can
be expected when the interaction energies of polymer: εap < 0 and/or εsp < εsa –
when polymer ‘likes’ to cohabit the gallery, interacting with intercalant chains
and/or the clay surfaces.
The total free energy change associated with polymer diffusion into
interlamellar galleries and increased interlamellar spacing may be calculated from
Equations 44-48. In Figure 62 the total free energy change during polymer
diffusion into the gallery space is presented for εap ≅ 0 (van der Waals interactions
between intercalant chains and macromolecules) and for four values of the
interaction parameter, εsp, sa. Other parameters were taken from Table 40.
As the author noted, the values for the interaction parameters, εij, are not
readily available. Thus, he proposed that these might be replaced by interfacial
energies between interacting species i-j, viz. εap ~ vap and εsp, sa ~ vsp – vsa. However,
since the interfacial energies are also inaccessible, Vaia adopted the procedure
proposed by van Oss [1994] of calculating the interfacial energy from the surface
energies of the interacting species. The procedure considers that the interactions
are composed of polar/associative ( ν ip ) and dispersive/dipolar ( ν id ) forces:
ν ij = ν ijp + ν ijd
ν ijp = 2⎛ ν i+ − ν i− − ν −j ⎞ (49)
⎝ ⎠
2
ν ijd = ⎛ ν id − ν dj ⎞
⎝ ⎠
where ν i+ and ν i− are respectively, the electron acceptor and donor contributions.
Luciani et al. [1996; 1997; 1998] showed that the interfacial properties are
dominated by the polar and hydrogen bonding interactions, whereas the bulk
properties are dominated by the dispersive forces. In consequence, another method
for calculating the interfacial energy has been proposed. The method involves
computation of the interfacial tension coefficient from the difference between
the dipolar, polar and hydrogen bonding components of the two interacting species
i-j, viz.:
n
( ) ( ) ( )
ν ij = k1 (T )⎧⎨Θ δ i, d − δ j, d + δ i, p − δ j, p + δ i, h − δ j, h ⎫⎬
2 2 2
(50)
⎩ ⎭
where k1(T) and n are equation parameters and Θ ≅ 0.4 is the relative measure of
the importance of the dispersive contribution (its value for bulk interactions is
4). Since the solubility parameter can be calculated from the group contribution
method [Hansen, 1967; 1994; 1995; 2000], Equation 50 is general.
3.1.3.4 Consequences of the Model

Vaia’s model predicts that the only source of favourable entropic contribution
toward intercalation originates in a greater number of possible configurations of
the tethered intercalant molecules. This contribution reaches maximum when in
the organoclay the intercalant has a highly ordered, pseudocrystalline structure
267
Figure 62 Changes of the free energy during intercalation/exfoliation by polymer

for four indicated values of the interaction parameter between clay and polymer.
With strong ‘specific’ energy of interaction the system is expected to exfoliate. For
middle values it may intercalate, while in the absence of energetic contribution
little change of Δd001 is expected. After [Vaia, 1995].
and it ‘dissolves’ into polymer diffusing into the interlamellar gallery. However,
reduction of entropy by such a ‘melting’ process is relatively small. Thus, the
theory predicts that the entropic effects are small and mainly detrimental to
intercalation by diffusion of macromolecules; hence the only method for achieving
intercalation is by ascertaining favourable energetic contributions.
Adopting the derivation by van Opstal et al. [1991], Vaia simplified the energetic
contribution given by Equation 48. The magnitude and sign of the effective
interaction parameters is related to pairwise interactions between the three
constituents, the accessibility of interaction sites, the interlayer packing density,
and the size of the intercalant chain. In most organoclays the intercalants have
apolar, paraffinic moieties, thus van der Waals dispersion forces dominate polymer-
intercalant interactions. In most cases, these interactions are characterised by a
small positive value of εap. By contrast, the clay surface is polar, thus if the diffusing
polymer has groups able to form polar or hydrogen bonds, the polymer-surface
interactions may be more favourable to exfoliation, thus εsp,sa < 0. In the case of
polar polymers, the favourable interactions may also be engendered by suitably
modifying the intercalant molecules. However, such a modification must be
carefully designed, as too strong interactions during an early stage of intercalation
may form a tightly packed polymer layer around the clay particles, slowing down
further polymer diffusion into the galleries.
The enthalpic contributions in Equation 48, εsp,sa and εap, are scaled with ho
and r2, respectively. Since, as discussed above, the former may be negative and
the latter positive, contrary to the expectations, better chances for exfoliation
may be found starting with organoclay having small (but adequate to polymer
268
Thermodynamics
diffusion) value of the interlayer spacing, d001 ≅ h0 + 0.96. On the other hand, for
reducing the small, parasitic contribution of εap the value of r2 should be maximised
by selecting intercalant with large molar volume moieties. Thus, not only the
magnitude of the energetic interactions, but the intercalant structure is important.
When the interaction parameter, εsp, sa = εsp – εsa < 0 an intercalation, then at
higher values, an exfoliation is possible. According to the adopted mechanism, it
is not a binary interaction parameter, but the relative magnitude of two binary
interaction parameters that counts. If exfoliation is to take place: εsp < εsa, i.e.,
clay must interact more strongly with the macromolecules than with the intercalant
chains. Accordingly, the role of the latter seems to be to sufficiently open the
interlamellar galleries facilitating the diffusion of macromolecules. Thus, again
the thermodynamic argument favours organoclays with small, but sufficient
interlayer spacing.
Serious difficulties are expected, and indeed found, when trying to exfoliate
organoclay with nonpolar olefinic macromolecules, e.g., PP. For these systems a
compatibiliser strategy has been used. Thus, polar groups are introduced (e.g.,
by maleation) into macromolecules having the same molecular configuration as
the nonpolar polymer. The key strategy is for these compatibilising
macromolecules to engender strong polymer-clay interactions. The nonpolar part
of these modified macromolecules must remain miscible with the nonpolar
polymer, ascertaining a single-phase structure of the matrix. Since the magnitude
of the Helmholtz free energy depends on the fine balance between small entropic
and enthalpic contributions, these ‘compatibilising’ strategies may be suitable
for the polymer-induced exfoliation.
In summary, the mean-field statistical lattice model is a first approximation
of the polymer melt intercalation. It is a simplified equilibrium thermodynamics
model, which considers only diffusion of molten polymer into a single gallery
formed by two organoclay platelets immersed in an infinite sea of polymer melt.
Of the three components: clay (s), polymer (p) and intercalant (a), the binary s-s
interactions have not been considered. Under normal circumstances these
interactions are about 100 times stronger than those between organic segments,
i.e., a-a or p-p. The s-s interactions are responsible for the difficulties in breaking
the clay particles into short stacks, doublets and finally into individual exfoliated
platelets. The model does not incorporate the ‘small system’ contributions
introduced by Hill. One must also ponder whether for the nanoscale system the
assumption of random mixing (e.g., absence of molecular adsorption on the
surface of crystalline solid) is valid. Furthermore, the model assumes absence of
external forces during melt exfoliation.
In spite of the simplifications and omissions the model helps in understanding
the mechanisms responsible for polymer intercalation. The insight gained leads
to recommended procedures for enhanced intercalation hence improved CPNC
performance. The recommendations are based on considerations of the entropic
and enthalpic contributions to equilibrium thermodynamics. The free energy of
the process is a fine balance of these two. The entropic penalty of macromolecular
confinement within the interlamellar galleries may be, at least partially,
compensated by the increased conformational freedom of the intercalant chain
as the gallery expands. The model indicates that to be successful in forming
exfoliated CPNC strong energetic interactions between the diffusing polymer
and clay are required. Vaia is less enthusiastic about inducing interactions between
intercalant and polymer, expecting hindered kinetics of polymer diffusion.
269
3.1.3.5 Model Prediction versus Static Intercalation Results

Vaia [1995] carried out static melt intercalation of several organoclays. Thus,
Li+-fluorohectorite (FH, CEC = 1.5 meq/g), Li+-saponite (S, CEC = 1.0 meq/g),
and Na+-MMT (MMT, CEC = 0.8 meq/g) were intercalated with excess of
dimethyl-dioctadecyl ammonium bromide (2M2ODA), trimethyl-octadecyl
ammonium bromide (3MODA), or a primary alkylammonium chloride
CnH2n+1NH3+Cl-, where n = 6, 9-16, and 18. To prepare the specimens, powders
of dry organoclay (25 mg) and polymer (75 mg) were mixed by hand and
compressed into a pellet, which was then statically annealed for up to 48 h under
vacuum at T > Tg. XRD was employed to detect the equilibrium intercalation. PS
(Mw = 30, 90 and 400 kg/mol), P4VP, poly-3-Br-styrene (PS3Br), and polyvinyl
cyclohexane (PVCH) were used as the matrix polymers.
Melt intercalation at 170 °C in PS30 of FH-ODA, FH-3MODA, MMT-2M2ODA,
and S-2MODA resulted in intercalation with gallery height expanded from ca.
1.5 to 2.3 nm; hence Δd001 = 0.8 nm. It is noteworthy that FH-ODA having high
CEC value was intercalated whereas its two analogues with lower charge density,
MMT-ODA and S-ODA, were not. Replacing the primary octadecyl chain (in
FH-ODA) by one in a quaternary onium (in FH-3MODA) resulted in a similar
behaviour, but replacing it by two octadecyl chains in quaternary onium (in
FH-2M2ODA) hindered diffusion of PS into galleries. Evidently, for melt
intercalation the packing density within the galleries as well as the thermodynamic
miscibility is important.
Pellets of PS30/FHn were annealed at 120, 140 and 160 °C (FHn = FH
intercalated with n–CH2 groups). No intercalation was observed for n ≤ 12 where
ho ≅ 0.8 nm, whereas for n > 12 (ho ≥ 1.0 nm) the final gallery height was independent
of T. However, at 180 °C intercalation takes place for all n ≥ 6 organoclays. A
possible explanation for such behaviour is the formation of a pseudocrystalline
alkyl phase near the clay surface, preferentially for shorter alkyls at T < 180 °C.
The structure may be distorted by too long alkyls or by high temperature.
Next, the influence of the matrix polymer was studied. Vaia observed that
the MW of PS affected the FH-ODA intercalation kinetics, but not the final
expansion of the gallery height. This could not be expected from the derived
model, as the entropic contribution, ΔSvpolymer, contains the term dependent on
the degree of polymerisation, m1. For PS30, PS90, and PS400 full intercalation
at 160 °C was reached after ca. 6, 24 and 48 h, respectively. As shown in Figure 63,
there is a strong correlation between the Mw and the time required to reach
equilibrium intercalation, teq.
Incorporation of MMT-2M2ODA into the styrene-derivative polymers resulted
in a logical sequence of increasing gallery heights. Thus, Δh ≡ h – ho = 0, 0.82,
0.96 and 1.0 were obtained for PVCH, PS, PSBr and P4VP, respectively. Such
ordering is to be expected when the critically important interactions between the
intercalating polymer and the silicate substrate take place. The pendant ring
polarisability increases in the order: PVCH << PS < PS3Br, P4VP, while the
intercalation rate decreases in reverse order: PS >> PS3Br, P4VP. The intercalation
kinetics depend not only on the Mw, but also on the degree of interaction between
the polymer and clay. At low clay loading, the large polarity of PS3Br and/or
P4VP may lead to exfoliation.
Thus, in accord with the thermodynamics calculations, formation of CPNC
depends on the sign and magnitude of the interaction parameters (εjk) and on the
initial interlayer structure of the organoclay. For the polymer to interact favourably
270
Thermodynamics
Figure 63 Empirical correlation between the PS matrix molecular weight and the
time required for reaching equilibrium intercalation under static melt annealing at
160 °C. Data [Vaia and Giannelis, 1997b].
with the clay, εsp,sa < 0 and the polar contribution to the interfacial
energy, ν ijp < 0; and ν ijp > ν ijd . According to Equation 48, the internal energy is
zero when:
ε sp, sa / ε ap = − h / r2 or when ε sp, sa / ε ap = ξc (51)
where εjk are the interaction parameters (the subscripts indicate: the silicate, s,
the tethered intercalant, a, and the polymer, p), h is the gallery height, r2 is radius
of the interacting species 2, ξc is a characteristic parameter of the system.
Substituting the corresponding surface energy contributions into this relation a
‘product map’ was constructed. The map (see Figure 64) defines the area where
the favourable (negative) values of the energetic contribution are expected.
3.1.4 Computations of Polymeric Brushes

Since the early 1990s the computer simulation of end-tethered molecules has
been gaining attention. While in the context of this book, the end tethering to a
plane is of central interest, the approach is more general – tethering to a point
(star molecules), line (graft copolymers) and self-tethering (network formation)
find applications in many fields [Grest and Murat, 1995]. The result of end
tethering to a plane has often been labelled in the literature as a ‘polymeric brush’,
‘grafted layer’ or ‘hairy clay platelet (HCP)’.
Two simulation methods have been used: Monte Carlo (MC) and molecular
dynamics (MD). The MC method stochastically generates molecular
configurations either on a lattice or off-lattice (in continuum). On the lattice the
chain molecules are modelled using self-avoiding random walk (SAW). Adopting
the non-reversal random walk reproduces the Rouse dynamics. However, the
271
Figure 64 A ‘product map’ showing that favourable energetic interactions (Δev < 0)
are expected for polymers with dominating acid or base character. After [Vaia and
Giannelis, 1997b], see text.
lattice (e.g., diamond or cubic) model limits the possible molecular configurations.
It works well for low segment density, but it is difficult to use when the density is
high, as for example in planes with end-tethered linear macromolecules. The
simulations show that as the grafting density increases the macromolecules, to
avoid overcrowding, stretch in the vertical or z-direction. In the absence of a
solvent (‘dry brush’) the incompressibility of the polymer chain is responsible for
the stretching.
The off-lattice continuum models, MC or MD, perform better at high segment
density. Here the bond angle and/or length are allowed to vary, i.e., in the ‘pearl-
necklace’ model bond length is fixed while in the ‘bead-and-spring’ model it is
not. MD solves equations of motions for each statistical segment, i:
( )
m d 2 ri / dt 2 = −∇Ui − mΓ ( dri / dt ) + Wi (t ) (52)
where Ui is the total potential for segment i, Γ is the bead friction and Wi is a
random force acting on each bead. The interactions are assumed to follow the
Lennard-Jones potential within specified radial distances for the repulsion and
attraction.
The numerical method that is important in describing the configuration of
polymeric brushes is based on the self-consistent mean-field approach.
3.1.5 Balazs Self-Consistent Field Approach

The self-consistent field (SCF) lattice modelling of polymer adsorption on a solid
surface is relatively recent [Fleer et al., 1993]. The 3D lattice facilitates counting
of the possible number of conformations, for example by the step-weighed Markov
process. This modern approach to thermodynamics heavily depends on
272
Thermodynamics
computational techniques. The method is well described by Fleer et al., in the

cited reference.
The SCF approach, developed for describing polymers at interfaces, is
particularly useful for modelling the thermodynamic behaviour of systems
comprising nanoparticles. For example, Nowicki [2002] described the
conformational properties of long polymer chains in the presence of nanoparticles.
The author used a random self-avoiding walk (SAW) model on a 3D lattice. The
computed properties included the conformational entropy, segment distributions
in the not necessarily Gaussian coils, and dimensions of the coiled chain attached
to a particle.
Since 1997 Balazs and her colleagues have published several articles exploring
the SCF model capabilities for the description of the equilibrium thermodynamic
properties in CPNC. The authors modelled the systems by combining Markov
chain statistics with a mean field approximation for free energy. The aim was not
to obtain quantitative predictions, but rather to show how the system may be
designed for the best performance.
3.1.5.1 Numerical Simulation

To study the effects of interactions, the authors adopted a model system that
resembles the one used by Vaia, i.e., a sandwich of two infinitely large clay platelets
immersed in a ‘bath’ of molten polymer [Balazs et al., 1998]. For the computations
a 3D lattice was divided into z = 1 to M layers. The lattice was assumed
incompressible, with all sites occupied by statistical segments, without voids or
small molecules. The intercalant chains were assumed to be linear alkyls, end-
tethered to the platelet surface. Initially they formed a melt pool inside the
sandwich, i.e., between two confining walls, into which the polymer may diffuse
under the influence of favourable thermodynamic interactions. The equations
for such a model can be solved self-consistently. The self-consistent potential is a
function of the polymer segment density distribution and the Huggins-Flory type
binary interaction parameters between all components.
Properties of the system are averaged over the x and y directions, but they
change perpendicular to the clay platelet z-direction (hence ho ≤ z ≤ h). As in the
earlier lattice models, here also the excess free energy is expressed by entropic
and enthalpic terms, the first one computed from the configurational probability,
Gi(z), the other expressing the energetic change caused by two interacting elements:
F( z ) = ∑ φ (z) ln G (z) + (1 / 2)∑ χ ∫ η(z − z')φ (z)φ (z')dz'

i
i i
ij
ij i j (53)
where φi is the polymer concentration, χij is the Huggins-Flory type binary

interaction parameter between species ‘i’ and ‘j’ and η(z - z′) is the short-range
interaction function. The connectivity of segments belonging to the same
macromolecule was incorporated by means of Green’s function. Assuming the
initial composition of the system, number of segments per species and the
magnitude of the binary interaction parameters leads to determination of the
self-consistent concentration profile as a function of the gallery height, z.
The authors considered the binary interaction parameters between three
components: clay platelets (s), polymer (p) and intercalant (a), identified as,
χsa = χsp = 0; χap = χ (variable). As the polymer diffuses from the surrounding
‘bath’ into the interlamellar gallery the distance between the two platelets increases
273
from the initial value ho to h. The free energy change during intercalation is
computed as: ΔF = F(h) – F(ho).
It is noteworthy that in these computations the interactions between the clay
platelet and either intercalant or polymer were assumed neutral, non-perturbing.
The only type of interaction of interest was the one between intercalant and
polymer. This focused interest contrasts with the opinion expressed by Vaia. Balazs
et al., admit that the intercalant-polymer interactions may unfavourably affect
the kinetics of polymer diffusion into the galleries. However, there is nothing in
the SCF methodology that would preclude systematic studies of the property
changes when varying other interaction parameters.
For the case of a non-intercalated clay sandwich immersed in a molten polymer
(see Figure 65) computations of the free energy per unit area as a function of the
interlamellar gallery height, ΔF/A = f(h), show that even for χsp = 0 the free
energy is positive, and thus intercalation is unfavourable. The effect is entropic –
the macromolecules in contact with the surface have reduced conformational
probability. When to start with the clay is intercalated and the macromolecules
are able to interact with the intercalant chains the enthalpic contribution may
compensate for the confinement effects. The computations for χap = -0.01 to
0.02 show a systematic increase of the free energy, ΔF/A = f(h). For polymer with
Np = 100 statistical segments, intercalant with Ni = 25 and the intercalant grafting
density ρ = 0.04, the polymeric intercalation was predicted only for χap ≤ 0.005.
However, when Np = 300 was assumed, no intercalation was predicted for χap = 0.
In other words, the miscibility between intercalant and macromolecules is reduced
with increased polymer molecular weight. To compensate for this effect one may
want to increase the Ni value from 25 to 50 or 100 – indeed, the computations
show that for χap = 0, this strategy leads to exfoliation, for χap = 0.01 it allows for
the polymer to intercalate, but for χap = 0.02 it makes the matter worse. These
observations based on the free energy changes are supported by the computed
segmental density profiles φ = φ(z).
While some results of the numerical calculations could be reasoned out from
the thermodynamic principles of polymeric systems, the effects of changes on the
clay platelets’ grafting density, ρ = 1/s (where s is the surface area per one
intercalant molecule), would be difficult to predict. Note that this parameter is
related to the intercalant concentration in the system, intercalant structure and
to the CEC of the clay (e.g., for MMT with CEC = 1 the surface area per one
ionic group is 1.244 nm2). The CEC varies (see Section 2.2) from 0.02 (kaolin) to
1 (MMT) to 2.5 (hectorite). SCF computations for ρ = 0.04 to 0.12 show that for
the latter value ΔF is high, thus as the packing density within the gallery increases
it becomes harder for the macromolecules to diffuse into it and mix with
intercalant chains. In short, on the one hand it is hard for macromolecules to
diffuse in between non-intercalated clay platelets, but on the other diffusion is
difficult when the intercalation density is high, i.e., there is an optimum in grafting
density for forming polymer/clay nanocomposites.
According to these computations the optimum value of CEC (or ρ) depends
on the interaction between the polymers and the intercalant, χap. In practice, the
intercalant ions may be primary, secondary, tertiary or quaternary ammonium
or phosphonium; they may have shorter or longer hydrocarbon chains, and (in
the case of the most popular quaternary type) they may have one to four long
chain groups. In the latter case, the results of SCF computations predict that the
intercalant with a single long tail should be better than the one with two or
274
Thermodynamics
Figure 65 Free energy per unit area as a function of surface separation, h, for five
different values of the polymer-intercalant interaction parameter, χap. Other
parameters are: N = 100; Ni = 25 and χsa = χsp = 0. The grafting density ρ = 0.04
and 0.12 for Figure (a) and Figure (b), respectively. The cartoons (c), left and right
show, respectively, the initial and final state, where the surfaces are separated by
macromolecules [Balazs et al., 1998].
Reprinted with permission from [Balazs et al., 1998]. Copyright 1998 American
Chemical Society.
275
three. This may explain the behaviour observed for the melt exfoliation of PA-6
[Dennis et al., 2000; 2001]. The authors melt blended PA-6 with 5 wt% of either
Cloisite® 15A or Cloisite® 30B. TSE compounding with the former organoclay
resulted in intercalation, whereas that with the latter in exfoliation. Both are
based on montmorillonite intercalated with quaternary ammonium ions: dimethyl
dihydrogenated tallow quaternary ammonium chloride and methyl tallow
bis-2-hydroxy ethyl quaternary ammonium chloride (MMT-2M2HTA and
MMT-MT2EtOH, respectively). Thus a higher packing density is expected for
Cloisite® 15A than for Cloisite® 30B. Evidently, the ability of macromolecules to
diffuse into interlamellar galleries of pre-intercalated clay depends not only on
the type of radicals (e.g., aliphatic versus aromatic) but also on the intercalant
structure, viz. the number of long aliphatic chains attached to onium ion. Vaia
[1995] observed that the kinetics of intercalation for FH clay intercalated with
2M2ODA is slower than that with either ODA or 3MODA.
The SCF numerical computations were also carried out for CPNC systems
with a compatibiliser. Two methods of compatibilisation were explored: (1) by
addition of compatibiliser between the intercalant chains and the polymer, and
(2) by addition of a compatibiliser, which is miscible with the polymer and able
to bind directly to the clay surface.
1. To examine the efficiency of the first approach, the computations were carried
out for the system with Na = 25, Np = 100, and χap = 0.01. Different amounts
of a polymeric compatibiliser (subscript c; Nc = 100) were added. The
interactions of compatibiliser with intercalant (subscript a) and polymer
(subscript p) were assumed to be: χac = χpc < χap. The simulation showed, as
expected, that addition of a compatibiliser improves the ability of polymer
to intercalate. However, the process was found inefficient, requiring at least
10% of the compatibiliser that forms an interphase between the tethered
intercalant layer and molten polymer. Evidently, the need for a large amount
of compatibiliser would have a negative effect on CPNC cost and performance.
Furthermore, enhanced interaction between the intercalant and polymer may
hinder the intercalation/exfoliation process not only for kinetics reasons,
but also owing to the loss of the conformational entropy.
2. To examine the efficiency of the second approach, computations were carried
out for the system where bare clay platelets are dispersed in a mixture of a
polymer with its homologue containing reactive group (called a ‘sticker’) at
one chain end. Aside from the sticker, the functionalised chains were
chemically identical to the matrix polymer. For the computations, the polymer
and compatibiliser chain lengths were assumed to be: Np = 100 and Nf = 75,
respectively. Strong interactions between the clay and the sticker group were
assumed (χsf = -75), while the other interaction parameters were set equal to
0. Figure 66 indicates that this approach is highly promising. There is a
substantial effect upon addition of 5% of the functionalised polymer, but
little further gain upon addition of up to 70%. The dependence shows that
the method leads to exfoliation, creating stable polymer/clay dispersions.
Evidently, in practice one may start with pre-intercalated clay, but one having
low grafting density, ρ.
The key to the second approach is the presence of the ‘sticker’ groups at the chain
ends able to strongly interact with the clay surface. In principle, such a functionalised
compatibiliser could be either a homopolymer with a strong polar group or an AB
276
Thermodynamics
Figure 66 Free energy per surface area versus gallery height for clay-polymer-
compatibiliser (functionalised polymer) system. The latter polymer content (0 to
70 wt%) is indicated.
diblock copolymer with, e.g., a short hydrophilic A-block and

B-block chemically identical to the matrix polymer. The large organophilic B-block
would extend away from the surface, mix with the matrix and cause separation of
the clay platelets. For the best performance the molecular weight of the B-block
should be higher than the entanglement molecular weight of the polymer;
Mn(B) > Me(B). Such a system would be sterically stabilised against re-aggregation.
Other numerical calculations (SCF with Markov-chain statistics) focused on
the effect of macromolecular architecture on the miscibility of the polymer-clay
system [Singh and Balazs, 2000]. Again, two infinite, parallel, organoclay plates
were immersed in a molten polymer. The value of the binary Huggins-Flory
interaction parameters was assumed χij = 0, intercalant chain length, Na = 25,
and its grafting density ρ = 0.04. The miscibility of the polymer/clay mixture was
studied by increasing the number of branches for polymers of fixed molecular
weight. The analysis showed that starting with linear macromolecules the free
energy per unit area ΔF/A < 0, thus the system is miscible. As the number of
branches increases the value of ΔF/A became more negative. The plot of ΔF/A
versus h indicates that changes in the macromolecular architecture affect the
CPNC morphology, viz. for a linear polymer there is a local minimum suggesting
preference for the intercalated structures, while for a ten-armed star there is a
preference for exfoliation. When the value of χap was assumed to be 0.01, ΔF/A
shifted to higher values – only for the ten-armed star there was a local, negative
minimum, indicating an intercalated structure. The enhanced miscibility between
the organoclay and the polymers with higher number of branches is mainly due
to the compactness of the macromolecules that can more easily interact with and
interpenetrate the short, grafted layer.
277
3.1.5.2 Analytical Self-Consistent-Field Theory for Compatibilised Systems

Since numerical analysis indicated that dispersion of clay in a mixture of
functionalised polymer and its non-functionalised homologue shows great
promise, the authors developed an analytical SCF theory [Balazs et al., 1998].
The adopted model is analogous to that evaluated by numerical means. Thus,
the polymeric phase comprises a volume fraction, φ, of monodispersed,
functionalised chains and (1 - φ) of polydispersed, non-functionalised chains.
The functionalised and non-functionalised chains are chemically identical, differing
by the presence of one terminal group in the functionalised chain. However, they
may also vary by the number of segments, N, each of diameter a. The end-group
is highly attracted to the clay surface, and reacting with it forms a HCP structure,
effectively pushing the sheets apart. However, these functional groups do not
interact between themselves or with the other components of the system. The
bare clay platelets are modelled as planar surfaces, each having an area A. The
degree to which the functionalised polymer binds to the surface is related to the
gallery height, h.
Within the gallery, the functionalised macromolecules (each of length N) are either
attached to the surface (na) or free (nf). Similarly, the number of non-functionalised
chains of length Pi is ni. Thus, the total number of segments between two clay
platelets is given by:
(
Ntotal = N na + n f + ) ∑
ni Pi = Ah / a3 (54)
i
and the total free energy of the system is:
(
ΔF = ΔFbrush − na + n f μ − ) ∑n μ i i
i (55)
ΔFbrush = ΔFstretch + ΔFmix + ΔEa
where μ is the chemical potential of the end-functionalised chain, μi is that of the
non-functionalised, polydispersed polymer, ΔFstretch accounts for the stretching
of the attached macromolecules, ΔFmix accounts for the free energy of mixing of
functionalised and non-functionalised chains, and ΔEa is the energy of attaching
the functional group to the surface. By substituting the appropriate terms the
following expression for the total free energy of the system was derived:
(ΔFtotal / RT )( N / Ntotal ) =
⎡ h ⎤
(
Nk 2 h2 / 3 − hmax
2
)
+ φ ⎢1 − exp − Nk 2 hmax
⎢⎣
2
{ }∫ {
exp − Nk 2 x 2 dx / h ⎥
⎥⎦
} (56)
0
⎡ h ⎤
∑
+ N (φi / Pi )⎢1 − exp − Pk
i ⎢⎣
i
2 2
hmax{ exp − Pki }∫ {
x dx / h⎥
2 2
⎥⎦
}
0
where the maximum platelet separation before a homogeneous matrix polymer

layer is formed is given by:
hmax = ( 2a / π ) 2N (ε / kT + 1 + ln φ ) / 3 (57)
In these relations: k ≡ 3π /8a N , while ε = –ΔEa/na is the energy gain per one
2 2 2 2
reactive group.
Note that for h > hmax, a layer of bulk polymer appears between the outer
edges of the two brushes. This however does not change the free energy of the
278
Thermodynamics
system. Thus, at h = hmax, the gain in free energy due to intercalation/exfoliation

by the polymeric matrix is at maximum. This limit depends only on the chain
length of the functionalised polymer, the reaction energy and concentration – the
latter in a logarithmic form, hence sensitive to small changes at low concentration,
but insensitive at high.
The adsorbed amount of functionalised polymer follows the dependence:
h
{
Θ (h) = h − φ exp − Nk 2 hmax
2
}∫ exp{− Nk x }dx
2 2
0
h
(58)
−N ∑ φ exp{
i
i − Pk
i
2 2
hmax }∫ exp{− Pk x }dx
i
2 2
Evidently, the amount of functionalised polymer that is bound to the surface

depends on the gallery height, h, with the slope increasing with molecular weight
of the functionalised (N) and non-functionalised (Np = Pi) chains.
In Figure 67 the function Θ = Θ (h) is presented for various values of the
length of non-functionalised chains, Np = 1 to 100. The length of the functionalised
chains, Nf = 75 and its volume fraction φ = 0.05 were assumed constant. The
interaction energy was set as ε = 12.5 kBT. Increasing Np reduces the miscibility
of the functionalised with non-functionalised chains, what causes the
functionalised chains to migrate to the strongly interacting clay surface. This in
turn leads to increased adsorption of the functionalised chains on the clay surface.
Up to ca. h = 20 the dependence Θ = Θ (h) is about linear. It is noteworthy that
for Nf = 75 the dependence is common for Np = 50 and Np = 100, suggesting that
as a rule of thumb Nf ≈ Np may offer the optimum condition for adsorption.
Figure 67 The amount of adsorbed functionalised polymer with Nf = 75 and

concentration φ = 0.05 for four chain lengths of the matrix polymer, Np = 1, 10, 50
and 100. After [Balazs et al., 1998].
279
It was found that the derived analytical expressions agreed well with the
numerical predictions by SCF. For example, the dependencies shown in Figures 66
and 67 could be generated by either of these two models. Similarly, the numerical
SCF data on the thickness of the unperturbed brush, hmax, also show satisfactory
agreement with the analytical prediction.
Recently, SCF was used to determine a range of independent variables that
guarantee thermodynamic miscibility in a realistic model system, which comprises
four components: solid clay platelets, low molecular weight intercalant, polymeric
matrix, and an end-functionalised compatibiliser [Kim et al., 2004]. In the
simulation, realistic values of the binary interaction parameters were used. The
results showed that intercalation and exfoliation is expected within limited ranges
of independent variables. Furthermore, it was found that the presence of bare
clay surface (e.g., generated by thermal decomposition of intercalant) strongly
hinders the clay dispersion. The 2D simulation successfully identified the most
influential factors (e.g., compatibiliser type and concentration) and established
their optimum ranges.
3.1.5.3 Phase Behaviour

SCF methods have been used to compute the phase behaviour for CPNC model
systems [Balazs et al., 1999]. The initial model considered a mixture of individual
clay platelets dispersed in polymer melt. The platelets were rigid disks of diameter
D and thickness L, while the polymer was made of flexible chains of length N.
The volume fraction of the platelets and the polymer in the incompressible mixture
was φd, and φp = 1 - φd, respectively. The interaction between the polymer statistical
segment and a platelet site was expressed by the Huggins-Flory interaction
parameter, χ.
Two miscible systems were distinguished: isotropic with clay platelets randomly
oriented in respect to each other, and a nematic with mutually aligned platelets.
Depending on the CPNC applicability, e.g., for the mechanical or barrier
properties, either one of these two structures may be preferred.
The formation of the isotropic and nematic structures was predicted using a
modified Onsager model for the nematic ordering of rigid rods. The following
expression was derived for the free energy:
[ ]
F = nd K + ln φd + σ − ln(1 − φd )(b / ν d )( ρ − 1) − χν d φd + n p ln φp (59)
where K is a constant, np is the number of polymer molecules, nd is the number of
platelets per unit volume, and vd = (πD2L)/4 is the volume of one disk. The
parameters: σ and ρ describe the orientation of the disks with respect to,
respectively, the nematic direction and each other. In the isotropic phase, σ = 0
and ρ = 1, while in the nematic phase:
[( ) ]
σ n = 2 ln −2ν d π −1 / 2 / b ln(1 − φd ) − 1
(60)
ρn ≡ ( 4 / π) sin γ = −2(ν d / b) / ln(1 − φd )
where γ is the angle between two disks. The analysis for disks with an aspect
ratio p ≡ D/L = 30 predicts the existence of a phase diagram with three regions:
immiscible, isotropic and nematic. The region of miscibility decreases with
increasing N and χ. Furthermore; increasing p promotes nematic ordering and
reduces the isotropic phase.
280
Thermodynamics
This initial investigation was significantly expanded during the following years
[Ginzburg and Balazs 1999; 2000; Ginzburg et al., 2000; 2001]. The new model
predicts phase diagrams that include: isotropic, nematic, smectic, columnar, plastic
(or house-of-cards), and crystalline structures. For these calculations, the authors
combined the SCF model with the Somoza-Tarazona formalism of the density
functional theory (DFT). The resulting free energy functional was minimised
with respect to both the orientational and positional single-particle distribution
function, potentially determining all phases and the coexistence regions.
The free energy of a system
r r was
r written
r as a functional of a single-particle
r r
distribution function, γ (r , n ) = ρ(r ) f (n ) , where
r r and n are the coordinate rand
the nematic director, respectively, while ρ(r ) is disk number density, and f (n ) is
the Onsager orientational distribution function. The fluid was assumed
incompressible; i.e., the sum of the volume fractions of polymer, φp, of intercalant,
φi, and clay, φc, equals 1: thus φp + φi + φc = 1.
The free energy consisted of three terms, Fid, Fster and Fint:
1. Fid – the free energy of an ‘ideal gas’ of polymer
This term can be written as a sum of the translational and orientational
contributions coming from the clay particles, and that originating from the
polymer, Fid = Fc + Fp, respectively, the latter calculated from the Huggins-Flory
theory:
r r r r r r r r
( )
Fid / kT = ρ(r ) ln ρ (r )dr + ρ (r ) f (n ) ln 4πf (n ) dndr + (ν / Nν m )φp ln φp (61)
∫ ∫ ( )
r
where N is the chain length of the polymer, ρ(r ) is the positional (or local) density
of clay platelets, n is the total volume of the system, vm is the monomer volume
and φp is the volume fraction of the polymer. For the intercalated organoclay
platelets the effective thickness is: Leff = L + 2ρNi, and the effective volume of
such a particle: Veff = (π/6)D2Leff.
2. Fster – the contribution due to the excluded-volume effects for clay platelets
A semi-empirical steric interaction expression was used:
r r r
[ ] (
Fster / kT = ρ(r ) Vexcl ( f ) / Vphe Ψhs Φ (r ) dr
∫ )
(62)
where Ψhs is the Carnahan-Starling function that describes the excess freer energy
density for hard spheres as a function of their packing fraction; Φ (r ) is the
smoothed, local volume fraction of clay; Vexcl(f) is the average excluded volume
per particle for a given orientational distribution; and Vphe is the excluded volume
per particle for perfectly aligned ellipsoids.
The sum of the free energy terms, Fid + Fster, describes an athermal dispersion
of hard ellipsoids in a polymer matrix, capable of forming liquid crystalline
(nematic) or crystalline phases. To generate smectic or columnar phases, strong
anisotropic long-range interactions are required. These are provided by the Fint
contribution.
3. Fint – the enthalpic interactions between clay platelets
This term was derived from the pair correlation function for the particles, g(1,2);
hence it is mostly determined by the excluded-volume effects:
r r r r r r r r r r r r
Fint / kT = (1 / 2) ρ (r1 ) f (n1 )ρ (r2 ) f (n2 ) × δ (1 − n1 n2 )g(1, 2)V (r1 − r2 )dr1 dr2 dn1 dn2 (63)
∫
281
where for overlapping or not-overlapping particles the mean-field pair correlation

function g(1,2) = 0, or g(1,2) = 1, respectively. The δ-function allows only parallel
disk configurations. The potential function V(r1 – r2) is expressed as:
r
V (r ) = ( π / 4) D2 ⎡1 − (r⊥ / D) ⎤U ( z )
2
(64)
⎣⎢ ⎦⎥
r
where r = (x, y, z), and r⊥ = (x2 + y2)1/2. The interaction potential per unit area,
U(z), has two components: U1(z) originating from electrostatic and van der Waals
interactions between ‘bare’ clay particles, and U2(z) originating from the
intercalant and polymer chain contributions within the interlamellar gallery. The
attractive and short-ranged U1(z) term depends on the chemical structure of the
clay, and a priori was written as:
[ {(
U1 ( z ) = Eo 1 − exp − z − Leff )}] (65)
where Eo is the interaction energy between clay platelets and Leff is an effective
thickness of clay platelet. The second component, U2(z), was computed using the
SCF method. The shape of this potential depends on N, Ni, ρ and the binary
interaction parameters, χ.
The equilibrium morphology was computed for the mixtures of a polymer
(N = 300) with intercalated clay platelets, modelled as oblate disks having D = 30,
L = 1, thus p = 30. Two values for the clay-clay interaction strength were used,
E0 = 0 (no long-range attraction), and E0 = 0.1 kBT/a2 (strong attraction). All the
binary interactions, except that between polymer and intercalant were assumed
= 0; the latter χap = χ varied from –0.05 to +0.05. As far as the intercalation was
concerned, the following systems were considered: (a) ρ = 0.2, Ni = 5, (b) ρ = 0.04,
Ni = 25, (c) ρ = 0.02, Ni = 50, (d) ρ = 0.04, Ni = 50, and (e) ρ = 0.02, Ni = 100.
Note that the total amount of intercalant in systems (a)-(e) was: θ = ρNi = 1, 1, 1,
2, and 2, respectively.
The calculations of the phase diagram were carried out in two steps:
1. Using SCF the free energy profile U2(z) was computed for the five systems,
varying the binary interaction parameter within the indicated range, first for
E0 = 0, then for E0 = 0.1 kBT/a2.
2. The phase diagram was constructed as a map: χ versus φ (see Figure 68). The
total volume fraction of the intercalated clay: φc ≤ 0.601. Schematic
representation of the phases is shown in Figure 69.
The phase diagrams for the considered systems are complex. For χ > 0, the systems
are immiscible, showing coexistence between the polymer-rich isotropic phase
and the clay-rich crystalline phase. For χ close to 0, the two-phase region becomes
narrower and splits into isotropic-nematic and nematic-crystal phases. The triple
point (I-N-Cr) and the width of the nematic phase depend on the system. The
computed smectic phases were always metastable. For χ < 0, the isotropic-nematic
and nematic-crystal coexistence regions become narrower and shift toward higher
values of φ. When χ is strongly negative, the new ‘plastic solid’ (or house-of-
cards) and columnar phases appear. Evidently, at low clay loadings, the strong
repulsion between neighbouring disks forces them to adopt more energetically
favourable ‘edge-to-face’ or ‘house-of-cards’ configurations. This leads to either
gelation or crystallisation. At higher clay volume fractions, the steric excluded
volume effects dominate the long range disk-disk repulsion, forcing the formation
of columnar and crystal phases.
282
Thermodynamics
Figure 68 The map of phase behaviour for polymer-clay mixtures, obtained by

varying the binary interaction parameter between polymer and intercalant, from χ
= -0.05 to +0.05 and the inorganic clay content from φ = 0 to 0.2. The 5 systems
are: (a) ρ = 0.2, Ni = 5, (b) ρ = 0.04, Ni = 25, (c) ρ = 0.02, Ni = 50, (d) ρ = 0.04, Ni
= 50, and (e) ρ = 0.02, Ni = 100 (see text). The interaction potential between clay
platelets, e0 = 0, was assumed. The phases are: I, isotropic; N, nematic; Cr, crystal;
PS, plastic solid; Col, columnar. Points represent calculated coexistence densities;
lines serve as a guide to the eye. Dashed lines represent approximate locations of
phase transition boundaries (exact calculation was not possible) [Ginzburg et al.,
2000].
Reprinted with permission from [Ginzburg et al., 2000]. Copyright 2000
283
Figure 69 Schematics of possible phase structures for dispersed platelets in a

polymer: (a) isotropic, (b) nematic, (c) smectic A, (d) columnar, (e) plastic solid
r
(house-of-cards), and (f) crystal. The nematic director n is aligned in the Z
direction, while the platelets lie in the XY plane.
284
Thermodynamics
The phase maps in Figure 68 show similarity for the same total intercalant
loading, θ = 1 and θ = 2, viz. systems (a)-(c) and (d)-(e), respectively. However,
for platelets intercalated with short densely grafted chains (system a), the
immiscibility between the clay disks and polymer dominates the phase behaviour
of the system. This observation confirms the previous SCF computations, which
suggested that the present strategy of intercalation leads to an unfavourable
thermodynamic environment. Instead of high saturation of clay surfaces with
C12 to C18 alkyls an intercalation with fewer, strongly bound to the surface, long
chain molecules should be carried out. Note that increasing Ni from 25 (system
b) to 50 (system d) moves the isotropic-nematic-crystal triple point upward,
extends the stability region of the nematic phase to higher χ values and narrows
the two-phase isotropic-nematic region, indicating thermodynamically stable
exfoliated composites. Comparing systems c and e leads to similar conclusions.
One may object to the above computations on the ground that assumption of
E0 = 0 for the clay particles is not realistic. It is known that the surface energy of
a crystalline solid is high and that there is a strong van der Waals interaction
between the clay platelets. Thus, it is interesting to see how the results are affected
by the imposition of the strong clay-clay attraction, viz. E0 = 0.1 kBT/a2.
For systems with θ = 1, the clay-clay attractions dominate the entropic
contribution of the surfactant molecules. The phase diagrams show the
immiscibility between polymer and clay within the full range of χ. For systems
with θ = 2 (see Figure 70) the miscibility is significantly diminished in comparison
to the corresponding E0 = 0 cases (compare with systems (d) and (e) in Figure 68).
The isotropic-nematic-crystal triple point is shifted downward, the areas occupied
by isotropic and nematic phases is reduced, and the nematic-crystal transition
occurs at lower values of φ.
3.1.5.4 Contribution and Potential of the SCF Method

The discussed SCF calculations start with a model of a two-platelet (intercalated
or not) sandwich in a molten polymer and consider the influence of diverse
parameters on the equilibrium thermodynamic properties, viz. miscibility and
phase diagrams. The kinetic aspects of the polymer intercalation or exfoliation
process are not being addressed. Furthermore, the effects introduced by energy
input from external sources have not been considered. The analysis of kinetics is
beyond the scope of the model, but the effects of the mechanical energy input
(e.g., during compounding in an extruder) are not.
Balazs and her colleagues applied the SCF model to study the influences of
such parameters as the molecular weight of the polymeric chain, size and grafting
density of the intercalant, magnitude of the binary interaction parameter for the
polymer, intercalant and clay, influence of the clay-clay interaction,
compatibilisation strategies using compatibiliser for the intercalant-polymer or
for clay-polymer interfaces. One may argue whether the magnitude of the selected
parameters has been optimal, but the numerical comparison of model predictions
with experimental data has not been the goal. However, these are the most
thorough fundamental studies of CPNC, offering guidance toward better methods
of exfoliation in thermodynamically stable systems.
One of the important findings of the SCF calculations demonstrated that
increasing the length of the intercalant chain (beyond the typically used C12-C20)
to oligomeric of polymeric values should enhance the thermodynamic stability
of exfoliated systems. Another highly practical finding is that there is little to be
285
Figure 70 Phase diagrams of polymer-clay mixtures:

(a) ρ = 0.04, Ni = 50, and (b)ρ = 0.02, Ni = 100. The interaction potential between
clay platelets, e0 = 0.1, was assumed. The phase diagrams for the other three cases
shown in Figure 68 indicate immiscibility.
gained from compatibilisation of the polymeric matrix with the intercalant chains
– a large quantity of the compatibiliser would be required. By contrast, direct
compatibilisation of the clay/polymer shows greater potential. For this purpose,
the end-terminated macromolecular chains with single strongly bonding group
(a ‘sticker’) are preferred. Their chain length should be smaller, but of the same
order of magnitude as that of the matrix polymer. Evidently, for the practical
reasons (kinetics) one would start with pre-intercalated clay, and use the functional
compatibiliser with molecular weight just above the critical value for
entanglement.
More recently complex phase diagrams were computed. This was accomplished
by combining the SCF-generated free energy profiles with the Somoza-Tarazona
free energy functional. The computations demonstrated how variations of the
principal parameters affect the formation of isotropic, nematic, smectic, columnar,
crystal, and plastic solid (house-of-cards) phases. The calculated phase diagrams
286
Thermodynamics
are in qualitative agreement with the predictions of the SCF model. As the length
of the grafted chains and/or their density increases, the miscibility between the
clay sheets and the polymer is improved, and the resulting mixture can exhibit
exfoliated (isotropic or nematic) structures for a range of clay volume fractions.
For short intercalant chains, the polymer is unable to penetrate the galleries and
the system becomes immiscible. The computations demonstrated that the phase
equilibrium of CPNC is sensitive to the specific features of clay-clay, clay-polymer,
intercalant-polymer and clay-compatibiliser interactions. For quantitative
prediction of the phase behaviour, one must correctly describe all these
interactions, e.g., by using molecular simulation.
There is a large difference between the idealised mathematical model of CPNC
and the physical reality. For obvious reasons the ingredients used in the simulation
are homogeneous, monodispersed in size and molecular properties. Furthermore,
the simulation is based on equilibrium thermodynamics – the forces responsible
for the evolution of idealised CPNC structures are exclusively thermodynamic
and the final morphology is at thermodynamic equilibrium in the molten state.
The reality is quite different as the ingredients are far from homogeneous, there
are numerous process additives in each commercial resin, the clays are mineral
products with a host of compositional and structural defaults, the system is
mechanically dispersed which may either disturb the shape of clay platelets
(attrition or bending) and/or induce platelet orientation, then usually cooled down
to room temperature which induces vitrification or crystallisation that cause
internal stresses, etc. These are some of the reasons that make direct comparison
between the model and reality problematic. The model can and does serve as a
guide – with future developments the guide will become progressively more
realistic, able to account for the numerous contributions mentioned in the
preceding sentences. However, considering the complexity of the CPNC systems,
molecular modelling is the only method to examine the contributions of each
element, the only way to understand the mechanisms involved, and the only
logical approach to maximise nanocomposite performance.
3.1.6 Scaling Theory for Telechelic Polymer/Clay Systems

Using numerical and analytical SCF calculations Zhulina et al. [1999] investigated
the interactions in a system composed of polymer mixture with a sandwich of
clay platelets dispersed in it. The mixture consisted of molten polymer with its
end-functionalised, telechelic homologue, containing two reactive ‘stickers’, one
at each end of the chain. These reactive groups were highly attracted to the
platelets’ surfaces. The computed free energy profiles showed distinctive minima,
even at low concentration of the end-functionalised chains. The studies showed
that the telechelic chains could react with both clay platelets of the model
sandwich, thus bridging the interlamellar gallery. The SCF computations showed
that telechelic polymers may promote the formation of thermodynamically stable
intercalated systems, but bridging the interlamellar gallery could prevent
exfoliation. However, it was not clear whether the presence of telechelic chains
necessarily prohibits exfoliation.
To search for possible conditions under which thermodynamically stable
exfoliated CPNC might be formed in the presence of telechelic polymers Kuznetsov
and Balazs [2000a; 2000b] applied the scaling theory. The computations again
started with a model of two clay platelets immersed in a polymer melt. Each
platelet had the surface area A and it was pre-intercalated with short alkyl chains
287
that reduced the clay-clay interactions to zero. The melt was a mixture of telechelic
flexible N-polymers (their volume fraction = φ) and non-functionalised P-polymer
(volume fraction = 1-φ). These polymers had P ≥ N >> 1 statistical segments,
each of diameter a. The N-polymer had two ‘sticker’ terminal groups, one at
each end of the chain. The groups could interact with the clay surface with the
energy per sticker-clay contact of ε.
Thus, the gallery between the platelets was filled by N- and P-polymers. A fraction
of the N-chains was anchored to the platelets with the rest (as well as P-chains) being
free (subscript f). The anchored chains could be attached to the surface by one
(subscript t for ‘tails’) or two ends (subscripts l or b for ‘loops’ or ‘bridges’,
respectively). The following values of the Huggins-Flory interaction parameters
were assumed: χNN = χPP = 0, and χ = χNP. The free energy of the chains within the
gallery was expressed as a sum of the individual contributions:
F = Fads + Fint + Fcomp + Fel + Fent + Fdem (66)
where Fads is the sticker-surface adsorption energy for N-chains, Fint is the
interaction energy between the N and P chains, Fcomp is the compression energy
for chains at relatively low interlamellar gallery height, h, and Fel is the elongation
energy for loops, tails, and bridges, Fent is the entropic energy for mixing the
different types of chain configurations within the brush layers, and Fdem is the
demixing energy associated with extracting N and P chains from the surrounding
melt and localising these chains in the confined layers.
The free energy of the system, F, was written deriving the six components of
Equation 66 and casting them in terms of the reduced gallery height: a = h/Na,
αp= h/Pa, αtot = htot/Na and αl = hl /Na, where htot stands for the total height of the
brush, htot ≤ h/2 (with h being the gallery height), and hl is the average distance
that a loop molecule reaches from the clay surface. Its value depends on the
energy per contact between the clay platelet and a functionalised chain end (ε/T),
the volume fraction of functionalised chains in the bulk melt, N and P, the numbers
of segments in each functionalised and non-functionalised chain, respectively,
and the Huggins-Flory interaction energy parameter, χNP. Next, F was numerically
differentiated to obtain the conditions for local minima in respect to individual
volume fractions: φP, φl, φt, φb, and φf, calculated from the respective number of
statistical segments:
φl, t, b, f = nl, t, b, f Na3 / Ah ; φ p = n p Pa3 / Ah ; ∑φ = 1
i
i (67)
The free energy, F, was computed in its reduced form (in respect to temperature
and surface area) as a function of the reduced gallery height:
( )
Fa2 / AT = α Na3 / Ah ( F / T ) versus α ≡ h / Na (68)
The initial computations were carried out for the dispersion of intercalated clay
in a telechelic, bi-functionalised melt (φ = 1). The results are presented in Figure 71
as the reduced free energy and volume fractions of different conformations versus
the reduced gallery height, α. Four regions are indicated:
(I) The chains t, l, and b are highly compressed. The reduced free energy rapidly
decreases with α to negative values (miscibility).
(II) A shallow, local minimum of free energy, which originates in weak stretching
of all the chains within the brushes. The number of bridges decreases and
tends to zero on the border of this region.
288
Thermodynamics
Figure 71 The reduced free energy for different conformations versus the reduced
gallery height, α. Four regions of behaviour are indicated. After [Kuznetsov and
Balazs, 2000a]. See text.
(III) This is the ‘relaxation’ region, where the free chains appear. The free energy
is further reduced with α.
(IV)Separate brush layers are formed with unperturbed Gaussian free chains filling
the space between them, thus exfoliation.
The minimum in region (II) is thermodynamically metastable hence there is no
optimal spacing (intercalation) other than exfoliation. This is surprising as it
could be expected that the bridging chains give rise to a thermodynamic barrier
to separating clay platelets beyond the point where the bridges are disrupted.
Evidently, this energy cost is compensated by that gained by adsorption of free
chains, which can penetrate the gap at larger α. The results imply that clay sheets
can be exfoliated in a melt of telechelic chains. However, the metastable minimum
in region (II) can lead to a kinetically trapped degree of dispersion.
Additional computations show that the magnitude of the local minimum can
be controlled by the sticker adsorption energy, ε/T, and the molecular weight of
the N-chain. Evidently, increasing the former and decreasing the latter forces the
reduced free energy deeper into the negative values, increasing the miscibility.
However, for practical reasons this may not be the best solution. For sufficiently
small values of the barrier height, an imposed stress or increased temperature can
help overcoming the kinetic barrier and lead to exfoliated CPNC.
In a system comprising intercalated clay dispersed in a mixture of
functionalised (N) and non-functionalised (P) polymers the plots of the free energy
per area (F/T)(a2/A) versus the reduced gallery height, α, are similar to that shown
in Figure 71. However, at low volume fraction of N-chains, φ < 0.05, and high
e/T-values, the minimum in region (II) is a global one, forcing the system into a
289
thermodynamically stable intercalation. One solution is to use a higher

concentration of the N-chains, another to increase interaction between N- and
P-chains, i.e., to have χNP < 0.
The phase diagram in Figure 72 summarises these findings. The data are plotted
in terms of ε/T versus the volume fraction of polymer-N, φ, for the case of N = 1000
and P = 100. The curves (calculated by equating the free energies) between the
intercalated, exfoliated and immiscible phases correspond to the first-order phase
transitions. At low contact energies between the sticker group and clay surface,
the system is immiscible, while at higher values of ε/T, it can either be intercalated
or exfoliated (at high φ). In the intercalated state, loops, tails and bridges fill the
gallery. In the exfoliated state loops and tails form the brushes. The transition
from an intercalated to an exfoliated system is related to the increased number of
tails, which in turn is facilitated by a higher value of φ and the formation of a free
polymer layer between the brushes. The relative magnitude of the intercalated-
to-exfoliated region very much depends on the N/P ratio. Figure 72 illustrates a
perverted case with the functionalised chains being ten times longer than the
matrix polymer. In practice, N ≤ P and under these conditions the intercalated
area is quite small, relegated to ε/T < 5 and φ > 0.15 – the miscible clay/polymer
systems are mainly exfoliated.
To summarise, the scaling theory was shown to be appropriate for the analysis
of free energy in three-component systems composed of pre-intercalated clay,
bifunctionalised (telechelic) compatibiliser and its non-functionalised homologue
within a wide range of parameters, viz. ε, N, P, φ and χ. The computations indicate
that in the melt of only N-chains there are no thermodynamically stable
intercalated states – the system is either immiscible or it exfoliates. It is easier to
Figure 72 Phase diagram for the polymer-clay mixture containing φ volume

fraction of functionalised polymer (N = 1000) and non-functionalised polymer
(P = 100). After [Kuznetsov and Balazs, 2000a]. See text.
290
Thermodynamics
expand the gallery height in a mixture of telechelic and non-functionalised

polymers.
The scaling-theory shows a significant influence of the chain length ratio N/P
on the location of the phase boundaries between the immiscible, intercalated and
exfoliated states of the polymer-clay mixtures. Increasing N at fixed P with N ≤ P,
causes the immiscible phase to transform into an intercalated or exfoliated one.
At the same time, the intercalated-exfoliated transitional volume fractions weakly
depend on N. When changing the value of P at constant value of N with N ≥ P,
the intercalated phase expands at a cost of the exfoliated one. Theoretical analysis
of the clay/polymer/functional polymer indicates that the most promising strategy
for exfoliation is by using long-chain functionalised compatibiliser of smaller
but comparable in magnitude molecular weight to the matrix polymer. Promising
results were obtained for functionalised linear polymers having either one reactive
chain-end, or two reactive chain-ends. Experimental confirmation of this
conclusion can be found, for example, in the work by Hoffmann et al. [2000a].
Since multi-block copolymers form morphologies that may be controlled by
the composition and molecular weight of the blocks, there is a concerted effort
to explore the potential structure formation of nanocomposites with block
copolymer as a matrix. Thus, for example, SCF was used to analyse the structure
of nanocomposite thin films (of di-block copolymer with nanoparticles) confined
between two walls [Lee et al., 2003]. In such restricted geometry, particles are
driven to the wall, effectively modifying their chemical nature and the film
structure. The changes are robust, relying on the entropic effects. They can be
exploited to form nanoscale devices with particles assembled into nanowires.
Another suggested application of the phenomenon is the use of such systems for
coatings – the high concentration of solid particles near the surface makes such a
coating more fracture and abrasion resistant.
3.1.7 Solid Surface Effects on Molecular Mobility

The effects of a solid phase on organic chain mobility are important for
understanding nanoparticle behaviour in a polymeric matrix. Crystalline solids
show high surface energy and a tendency for aggregation. The key to the success
of CPNC is the stable and uniform dispersion of exfoliated clay platelets or other
nanoparticles (e.g., carbon nanotubes).
3.1.7.1 Surface Energy of Solids

The surface energy depends on the nature and structure of materials. Its value is
defined in terms of the thermodynamic equilibrium of the solid with its saturated
vapour. Evidently, measurements of the surface energy of a liquid are significantly
more straightforward than those of the solids.
The surface energy, σs, is defined as:
σ s = U s − TS s = ν1 s + ∑μ n
i
s
i i (69)
where s is the surface area, the superscript ‘s’ indicates the surface quantities of
total energy (U), entropy (S) and the number of moles (n) of species ‘i’ with
chemical potential, μ i , adsorbed on the surface. Thus, the equilibrium
thermodynamics predicts that the total surface energy may change due to
temperature and composition. The variable, ν1, is the surface tension (subscript
1 indicates a single component in equilibrium with its vapours). In the absence of
291
adsorbed foreign substance (ni = 0) the surface tension coefficient, ν1, is given by
the ratio of surface energy to surface area; hence it may also be called the specific
surface energy.
The specific surface energy of solids, ν1, is difficult to measure as these are
often subjected to 3D residual stresses, surface roughness all the way to nanoscale,
readily adsorb environmental gas, vapour or liquid molecules and may be
contaminated by compounds that are difficult to remove. The highest measured
surface energy is for diamond: ν1(C-diamond) = 9820 mN/m. A high value was
also determined for orthoclase, KAlSi3O8, viz. ν1 = 7770 mN/m [Brace and Walsh,
1962]. The specific surface energy of a metal in equilibrium with its own vapour
is also high, viz. ν1(Cu) = 1,430, ν1(Au) = 1,510 mN/m, similarly for crystalline
oxides, viz. ν1(CaO) = 1,310, ν1(MgO) = 1,090 mN/m. By contrast, amorphous
bodies have significantly lower ν1 than crystalline. For example SiO 2 :
ν1(amorphous) = 260, ν1(hydrated, amorphous) = 130, while ν1(quartz) = 1030
and ν1(hydrated quartz) = 422 mN/m [Condon and Odishaw, 1967; Stokes and
Evans, 1997].
These values for crystalline solids should be compared with those of organic
compounds. For example, the polymer surface tension coefficients at 20 °C range
from 10 to 49 mN/m (for fluorinated acrylic to polyesters or polyamides,
respectively) [Brandrup et al., 1999]. Similar values have been measured for
organic liquids – the highest is ν1(glycerol) = 63 mN/m, with –OH groups on the
surface. In short, the surface energy of a crystalline solid is about two orders of
magnitude greater than that of organic liquids.
Owing to morphological nanorugosity the surface of crystalline solids is usually
highly complex. This is particularly true for mineral silicates where the surface
may be defined only in statistical terms. The clays, due to variation of composition,
show great variation of the surface heterogeneity [Papirer and Barard, 1998].
The latter also varies with the type of adsorbed compound. Evidently, adsorption
affects the surface energy of crystalline solids. For example, the specific surface
energy of freshly cleaved mica in vacuum is ν1 = 4,500 mN/m whereas that
measured in air is 375 mN/m.
One of the consequences of the surface energy contribution to the energetics
of a body is the dependence of the transition temperature on the degree of
dispersion. For example, the melting temperature of bulk PE is Tm ≅ 400 K, but
PE-particles with diameter varying from 13 to 5 nm have Tm = 266 to 218 K.
Another consequence of the high surface energy is the aggregation of solid
powders. According to Johnson et al. [1971], the force between two interacting
spheres (of radii R1 and R2) is given by:
ε = ν11πR1R2/(R1 + R2) (70)
For R1 = R2 the relation simplifies to read ε = ν11πR/2. Equation 70 is general and
independent of the elastic modulus. The attraction force is then proportional to
the radius – the smaller the particle, the smaller is the force of individual contact.
However, dividing the same mass of crystalline powder into the number of particles
requires that NiRi3 = NjRj3, thus a change of the total aggregation energy, E = Nε,
i.e.:
Niεi/Njεj ≡ Ei/Ej = (Rj/Ri)2 (71)
For example, to disperse the same volume of CaCO3 particles of about 10 nm diameter
would require 62,500-fold more energy than that needed for a standard filler powder
292
Thermodynamics
with diameter of about 2.5 μm. Furthermore, since the dispersing force during
compounding is given by the product of radius and stress, Rσij, to achieve the same
efficiency the stress should be increased by a factor of 200.
3.1.7.2 Polymer Adsorption on Solid Particles

As discussed by Fleer et al. [1993], any interface between two phases (solid,
liquid or gas) induces changes to properties. For example, solid readily adsorbs
macromolecules from a solution. The thickness of the adsorbed layer usually
extends to the magnitude of the radius of gyration of the macromolecular coil,
1 /2
sθ2 = 5 to 35 nm. The adsorption depends on the polymer (its chemistry,
conformation, molecular weight, polydispersity, etc.), on the solvent, temperature
and the substrate surface energy. The model computations indicate that in the
absence of direct chemical bonding, macromolecules interact with a solid surface
by physical contact of several statistical segments labelled as ‘trains’ (see
Figure 73). The trains create loops and tails. The relative proportion of these
structures depends on the molecular weight, e.g., loops are absent for short chains,
but dominant for long ones.
Recently van der Gucht et al. [2002] proposed a lattice model for describing
the behaviour of an ideal polymer solution at a surface. The ratio of the surface
excess volume fraction, φex, of polymer molecules with N-statistical segments, to
the bulk volume fraction of polymer, φb, was found to follow a simple dependence:
[ (
φ ex / φ b = A B + χ s − χ sc∞ )] (72)
where A ≅ 5/6 and B ≅ 1/5 are constants, χs is the Silberberg adsorption parameter,
and χ sc∞ is the critical adsorption energy for infinite chain lengths. With decreasing
chain length the adsorption/depletion transition shifts to lower χs values. This
effect is strongly enhanced if the end segments of the chain adsorb preferentially.
Cosgrove et al. [1987; 1991] used neutron scattering to study polymer
adsorption from dilute solutions on solids (mica or PS latex particles). The results
presented in Figure 74 indicated that homopolymer concentration exponentially
declines from the surface in the z-direction, while the copolymer concentration
profile follows a parabolic dependence. The thickness of the adsorbed layer varied
from one system to the next, but within a relatively narrow range of values. The
root-mean-square (rms) thickness was slightly larger than the unperturbed radius
of gyration, viz. 3.6 versus 4.8 nm for copolymer and 6.8 versus 9.0 nm for PS,
respectively. After evaporation of solvent the thickness of the adsorbed layer was
reduced by about 50% (viz. to 3.3 and 4.4 nm, respectively) indicating high
Figure 73 Schematic representation of adsorbed macromolecule. Loop, train and

tail are shown.
293
packing density in the original layer adsorbed from dilute solution. The rms
thickness of the adsorbed layer is one measure of the phenomenon, another being
the distance in the z-direction, zmax, over which the polymer concentration is
measurably higher than the bulk concentration, φ > φb. For the systems studied
by Cosgrove et al., zmax = 24 nm was reported. As shown in Figure 74, all other
parameters being the same, the magnitude of zmax very much depends on the
polymer molecular weight.
Israelachvili et al. [1984] reported that when two saturated layers of PS on
mica approach each other, starting at a characteristic distance, zc, they attract
each other. The experiment was conducted in a cyclohexane solution of PS, near
the Θ-condition using the surface force analyser (SFA; see Figure 75(a)) designed
and originally built by Israelachvili in 1978. The distance zc = 60 to 120 nm
depended on the PS molecular weight and the thermodynamic miscibility. The
results were well reproduced in two different laboratories.
3.1.7.3 Nanoscale Rheology

In the layer adjacent to the clay surface the adsorbed molecules have a tendency
to be strongly adsorbed [Israelachvili, 1985; Horn and Israelachvili, 1998]. This
solid-like behaviour of the first z = 2-9 nm thick surface layer is followed by
another one, in which the viscosity progressively decreases in the z-direction,
finally to reach the level of the bulk solution viscosity at z ≅ 120 nm. The force
measurements for PDMS squeezed between two mica plates showed a solid-like
behaviour at a distance of about 4 nm, and exponentially decreasing viscosity
toward the bulk value at a distance of about 17 nm. For the measurements the
Israelachvili’s surface force balance was modified to impose either a steady-state
or dynamic shearing (see Figure 75).
Figure 74 Concentration profiles of adsorbed PEG on deuterated PS latex

particles. Data [Cosgrove et al., 1987].
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Thermodynamics
Figure 75(a) The surface force analyser (SFA)

(a) Reprinted from Intermolecular and Surface Forces, J. Israelachvili.
Copyright 1992, with permission from Elsevier.
Figure 75(b) The SFA was used to measure the viscosity of adsorbed PS-X from a
toluene solution. The results indicate a solid-like behaviour for the first adsorbed
layer: 2z < 220 ± 10 nm [Klein et al., 1993]. See text.
(b) Reprinted with permission from [Klein et al., 1993].
Copyright 1993 American Chemical Society.
295
Confirming the earlier observations, Klein et al. [1993] reported that non-
functionalised anionic PS poorly adsorbs from dilute toluene solution onto a
mica surface. The measurements gave the correct magnitude of the solution
viscosity within a few nanometres from the surface. The situation was dramatically
different when the PS chains were terminated with the zwitterionic group,
-(CH3)2N+-(CH2)3SO3–, giving ammonium-terminated PS-X. The molecular weight
of PS-X was Mw = 375 kg/mol, Mw/Mn = 1.03 and the radius of gyration in
toluene, Rg = 57.5 nm. Figure 75(b) also shows variation of the ‘effective mobility’
parameter, G, in the z-direction, thus orthogonal to the mica surface. The ‘effective
mobility’ parameter was defined as:
( Ao / A) − 1 = 2( z − z H ) / ηo
2
G ≡ 6πR2 ω / K (73)
where R is the mean radius of curvature of the mica sheets, K is the spring constant,
ω is the frequency, A and Ao are amplitudes of oscillation, z is the distance from
the mica surface and zH is its value (known as the hydrodynamic thickness) at
which the extrapolated value G = 0, and ηo is the zero-shear viscosity of the bulk
liquid.
With the low grafting density (mean spacing between attached chains of s =
14.5 ± 1.5 nm) the hydrodynamic thickness nearly doubles the radius of gyration.
Furthermore, within the first layer from the mica surface (110 nm or so thick)
the segmental mobility of PS macromolecules is practically zero, indicating a
solid-like behaviour of the adsorbed chains.
More recently, the surface force apparatus was redesigned and the
nanorheological measurements were carried out on undiluted polybutadiene (PBD;
Mw = 6.95 kg/mol; the entanglement molecular weight, Me = 1.85) [Luengo et
al., 1997]. The initial measurements of the normal forces at very slow approach
(2-3 min per point) indicated the presence of two regions: (1) a steeply repulsive
force with an incompressible ‘hard wall’ at zhw ≅ 5 nm of solid-like PBD adsorbed
on the mica surface, and a roughly exponential decay at larger distances. The
exponentially decaying region had a decay length of about 3.5 nm, which is close
to the unperturbed radius of gyration, Rg = 3 nm. These repulsive forces indicate
strong binding of polymer to the surface, at least over the time scales of the force
runs (1-2 h), and an immobilised layer of thickness of about 1.5 Rg per surface.
The chain conformations in such confined surface layers may be in the glassy or
rubbery state.
Next, the dynamic oscillatory measurements were carried out at strains γ < 30%,
frequency, ν (Hz) = 0.03 to 80 and with the separation distance, 2z = 10 to
250 nm. As the distance between two mica sheets decreased, three regions of the
dynamic behaviour could be distinguished: (1) bulk, (2) intermediate, and (3)
tribological. Figure 76 and Figure 77 present results of these measurements.
(1) Bulk: For 2z > 200 nm the phase angle (between strain and stress signals) δ ≈ π/2,
and the measured storage and loss shear moduli (G´ and G´´, respectively)
followed the bulk behaviour.
(2) Intermediate: At smaller z-gaps, δ < π/2 while the values of the shear moduli
were higher, showing an ‘elastomeric-like’ plateau indicating a 3D structure.
(3) Tribological: At the smallest gaps, 2z ≤ 12 nm, δ = 0, or a Hookean-type
response of an elastic body was obtained. On the flow curve (log viscosity
versus log deformation rate) the data followed a straight line with the slope
= –1, i.e., η ∝ 1 / γ˙ ; or : G ′ ∝ ν 2 and G ′′ ∝ ν where ν is the radial frequency.
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Thermodynamics
Figure 76 Effect of surface separation (distance D = 2z) on the storage (G´) and
loss (G´´) moduli of PBD at T = 25 °C and frequency n = 13 Hz. Data [Luengo et
al., 1997].
Figure 77 Effect of frequency on the shear moduli for PBD at T = 25 °C,

D = 2z = 10, 30, 180 and 250 nm [Luengo et al., 1997]
Copyright 1997 American Chemical Society.
297
The authors also reported the presence of normal stresses during the steady-
state shearing. Caused by them, initially the gap between mica sheets would
increase toward an equilibrium separation, to return to the original separation in
about one minute after stopping. The effect depended on the initial separation
and the shear rate. Since a similar behaviour has been observed for ‘brush’ layers
of zwitterion-terminated PS end-grafted to mica in toluene, the inference is that
PBD coils are effectively bound to the surfaces not by ionic but van der Waals
forces.
It should be stressed that such behaviour is not limited to macromolecules.
Low molecular weight organic solvents having either spherical or short-chain
molecules (e.g., alkanes, octamethyl-cyclotetrasiloxane, oligomers, etc.) behaved
similarly under confinement [Gee and Israelachvili, 1990; Granick, 1991; Hu
and Granick, 1992]. For example, when dodecane was confined to a diminishing
gap from ca. 5 to 2.8 nm it underwent an abrupt transition (similar to
crystallisation) to a solid-like state. Virtually all confined liquids solidified on the
mica surface. Since the process is rate-dependent (time scale ranges from minutes
to hours), the thickness of the solidified layer varied from two molecular layers
up. In some cases, with increasing confinement some liquids showed a smooth
increase of viscosity by up to 7 orders of magnitude. For either of these two types
of low molecular weight liquids the layer thickness within which the viscosity
was above that in the bulk was quite large.
3.1.7.4 Molecular Modelling of Nanoconfined Molecules (Intercalation)

The behaviour of molecules in the direct proximity of a smooth solid surface has
been studied for a number of years. The research has been motivated not only by
intellectual curiosity, but also by practical concerns in geology, biology, pharmacy,
etc. Surface force measurements, surface force microscopy, surface tunnelling
microscopy, X-ray or neutron scattering and other modern methods have replaced
the classical measurements of the adsorption isotherms. However, the biggest
progress in understanding the solid/liquid interaction has been gained from
computer simulation techniques, using Monte Carlo (MC) or molecular dynamic
(MD) procedures. This work is of particular interest to the CPNC technology as
in these materials the specific surface area, A(MMT) ≅ 800 m2/g, has a strong
multiplying effect, even at low clay loading. As it was discussed in the preceding
parts, molecules (short chains as well as macromolecules) strongly adsorb on the
crystalline surface either from solution or from melt. While the solid-like behaviour
extends only to 2 to 9 nm, the reduced mobility may extend to over 100 nm.
Considering that the thickness of a MMT platelet is 0.96 nm, even the minimum
level of immobilisation has a large multiplying effect on the reinforcing solid
content.
Two excellent overviews on the molecular modelling of adsorption and
ordering at solid interfaces are available [Hentschke, 1997; Binder et al., 2004].
The former author discusses both aspects of adsorption, chemosorption involving
direct chemical bonding to substrate and physicsorption, involving repulsive,
dispersive, multipole and induced interactions. Several examples of good
agreement between the computational and experimental data are shown. By
contrast the approach of Binder et al. is more pedagogical – a tutorial introduction
to the techniques and the basic algorithms of MD. As an example, the authors
computed self-diffusion constants, viscosity, and thermal conductivity of molten
SiO2, as well as vitrification – a non-equilibrium behaviour.
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Thermodynamics
Computations using MC or MD methods, as well as various models have

shown that macromolecules near solid surfaces are greatly affected – their
molecular arrangements, conformations and dynamics are strongly perturbed
with respect to the isotropic bulk [Brown et al., 2003]. Thus, the surface layers
in contact with a solid are densely packed with chain segments. The ordered
layers extend into the liquid phase for two to three times the transverse diameter
of the macromolecular chain. The surface also distorts the Gaussian distribution
of chain segments to a length of about the radius of gyration of the polymer. In
consequence, the chains whose centre of mass is close to the surface are flattened
with a substantial fraction of segments forming the first densely packed layers.
Furthermore, the diffusivity is non-isotropic – hindered in the vertical z-direction
and enhanced in the planar xy-direction.
MC simulations are mostly carried out on a lattice. While the model greatly
reduces the computing time, it is not totally realistic. The simulations have been
limited to systems with polymeric chains represented as random, self-avoiding
walks on simple lattices. The computations have been used for clarification of
specific aspects, for indicating a solution to specific problems. However, the lattice
models are not suitable for studies of packing and ordering. For this purpose
out-of-lattice models are more realistic [Binder, 1995].
MD simulations were used to study the static and dynamic properties of 2:1
layered silicates (CEC = 0.8, 1.0 and 1.5 meq/g for two MMT clays and a hectorite,
respectively) intercalated with alkyl-ammonium ion, having 6 to 18 -CH2- groups
[Hackett et al., 1998]. The results indicated that within the gallery, the alkyl
chains show strong layering tendencies. Shorter alkyl chains form stable
‘monolayers’ with d001 = 1.32 nm. The space between the clay surface oxygen
atoms is about equal to the diameter of a single -CH2- group. As the alkyl chain
length increases, a bilayer (d001 = 1.8 nm) and trilayer (d001 = 2.27 nm) disordered,
intertwined structure was predicted. For most bilayer configurations, nearly half
of the -CH2- groups are in the layer opposite the grafted ammonium group of
that chain. In a trilayer configuration, -CH2- groups tend to jump to the middle
layer, but few to the layer opposite to the grafted chain end. The trans-gauche
conformer ratios as well as the trans-gauche transition rates were computed. The
data were found to agree with FTIR observations by Vaia et al. [1994]. Thus,
within the interlamellar galleries of alkyl ammonium intercalated clay the alkyls
show dual structure – crystal-like for the surface-bonded trans-trans part and
disordered, liquid-like away from the surface.
According to a terse announcement, Amcol International developed a computer
model that predicts the type of organoclay structure that will form with a given
intercalant [Beall, 1999]. The model is reported to quantitatively predict the
d001-spacings. It may also be used to compute the energetics of exfoliation by a
polymer to form a CPNC with ionic or ion-dipole bonding. As an example, the
predicted versus experimental d001 spacing of MMT was given. The values
reproduced in Table 41 have a standard deviation of ± 0.06 nm.
Molecular modelling has also been used to examine the validity of several
theoretical assumptions, confronting them with directly performed numerical
‘experiments’. In 2000 Sumpter et al. [2000] used MD to simulate polymer
nanoparticles comprising up to 300,000 atoms, with a variety of chain lengths.
The results showed that the ratio of surface atoms to the total number of atoms
for the nanoparticles is very large and the surface effects are responsible for the
properties of CPNC being so different from those of the bulk polymer.
299
Table 41 Comparison between MD-computed and XRD-measured

interlayer spacing, d001 ± 0.06 nm, for MMT-intercalant systems
[Beall, 1999]
Intercalant Computed d001 Measured d001 Δd001 (nm)
(nm) (nm)
(None) 0.91 0.96 0.06
Water 1.22 1.26 0.04
Caprolactam 1.61 1.68 0.07
Butyrolactam 1.82 1.90 0.08
2-Pyrrolidone 1.90 1.90 0.00
N-Ethyl hydroxy-pyrrolidone 2.00 2.00 0.00
Dodecyl pyrrolidone 4.50 4.40 -0.10
Monostearyl 1.73 1.79 0.06
Glycerol 3.84 3.94 0.10
The dynamics of the organic phase were studied using NMR surface-sensitive
cross polarisation and bulk-sensitive spin-echo experiments. Synthetic, Fe3+-free
fluorohectorite (FH) was intercalated with ODA, and then melt-annealed with
PS under static conditions [Zax et al., 2000]. Within the gallery the polymer
constituted 68 wt% (ODA the rest). The molecular dynamics simulation suggested
the presence of a symmetrical five-layer structure of the organic phase. Thus,
near the surface there was a preponderance of phenyl groups, next the backbone
carbons intermixed with the alkyl groups. The highest probability of finding the
intercalant carbon was within the central layer. The NMR results showed that
the chain segments (both phenyl and -CH2- groups) that interacted with the surface
were dynamically inhibited. By contrast, within the central layers the segments
were more mobile than in the bulk at comparable temperature. The transition
from the glassy to molten state took place over a wide temperature range – starting
at lower T and ending higher than for the bulk PS. Furthermore, by contrast
with the bulk behaviour, the PS inside the interlamellar gallery space did not
show the customary, isotropic molten phase behaviour.
Anastasiadis et al. [2000] used dielectric spectroscopy to study the segmental
dynamics of 1.5 to 2.0 nm thick polymer film confined between clay platelets in
a nanocomposite. For the study hectorite and MMT were intercalated with
dimethyl-dioctadecyl-ammonium bromide (2M2ODA). Mixing the dry
organosilicate with up to 30 wt% of poly(methyl-phenyl siloxane) (PMPS,
Mw = 2.6 kg/mol, Mw/Mn = 1.2) resulted in formation of h = 1.5 to 2 nm thick
polymeric films inbetween the organically modified silicates. The PMPS segmental
motion is dielectrically active. Three processes were detected: (1) slow, resembling
the one for bulk-PMPS; (2) intermediate, possibly related to orientational motions
of the intercalant; and (3) fast due to the confined PMPS.
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Thermodynamics
Measuring the dielectric spectra of PMPS with 2M2ODA eliminated the

possibility that the fast relaxation was due to the presence of intercalant. The
other possible mechanisms include the restriction placed by the interlayer spacing
on the cooperative volume. The effective confinement of the polymer chain was
of the order of a few statistical segment lengths of PMPS. The effect of confinement
leads to the local reorientation of macromolecules which in turn changes the
local dynamics, evidenced by the presence of a new faster mode than that in the
bulk polymer with weaker temperature dependence. Simulations showed that
chains adopt a preferentially parallel configuration near a wall with oscillations
in the monomer density profile. These lead to a dynamic anisotropy with enhanced
parallel and reduced perpendicular monomeric mobility extending over distances.
Under severe confinement this interphase is anticipated to extend over the whole
film thus leading to fast relaxation.
Interesting MD studies were carried out by Yu et al. [2000b]. For over 60 years
methylene blue (MB) has been used to measure clay surface area and CEC. The
authors computed adsorption of MB on a model beidellite, MMT and muscovite
mica, in the presence or absence of water. A variety of configurations, including
single and double layers, parallel or inclined to the basal surface were found in
agreement with the XRD results. The MD computations indicated that this
traditional method of clay characterisation has hidden dangers. As far as the
CPNC technology is concerned these MD simulations demonstrated the
possibilities of formation of diverse structures, dependent on the type of clay,
intercalant loading, and possible contamination by other substances (e.g.,
moisture).
Vacatello [2001a] carried out MC simulations for dense polymer melts with
solid, spherical nanoparticles. The model incorporated off-lattice approximation
and conformational distribution of the simulated chains, similar to that of real
polymers. The results showed that at the interface the polymer segments are
densely packed in the form of ordered shells around the nanoparticles, analogous
to the layer formation near a planar solid surface. The thickness of the shells was
approximately twice the transverse diameter of the polymer isodiametrical (to
occupy a single lattice site) segments. The size of these (adopted after Flory et al.
[1984]) was taken to be equal to about 3.5 -CH2- units hence having a diameter
of ca. 0.45 nm. The nanoparticles behaved as highly functional physical crosslinks,
reducing mobility of the polymer chains. Since the effect was related to specific
surface area, it increased with 1/R2, where R is the radius of the particle.
Furthermore, the conformational distribution of the polymer was perturbed by
the presence of these solid nanoparticles. Thus, for example, the average dimension
of chain segments was reduced, the polymer chains were either totally contained
within the interface shell of a single particle or they formed bridges connecting
different particles. Some macromolecules visited several nanoparticle shells, and
each particle was in contact with many different polymer chains.
These calculations simulate the structure and dynamics of a polymer/solid
surface system well. The results, determined by topology and entropy, are
applicable to diverse situations, including clay intercalation. The presence of
preferential interactions between polymer and solid should not significantly change
the computed structure, the order of the interface shells and the conformations
of the polymer chains. Obviously, since so far computations have been carried
out for binary clay/polymer systems, the presence of a third component will affect
the structure. This would be expected for clays modified with quaternary onium
301
ions having more than one type of substituent groups. However, the overall image
that emerges from these models is expected to remain intact: reduced segmental
mobility near the high-energy clay surface, increasing towards the characteristic
bulk melt mobility at a distance of ca. 100 nm.
Manias and Kuppa [2002] provided a short topical review, focusing on the
simulation of structure and dynamics of PS macromolecules in slits. The MD results
were compared to experimental results for CPNC containing onium-modified
fluorohectorite dispersed in a PS matrix. Reasonable agreement was found.
3.1.8 Kinetics of Polymer Intercalation

The term ‘kinetics of polymer intercalation’ has several meanings. To theoreticians
considering a model sandwich in molten polymer ‘bath’ it describes how fast the
two platelets will move apart under the influence of the matrix polymer diffusing
into the interlamellar gallery. To an academic researcher investigating diverse
aspects of intercalation/exfoliation (viz. effects of intercalant, type of clay,
molecular parameters of the matrix polymer, processing conditions, etc.) under
static conditions, it may mean the rate with which the position of the XRD peak
is displaced. To most industrial researchers the term immediately conjures image
of a compounding line – will the diffusion be fast enough to engender exfoliation
during the available residence time?
Evidently the three cases are related, but there is a level of increasing
complications. The model sandwich is the simplest case. The static intercalation
is complicated by the presence of stacks of organoclay platelets. The stacks have
different number of platelets, up to 300 or so. While intercalation of the external
layers may resemble that of the model sandwich, the internal layers will see a
hindered process all the way to the centre. The simplest analogy would be a
stack of cards subjected to simultaneous separation from the edges by balls having
larger diameter than the thickness of the card. The process would lead to
progressive bending of the cards from the centre toward the margin, requiring
extra energy. Melt compounding in an extruder is further complicated by the
presence of intricate stress fields that are expected to accelerate the static
intercalation process, but at the same time may cause attrition and reaggregation
under compressive stresses.
3.1.8.1 Macromolecular Diffusion

As was mentioned in Section 3.1.3, diffusion of a polymer into the interlamellar
gallery very much depends on the magnitude of the driving thermodynamic forces.
Considering the results of the equilibrium thermodynamic computations one must
realise that owing to the loss of entropy the diffusion must involve enthalpic
interactions, hence it is not of the entropy-driven self-diffusion type. The required
energetic interactions may take place between the polymer and either intercalant
(χap), or clay (χsp) or both. For χap < 0 the polymer diffuses into the energetically
favourable gallery and it interacts with the two intercalant layers, which could
lead to a kinetically trapped intercalated state. If χap < 0 leads to the prediction of
kinetically trapped intercalation, then a solution may be that reverse magnitude,
χap ≥ 0, is needed. However, the SCF calculations indicated that when polymer
and organoclay are immiscible the expansion of galleries by polymer diffusion
would not take place. An elegant solution to the problem is to use a mixture of
functionalised and non-functionalised polymers, where the end-functionalised
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Thermodynamics
macromolecules strongly interact with clay, i.e., χsp << 0. The tails of these
compatibilising macromolecules should not favourably interact with intercalant
chains, i.e., χap ≥ 0, but be miscible with the matrix polymer. The kinetics of
intercalation for this case depend on the system (magnitude of interacting energies,
intercalant density and structure) as well as on the molecular weight of the
diffusing macromolecules [Balazs et al., 1998].
Diffusion is defined as a change of the centre-of-mass position of a
macromolecule (rCM) over time that is significantly longer than that required for
the configurational rearrangements. The simplest case is entropy-driven diffusion
of a molecule in a background of identical molecules – self-diffusion, Ds. When
the background molecules are not identical the process is called tracer diffusion,
D*. When the diffusion takes place in a mixture of two species, the mutual
diffusion coefficient is given by Fick’s law, as a ratio of the flux (J) to the
concentration gradient (∇c): DM = –J / ∇c. In the entangled melts the diffusion is
slow, with Ds = 10-10 to 10-16 m2/s, thus 1 h diffusion results in the displacement:
ΔrCM = 6tDs = 1.5 mm to 1.5 μm, respectively [Kausch and Tirrell, 1989].
The MW-dependence of the diffusion coefficient can be calculated from the
Rouse beads-and-springs model of polymeric chains as DRouse = (kBT/ζ)/N, where
ζ is the friction coefficient and N is the number of beads (proportional to MW),
and the longest relaxation time, τRouse ∝ N2. The Rouse model is adequate for Ds
and D* of low molecular weight species. For high molecular weight melts Doi-
Edwards reptation model still uses Rouse kinetics within the confining tube, but
to escape from the tube it must move over its primitive path:
⎧ D ∝ 1 / M for M ≤ Me
Dreptation = (4 / 15)( Me / M ) DRouse ⎨ s (74)
⎩ Ds ∝ 1 / M for M > Me
2
The prediction of the Doi-Edwards theory was experimentally confirmed, e.g.,

by Klein et al. [1983] who showed that for linear PBD for logDs versus logMw,
the slope: n = –1.95 ± 0.1. Similar values were reported for other polymers, viz.
for PE and PS [Fleischer, 1987]. A wider range of the slope values, n = –1.66 to –2.25
was reported by von Meerwall [1983].
In the case of mutual diffusion of polymer M in a matrix of polymer P with
energetic interaction between the two species, the chemical potential and the
concentration gradient control the process. Thus, DM contains terms related to
the binary interaction coefficient, χ12 ≤ 0, and the volume fraction of the
components, φ [Brochard et al., 1983]:
( )
DM = φ (1 − φ ) 2 χ12 Me / M DRouse (75)
The dependence indicates that while DM is a function of other variables, the
MW-dependence is stronger than in the self-diffusion case. The mutual diffusion
is related to the molecular weight of the diffusing molecules, but not of the
surrounding matrix, P. This conclusion originates from the assumption that the
process is reptation-controlled and at large values of matrix molecular weights:
P > 2Pe the reptation tube is independent of P. The relation is limited to miscible
systems, χ12 ≤ 0, since when the interaction coefficient is positive the system
phase separates and mutual diffusion does not take place.
When the molecular weight P < Pe the tube undergoes continuous renewal –
the surrounding molecules are releasing the confinement and rebuilding it. Within
303
this region there is a strong dependence of DM on P-a, with a = 2.5 or 3.0, dependent
on the assumption. At a still lower range of non-entangled matrix, P << Pe, a = 1.
The derived relationships are based on the mean-field approach, where each
statistical element within either the diffusing or surrounding chain has the same,
average character. In consequence, these relationships are well applicable to
intercalation where the polymeric chain diffusing into the gallery is composed of
statistical segments favourably interacting with either the intercalant segments
or the clay. Diffusion of the end-functionalised compatibiliser macromolecules
will require further considerations.
3.1.8.2 Stationary Intercalation

Vaia et al. [1995b] studied the kinetics of stationary melt intercalation. The
organoclay was synthetic fluorohectorite (FH), ion exchanged with octadecyl
ammonium (ODA) or MMT intercalated with dimethyl-dihydrogenated tallow
ammonium (2M2HTA; Claytone-40). Four narrow molecular weight PS resins
(Mw = 30, 68, 90 and 152 kg/mol) and one polydispersed commercial PS (Styron
685, Mw = 300, Mw/Mn = 2.6) were used. The organoclay and PS were ground to
the nominal size of 175 ± 25 μm. Melt intercalation was carried out using a pellet
(containing 25 mg of organoclay and 75 mg of PS) at T > Tg = 100 °C, under
vacuum. The kinetics of PS diffusion into the galleries was followed by XRD (in
situ and ex situ). For FH-ODA with PS-30 the measurements showed progressive
disappearance of the d001 = 2.13 nm peak and growth of another at d001 = 3.13 nm.
The XRD peak intensity, Iij,(of the i-th peak and the j-th substance) is
proportional to its weight fraction, wj:
w j (t ) = Iij (t )ρj μ T* / Kij ⎫⎪

⎬ ⇒ ζ(t ) ≡ w j (t ) / w j (∞) = Iij (t ) / Iij (∞) (76)
w j (∞) = Iij (∞)ρj μ T* / Kij ⎪⎭
where ρj, μ T* and Kij are, respectively, density, mass absorption coefficient and a
constant. The time-dependent quantity ζ(t) is a fraction of the melt-intercalated
organoclay. The kinetic curves, ζ(t) versus t, depend on composition (organoclay,
polymer, its Mw), temperature (T), pressure (P), etc. The kinetic of intercalation
curves were fitted to the relation derived by Breen et al., [1987] for vapour sorption
of MMT:
∞
ζ(t ) = 1 − ∑ (4 / α ) exp{− Da
m =1
2
m
−2
α m2 t } (77)
The latter authors modelled MMT as a cylinder of stacked circular disks, each of
the radius α. The diffusion was assumed Fickian, with the diffusivity constant,
D. Integration of the diffusion equation yields the above relation, where am is the
m-th positive root of the zero order Bassel function. The predicted dependence is
shown in Figure 78.
Fitting the kinetic data to Equations 76 and 77 Vaia et al., were able to determine
the effective diffusion rate parameter, D/a2. For the PS30/FH-ODA system the
temperature dependence was of the Fulcher-type: log(D/a2) = ao – a1/(T – T∞),
where a1 = 604 ± 40 K and T∞ = 322 K. For the series of narrow molecular
weight distribution (MWD) PS the data followed Equation 74. In Figure 79 the
self-diffusion data extracted from these measurements (FH-ODA with
monodispersed PS resins) as well as for PS fractions [Fleischer, 1987; Antonietti
304
Thermodynamics
Figure 78 Kinetics of melt intercalation under static conditions displayed as a

change of the fraction of melt-intercalated organoclay, ζ(t), with diffusion time.
The Breen et al., function for D/a2 values from 0.002 to 0.03.
Figure 79 Molecular weight dependence of the effective diffusion coefficient, D/a2,

for PS at 180 °C and for the self-diffusion coefficient of monodispersed PS resins
with FH-ODA. After [Fleischer, 1987; Antonietti and Sillescu, 1985] – see text.
305
and Sillescu, 1985] are plotted versus Mw. The solid lines are drawn with the
theoretical slope of –2, predicted by the reptation theory. The coefficient governing
the kinetic diffusion into galleries, Da-2, is ten decades larger than Ds for PS.
Assuming that the diffusion into the galleries is the same as in the case of self-
diffusion, one obtains for the apparent radius of the FH platelets a = 214 nm.
This seems to be the right order of magnitude. The reasonableness of this quantity
implies that diffusion into a gallery with, h = 1.2 to 2.2 nm, is not particularly
affected by the narrow slit geometry. This is striking, since the unperturbed radius
1 /2
of gyration of the PS samples used was rΘ2 = 5 to 15 nm (for Mw = 30 to
300 kg/mol) hence significantly larger than h. Thus PS macromolecules do not
diffuse as a Gaussian coil but as extended macromolecules with chain diameter
controlled by the segmental motion. According to Flory, the average diameter of
a paraffinic chain is equal to about 3.5 -CH2- units, thus having the diameter of
ca. 0.45 nm, for PS this magnitude is about twice as large, ca. 0.90 to 0.95 nm.
In another publication [Vaia et al., 1996] melt intercalation was carried out
on synthetic FH pre-intercalated with either dodecyl (DDA) or octadecyl (ODA)
ammonium ion. Two narrow molecular weight PS resins, with Mw = 30 and
400 kg/mol, and one poly-3-bromo-styrene (PS3Br) PS with Mw = 55 and Mw/Mn = 2
were used. XRD studies showed that in contrast with intercalated PS30/FH-DDA,
the PS3Br/FH-DDA system was exfoliated. Clearly, the polar Br-group in the
para position increased the polymer-silicate interactions to the extent that
exfoliation was possible. The exfoliation was partially confirmed by TEM.
Stacking of 5 to 20 layers with interlayer spacings of between 2 and 4 nm and the
presence of the original crystallites or the primary particle were discernible.
Individual silicate layers were observed near the edge whereas small coherent
layer packets separated by polymer-filled gaps are prevalent toward the interior
of the primary particle. The larger expansion of the gallery height and disordered
structure were apparently responsible for the disappearance of the XRD peak.
The heterogeneity of the CPNC structure, stacking in the primary particle
implies that the process is more complex than simple sequential separation of
individual layers starting from the surface of the primary particle. Long-range
forces (e.g., stresses associated with gallery expansion and layer bending) will
maintain stacking of an optimal size. Layer-by-layer delamination may take place
near the edge of the primary particle but it is unlikely in the central part. The
increased polarity of PS3Br (with respect to PS) will interact more with the polar
FH surface. As a result, the frictional coefficient, associated with polymer diffusion
into the gallery, should increase slowing the melt intercalation kinetics.
Qualitatively, these effects were observed.
Chen et al. [2003] followed the procedure used by Vaia et al. However, in this
case poly(styrene-b-isoprene) block copolymers (PS-b-PI) diffused into
interlamellar galleries of synthetic fluorohectorite, pre-intercalated with ODA.
Intercalation at T = 100 to 170 °C was followed by XRD for up to 70 h. The
copolymer diffused similarly on either side of the order/disorder transition
temperature. The intercalation rate decreased as the PS block increased.
3.1.8.3 Simulation of Melt Intercalation Kinetics

Melt intercalation can be visualised as a flow of molten polymer into narrow
slits. As discussed before, the driving force for the process is not the configurational
entropy, but enthalpic interactions with either low molecular weight intercalant,
306
Thermodynamics
or (preferably) with clay. In other words, it is the gradient of chemical potential

that drives the diffusion. In the presence of flow, there is also frictional resistance
retarding the process. Thus, the flux of melt from the molten matrix reservoir
into the gallery in the x-direction has diffusional and viscous components [Mason
and Viehland, 1978]:
c( x) Do ∂μ c( x) Bo ∂p
−J = + (78)
k B T ∂x η ∂x
where c(x) is molecular concentration in x-direction of flow, Do is the diffusion
coefficient, μ is the chemical potential, Bo ≅ h2/12 is a geometric factor, η is
viscosity and p is mean value of the driving pressure in the x-direction. From the
Gibbs-Duhem equation and Fick’s law this dependence can be used to express
the effective transport diffusion coefficient as [Nicholson et al., 1996]:
∂μ ⎡ Do c( x ) Bo ⎤ ⎛ ∂μ ⎞ ⎛ Do ⎞ ⎡ c( x )h2 k B T ⎤
Dtrans = ⎢ + ⎥ ⎜ ⎟⎜ ⎟ ⎢1 + ⎥ (79)
∂ ln c( x ) ⎣ k B T η ⎦ ⎝ ∂ ln c( x ) ⎠ ⎝ k B T ⎠ ⎢⎣ 12Doη ⎥⎦
For the non-entangled melts, the Stokes equation holds, hence Doη/kBT = 1/3πa
(where a is segmental diameter). Thus, the diffusional component dominates for
small slit height, h, and the viscous one when the gap is wide.
The kinetics of melt intercalation by polymer diffusing into a clay slit under
stationary (no mixing) conditions was modelled using MD [Lee et al., 1998a;
1999; 2000; Baljon, 1999]. The simulation model was a face centred cubic lattice
oriented with planes parallel to the xy plane of the clay platelet. On each side of
the lattice stack there was a reservoir of molten polymer, equilibrated at constant
T and P. To start the process, two central lattice layers were removed to form a
rectangular slit into which the polymer could diffuse. The size of the slit was
fixed, non-expanding by the diffusion process. The system was strictly binary,
without a low molecular weight intercalant. The polymer molecules were
represented by anharmonic bead-spring chains. Polymer beads, separated by a
distance r, interacted with the interaction energy ε according to the truncated,
repulsive Lennard-Jones potential for r ≤ rc ≡ σ21/6. The finite extendable non-
linear elastic (FENE) model was used to express the bonding potential between
nearest-neighbour beads along the chain, separated by distance r. The bead-lattice
potential with the interaction energy εbl was given by truncated, attractive Lennard-
Jones potential at rc = 2.2σ. Thus, the bead-bead interactions were either zero or
repulsive at short distance, while the bead lattice was attractive. The simulations
were performed at constant T* =kBT/ε = 1, assuming that the ratio of the
interaction parameters, ε/εbl = 1, 2 or 3 (in latter publications the ratio went up
to 10), and the random force in y and z directions obeys the Gaussian statistics.
An analytical model for diffusion of polymer into a slit gallery of length L in
the x-direction was derived in the form of Laplace transforms:
sinh Ψ
ζˆ (s) =
[
sΨ cosh Ψ + (din / Dout )1 / 2 sinh Ψ ] (80)
Ψ ≡ sL / 4 Din
2
where Din and Dout are diffusion coefficients inside and outside the slit. Since the
Laplace transform is a function of sL2 divided by s, the intercalation kinetics,
307
ζ(t), depend on tL-2. The superposability of the kinetic curves computed for
different values of L would provide evidence that melt intercalation is a diffusion-
controlled process.
The computations were performed for L = 43σ to 341σ. The results ζ(t) versus
t/L2 indeed superposed onto a single curve. Assuming that Dout = ∞ the effective
diffusion coefficient, Din = Deff was calculated from Equation 80 by fitting the
dependence to the simulated kinetic curve. Excellent agreement between the
simulated data and the analytical prediction with the fitted value of Deff was
obtained.
It is important to note that as the interaction ratio, ε/εbl, increases the computed
kinetics slow down and the diffusion coefficient decreases. Since the diffusion
driving force is proportional to this ratio, crowding at the entry to the slit is
evidently slowing down the intercalation – the macromolecules want immediately
to interact with the slit walls instead of diffusing further into the gallery in a
more civil way. Crowding at the gap by macromolecules eager to interact with
slit surfaces also slows the intercalation process. As a result, the polymer
concentration decreases linearly in the x-direction and shows two local maxima
in the z-direction. While the x-gradient is a measure of the non-equilibrium aspect
of the process, the enhanced concentration of the interacting polymer segments
near the silicate wall is not.
Simulation was also carried out to determine the centre of mass diffusion of
polymeric chain within the reservoir. The computations determined that the
equilibrium, bulk self-diffusion coefficient, Ds = 0.006σ2/τ, but the effective
diffusion coefficient governing the intercalation Deff = 3σ2/τ, hence 500 times
larger. The authors argued that once the slit is open the process is no longer
governed by the equilibrium properties. Computations of the centre of mass
displacement of the 1st chain to enter the slit show that its diffusion coefficient is
comparable to Deff, while the macromolecules that follow diffuse more slowly.
Simulation of diffusion inside the gallery, in the y-direction gave very small values
– about 1/10 of the equilibrium Ds.
The amphiphilic intercalant may enhance the intercalation kinetics (relative
to the case of homopolymer intercalants) and form novel structures. Thus, in the
last publication of this series melt intercalation with symmetrical diblock
copolymer was simulated [Lee et al., 2000]. The model slit surfaces were assumed
grafted with low molecular weight intercalant. The system was maintained at
constant pressure to permit the slit to open as polymer intercalates. The kinetics
of intercalation were simulated for different values of surface-block-A and surface-
block-B interaction parameters. It was concluded that suitable diblock copolymers
might be used to intercalate clay.
Starting with the Landau and Lifshitz one-dimensional equation of motion,
Ginzburg et al. [2001] derived a simple relation that describes the dynamics of
melt intercalation. The derivation is based on a model, which assumes the presence
of ‘kinks’ – a sudden, local expansion of the interlayer spacing between two clay
platelets. Accordingly, intercalation is a process of localised excitations that move
the kink, opening the interlamellar space. The model stipulates that the kinks
originate in the interplay between the double-well potential for the clay-clay
long-range interaction, bending elasticity of the platelets, and sufficiently strong
external shear force.
308
Thermodynamics
3.1.9 Pressure-Volume-Temperature Dependence for CPNC

There are several reasons for the study of the pressure-volume-temperature (PVT)
properties of a condensed system. These are pertinent for materials processing –
the compressibility and the thermal expansion coefficients are required for the
modelling of flow through virtually any processing machine. However, there is a
stronger reason for these measurements – describing the experimental data by
means of an adequate theory, provides an insight into intermolecular attractions
and repulsions in a given system. Furthermore, a free volume parameter may be
extracted from the PVT data, and then used to predict dynamic and kinetic
properties, viz. flow, ageing, viscoelasticity. Finally, it is important to establish
the effects of additives (gaseous, liquid or solid!) on all these properties.
3.1.9.1 Equations of State (eos)

In his PhD thesis of 1873, van der Waals proposed the first equation of state (or eos).
The relation is usually written in terms of reduced variables (indicated by tilde):
( P + a / V )(V − b) = T / R
2
( )( )
or P˜ + 3 / V˜ 2 3V˜ − 1 = 8T˜
V˜ = V / V*; T˜ = T / T*; P˜ = P / P * (81)
V* = 3b = Vc ; T* = 8a / 27 Rb = Tc ; P* = a / 27b2 = Pc
Pc Vc / RTc = 3 / 8
Of interest to van der Waals were low molecular weight liquids with a well-
defined critical point – the coordinates of this point, Pc, Vc and Tc, were used as
the reducing parameters. For T = 0 the hard-core volume, Vo = b. van der Waals
considered that molecules move in ‘cells’ made by the surrounding molecules
with uniform potential. The volume, within which the centre of a molecule can
freely move, is what defines the free volume. The free volume fraction is usually
defined as: f = Vf /V = V – Vo/V, where Vf = V – Vo. Detailed methods of
computation of Vo from the chemical structure have been developed, viz. [Bondi,
1968; van Krevelen, 1993; Porter, 1995].
Several comprehensive reviews of the eos’s used for polymeric liquids have
been published. For example, Rodgers [1993] collected PVT data for 56 polymers
at P ≤ 200 MPa and melting T-range from 50 to 170 °C. The review presents
fundamentals of the theories and it evaluates fit to experimental data. Five
prominent eos were examined. These are listed in chronological order.
1. Flory-Orwoll-Vrij (FOV) [1964]:
˜ ˜ / T˜ = (1 − V˜ −1 / 3 ) −1 − 1 / VT
PV ˜˜
˜ ˜ ˜
V = V / V*; T = T / T*; P = P / P * (82)
V* = ρ ; T* = s*η* /(c* k B ); P* = c* k B T * / V *
*
3
where: ρ*, s*, η*, c* are respectively: the ‘hard-sphere’ radius, number of
contacts per segment, the segment-segment interaction energy, and the
coordination number (kB is the Boltzmann constant).
2. Simha-Somcynsky [1969] (S-S) – will be discussed in the next section.
3. Sanchez-Lacombe [1978] (S-L):
309
[ ]
˜ ˜ / T˜ = −V˜ ln(1 − ρ˜ ) + (1 − 1 / r )ρ˜ − 1 / TV
PV ˜˜
ρ˜ = 1 / V˜ = V * / V ; T˜ = T / T*; P˜ = P / P * (83)
where r = M w P * / RT * ρ*; T* = ε * / k B
where M w is the weight-average molecular weight, while ρ* is the
characteristic density parameter. The parameter r represents the number of
lattice sites occupied by the r-mer. Evidently, its presence in the eos negates
the principles of corresponding states – it can be recovered only for r → ∞.
4. Hartmann and Haque [1985] (H-H):
˜ ˜ 5 = T˜ 3 / 2 − ln V˜
PV
(84)
V˜ = V / V0 ; T˜ = T / T0 ; P˜ = P / B0
The characteristic pressure reducing parameter, B0, has been identified as the
isothermal bulk modulus extrapolated to T = 0 and P = 0.
5. Dee and Walsh [1988] (D-W):
( ) − (2 / T˜ )(1.2045V˜ )
−1
˜ ˜ / T˜ = 1 − 0.8909qV˜ −1 / 3
PV −2
− 1.011V˜ −4
(85)
q ≅ 1.07 ; V˜ = V / V*; T˜ = T / T*; P˜ = P / P *
Within the low-pressure region Rodgers found that all these five eos are adequate
– the worst performance was of S-L and the best of S-S theories. However, as the
pressure increased, FOV and S-L dependencies started to perform poorly, while
S-S and D-W continued to provide good description. Rodgers cited the following
deviations: for FOV ΔV × 104 = ± 22 (7), for S-L ΔV × 104 = ± 33 (10), for H-H
ΔV × 104 = ± 9 (6), for D-W ΔV × 104 = ± 6 (5), and for S-S ΔV × 104 = ± 7 (4).
These differences were computed for the full pressure range; the values in
parentheses are for the low pressure range, P ≤ 50 MPa.
3.1.9.2 Simha-Somcynsky (S-S) Equation of State

The Simha and Somcynsky [1969] (S-S) theory is based on the lattice-hole model
presented in Figure 80 for a binary mixture of two liquids with linear chain
molecules (A and B) and with holes or vacancies (V). The model assumes that
molecular segments occupy y-fraction of the lattice sites. The remaining part, h=
1 – y, is occupied by holes simulating the molecular disorder. The fraction h may
be viewed as a particular measure of free volume content. The placement of the
occupied and vacant sites is random. For a simple liquid (A = B) the configurational
thermodynamic properties, such as the PVT (eos) relations, or the cohesive energy
density, are characterised by three quantities: the maximum attraction energy,
ε*, between a pair of chain segments, the corresponding segmental repulsion
volume, v*, and the number 3c of volume dependent, external degrees of freedom.
In terms of these quantities and the number of segments per chain, s, the
characteristic pressure, temperature and volume parameters can be defined, viz.:
P* = qzε*/(sv*); T* = qzε*/Rc; V* = v*/Ms hence: P*V*/RT* = c/sMs(86)
with Ms the molar mass of the statistical segment, qz = s(z-2) + 2, the number of
interchain contacts in a lattice of coordination number z = 12, and R the gas
constant. The variables of state, P, T, V, are then scaled in terms of these. Since
the theory is based on the corresponding-states principles, these reduced variables
310
Thermodynamics
Figure 80 Simha-Somcynsky lattice-hole model for two constituent liquid

molecules (A and B) with vacancies (V). The energetic binary interaction
parameters are also shown [Simha et al., 2001].
define a universal, reduced P˜ − T˜ − V˜ surface for all liquids. In other words, they
generate master isotherms and isobars. Provided the theory is quantitatively
successful, a superposition of experimental and theoretical lines will yield the
scaling parameters and thus the material characteristic interaction parameters,
ε* and v*.
To derive the eos, S-S first calculated the partition function, Z, for all possible
numbers of arrangements of occupied sites and empty holes in a lattice with z
coordination number. The Helmholtz free energy is directly given as: F = -RT
lnZ. In reduced variables the obtained free energy function F̃ has the
form: F˜ = F˜ [V˜ , T˜ , h(V˜ , T˜ )] . Thus, in addition to the usual volume and temperature
dependence, F̃ contains the hole fraction h, which in turn must vary as: h = h(V˜ , T˜ ) .
This variation is obtained by minimising the free energy at a specified volume
and temperature, i.e.:
(∂F˜ / ∂V )V˜ , T˜ = 0 (87)
From the Helmholtz free energy the pressure is obtained as:
P˜ = −(∂F˜ / ∂V˜ )T˜ (88)
From the above relations the S-S eos is derived in the form of coupled equations:
˜ ˜ / T˜ = (1 − η)−1 + 2yQ2 (1.011Q2 − 1.2045) / T˜
PV (89)
3c[(η − 1 / 3) /(1 − η) − yQ (3.033Q − 2.409) / 6T˜ ] + (1 − s) − sln[(1 − y) / y] = 0 (90)
2 2
with Q = 1 /(yV˜ ) and η = 2-1/6yQ1/3. The two equations not only predict how the
specific volume varies with pressure and temperature, but at the same time how
the free volume parameter, h, changes with these. Of all the eos, only the one
derived by S-S explicitly gives the hole fraction, h = 1 – y, which is directly related
to the free volume fraction, f. Equations 89 and 90 provide a corresponding
states description of the PVT behaviour of any liquid. Once the four characteristic
311
parameters: P*, V*, T*, and 3c/s are known, the specific volume and all its
derivatives are known in the full range of P and T. For linear molecules the external
degrees of freedom are proportional to the number of segments: 3c = s +3. Thus,
for linear polymers, where s >> 3, the external degree of freedom: 3c/s ≅ 1; hence
for polymers, only three parameters: P*, V*, and T*, are required.
The S-S theory also provides a simple expression for the reduced cohesive
energy density (CED):
[
˜ = U˜ / V˜ = −( y / 2V˜ )( yV˜ )−2 2.409 − 1.001( yV˜ )−2
CED ] (91)
where U is the internal energy of the system – one of the intensive thermodynamic
quantities. From CED the solubility parameter can be calculated as
δ = CED = CED ˜ × P * . Accordingly, δ is also an intensive function of
independent variables: δ = δ(T, P), independent of other variables, viz. the type
of solvent used to dissolve a given polymer. Recent analysis of δ for 38 different
molten polymers shows that, in accord with van der Waals prediction, the product
˜ ˜ )1 / 2 is approximately constant, thus δ is proportional to polymer density,
δV ∝ (UV
ρ = 1/V, which in turn depends on T and P [Utracki and Simha, 2004; Utracki,
2004]. Comparison with the values listed in handbooks for δ indicate that these
are significantly lower than computed from the polymer melt properties. The
origin of this discrepancy has been traced to the free volume contribution – since
the experimental values for δ are determined in solution, the macromolecular
environment there (i.e., free volume) is equivalent to that found in molten polymer
at high temperature, viz. T ≅ Tg + 300. Considering that different polymers have
different compressibility and thermal expansion coefficients, the difference
between the solubility parameters of two liquids (supposedly related to their
miscibility) will change with T and P. Users beware!
The full range of the reduced independent variables of polymer melts was
calculated as [Utracki and Simha, 2001a]:
1.6 < 100 × T˜ < 7.1 and 0 < 100 × P˜ < 35 (92)
Owing to the overlapping properties of polymers, the range of variables in these
inequalities is much wider than that experienced by a single resin. Within these
limits the coupled eos in Equations 89 and 90 can be approximated by
polynomials. The goodness of fit was judged by considering the values of the
standard deviation (σ), the correlation coefficient squared (r2) and the coefficient
of determination (Cd). The reduced specific volume follows the dependence:
[ ( ) ]
ln V˜ = ao + a1 T˜ 3 / 2 + P˜ a2 + a3 + a4 P˜ + a5 P˜ 2 T˜ 2 (93)
The values of ai parameters and the statistics of fit are listed in Table 42.
Considering the value of the standard deviation (σ = ± 0.18%) the fit is considered
satisfactory.
The following expression well approximates the hole fraction:
( )
h V˜ , T˜ = ao + a1 / V˜ + a2 T˜ 3 / 2 + a3 / V˜ 2 + a4 T˜ 3 (94)
Again, the goodness of the fit can be judged by the parameter values listed in
Table 42. However, even with only three parameters (i.e., assuming that a3 = a4 = 0)
the standard deviation of σ = 0.55% was computed.
312
Thermodynamics
Table 42 Statistics of the polynomial data fit to S-S eos: V˜ = V(T,

˜ ˜ P)
˜
˜ ˜; Equation 93 and 94, respectively.
and h = h(V,T)
Data [Utracki and Simha, 2001a]
Parameters Values for log (V/V*) Values for h
a0 -0.10346 ± 0.00034 1.203 ± 0.020
a1 23.854 ± 0.032 -1.929 ± 0.047
a2 -0. 1320 ± 0. 0012 10.039 ± 0.249
a3 -333.7 ± 2.5 0.729 ± 0.026
a4 1032.5 ± 23.6 -218.42 ± 10.29
a5 -1329.9 ± 52.8 —
_ 0.00183 0.00253
r2 0.99973 0.99965
Cd 0.99967 0.99899
Comments Most errors at

V˜ ≤ 0.93
˜ -values computed from the S-S eos were

Furthermore, the scaled CED
approximated by:
˜ = ao + a1 / V˜ 2 + a2 T˜ + a3 / V˜ + a4 VT
CED ˜˜ (95)
The reduced solubility parameter, δ˜ = δ˜ (T˜ , P˜ ) was well approximated by:
( )
δ˜ = ao + a1 P˜ / T˜ + a2 + a3 P˜ + a4 P˜ 2 T˜ (96)
The numerical values of the fitting parameters for equations 95 and 96 are listed
in Table 43. Evidently, the polynomial expressions well approximate the eos
prediction, even with three parameters.
There are several practical advantages of these polynomial relationships. In
spite of their simple form they provide good approximation of thermodynamic
properties in the molten state within the full range of P and T. Their derivatives,
e.g., the thermal expansion coefficient and the compressibility factor:
α ≡ (∂ ln V / ∂T ) P−const and β ≡ (∂ ln V / ∂P)T =const
respectively, can easily be calculated for any temperature and pressure.
Furthermore, fitting Equation 93 to experimental data results in rapid
determination of the reducing parameters, P*, V* and T*. When highly accurate
values of these parameters is required (viz. for determining the binary interaction
parameters, ε* and v*), the latter values may be used as the initial estimates for
the iterative fitting of the data to the coupled Equations 89 and 90. This approach
greatly shortens the iteration process and provides highly reliable solutions.
313
Table 43 Algebraic representation of the reduced cohesive energy

˜ , and reduced solubility parameter, δ̃δ.
density, CED
Data [Utracki and Simha, 2001a]
Parameter ˜
Reduced CED Reduced δ̃δ
Version #1 Version #2 Version #1 Version #2
a0 0.1323 ± 0.0044 –1.053 ± 0.061 0.9505 ± 0.95788 ±
0.0013 0.00088
a1 0.5659 ± 0.0033 –0.592 ± 0.056 az –0.00085 ±
0.00005
a2 –0.8892 ± –4.97 ± 0.26 –4.782 ± 0.031 –5.108 ±
0.0340 0.020
a3 az 2.36 ± 0.12 6.091 ± 0.090 10.73 ± 0.16
a4 az 3.74 ± 0.24 az –13.20 ± 0.49
σ 0.00392 0.00189 0.00673 0.00289
r2 0.99996 0.999991 0.99993 0.99999

Cd 0.99876 0.999714 0.99153 0.99844
Comments Excellent fit Most errors at Good fit with 3 Most errors at
with 3 constants V˜ ≤ 0.95 constants P≅0
az = assumed zero
It is evident that the reducing parameters of the S-S eos, P*, V* and T* (or the
interaction parameters incorporated there) must depend on the polymer molecular
characteristics (its conformation, configuration, molecular weight, etc.) as well
as on the additives, present in all commercial polymers [Utracki, 2002b].
As an example Table 44 lists the values of the reducing parameters for several
PS resins. The molecular weight of resins marked Z (for Zoller) is Mw = 110 to
0.9 kg/mol. Nova PS1301 (Mw = 270 kg/mol) is a ‘crystal’ (transparent) PS for
extrusion, thus probably relatively free of additives. Dow 667 is an injection
moulding grade containing 2.5 wt% mineral oil. The other commercial resins,
BASF 1424 and Monsanto HH105, have unknown additives. The indicated
authors computed the last four sets of parameters from the same set of
experimental data (measured by Quach and Simha in 1971), but using different
procedures. Evidently, the characteristic parameters depend not only on polymer
MW and diverse additives, but also on the routine used to compute them, viz.
sequential or simultaneous, the criteria used for minimisation of deviations, etc.
In many cases, only a relative change of polymer specific volume is of interest
and the use of listed in the literature values of P*, V* and T* is acceptable. In
this case it is possible to compute the PVT surface and obtain all the derivative
properties (viz. thermal expansion coefficient, compressibility, etc.) using tabulated
parameters. When more fundamental information is required, repetitive tests of
a given resin must be conducted with precision ΔV < 0.2%.
314
Thermodynamics
Table 44 Interaction parameters computed for different PS resins

PS Resin P* T* V* Mo v* ε*
(MPa) (K) (ml/g) (g/mol) (ml/mol) (kJ/mol)
Z-110 738.7 11920 0.96310 46.49 44.78 33.07
Z-34 786.1 11836 0.96530 43.42 41.92 32.94
Z-9 794.5 11670 0.96920 42.74 41.42 32.87
Z-09 779.1 10504 0.98750 44.41 43.85 33.75
Nova PS1301 743.5 11723 0.95259 45.87 43.69 32.49
BASF 1424 813.4 11379 0.94770 40.98 38.83 31.53
HH105 811.1 11265 0.93390 41.21 38.49 31.22
Dow-667 774.0 11728 0.95021 44.19 41.99 32.50
Quach and 745.3 12680 0.95980 49.12 47.15 35.14

Simha [1971]
Utracki and 699.5 12684 0.96230 52.22 50.25 35.15

Simha [2001a]
Hartmann et 715.7 12791 0.96260 51.45 49.53 35.45

al., [1989]
Rodgers [1993] 715.9 12840 0.96340 51.59 49.70 35.58
Note: The first 8 sets of parameters in this table were computed by the author
(LAU)
3.1.9.3 Extension of S-S eos to Binary Miscible Systems

Extension of S-S theory to CPNC systems can be carried out in three logical
steps:
(1) Extension of the original theory for one-component liquids to two-component
miscible systems,
(2) Extension of the latter theory to suspensions of solid particles in polymeric
liquid and
(3) Development of a specific model for CPNC.
During the last 30-odd years S-S eos has been used to describe a variety of
equilibrium and non-equilibrium thermodynamic problems in single and
multicomponent systems, viz. solutions, blends, foams and composites. In this
section the use of S-S eos for bicomponent, miscible systems will be outlined. A
major assumption of these derivations is the mean-field approach – the miscible
components (e.g., polymer segments or solvent molecules) are randomly placed
on the lattice.
315
Jain and Simha [1980; 1984] demonstrated that for such binary mixtures the
S-S theory is directly applicable provided that the reducing and interaction
parameters are treated as averages. Thus, fitting Equations 89 and 90 to
experimental data yields the composition-dependent averages indicated by the
angular brackets, viz. X . Extension of the S-S theory has to account for the
presence of component-1 (mole fraction x1) and component-2 (x2 = 1 – x1):
( )
P * = qz ε * / s ν * ; T * = qz ε * / R c ; V * = ν * / Mo
P * V * / R T * = c / s 1 / Mo ( )( ) (97)
c = c1 x1 + c2 x2 ; s = s1 x1 + s2 x2
Mo = ( Mo1 s1 x1 + M02 s2 x2 ) / ( s1 x1 + s2 x2 )
Similarly, the interaction parameters ε* and v* are becoming compositional

averages over 11, 22 and 12 interactions. The interacting site fractions, X1 and
X2 = 1 – X1, are determined by the lattice interchain contact, zqi, and the mole
fractions xi, thus:
Xi = qi zxi / ∑ q zx i i (98)
where: zqi = si(z – 2) + 2 with z = 12. Then the averages <ε*> and <v*> are
related to the individual interactions as follows:
p
ε* ν* = X12 ε11ν11 + 2 X1 X2 ε12
* *p
ν12 + X22 ε 22
* *p *p
; p = 2, 4 (99)
The two values of p reflect the assumed Lennard-Jones 6-12 pair potential. The
two relations in Equation 99 have six parameters, four of which are accessible
from the PVT measurements of the neat components (i.e., polymer-1 and polymer-2),
thus the two cross-interaction parameters, ε12
*
and ν12
*
can be determined. Their
value may indicate attractive or repulsive cross-interactions, but as experience
with liquid mixtures showed, the strong attractive energetic interactions usually
lead to a smaller value of the volumetric interaction parameter. To facilitate
computations, Equation 99 can be transformed into:
2 Ξ4 Ξ2
ν* = × ν11
*2
; and ε * = 2 × ε11
*
Ξ2 Ξ4
⎛ ν * ⎞ ⎛ ε* ⎞
2
Ξ2 ≡ X12 + 2 X1 X2 e12 ν12

2
+ X22 e22 ν222 =⎜ * ⎟ ⎜ * ⎟ (100)
⎝ ν11 ⎠ ⎜⎝ ε11 ⎟
⎠
⎛ ν * ⎞ ⎛ ε* ⎞
4
Ξ4 ≡ X12 + 2 X1 X2 e12 ν12

4
+ X22 e22 ν422 =⎜ * ⎟ ⎜ * ⎟
⎝ ν11 ⎠ ⎜⎝ ε11 ⎟
⎠
with the following definitions:

e12 ≡ ε12
*
/ ε11
*
; e22 ≡ ε 22
*
/ ε11
*
; ν12 ≡ ν12
*
/ ν11
*
; ν 22 ≡ ν 22
*
/ ν11
*
;.
The outlined extension of the S-S theory to binary systems has been successful
in describing thermodynamics, e.g., phase equilibria, and solubility of gases [Xie
and Simha, 1997; Simha and Moulinié, 2000]. As shown in Figure 81 the
316
Thermodynamics
assumption of random mixing is also valid for miscible polymer blends of

polyphenylene ether (PPE) with PS [Utracki and Simha, 2001a].
Furthermore, the hole fraction, h, computed from PVT data was found to
correlate with the dynamic properties, e.g., flow of low molecular weight liquids
and their solutions, that of polymers, their blends and foamable compositions
[Utracki, 1986; Utracki and Simha, 2001b].
Thus, the random mixing assumption was proved adequate for describing
the compositional variation of PVT surfaces in a wide range of miscible, binary
liquids. Several sets of binary interaction parameters, ε12 *
, ν12
*
, were extracted
from the experimental data. Analysis indicates that they may be well approximated
by simple geometric (Berthelot’s) and algebraic (in radius) averages, respectively:
( )
1 /2
ε12
*
= δ e ε11
*
× ε 22
*
3 (101)
( )
⎡ * 1 /2
( )
1 /3 ⎤
ν12
*
= δ ν ⎢ ν11 + ν 22
*
⎥⎦/ 8
⎣
In these dependencies the two adjustable parameters are close to unity, δe, δv ~ 1
(maximum departure from unity was reported by Simha and Moulinié [2000] to
be ca. 13%). Note that the Berthelot’s geometric mean rule with δe = 1 has been
shown to be valid in many applications.
The next step is extension of this binary treatment to suspensions.
3.1.9.4 Extension of S-S eos to Suspensions

The key in extending the S-S multicomponent theory to suspensions is the
assumption that the solid particles can be treated as giant, rigid molecules, differing
Figure 81 Scaling volume, V*(ml/g) T*(k), and temperature parameters as

functions of composition (mol fraction) in PPE/PS blends: the correlation
coefficient, r, is also given [Utracki and Simha, 2001a].
Reproduced with permission, Copyright 2001 Wiley-VCH-Macromol.
317
from the matrix macromolecules by size and the interaction parameters. Both
components, the matrix and the solid particles, are placed on a lattice, assuming
that hard-core specific volumes of the components are about equal: ν11 *
~ ν 22
*
.
For the flexible polymeric chain the external degree of freedom, 3c, is assumed to
be proportional to the number of statistical segments, s, and for macromolecules
3c1/s1 → 1. By contrast, for solid particles this parameter tends to zero, 3c2/s2 → 0.
Furthermore, since now the PVT behaviour of component 2 (solid particles!) is
not accessible, additional assumptions are needed to solve Equation 99.
The validity of these assumptions was demonstrated by Simha et al. [1984;
1986] and by Papazoglou et al. [1989]. The aim of these studies was to examine
the suitability of the S-S eos theory for describing the observed changes in the
system modulus, thermal expansion coefficient and the compressibility engendered
by the addition of solid particles. The authors computed these functions for specific
ratios of the interaction parameters, viz.:
3
⎧⎡
( ) ⎫
1 /3 ⎤
ν 22
*
/ ν11
*
= 1 : 1; ν12
*
/ ν11
*
= ⎨⎢1 + ν 22
*
/ ν11
*
⎥⎦ / 2⎬ = 1.0492
⎩⎣ ⎭ (102)
ε *
22 /ε
*
11 = 5; ε
*
12 /ε
*
11 = 1.2 − 10
It has been shown that the extended S-S theory was able to account for different
experimental sets of data and demonstrated that for an optimised ‘adhesion ratio’,
∗ ∗
ε12 /ε11 , good agreement between the S-S eos and several continuum-based theories
of the system modulus was achieved.
It is noteworthy that the relationships in the first line of Equation 102 are
consistent with the fundamental assumption of the lattice theories that the cell
size for any component in the system should not differ by more than 10% from
the average. The Berthelot’s geometric mean rule was also assumed valid, thus:
ε12
*
/ ε11
*
= ε 22
*
/ ε11
*
≅ 2.24 .
3.1.9.5 Extension of S-S eos to Nanocomposites

The effect of nanoparticles on CPNC behaviour seems to be disproportionate to
the clay content. For example, addition of 0.64 vol% of MMT increased the
HDT of a PA-6 matrix by 70 °C, tensile modulus by 70%, and flexural modulus
by 130%, but reduced oxygen permeability to 50%, etc.
While XRD, TEM and SEM provide an assessment of the inorganic phase
dispersion in a polymeric matrix they do not provide information on the
interactions involved. Rheology (discussed in the following part of this book) is
a sensitive tool for observation of the interaction and structural effects on the
behaviour of multiphase systems, but owing to its sensitivity to structure and
orientation it cannot be used for the direct determination of interactions [Utracki
and Kamal, 2002a]. In this part the utility of the PVT measurements for this
purpose will be examined.
In the simplest case, dilute CPNC may be visualised as a three-component
mixture: polymer, clay particles (stacks of platelets or aggregates), and exfoliated
clay platelets with attached polymer chains. However, in many systems, low
molecular weight intercalants as well as standard additives (stabilisers, lubricants,
etc.) are also present.
318
Thermodynamics
The PVT behaviour represents a volume-average response hence the computed

parameters, P * , V * , T * , ε * and ν * , are volume averages.
Furthermore, the data fitting to eos makes it possible to compute the hole fraction
within the full range of independent variables. This function is also an average
response of the matrix and dispersed phases. Up to this point the procedure is
straightforward, identical to that applied for a single-component system. Thus,
for each composition one obtains predictive behaviour for V = V(P, T), h = h(P,
T) as well as the average values for the reducing and interaction parameters. A
plot of these parameters versus composition offers an opportunity to predict the
PVT behaviour of intermediate compositions as well.
However, to calculate the magnitude of the individual binary interaction
parameters, ε ij* , ν ij* , i , j = 1, 2, the system structure must be modelled. The
model is an idealisation of the perceived CPNC structure, formulated assuming a
binary system. The assumptions introduced ought to be simple but realistic. There
is a multitude of CPNC types (intercalated and exfoliated; end tethered and with
an intermediate layer of low molecular weight intercalant molecules forming a
cloud around clay platelets; systems with compatibiliser or without; etc.).
Furthermore, the structure may vary with concentration and process variables,
viz. exfoliated in diluted systems under large strains, forming short stacks at
higher concentration and/or high stress and temperature. For these reasons,
different models may be required to interpret different CPNC behaviour. The
simplest would be the one for randomly dispersed clay platelets in a molten matrix
– expected to be valid for diluted, exfoliated nanocomposites.
3.1.9.5.1 Diluted, Exfoliated CPNC – Simplified Approach

The PVT behaviour of PA-6 and a CPNC containing this matrix polymer may
serve as an illustration of eos applicability to CPNC. Two commercial resins
from Ube Ind., PA-1015B and PA-1015C2 were used. According to the
manufacturer’s information, the former is a neat PA-6 and the latter is a
nanocomposite based on PA-6 containing 2 wt% organoclay, i.e., 1.6 wt% (or
0.64 vol%) of clay. In the following text these resins will be labelled PA and PANC,
respectively. Their PVT behaviour was measured within the ranges T = 300-580 K
and P = 0.1 to 190 MPa. Prior to testing the material was dried for 48 h at 80 °C.
Since the instrument used measures only the incremental changes of the specific
volume as a function of P and T, first an absolute value of the specific volume at
ambient condition was measured in a glove box with an accuracy of Δ ≤ ± 0.001 ml/g
[Simha et al., 2001].
For each resin at least six runs were carried out, two isobaric the others
isothermal. Furthermore, some runs were repeated up to three times. Owing to
thermal decomposition at higher temperatures, the reproducibility between these
two types of measurements was poor, worse for PANC than for PA. For this
reason only single sweep, isothermal data were considered reliable. The specific
volumes of molten PA and PANC at ambient pressure and T = 240 °C were
determined as: V240 = 1.0182 ± 0.0154 and 1.0009 ± 0.0150, respectively. The
observed reduction of the specific volume, V, (by 1.7%) is greater than that
expected on the basis of additivity (1.2%). Examples of the experimental data
and the ability of S-S eos to describe the behaviour are displayed in Figure 82.
Evidently, eos describes the observed behaviour for molten PA and PANC well.
319
Figure 82 Comparison of experimental (solid circles) and computed data from

Simha-Somcynsky eos (open circles) isotherms in the molten state for two Ube
resins; PA-6 and PANC within the range of pressure from ambient to 200 MPa
(every 10 MPa).
Reprinted with permission from [Utracki et al., 2003]. Copyright 2003 American
Chemical Society.
320
Thermodynamics
The deviations from the theoretical dependence at ambient P and the highest T
are caused by thermal decomposition and degassing.
The reducing parameters (P*, V*, T*) were obtained by the simultaneous least
squares fit of all data points to the S-S eos (Equations 89 and 90). Their values, the
statistics of fit, and interaction parameters computed from Equation 86 are listed
in Table 45. To directly compare the specific volume variations, V = V(P, T), for
PA and PANC the predicted dependencies were computed by substituting the
reducing parameters from Table 45 into Equations 89 and 90. To avoid crowding
the figure, only five pressures are shown. Computations simultaneously provided
h = h(P, T). The results are presented in Figure 83.
In Figure 84 the ratios V(PA)/V(PANC) and h(PA)/h(PANC) at the same T
and P are shown. While the addition of organoclay to PA reduced the specific
volume by about 1% (insensitive to P and T) the effect on the hole fraction is
more pronounced (by ca. 15%) and more dependent on the independent variables.
Up to this point the treatment of the PVT data for PA and PANC were identical
– for the former it resulted in the material-characteristic reducing and interaction
parameters, whereas for the latter only average values were obtained. To calculate
the individual binary interaction parameters of Equation 99, the site fractions,
Xi, must be calculated from a CPNC model.
The CPNC from Ube is known to be exfoliated, free of interfering low
molecular weight intercalant and the clay concentration is low. Thus, the first
proposed model is that of randomly dispersed clay platelets in a molten PA matrix.
Accordingly, the clay platelets may be approximated by disks of diameter
d = 200 nm and thickness t = 1 nm, density, ρ = 2.5 g/ml, with ‘molecular’ mass,
M = NAρπd2h/4 = 47,296 kg/mol and ‘molecular’ volume Vp = M/ρ = 18.92 × 106
ml/mol. This volume is assumed to occupy s2 lattice sites. In the lattice model of
a mixture, the hard-core volumes of the constituents should not differ too much.
For the assumed 6-12 potential the factor 21/6 relates the positions of potential
Table 45 Eos fit to PVT data for PA-6 and PANC from Ube. Data
[Simah et al., 2001]
Parameter PA-6 PANC
Correlation coefficient squared, r2 0.999999 0.999998
Standard deviation of data, σ 0.00112 0.001271
Coefficient of determination, CD 0.998602 0.998550
P* (MPa) 1257 ± 8 116 4 ± 13
T* (K) 11134 ± 32 1130 7 ± 54

4
10 V*(ml/g) 8919.3 ± 9.6 8888.6 ± 16.2
Ms (g/mol) 27.512 30.288
ε11 (kJ/mol) ε11* = 31.23 ± 0.09 <ε*> = 31.71 ± 0.15
v11 (ml/mol) v11* = 24.54 ± 0.03 <v*> = 26.92 ± 0.05
321
Figure 83 Specific volume (a) and hole fraction (b) for PA-6 and PANC versus
temperature at five pressures: ambient, 50, 110, 150 and 190 MPa. Note that a
small difference in density translates to a substantial loss of the free volume
parameter, h.
Chemical Society.
minimum and onset of repulsion. For PA ν hard *

(PA) = v*/21/6 = 21.86 ml/mol. The
chain length of PA-6, s1 = 801, and that of clay, s2 = Vp / ν hard
*
= 7.8677 ×105.
With these numbers and the inorganic clay content of 1.6 wt% and the mole
fractions, xi, then the site fractions X1 = 0.99263, X2 = 1 – X1 are calculated.
322
Thermodynamics
Figure 84 The V and h data from the preceding figure are plotted as ratios at the
same T and P (for each point). Note the reverse P-dependence – while the ratios of
h increase with P, those of V decrease.
Chemical Society.
As stated before, Equation 99 contains six interaction parameters, viz. two

experimentally determinable quantities, ε11 *
and ν11*
and four unknown:
ε12
*
, ν12
*
, ε 22
*
and ν 22 *
that must be determined. However, the lattice model
requires that ν11 *
~ ν 22
*
, thus as before ν 22
*
= 1.11ν/ 211
*
may be assumed. The use of
*
(
Berthelot’s geometric mean rule, ε12 = ε11ε 22 * *
) , reduces the problem to two
unknowns ν12 *
and ε 22 *
.
The adopted model leads to the following results (‘11’ represents polymer-
polymer, ‘22’ represents clay-clay and ‘12’ represents polymer-clay interactions)
[Simah et al., 2001]:
ε11
*
= 32.09 ; ε12
*
= 313.54 and ε 22
*
= 3, 063 (kJ / mol)
ν11
*
= 24.89 ; ν12
*
= 33.53 and ν 22
*
= 24.89 (ml / mol)
In summary, the model of bare clay platelets randomly dispersed in the PA-6
matrix resulted in determining that ε ∗22 ≅ 95ε11*
, i.e., that ε 22
*
, is about two orders
∗
of magnitude larger than the liquid-liquid interaction parameter, ε11 . This large
difference is consistent with the values of the specific surface energy discussed in
Section 3.1.7.1. However, the model resulted in inconsistency as far as the
repulsion volume parameter is concerned. Even assuming near identity of the
interacting volumes, ν11 *
= ν 22
*
, the computed value for the 12 interaction,
ν12 ≅ 1.35 × ν11 , is much larger than the theoretical requirement of ν ij* ≤ 1.1 × ν11
* * *
.
To examine the validity of the additive model an intermediate composition
was prepared by mixing equal portions of PANC and PA. The PVT behaviour
was determined and the values of the average parameters, ε * and ν * , were
extracted. The use of the simple model failed to yield consistent values for the
binary interaction parameters – again ν12 *
> 1.1 × ν11*
was obtained.
323
Besides the unexplained large value of the volume repulsion parameter, ν12*
,
the disproportionately large reduction of the matrix free volume by addition of
0.64 vol% of clay is inconsistent with the model – the model simply does not
offer any mechanism that could justify these results. The assumption of naked
clay platelets randomly floating in molten PA-6 contradicts the high energy of
crystalline solids discussed in Section 3.1.7.1, the results computed from MD
adsorption of organic molecules on the clay surface, and the direct measurements
of solidification of macromolecules (by means of surface force apparatus and
neutron scattering) on the high-energy solid surface (see Section 3.1.7.2). Thus,
the simple, additive model had to be modified.
3.1.9.5.2 Dilute, Exfoliated CPNC – Gradient Mobility Approach

Again, two commercial resins from Ube, PA and PANC, were used [Utracki et al.
2003]. An intermediate composition of PA:PANC = 1:1 was prepared. Since the
diluted composition was extruder-blended in a TSE, the original resins were also
re-extruded under the same processing conditions. As shown in Table 46 the
PVT dependence of the three compositions was well described by S-S eos. The
new scrupulous measurements confirmed the previously reported large reduction
of the free volume parameter, h = h(P, T).
The new CPNC model used for the interpretation of the experimental values
of the average binary interaction parameters: ε * and ν * , is based on three
sets of information:
Table 46 Statistics of fitting S-S eos to the experimental data of PA,

PANC and their 1:1 mixture [Utracki et al., 2003]
Parameter PA PA/PANC = 1:1 PNC
Correlation 0.999999 0.999998 0.999998

coefficient, r2
Standard deviation 0.00112 0.00145 0.00127

of data, σ
Coefficient of 0.998602 0.998501 0.998550

determination, CD
P* (MPa) 1257 ± 8 1186 ± 11 1164 ± 13
T* (K) 11134 ± 32 11364 ± 49 11307 ± 54

4
10 V* (ml/g) 8919.3 ± 9.6 8943.1 ± 14.3 8888.6 ± 16.2
Ms (g/mol) 27.512 29.700 30.288
ε11 (kJ/mol) ε11* = 31.23 <ε*> = 31.49 <ε*> = 31.71

± 0.09 ± 0.29 ± 0.15
v11 (ml/mol) v11* = 24.54 <v*> = 26.56 <v*> = 26.92

± 0.03 ± 0.36 ± 0.05
324
Thermodynamics
(1) The reduction of molecular mobility near the crystalline surface computed
from MD and measured experimentally. This has been discussed in Section
3.1.7. Several researchers reported an increase of viscosity as the distance
from the clay platelet decreased toward the last 4 to 6 nm – at that stage the
viscosity reached an immeasurably high value, taken as an indication of
solidification. For example, the dynamic oscillatory measurements identified
three regions: bulk behaviour for z > 100 nm, intermediate, and solid-like
for z > 6 nm where Hookean-type stress-strain behaviour was observed
[Luengo et al., 1997].
(2) The molecular structure of Ube PANC. According to an early patent, the
preparation of exfoliated PNC involved three steps [Deguchi et al., 1992]:
(a) intercalation of MMT with ω-dodecanoic acid ammonium chloride (ADA),
(b) mixing the intercalated clay with ε-caprolactam and water, and (c)
compounding the adduct in a TSE with ca. 70% of PA-6. Chain-ends titration
indicated that about 1/3 of the macromolecules were end-tethered to the
clay surface.
(3) The observed PVT behaviour of PA, PANC and their 1:1 mixture. The PVT
data were collected with painstaking care, investigating all possible influences,
sources of error and ad nauseam verifying the reproducibility. The new sets
of data for PA and PANC confirmed the accuracy of the preliminary findings,
and lead to similar values of the interaction parameters. However, calculation
of the binary interaction parameters using different pairs of the three polymeric
compositions (PA, PNC and their 1:1 mixture) resulted in different values of
the binary interaction parameters. The assumption of random mixing is
probably not correct for the CPNC system studied, and a different model
must be proposed.
The new model considers that in these diluted and exfoliated PNC:
1. Clay platelets are exfoliated and at the concentration of 0.64 vol% (hence φ
= 0.0064) they are randomly distributed in the PA-6 matrix.
2. 1/3 of clay cations are used for end-tethering the PA-6 macromolecules.
3. Contrary to the previous assumptions, the clay platelets are not bare, but
rather they are enrobed in two PA-6 layers of different structure and
properties.
4. Directly on a clay platelet there is the first or inner layer of solidified PA-6,
zsw ca.6 nm thick. As the distance from the clay platelet surface exceeds this
limit, an intermediate layer starts. This layer, where PA-6 chain mobility
progressively increases, extends from ca. 6 to ca. 100 nm from the platelet
surface, thus 6 ≤ zin (nm) ≤ 100. At still larger distance, z > 100 nm, the
segmental mobility of this exterior layer is the same as that in the bulk
polymeric matrix.
This model of ‘hairy clay platelets’ (HCP) [Utracki and Lyngaae-Jørgensen, 2002]
implies that only at φ < 0.005, where the clay platelets are more than 200 nm apart
(the assumed diameter of the model disk is 200 nm), are the values of the interaction
parameters expected to be constant. At higher concentrations, φ > 0.005 or w > 1.2
wt%, the HCPs overlap, PA-6 macromolecules with bulk properties are absent,
and the interactions depend on composition. Thus, the adopted model considers
individual clay platelets to be covered by solidified polymer and dispersed in a
matrix composed of PA macromolecules of the intermediate and exterior layers. It
325
is important to note that in this new model the random placement of binary
component has been assured by virtue of redefining the dispersed particles as HCP.
In the calculations it was assumed that the ‘12’ parameters characterising the
hetero-contacts are approximated by averages – the repulsive volume by the
algebraic average of the radii, the attractive interactions by Berthelot’s geometric
mean rule, i.e., that in Equation 101: δe, δv = 1. Applying the model to Equation
99 resulted in the sets of binary interaction parameters listed in Table 47. The
model considers the clay platelets to be covered by two layers of PA-6 with the
segmental mobility increasing with the distance z from the platelet surface. In
consequence it is expected that the interaction parameters will be similar
ε11
*
≈ ε12
*
≈ ε *22 . This is indeed shown by data listed in Table 47.
Thus, for the simplest diluted and exfoliated CPNC systems, the PVT
measurements provide well-defined functions of V = V(P, T) and h = h(P, T).
Furthermore, from the reducing parameters the average values of the energetic
and volumetric parameters can be unambiguously calculated. However, the
calculations of the individual interaction parameters ‘11’, ‘12’, and ‘22’ very
much depend on the adopted model – on the definition of what physically are the
interacting species ‘1’ and ‘2’. Thus, when ‘1’ is taken as an average statistical
segment of the PA macromolecule and ‘2’ an inorganic ‘bare’ clay platelet the
energetic interactions: ε 22 *
≅ 95ε11
*
are found. On the other hand, when the model
specifies that species ‘1’ are statistical segments of PA in the melt and ‘2’ are
inorganic clay platelets embedded in layers of PA with reduced chain mobility,
the energetic interactions change dramatically to ε 22 *
≅ ε11
*
.
On face value both approaches are correct and the relative magnitudes of the
energetic interactions have physical sense. However, while the former model was
unable to explain the significant reduction of free volume, the latter model provides
a direct and unequivocal response: it is precisely the strong interaction between
the clay surface and PA-6 segments that causes the reduction of segmental mobility
and the reduction of free volume. The latter model also agrees with the well-
documented adsorption of organic molecules of inorganic, high surface energy
substances. It is consistent with our understanding of this type of CPNC.
Table 47 Interaction parameters in PA, PANC and their 1:1 mixture.

Data [Utracki et al., 2003]
System PA-6 PA/PANC = 1:1 PANC
Contacts
ε*ij v *
ij ε*ij *
v ij ε*ij v*ij
(kJ/mol) (ml/mol) (kJ/mol) (ml/mol) (kJ/mol) (ml/mol)
11 31.23 24.54 31.21 24.54 (26.69) 24.54
12 — — 31.53 25.75 (29.16) 25.75
22 — — 31.86 26.99 31.86 26.99
Notes: In the PA/PANC mixture and in PANC the variations of v*ij are as
postulated in the text. Values of ε*ij in parentheses were computed for matrices of
different mobility hence they are fitting averages. The experimental error for ε*ij
and v*ij is ± 1.5 and ± 1.0%, respectively.
326
Thermodynamics
3.1.9.5.3 Intercalated CPNC – Concentration Gradient

Polystyrene-based CPNC serve as an example of the third type of PVT behaviour
[Tanoue et al., 2003a]. Commercial polystyrene (PS1301; Mw = 270 kg/mol,
melt flow rate MFR = 3.5 g/10 min) was compounded with organoclay (Cloisite®
10A = MMT intercalated with 1.25 meq/g of 2MBHTA d001 = 1.92 nm). The
compounding was carried out in a Leistritz co-rotating TSE-34 (L/D = 40) at
uniform barrel temperature of 200 °C, screw speed of 200 rpm, and feed rate of
5 kg/h (the average residence time t = 240 s). The organoclay (according to
subsequent TGA: 0, 1.4, 2.8, 5.7, 10.6 and 17.1 wt%) was added to molten
polymer using a side-feeder.
XRD analysis showed that the melt compounding resulted in a partial
intercalation (interlayer spacing increased to d001 = 4.2 to 4.8 nm) accompanied
by a simultaneous collapse of the interlamellar gallery spacing (d001 decreased
from 1.92 to ≤ 1.7 nm) caused by the thermo-oxidative decomposition of the
organoclay. TEM showed the presence of short stacks with few exfoliated platelets.
Enhancement of the mechanical properties by addition of the organoclay was
poor.
The PVT data were collected within the range of temperatures (T = 300-520 K)
and pressures (P = 0.1 to 190 MPa). For each composition two to five isothermal
runs were carried out. A high degree of reproducibility was obtained. As before,
the data were fitted to S-S eos, Equations 89 and 90. The non-linear least square
fit yielded the reducing parameters, P*, V* and T*, as well as the free volume
function, h. The parameters and the statistics of the fitting procedure are listed in
Table 48. Using Equation 86 the average interaction parameters, ε * and ν * ,
were calculated from the computed values of P*, V*, and T*. As an example, the
h = h(P, T) dependence for neat PS 1301 is shown in Figure 85 – the ones for
other compositions were similar. As expected, h increases with T and decreases
with P.
Figure 85 Hole fraction as a function of temperature and pressure for neat PS 1301.
327
328
Table 48 Statistics of fitting the Simha-Somcynsky eos to experimental data and the computed parameters for PS,
and PNC containing 1.4 to 17.1 wt% Cloisite‚ 10A [Tanoue et al., 2003a; 2004]
Parameter PS1301 HS16A HS17 HS18 HS19 HS20
C10A (wt%): 0 1.4 2.8 5.7 10.6 17. 1
σ 0.0011119 0.0014205 0.0009326 0.0014970 0.0023897 0.0025876
r2 0.9999987 0.9999980 0.9999991 0.9999977 0.9999939 0.9999924
Correlation 0.9994420 0.9990610 0.9995868 0.9989405 0.9971886 0.9967893

P* (MPa) 743 ± 3 749 ± 5 747 ± 3 756 ± 6 747 ± 8 75 1 ± 9
T* (K) 11723 ± 22 11938 ± 46 12010 ± 29 11975 ± 48 11834 ± 74 1171 1 ± 73
104 × V* (ml/g) 9525.9 ± 4.7 9583.7 ± 9.6 9567.8 ± 5.9 9458.8 ± 9.8 9259.6 ± 15.1 9011.2 ± 14.6
Mo (g/mol) 45.869 46.079 46.537 46.433 47.407 47.770
<εij> (kJ/mol) 32.49 ± 0.06 33.08 ± 0.14 33.28 ± 0.08 33.19 ± 0.13 32.80 ± 0.20 32.45 ± 0.20
<vij> (ml/mol) 43.69 ± 0.23 44.16 ± 0.48 44.53 ± 0.30 43.92 ± 0.50 43.90 ± 0.77 43.05 ± 0.78
Thermodynamics
The most interesting question was how the addition of different amounts of
organoclay affected the free volume fraction, i.e., the h-function. A plot of the
relative hole fraction, h(PNC)/h(PS) at constant pressure P = 1 MPa and three
temperatures, T = 360, 460 and 560 K, is shown in Figure 86. A similar plot of
the relative specific volume, V(PNC)/V(PS), versus w linearly decreased in the
full range of composition, consistently with the constant ratio of densities in the
molten state: ρ(organoclay)/ρ(PS) = 1.49.
The free volume in PANC with 2 wt% organoclay dispersed in PA-6 at
T = 300-590 K and P = 0.1 to 200 MPa was lower by 12 to 17% than that of the
matrix (see Figure 84). Since during the reactive exfoliation the intercalant
(ω-amino dodecyl acid (ADA)) became the first mer that end-tethered PA-6
macromolecules to the clay surface, there was nothing in these nanocomposites
to prevent adsorption of PA-chains on the high surface energy clay platelets. The
adsorption and resulting reduction of chain mobility caused such a large loss of
free volume. The dependencies displayed in Figure 86 are most interesting since
in these PS-based CPNC the degree of intercalation/exfoliation is incomparably
lower than that in PA-6/MMT. Furthermore, here the 2MBHTA intercalant is in
stoichiometric excess (over MMT CEC), thus it forms an intermediate layer
between the inorganic, high-energy clay surface and PS matrix. As a consequence,
one would not expect PS macromolecules to be adsorbed and loose mobility.
Apparently, in spite of these obstacles, the clay is able to reduce PS segmental
mobility. Furthermore, the data show that initially the relative loss of free volume
is proportional to the clay content – more clay, less free volume. Figure 86 indicates
that h(PNC) < h(PS) for organoclay content from 0 to ca. 16 wt%. However, the
dependence reaches a local minimum at ca. 4 wt% organoclay (4 to 6% loss of
the free volume) then starts to increase with the organoclay loading. The latter
effect is related to progressively poorer dispersion of clay platelets.
Figure 86 The relative hole fraction of PS-based CPNC versus organoclay

concentration at P = 1 MPa and T = 360, 460 and 560 K.
329
The dependencies in Figure 86 seem to suggest that should the concentration

increase still further the hole fraction of CPNC would exceed the value of the PS
matrix. Olson et al. [1997] used positron annihilation lifetime spectroscopy (PALS)
for CPNC containing 75 wt% organoclay (FH-ODA) within the range of
temperature from –60 to 140 °C. The CPNC was prepared by dry blending the
component powders, compressing and annealing it for 48 h at 170 °C. Annealing
increased the organoclay interlayer spacing from d001 = 2.253 to 3.031 nm.
From the PALS data the free volume fraction, f, can be calculated as
proportional to the product of the positron lifetime, τ3, and intensity, I3.
Accordingly, the ratio: f(CPNC)/f(PS) was calculated from the cited data for T= –60
and 140 °C – the ratio was found equal to 0.535 and 0.544, respectively. Thus,
in these non-degraded, highly loaded CPNC the free volume fraction is about
46% smaller than that in PS. Even correcting for the reduction of the organic
phase content (in these CPNCs there is about 40 vol% clay) these measurements
still indicate a reduction of free volume by about 10%, both in the glassy as well
as in the molten state of PS.
Using Equation 86 the average interaction parameters, ε * and ν * , were
calculated (see the last two rows of Table 48). Their parallel variation with
composition is noteworthy (they are linked through the Lennard-Johnson
potential). In Figure 87 the relative free volume at three temperatures (the same
data as shown in Figure 86) is plotted versus ε * . The dependence is linear with
a high value of the correlation coefficient r2 ≥ 0.99992. In the lower part of the
figure the organoclay loading is indicated – evidently the reduction of h is related
to the average interaction parameters, thus indirectly to the clay loading.
Figure 87 Relative hole fraction of PS1301 with 0 to 17.1 wt% of Cloisite® 10A at
T = 360, 460 and 560 K as a function of the average energetic interaction
parameter, ε * . In the upper part the linear regression results are shown; in the
lower part the organoclay concentration for each data point is given. Data
[Tanoue et al., 2003a; 2004].
330
Thermodynamics
3.1.9.5.4 PVT – Concluding Notes

PVT measurements offer unique insight into the structure and interactions of
CPNC. The experimental data can be well described in terms of the Simha-
Somcynsky equation of state (S-S eos). The relation provides two sets of valuable
information; the functional dependence of the free volume parameter, h, and the
average interaction parameters, ε * and ν * .
From the admittedly limited information on the PVT behaviour of CPNC it
seems that h provides a relatively simple and accurate measure of the average
degree of exfoliation – as the degree of exfoliation increases the free volume
content in CPNC decreases. Since the mechanism is based on the degree of
macromolecular adsorption on the clay surface, the decrease must be related to
the magnitude of the clay-polymer interactions and composition. The latter
variable has two influences as initially its increase provides a larger surface for
the polymer to adsorb onto, and at higher concentration it reduces the interlayer
spacing, thus reducing the total surface available for adsorption. Recently, from
analysis of the PVT and PALS data for PP the authors determined that at ambient
pressure, within the range of T = 300 to 400 K the hole volume increases linearly
from vf = 0.12 to 0.22 nm3, while the number of holes per gram remains constant
Nh ≅ 0.38 (±0.02) × 1021, or ca. 0.34 holes per nm3 [Kilburn et al., 2003].
Analysis of the concentration dependence of the average interaction
parameters, ε * and ν * offers invaluable insight into the interactions inside
CPNC. The calculated values of the individual binary interaction parameters
very much depend on the adopted model. So far the adopted models have been
simple. The insight gained suggests that for the interpretation of CPNC data the
present version of the S-S theory (derived for binary, randomly mixed systems)
should be extended to non-random mixtures. Xie et al. [1992] have made
preliminary efforts in this direction.
331
332
Thermal Stability
3.2
Thermal Stability
3.2.1 Thermal Stability During Processing

The stability of the clay-intercalant complex is essential for the melt exfoliation
process to succeed. Experience shows that the lack of thermal stability complicates
the production and forming processes of CPNC not only for engineering and
speciality resin (which require high processing temperature), but also for CPNC
based on PO or PS. Owing to the lack of polar groups these polymers need well-
intercalated clay and a compatibiliser (a functionalised polymer or copolymer).
The stability aspect is also important for the characterisation of CPNC, viz. PVT
or rheological measurements where CPNC may be exposed to high temperature
for long periods. Several researchers reported that MMT intercalated with a long
chain aliphatic quaternary ammonium cation is unstable at temperatures above
180 or 200 °C. A brief summary of the work on the thermal stability of
organoclays is provided in Table 49 and Table 50.
Early studies on the thermal decomposition of n-alkyl amines were published
by Ogawa et al. [1992] and by Menéndez et al. [1993]. The former team
intercalated MMT with quaternary ammonium chloride, (CH3)3CnH2n+1N+Cl-
(where n = 8, 12, 14, 16, and 18), while the latter used primary amine,
CnH2n+1NH2 (n = 1 to 6) to intercalate γ-titanium phosphate in either vapour or
aqueous phase: γ-Ti(H2PO4)(PO4)×2H2O, (TiP) to obtain TiP with 1.3 mol of
alkyl amine. In both cases the interlayer spacing increased linearly with n:
d001 = ao + a1n (nm) (103)
For the MMT with quaternary ammonium ions the parameter values were: a0 = 0.7311
and a1 = 0.0851 with the correlation coefficient squared r2 = 0.9947, while for
the TiP systems a0 = 1.12 and a1 = 0.230. The n-alkyl amines formed bimolecular
layers.
To follow the thermal degradation processes, the intercalated TiP was heated
up to 600 °C. Two weight loss processes were identified: (1) at T = 80-110 °C loss
of crystallisation water; and (2) a complicated thermal decomposition occurring in
discreet steps, evidenced as peaks in DSC thermograms. The first step at T = 130 to
195 °C was caused by a loss of ca. 30% of n-alkyl amine and a reduction of d001;
now a0 = 1.12 and a1 = 0.189. The second step at T = 190-270 °C involved loss of
another 30% of n-alkyl amine, reduction of d001 to a0 = 1.12 and a1 = 0.157, but the
bimolecular structure survived up to this point. The third step at T = 335-375 °C
was caused by a loss of another 40% and a reduction of d001 that involved both
parameters of Equation 74; now a0 = 0.89 and a1 = 0.044. Other peaks followed.
Maxfield et al. [1995; 1996] reported that incorporation of a traditional ‘sizing
agent’, e.g., silane or titanate, enhances the thermal stability. More recent work
by Yu et al. [2003] places some doubts on the generality of such a statement.
333
Table 49 Reports on the thermal stability of organoclays

Polymer Intercalant Comments Reference
+
None MMT(CH3)3CnH2n+1N ; DTA: exothermic peak Ogawa et al.,
n = 8, 12, 14, 16, & 18 started at ca. 240 °C 1992
None γ-titanium phosphate Thermal decomposition Menéndez et
intercalated by n-alkyl in several steps at 130 al., 1993
amines; n = 1-6. to 500 °C
None 3M-alkyl amine added d001 linearly increased Ogawa, 1994
(CnH2n-1); n = 6-12 with n; degradation
starts at ca. 200 °C.
PE MMT intercalated with Compounding 5 min at Heinemann et
di-methyl stearyl benzyl 190 °C reduced d001 al., 1999
ammonium ion from 1.94 to 1.41 nm
None MMT with [Ni{di(2- Thermal stability of Ni- Bora et al.,
aminoethyl)amine}2 or amines was 50 and 150 2000
[Ni(2,2´:6´,2´´- °C higher than that of
terpyridine)2] metal-free amines
PS 2M2ODA Degradation during Gilman et al.,
extrusion at 185 °C 2000
PP/PP-MA Cloisite® 20A or 30B Loss of about 10 wt% Lee et al.,
of the organic 2000a
constituent
None MMT with tri-methyl TGA: T = 200 to Xie et al.,
dodecyl or octadecyl, 300 °C the 2000
3MDDA or 3MODA decomposition of C12
to C17 unsaturated
hydrocarbons
PA-6 MMT with quaternary TGA: lower stability Cho and Paul,
alkylammonium than neat PA-6; 5 wt% 2001
loss at 271 °C.
PS Ammonium or See Table 50 Zhu et al.,
phosphonium cation 2001a
PS Ammonium or T > 200 °C to d001 Zhu et al.,
phosphonium cation reduced to 1.58 nm 2001b
Styrenic 2MDBHTA quaternary Heating at 210 °C Yoon et al.,
copolymers ammonium ion reduced d001 from 3.5 to 2001
1.9 nm
PS, 2M2HTA quaternary 10 min at 210 °C Lim and Park,
PS-co-MA, ammonium ion reduced d001 from 3.18 2001
PE-g-MA to 2.94 nm
Polyimide Quaternary ammonium See text Delozier et al.,
with tallow radical 2002
PS Cloisite® 10A Oxidative Tanoue et al.,
(2MDBHTA) decomposition of 2003a; 2003b
organoclay at 200 °C
334
Thermal Stability
The authors did not observe any significant changes to the thermal decomposition
of organoclay treated with t-butyl dimethyl chlorosilane. In air, the decomposition
started with a small TGA peak at about 150 °C and a major one centred at
250 °C. Under nitrogen the decomposition started at ca. 180 °C and proceeded
in three steps with peaks at 254, 320 and 438 °C.
In their patent of 1998, Christiani and Maxfield noted that a MMT-ammonium
complex with secondary amine was more thermally stable (onset of decomposition
at T = 275 °C) than that with either tertiary or quaternary ones. Thus, for melt
exfoliation in a PA matrix, they preferred MMT pre-intercalated with dipentyl
ammonium chloride.
Gilman et al. [2000a; 2000b] reported that during extrusion compounding
of PS with MMT-2M2ODA (dimethyl dioctadecyl ammonium chloride) at 185 °C
the intercalant was thermally degraded. The authors pointed out two factors
causing this unwanted effect: increased temperatures and the presence of air. The
oxidative degradation also affected the matrix PS, broadening its polydispersity,
Mw/Mn from 1.8 to 2.40. The degradation was found detrimental to the flame
retardancy of CPNC, as the re-aggregated clay offered less protection to the
polymer. Since extrusion of PS with inorganic NaMMT, under the same processing
conditions, did not affect the PS, it was concluded that the free radicals formed
during the intercalant degradation were to blame. The authors proposed the
mechanism, where the byproducts of the Hofmann elimination mechanism
[Hofmann, 1851] of quaternary ammonium reacted with oxygen to give peroxy
radicals, which in turn attacked the PS macromolecules.
Tanoue et al. [2004a; 2004b] reported similar observations for CPNC prepared
by melt compounding PS with MMT-2MBHTA (Cloisite® 10A; C10A) at 200 °C.
FTIR transmission spectra were measured on a Thermo Nicolet spectrometer at
a resolution of 4 cm-1 and with an accumulation of 128 scans. To enhance
detectability of the chemical changes, difference spectra were calculated for the
extruded samples by subtracting out the spectrum of neat PS and comparing the
results with the spectrum of C10A. The analysis identified characteristic peaks
of the dimethyl benzyl amine (2MBA) - a byproduct of the Hofmann
decomposition [Aldrich Co., 1997; Bellamy, 1975]. In addition to these peaks,
there are strong carbonyl peaks at 1705 and 1736 cm-1 in most of the extruded
samples containing organoclay, which corresponds to =C=O groups formed by
oxidation of the double bond in the long-chain olefin - another byproduct of the
Hofmann decomposition. Finally, there is evidence of a ketone carbonyl group
present in PS. The rheological measurements of the re-extruded CPNC showed
that the zero-shear viscosity, ηo, was reduced by about 30% each time. This is
particularly noteworthy since increasing the residence time in a TSE by a factor
of up to 10 did not further reduce the CPNC matrix viscosity. Similarly, extrusion
of neat PS had only a small (ca. 2%) effect on ηo. Thus, the combination of
oxygen, temperature and organoclay was responsible for the degradation of PS.
CPNC of PP (Mw = 278, Mn = 72 kg/mol), PP-MA (Mn = 23 kg/mol; 2 wt%
MAH) and an organoclay (Cloisite® 20A or 30B; C20A = MMT-2M2HTA or
C30B = MMT-MT2EtOH) were prepared by melt blending to have about 5 wt%
of clay [Bellamy, 1975]. These dry blends were compounded at 210 °C for 10 min
in an internal mixer at 50 rpm. During the process both organoclays lost a
proportional amount (to the initial) of the constituent elements (e.g., lost of about
10% of C), which indicates that thermal decomposition took place even under
these relatively mild conditions. This confirmed the suspicions that thermal
335
desorption of intercalant takes place during thermal treatment, leading to a

decrease of the interlayer spacing, viz. for C20A from d001 = 2.49 to 2.40 nm and
for C30B from d001 = 1.84 to 1.50 nm, respectively.
Bora et al. [2000] studied the thermal decomposition of MMT intercalated
with either [Ni{di(2-aminoethyl)amine}2 (Ni1) or [Ni(2,2':6',2'-terpyridine)2]
(Ni2). The thermal stability of these Ni-containing amines was 50 and 150 °C
higher compared to their metal-free compounds. On heating, the interlayer spacing
of the first compound decreased from d001 = 1.45 (at 50 °C) to 1.35 (at 250 °C)
while the second decreased from d001 = 1.94 (at 50 °C) to 1.90 (at 350 °C). DTA
of Ni1 had 5 peaks indicating loss of water at 140 °C, and then a stepwise
exothermic (oxidation) decomposition of the amine at 273 °C (5.5% mass loss),
at 354 °C, 456 °C and 557 °C. Ni2 also showed five DTA peaks, first at about
100 °C (loss of water), and then a series of exothermic (oxidation) peaks at ca.
340 °C, 400 °C (3.5% loss), 505 °C (8.5%), and 645 °C. XRD showed a constant
position for the interlayer spacing up to about 350 °C, starting to decrease at ca.
400 °C.
Zhu et al. [2001a] described the properties of PS-based CPNC prepared by
bulk polymerisation in the presence of onium salts: N,N-dimethyl-n-hexadecyl-
(4-vinyl benzyl) ammonium-Cl (VB-16), N,N-dimethyl-n-hexadecyl-(4-hydroxy
methyl benzyl) ammonium-Cl (OH-16) and n-hexadecyl triphenyl phosphonium-
Cl (P-16). XRD showed that the interlayer spacing of Na-MMT (d001 = 0.96 nm)
increased after intercalation by VB-16, OH-16 and P-16 to, respectively, 2.87,
1.96 and 3.72 nm. After polymerisation the first system was exfoliated whereas
the latter two intercalated with d001 = 3.53 and 4.06 nm, respectively. Accordingly,
TEM showed discrete clay layers for CPNC with VB-16, only intercalated short
stacks for CPNC containing OH-16, and a mixture of both intercalated and
exfoliated structures for CPNC with P-16. TGA/FTIR studies indicated that both
ammonium and phosphonium compounds degrade by a Hoffmann elimination
mechanism, schematically shown in Figure 88.
As shown in Table 50, the MMT-P-16 system was the most thermally stable
- the onset of degradation took place at a temperature ca. 30 to 50 °C higher
than that of the MMT-ammonium. This may be useful when CPNC must be
processed at temperatures up to ca. 240 °C. TGA also showed that CPNCs start
degrading at higher temperatures than the matrix polymer. Cone calorimetry
data revealed a significantly reduced rate of heat release for the nanocomposites.
X-ray photoelectron spectroscopy (XPS) was used at T ≤ 500 °C to examine
these PS-based CPNCs [Wang, et al., 2002a]. Degradation of the organic
components was detected at T = 100 to 200 °C, while at T = 200 to 250 °C
MMT started to decompose into SiO2 and Al2O3. Similarly, Du et al. [2002] used
XPS to investigate the thermal degradation of PMMA nanocomposites containing
Figure 88 Hofmann elimination mechanism for the thermal decomposition of an

ammonium cation. After [Saunders, 1965].
336
Thermal Stability
Table 50 Stability of MMT intercalated with ammonium or

phosphonium salts – TGA/FTIR. Data [Zhu et al., 2001a]
MMT-VB-16 MMT-OH-16 MMT-P-16 Decomposition
products
T (°C) wt% T (°C) wt% T (°C) wt%

loss loss loss
185-235 1 210-250 2 240-290 2 hexadecene
235-340 10 250-340 6 290-340 9 hexadecene,

hexadecanal, or
hexadecanone
340-400 7 340-370 8 340-490 19 hexadecene, (PPh3)
400-600 8 370-560 16 490-600 5 Me2NCH2-C6H4-CH=

CH2 or PPh3
Total 26 32 35
Notes on the intercalating salts: VB-16 is N,N-dimethyl-n-hexadecyl-(4-vinyl

benzyl) ammonium chloride; OH-16 is N,N-dimethyl-n-hexadecyl-(4-hydroxy
methyl benzyl) ammonium chloride; and P-16 is n-hexadecyl triphenyl
phosphonium chloride.
MMT pre-intercalated with VB16, hexadecyl-allyl dimethyl ammonium chloride

(Allyl16), and hexadecyl vinyl-benzyl dimethyl ammonium chloride (Bz16). The
three CPNCs were prepared by bulk polymerisation. For both series of CPNC
with PS or PMMA as the matrix, the authors demonstrated that during the thermal
degradation, the clay accumulates on the surface. Its composition changed at
T = 200 to 300 °C. The change (presented as changes of the Si/Al ratio) was
found to depend on the type of intercalant, viz. 2MBHd, 2M-allyl-Hd, or
2M-styryl-Hd (Hd = hexadecyl).
Zhu et al. [2002] also studied the thermal degradation and flame retardancy (by
TGA and Cone Calorimetry, respectively) of the latter systems (PMMA/MMT-VB16,
-Allyl16 or -Bz16). Using XRD and TEM the authors found that the
nanocomposites obtained by bulk polymerisation of MMA in the presence of
organoclays having reactive groups (C=C double bonds) showed better dispersion
of platelets than those obtained with MMT-Bz16, but all these systems were only
intercalated. The thermal stability (by TGA) was found to be improved by
incorporation of 3 wt% of clay; the temperature for 10 wt% loss for neat PMMA,
and nanocomposites with MMT-Bz16, MMT-VB16 and MMT-Allyl16 were
recorded as: 246, 235, 271, and 295 °C, respectively. Recent publications from
the same laboratory describe the thermal stability and flame retardancy (by TGA
and Cone Calorimetry, respectively) of nanocomposites in a PE [Zhang and Wilkie,
2003] and PP [Wang and Wilkie, 2003] matrix. These intercalated nanocomposites
have been prepared by melt blending in an internal mixer. The PO-organoclay
systems showed mixed immiscible-intercalated structures that improved when
337
PO-MA graft copolymer was incorporated. The results from cone calorimetry
suggest that nanocomposite formation has occurred, since there is a significant
reduction (by 30 to 40%) in the peak heat release rate (for more information on
flame retardancy see Section 5.2). However, these data do not differentiate between
the stability of the clay-intercalant complex and that of the matrix.
Delozier et al. [2002] performed the TGA analysis of their organoclay (MMT
with a quaternary ammonium containing tallow group) in air and nitrogen. The
organoclay started to degrade in air at 150 °C, lost approximately 1% weight at
200 °C, 5.5% at 250 °C, and 12% at 300 °C. Under nitrogen the organoclay was
more thermally stable, viz. at 250 °C the weight loss was 4% and at 300 °C it
was 9%. The effects were specifically blamed on the degradation of the long
hydrocarbon tails. The process is known to begin near 200 °C and it accelerates
as the temperature increase [Xie, et al., 2000].
Degradability of CPNC, comprising PA-6 and 5 wt% of MMT pre-intercalated
with ω-amino dodecyl acid (ADA) was studied [Davis et al., 2003]. Compounded
and dried specimens of neat PA-6 and CPNC were injection moulded at 300 °C.
Under identical conditions, CPNC degraded (Mn decreased by ca. 40%), while
PA-6 did not. ε-Caprolactam and terminal vinyl groups were detected in the
product.
The Hofmann elimination mechanism was used to explain the discoloration,
molecular weight decrease, and reduction of mechanical performance of CPNC
with PA-6 as the matrix [Fornes et al., 2003; 2004]. The authors compounded
the CPNC in a TSE at 240 °C and then injection moulded at 260 °C. The relative
(to extruded PA-6) colour index decreased (i.e., colour intensity increased) with
organoclay loading. However, the value for CPNC (proportional to that of neat
organoclay) decreased with the reduction of matrix molecular weight. Intercalants
with more unsaturation, -C=C-, and/or hydroxyl-ethyl groups, -C2H4-OH,
developed stronger discoloration. The authors concluded that more thermally
stable intercalants are needed. Similar observations were reported for CPNC
with PC as the matrix [Yoon et al.; 2003].
Evidently, thermal degradation of the organic cation poses a serious problem
when preparing and processing CPNC. The experience shows that when
blanketing by nitrogen is not used, the degradation mainly depends on the number
of reprocessing steps and to a minor extent on the total residence time at higher
temperature. The organoclays containing quaternary ammonium intercalants are
thermally unstable at temperatures above 150 to 165 °C. However, the onset of
degradation can be pushed up to above 200 °C by ascertaining the absence of O2
and controlling the composition, the method of treatment (e.g., extent of shearing)
and time of heating. Furthermore, the decomposition of intercalant in case of
highly polar macromolecules that may directly interact with clay surface, e.g.,
PA, is not as critical as that in the case of hydrophobic polymers with low polarity,
such as PO or styrenics.
The use by Inoue et al. [2002] of melamine as an intercalant is an important
development. This the first time a compound known as a flame retardant has
been used as intercalant, replacing the notoriously unstable quaternary
ammonium. This promising route is very much worth pursuing.
From the chemical point of view, the least stable are the quaternary ammonium
ions with a structure: Ri4N+, where Ri is a straight paraffinic chain. Reduction of
the degree of substitution is expected to improve the thermal stability, i.e.,
RiH3N+ > Ri2H2N+ > Ri3HN+ > Ri4N+ (but at the same time the ionic strength
338
Thermal Stability
may decrease). Another method for improving the thermal stability involves double
alkylation of the β-carbon(s), e.g., replacing straight paraffinic chain, viz.
RCH2CH2-N+ by RC(CH3)2CH2-N+ [Starnes, 2002]. The enhancement of MMT-
ammonium stability by the use of ammonium-Ni complexes has been reported;
the decomposition temperature was 50 to 150 °C higher than that without the
Ni-complex. Another method of enhancing thermal stability is by the use of the
‘sizing agents’, e.g., silanes or titanates [Maxfield, 1996].
Much less information is available on the stability of phosphonium systems.
Stability up to 370 °C was claimed by Ellsworth [1999], but more recent work by
Zhu et al. [2001a] indicates a more modest effect, viz. stability of MMT-phosphonium
higher by ca. 30 to 50 °C than that of MMT-ammonium. One possible source for
such discrepancy is the method used for defining the onset of decomposition.
When the degradation products have low vapour pressure and high solubility in
the degrading specimen the TGA analysis may be misleading - degradation may
have taken place, but the byproducts did not evaporate. For this reason, XRD/FTIR
followed by evaluation of the key properties after heating is essential.
During the last 10 years or so, the search for more thermally stable organoclays
has intensified (see Sections 2.3.2 to 2.3.7). The research on inorganic intercalants
was a significant step in this direction, but owing to the complexity and associated
costs so far this approach has not gained industrial approval. Observations that
clay readily interact with complex, aromatic salts resulted in repeated attempts
to incorporate these, more thermally stable molecules as intercalants. Thus,
replacing ammonium salt by that of a cyclic tertiary amidine leads to greater
thermal stability and more efficient intercalation of clay [Zilg et al., 1999]. Since
complex, aromatic molecules are often either functional or coloured (conjugated
double bonds), Eastman and TNO patented the use of dyes as intercalants [Barbee
et al., 2000c; Fischer et al., 2001]. For similar purposes, Imai et al. [2002]
developed intercalant (dimethyl isophthalate substituted with a triphenyl-
phosphonium group) able to react with PET, bind to clay and be stable up to at
least 275 °C.
Evidently, other stable organic compounds may be used for this purpose -
limitations are only imposed by availability and costs.
3.2.2 Flame Retardancy and High Temperature Stability

The advantageous properties of CPNC include increased thermal stability and
reduced flammability [Gilman et al., 1998; 2001]. In 1998 NIST organised an
industrial consortium to study the flammability of polymers and their CPNCs.
The results of the first year of studies were summarised as follows. (1) In CPNC
with 2% to 8% MMT, flammability was reduced by 50 to 80%, without an
increase of smoke. (2) The reduced flammability was achieved along with
improved physical properties. (3) Incorporation of MMT enhanced char
formation, which acts as an insulator and a mass transport barrier. (4) Imidazolium
treated MMT showed greater thermal stability and formed finely dispersed
nanocomposites with PS and PA-6.
The flame retardancy is often accompanied by increased high temperature
stability as measured by thermogravimetric analysis (TGA). One of the reasons
for such a correlation is the amount of volatiles - the higher their volume, the
greater is the weight loss and the greater the flame intensity. However, in the case
of CPNC, this relationship very much depends on the relative flammability, the amount
of the matrix polymer and the organoclay intercalant [Zhu et al., 2001a, b].
339
The TGA results are usually presented in the form of three parameters: T10
(°C), T50 (°C), and char content (wt%); the first two indicating the temperature
at which 10 or 50% weight loss was recorded, and the last represents the fraction
of material which remains at 600 °C. It is evident that even the initial 10%
weight loss takes place at much higher temperatures than the thermal degradation
of organoclay (see Section 3.2.1). Recently, MMT was intercalated with oligomeric
molecules, bringing the organic content in the organoclay to 65-73 wt% [Su et
al., 2004]. In this case, both flammability, and T10 decreased with organoclay
loading.
3.2.3 Photo-Oxidative Stability

To study the effect of organoclay on the photo-oxidative degradation of PP, four
film specimens were extruded, and then irradiated in the presence of oxygen at
λ > 300 nm, 60 °C for up to 120 h [Morlat et al., 2004]. Besides neat PP, the
specimens comprised organoclay (MMT with dimethyl ditallow ammonium), or
maleated-PP, and both of these additives. The authors reported that while the
mechanism of PP photo-oxidation did not change, the induction period and the
rate of oxidation were modified, resulting in a decrease in material stability, but
the same degradation products were formed, in the same relative concentrations.
While the reason for the reduced photo-oxidative stability was not identified,
several contributing mechanisms have been postulated. (1) Hofmann elimination
process during extrusion that engenders unsaturated end groups, which could
combine with oxygen during irradiation. (2) MMT may catalyse polymer
degradation, especially in the presence of Fe2+ and Fe3+ ions, detected in the
organoclay. (3) Maleated-PP readily photo-oxidises, forming volatile byproducts.
The catalytic and sometimes inhibiting (catalyst poisoning) activities of clays
have been known for a long time, e.g., as suspected agent of life on Earth [Ferris,
2002], in the petroleum industry [Hettinger, 1991], and in general chemical
reactions [Newman, 1987]. The catalytic activities of MMT and its derivatives
have been reported frequently [see for example: Okada et al., 1988; Usuki et al.,
1989; Lan and Pinnavaia, 1994; Biswas and Ray, 1998; Heinemann et al., 1999;
Agag and Takeichi, 2000; Pullukat and Shinomoto, 2001; Lü et al., 2001; Wypart
et al., 2002; Sun et al., 2002]. Stackhouse et al. [2001] investigated self-catalysed
in situ intercalative polymerisation within Na-MMT. The authors have shown
that catalysis occurs at the clay lattice-edge where -OH groups and exposed Al+3
ions act as strong Brønsted and Lewis acid sites, respectively.
340
Rheology
3.3
Rheology
Modern rheology is expanding into new domains of research, which include

parallel observations of flow behaviour along with other, flow-imposed physical
properties, viz. orientation, electrical conductivity, magnetic properties,
birefringence, etc. For example, small-angle neutron scattering (SANS) has been
used to characterise clay dispersion in non-aqueous media [Ho et al., 2001].
More recently the focus has been on rheology performed on a progressively smaller
scale [Mukhopadhyay and Granick, 2001]. The use of surface force apparatus
makes it possible to study the steady-state and dynamic shear behaviour of liquid
films 0.3 nm to 1 μm thick.
However, the credit for the ultimate reduction of scale goes to Sakai et al.
[2002]. The authors carried out steady-state and dynamic rheological
measurements on a single telechelic, HS-terminated PS macromolecule (Mw = 39,
Mn = 22 kg/mol). The force-extension data followed the worm-like chain model,
giving the ultimate extension length, lmax = 20 to 60 nm, which agrees with the
theoretical value of the macromolecular contour length. The dynamic
measurements performed at frequency ν = 0.3 to 30 Hz and different extensions
of the macromolecule offered a unique method for determining the inter- and
intra-molecular interactions and their effects on segmental mobility.
3.3.1 Introduction
Before discussing the flow behaviour of CPNC it is worth summarising
information on the flow of clay suspensions.
• The early application of clay suspensions was for increasing the viscosity of
aqueous or organic liquids, to ‘give body’ and facilitate application, e.g., in
paints or greases. This has been efficiently accomplished by the ability of
clay to form face-edge interactions that leads to ‘house-of-cards’ 3D (gelled)
structures. The suspensions showed strong thixotropic effects, rapidly
increasing with concentration up to full gelation of the system at about
5 vol%.
• The computational and experimental data show that molecules form layered
structures on the face of crystalline solids. The first 2-3 layers show solid-
like behaviour and the solid surface effect stretches a long distance in the
z-direction. The z-distance where the viscosity is equivalent to that of neat
liquid depends on the molecular mobility; on average it stretches to 10-
12 layers, but in the case of macromolecules the distance may be as large as
100 to 120 nm.
341
• The crystalline solid-induced low mobility is reflected in the reduced free

volume (in comparison to the neat matrix polymer at the same T and P
conditions) that leads to increased viscosity, Tg, stiffness, etc.
• In CPNC there are at least three material components: polymeric matrix,
clay and intercalant. The degree of dispersion and the type of structure very
much depend on the interactions between the components (equilibrium
thermodynamics), the intercalation kinetics, and imposed stresses/orientation
(non-equilibrium effects).
• Owing to anisometry of the clay platelets six types of morphology have been
predicted: isotropic, nematic, smectic, columnar, house-of-cards, and
crystalline. The phase diagram at thermodynamic equilibrium depends on
the concentration and relative strength of interactions between the three
components. Evidently, the external stress field (imposed by flow, sonification,
pressure cycling, etc.) affects these structures. Once disturbed, the system
takes a long time (from minutes to hours) to return to equilibrium.
• Depending on the method of preparation, the CPNC is either end-tethered
or non-tethered. The former resemble highly branched, ‘hairy clay platelet’
structures with ca. a thousand macromolecules attached to the clay platelet
through the initial intercalant. The latter systems resemble a composite:
polymer reinforced with plate-like solids whose inorganic-phase dimensions
are enlarged by the intercalation and adsorption of organic molecules.
• Evidently, the degree of dispersion (intercalated versus exfoliated) and clay
content affects CPNC performance.
• Owing to the thermo-oxidative degradability of the ever-popular quaternary
ammonium intercalants at T > 200 °C, the time the material spends at these
temperatures may seriously affect its composition and structure, and hence
the flow behaviour.
It is known that the flow of multiphase polymeric systems is sensitive to the
dispersed phase size, shape, and surface characteristics as well as to the transient
geometric structures and interactions between the components, i.e., the matrix
polymer, clay and intercalant [Utracki, 1989; 1995; Utracki and Kamal 2002b].
Thus, rheology not only complements the traditional methods of CPNC
characterisation (such as XRD and TEM), PVT measurements, permeability and
mechanical testing, but in addition it provides information on the dynamic
behaviour of these complex materials.
3.3.2 Multi-Phase Flow Behaviour – An Overview

Rheology is a part of continuum mechanics hence the principles of continuity,
homogeneity and isotropy are normally assumed to hold. The continuity principle
requires that there is no discontinuity of material properties from one mathematical
point to another; homogeneity demands that there is no concentration gradient,
and isotropy implies that the flow does not impose orientation on the flow
elements. In molten multiphase systems (i.e., in polymer alloys, blends, composites,
foams and nanocomposites) these three principles are rarely valid. Thus, the
rheology of the multiphase systems follows its own principles, extending the use
of the general rheological dependencies. Obviously, the basic definitions of
rheological functions, e.g., viscosity, η, dynamic shear moduli, G´ and G´´, dynamic
shear compliance, J´ and J´´, etc., are identical. However, owing to the numerous
342
Rheology
influences, viz., concentration, morphology, flow geometry, timescale, type of

flow field, thermodynamic interactions between the phases, and many others, it
is difficult to relate the measured rheological functions to the intrinsic physical
properties of the CPNC.
The major distinction between single-phase and multiphase rheometry is the
effect of the flow field on the rheological response. Depending on the type and
intensity (strain) of the flow field the morphology of the tested fluid may be
modified. Since the structure modification is related to strain, it is to be expected
that responses at high and low strains will differ. For this reason, the selected test
method should reflect the final use of the data. Because of the sensitivity of
morphology to the test conditions, there is a serious disagreement between
predictions of the continuum-based theories and experiments, summarised in
Table 51. Since morphology is the characteristic property of a given material
(e.g., it affects the performance), testing the same multiphase system under different
flow conditions is equivalent to testing different morphologies, thus different
materials. When simulation of flow through a die is attempted, large strain
capillary flow is useful, but if the material characterisation is important, low
strain dynamic testing should be used [Utracki, 1988].
Flow fields affect the morphology of individual dispersed particles (orientation,
dispersion, coagulation, etc.) as well as the structure of the whole deformed body
(e.g., skin-core effect, weld-lines, flow encapsulation). The most efficient
orientation fields are extensional. Using convergent and divergent flow one may
control orientation of anisometric particles, e.g., in fibre-filled materials, in
semicrystalline polymer melts, in liquid crystal polymers or in CPNC. There is
less information on the flow-induced orientation of clay platelets, since due to
their size these particles are less susceptible to orientation than fibres. Furthermore,
their orientation seems to depend on whether they are end-tethered or not. In a
strong extensional flow field the former may orient perpendicularly to the
stretching direction (entangled matrix stretching), whereas the latter will normally
orient parallel to the stresses. A two-stage orientation mechanism was observed
in converging flow, but studies of the effect of flow on the orientation of nanofiller
have just begun.
Table 51 Comparison of continuum-based predictions for simple

fluid with experimental observations for multiphase fluids.
Data [Utracki, 1995].
Rheological Simple fluid Multiphase fluid
function
Viscosity at lim η(γ˙ ) = lim η ′(ω ) = lim η E (ε˙ ) / 3 lim η(γ˙ ) ≠ lim η ′(ω ) ≠ lim η E (ε˙ ) / 3
vanishing γ˙ →0 ω →0 ε˙ →0 γ˙ →0 ω →0 ε˙ →0
deformation rate
Extensional ηE = ηE (entrance pressure) ηE ≠ ηE (entrance pressure)

viscosity [Cogswell, 1972]
First normal stress N1 = N1 (extrudate swell) N1 ≠ N1 (extrudate swell)

difference [Tanner, 1970]
343
The time-temperature superposition principle, t-T, has been a cornerstone of

viscoelastometry. It has been used to extend the customary 2-4 decades of
frequency measurements to the whole range of variability of at least 15 decades.
The t-T principle breaks down in any mixture with more than one type of
relaxation time distribution, viz. in polymer blends (miscible or not), in LCP
over the range of transition temperatures, or in polymer-filler system with
temperature-activated association modes. In CPNC the t-T principle is expected
to hold for the end-tethered systems over a limited (by the transition temperature)
range of conditions. Evidently, any change of miscibility between matrix polymer,
intercalant and/or compatibiliser will affect the t-T behaviour.
3.3.3 Rheology and Microrheology of Disc Suspensions

The simplest rheological dependence for Newtonian suspensions is that of relative
viscosity ηr, versus volume fraction of the suspended particles, φ:
( )
ηr = 1 + [η]φ + k1 [η]φ ([ ] )
2 n
+ K + kn−1 η φ (104)
where the intrinsic viscosity, [η], depends on the rigidity and shape of the
suspending particles. The first of the equation parameters, k1 = kH is known as
the Huggins constant, indicating the interaction between the dispersed phase
and the matrix. In shear fields the particles rotate with the period dependent on
the rate of shear, γ˙ , and the aspect ratio, p:
t = ( 2π / γ˙ )( p + 1 / p) (105)
There are two conventions for defining the aspect ratio of ellipsoids. According
to one school, there is a continuity of transition from one type of ellipsoid of
rotation to the other and the aspect ratio is defined as a ratio of the major to
minor axes; p´ = a1/a2. Thus, for prolate ellipsoids p´ > 1 and for oblate p´ < 1 with
spheres being the intermediate step with p´ = 1. In this convention t-dependence
predicted by Equation 105 is perfectly symmetrical, giving the same period of
rotation for the rodlike ellipsoid with p´ = pr and for the disk-like ellipsoid with
p´ = pd = 1/pr [Goldsmith and Mason, 1967]. However, this symmetry is not
observed for the intrinsic viscosity ([η] is a measure of hydrodynamic volume).
According to the second convention p is defined as the ratio of the largest to the
smallest dimension, thus for rods: p = length/diameter > 1, whereas for discs,
p = diameter/thickness > 1. The latter system is used in this book, thus p = p´ for
fibres and spheres, whereas p = 1/p´ for discs.
Owing to the rotation, discs generate the maximum resistance to flow in one
position (perpendicular to the flow direction) and the minimum in another. For
this reason [η] is a periodic function of two angles of orientation in flow
[Goldsmith and Mason, 1967], from which one can compute the upper and lower
bound as well as the time-averaged value. In their excellent chapter on
microrheology the authors wrote the time-averaged intrinsic viscosity as:
[η] = ( p / 0.74)[3 ln(2 p) − 5.4] (106)
The experimental data of [η] versus p for anisometric particles gave empirical
relationships for rods, discs or hard spheres [Utracki, 1989]. For discs with p ≤
300 the following relation was found:
[η] = 2.5 + a( p b
)
−1 (107)
344
Rheology
where a = 0.025 ± 0.004 and b = 1.47 ± 0.03 with the correlation coefficient
squared, r2 = 0.9998 and standard deviation, σ = 0.622. Brodnyan [1959] adopted
Mooney’s relation between relative viscosity and volume fraction of hard spheres
and proposed an experimentally modified formula for prolate ellipsoids. At infinite
dilution this formula has the same form as the relation between [η] and p given
in Equation 107 for discs, but with a = 0.399 and b = 1.48.
For freely rotating prolate ellipsoids (rods) with p > 20 the following
dependence was derived [Simha, 1940; Simha, 1952; Frisch and Simha, 1956]:
2 ⎡ ⎤
[η] = 14 +
15 5
p
⎢
1
+
1
⎥
⎢⎣ 3 ln( 2 p) − 4.5 ln( 2 p) − 0.5 ⎥⎦
(108)
while for the oblate ellipsoids (discs) with p >> 1 Simha [1940] derived:
[η] = (16 / 15)( p / arctan p) (109)
Figure 89 shows that [η] very much depends on the shape and the aspect ratio of
anisometric particles. As is to be expected, the strongest enhancement of [η] with
p is observed for rods (prolate ellipsoids or fibres). Oblate ellipsoids (disks) show
intermediate behaviour between that of prolate ellipsoids and hard spheres. For
disks the prediction by Simha virtually superimposes on that by Kuhn and Kuhn
[1945] – they both form the upper bound for [η]. Goldsmith and Mason [1967]
proposed a relation that gives a lower bound, while the experimental values are
located in-between. The [η] is sensitive to polydispersity as well as to the regularity
of shape.
Figure 89 Intrinsic viscosity for rods and discs versus aspect ratio. In the latter
case the theoretical, (time-averaged) and the experimental dependencies are shown.
The Einstein value for monodispersed hard spheres, 2.5 for p = 1 is illustrated by
the horizontal line.
345
The plotted dependencies are averages – when initially the particles are all
aligned (e.g., in an electric field) and upon imposition of flow they start to rotate,
the rheological response (e.g., shear viscosity or [η]) will vary with the period
given by Equation 105. Ivanov et al. [1982] reported on the periodic oscillatory
nature of suspension viscosity in shear flow.
The above relations are valid within the high dilution region where the free
rotation of anisometric particles is feasible. Detailed analysis of flow within this
region is available [Goldsmith and Mason, 1967; van de Ven, 1989]. As the
concentration increases the particle-particle interaction becomes stronger and
the higher terms in Equation 104 have to be included. The relation breaks down
once the concentration of particles exceeds the limit of possible free rotation.
This limit, φ > φmax, can be calculated assuming that the discs are circular and the
volume they require for free rotation is that of the encompassed sphere. For the
monodispersed hard spheres and oblate ellipsoids the (experimental) maximum
packing volume fraction is φm ≅ 0.62 and φmax = 0.62/p. Empirically, for p < 50 a
weaker dependence was found:
φmax = (1.55 + 0.0598 p)
−1
(110)
As shown in Figure 90, the empirical dependence for φmax predicts higher values.
The most probable reason for the disparity is the tendency of discs to align parallel
to each other, even at low concentration (the same reason why, in suspensions,
the spheres readily make doublets), thus prematurely forming the structures
expected within the φ > φmax region, where the discs must adopt locally parallel
orientation with the spacing dependent on concentration, d001 = a0 + a1/φ (see
Figure 44 in Section 2.4).
These simple relations are valid for suspensions without strong interactions.
Dispersion of clays in aqueous media is complicated by the presence of electrostatic
Figure 90 Maximum packing volume fraction for freely rotating discs versus
aspect ratio. Lower solid line – theoretical, assuming monodispersed particles,
upper broken line – empirical, Equation 1.
346
Rheology
forces, which results in the formation of 3D structures (e.g., house-of-cards) or

aggregation [Jogun and Zukoski, 1996].
3.3.4 Similarity Between CPNC and Liquid Crystal Flow

As discussed in Section 3.1.5.3, the equilibrium thermodynamics predicts that
depending on the interactions and concentration in CPNC six phase structures
are expected: isotropic, nematic, smectic-A, columnar, house-of-cards, and crystal.
A similar list of phase structures is known for liquid crystal polymers (LCP):
isotropic, nematic, cholesteric, smectic-A and smectic-C. However, while in CPNC
platelet orientation creates these diverse structures, in LCP the focus is on the
rod-like molecules or side groups with the transition between the phases dependent
on temperature.
Liquid crystals are defined as systems ‘that are molecularly ordered yet possess
mechanical properties resembling those of fluids’ [Porter and Johnson, 1967].
Considering that it is more difficult to build disc-shaped molecules than rigid-
rod type, the focus of LCP has been on the latter systems. Furthermore, there are
significant difficulties in developing theoretical treatment for LCP with disc
moieties [Ciferri, 1991].
To simplify interpretation of the flow behaviour, rheological tests are usually
carried out either within a specific phase or at the phase boundary. There are
numerous publications describing behaviour of nematic LCP, modelled as a system
of rods, which during the shear flow may undergo periodic rotation. Rheology
of the smectic (layered grease structure) and cholesteric phases is not as well
documented. However, it seems that there are similarities between the flow
behaviour of nematic LCP and CPNC, especially these containing end-tethered
macromolecules.
Figure 91 Three regions of flow of nematic LCP. The viscosity versus shear rate
dependence as generalised by Onogi and Asada [1980].
347
In nematic LCP, the morphology is characterised by local orientation within

each domain, evident in rheo-optical studies. As shown in Figure 91, there are
three regions of flow for nematic LCP: (I) low deformation rate shear-thinning
region; (II) the (Newtonian?) plateau region; and (III) the power law shear thinning
region [Onogi and Asada, 1980]. Within region I, the polydomain structure
dominates the flow. The authors remarked that here the rheological response is
highly variable, depending on the history of the sample, method of preparation,
wall temperature, etc. Depending on these, the size of the domains and the extent
of the interdomain interaction varies. Rheo-optics indicates that as the rate of
shear increases the intensity of transmitted polarised light also increases. However,
only within region II does the polarised light show systematic oscillations of
intensity, indicating rotation of the nematic domains. Thus, while in region I
there is strong interaction between nematic domains that rheologically mimic
the yield stress, within region II the domains are dispersed in a monodomain
continuous matrix, which also dominates region III. In this region, initially domain
flow proceeds by the tumbling motion, but as the deformation rate increases the
tumbling is replaced by flow alignment.
One of the most intriguing characteristics of nematic LCP is the behaviour of
the first normal stress difference, N1. Experiment and theory indicate that for the
flow of nematic LCP there is a region of the deformation rates where N1 < 0 [Kiss
and Porter, 1980; Marrucci, 1991]. The change from the tumbling to flow-aligned
stationary monodomain flow takes place at shear rates in the middle of the negative
N1 range. Theory also predicted negative values of N1 for the transitory response
after start-up at low shear rates.
Owing to the diversity of CPNC structures one must be careful in comparing
their flow to that of nematic LCP. In LCP the structure is defined by the molecular
constitution and temperature, while in CPNC it depends on composition, degree
of tethering and exfoliation. Thus, similarity of flow behaviour is expected for
the nematic LCP and diluted end-tethered CPNC, but not for the CPNC where
platelets enrobed in intercalant are dispersed in a polymeric matrix. The three
regions of flow observed in LCP have also been observed in end-tethered PA-6/MMT
systems, but the negative values of N1 were not found [Utracki and Lyngaae-
Jørgensen, 2002]. The reason may be greater difficulty in tumbling flow for the
hairy clay platelets, HCP, the heterogeneity of sizes and structures responsible
for a broad transition range, inherently weaker effects of the aspect ratio for
platelets than that for rods, unsuitable timescale of the experiment, experimental
difficulties, etc.
Another similarity in the rheological response between CPNC and LCP is the
transient behaviour at start-up [Metzner and Prilutski, 1986]. During the steady-
state shearing of hydroxypropyl cellulose solution in a cone-and-plate geometry
the shear stress, σ12, overshoot reached a value of 20 Pa then decreased to 12.5
and after 250 s of shearing it increased to a steady-state value of 22 Pa. Even
stronger and slower responses were reported for N1. Over the years many studies
of stress overshoot have been reported. It was noted that the magnitude depends
on the shear history – the longer the specimen is undisturbed the larger is the
stress overshoot (up to a limit).
Two mechanisms could account for this: (1) orientation of anisometric particles
and (2) interaction between the domains. However, the consensus seemed to
emerge that the latter process, a disruption of the polydomain structure during
flow, is the correct one [Viola and Baird, 1986]. The latter authors carried out in
348
Rheology
parallel rheological and WAXS studies of stress growth, interrupted stress growth,
stress growth after flow reversal and stress relaxation. In spite of large rheological
effects, WAXS provided strong evidence that orientation effects were absent during
the shear flow. The extensional flow produced orientation, but its changes occurred
on a different timescale to those in the stress field. Thus, the disruption of the
interactive domain structure was proposed as the stress overshoot mechanism.
Pitches are notoriously complex comprising at least 461 identified chemical
components, with molecular weights ranging up to 2 kg/mol [McNeil, 1983].
Owing to unsaturation, some of the molecules have a rigid rod structure, while
some others (formed by fusing 4 to 10 aromatic rings) are discotic, hence their
structure may be considered intermediate between the rod-like LCP and CPNC.
The presence of these anisometric molecules is responsible for the nematic pitch
behaviour. The anisometric compound content may be adjusted by extraction or
by addition of synthetic compounds.
Fleurot and Edie [1998] studied the rheology of three mesophase pitches used
for production of carbon fibres. The steady shear data placed them within regions
I and II of the Onogi and Asada classification. The transient shear response was
determined by pre-shearing the samples at γ˙ = 0.5 s-1 for 2 min then letting the
sample rest for 8 to 4000 s, and then restarting the flow. The results are shown in
Figure 92. For all three samples the stress growth depended on composition. The
normalised peak height increased with the rest time after pre-shearing, but for
different pitches the form of the dependence was different and a master curve
could not be generated. The determined domain size was large, decreasing with
shear rate ( γ˙ = 0.5 to 10 s-1) from a = 16 to 6 μm. The authors applied the
domain theory of LCP with a qualitative success.
Figure 92 Normalised stress growth peak for three mesophase pitches versus rest
time before re-shearing at the rate of shear of 0.5 s-1. After [Fleurot and Edie,
1998].
349
Marrucci [1984] formulated the domain flow theory assuming a balance between
the alignment tendency of the velocity field and the elastic resistance to deformation
of the director field. The Eriksen distortion stress, σE, was taken as proportional to
the elastic constant, K, and inversely proportional to the domain size. Noting the
domain size within the polydomain region I as ao and during the flow as a, the
stress associated with the recoverable (elastic) energy was calculated as:
(
σ E ~ K a −2 − ao−2 ) (111)
While the average stress is given by this dependence, the flow depends on the
local orientation – high velocity is expected in the region where the orientation
director and velocity vector are parallel to each other, and low velocity for the
opposite case. As a result, the rheological relation between the shear stress and
the deformation rate was scaled down to read:
σ = ηequilγ˙ao / ( ao − a) (112)
Equating these two equations gives the relation between the reduced viscosity,
( )
η/ηequil, and the reduced deformation rate, γ˙ redu = γ˙ ao2 ηequil / K (see Figure 93a).
Figure 93b shows the complementary dependence of the relative domain size
reduction versus the relative deformation rate. The derived relation has two
asymptotic limits. At low deformation rates the initial slope is predicted to be –1/2
(in contrast to the value of –1 predicted for the yield stress). This slower decrease
of the reduced viscosity with shear rate is in good agreement with many
observations of LCP flow. The second asymptote is obtained at higher rates,
where the plateau value of region II is recovered. Thus, as simple as the derivation
is, it provides sound explanations for the shape of the flow curves of LCPs. Since
the basic assumption was the presence of large domains with aligned particles,
this treatment may be useful for interpreting the flow behaviour of CPNC systems.
3.3.5 End-Tethered versus Non-Tethered CPNC

The rheological studies on CPNC are quite recent. A relatively early publication
reported on the steady-shear flow of MMT-2M2T dispersed in either diphenyl
dimethyl siloxane or in polydimethylsiloxane (PDMS) [Krishnamoorti et al.,
1996]. In the former system clay was intercalated, whereas in the latter it was
exfoliated. Characteristically, the flow curves for both systems showed a large
Newtonian plateau. As expected, the zero-shear viscosity, ηo, increased with
organoclay loading, but at high deformation rates matrix viscosity was recovered.
The plot of ηo versus concentration is presented in Figure 94 and that of relative
viscosity ηr versus φ in Figure 95. The presence of a Newtonian plateau indicates
that there is no 3D structure in these systems; hence the interactions between
organoclay particles are weak. However, the ηr versus φ dependence in the latter
Figure shows that while for the exfoliated system (up to 13 wt% clay) the
dependence is typical for diluted suspensions with high value of the intrinsic
viscosity, [η] = 9.3, the intercalated system gives evidence of interactions at a
loading of ca. 4 wt%. Furthermore, its value of [η] is lower than that calculated
for the exfoliated system, indicating lower apparent aspect ratio, hence stack
formation. Such behaviour is typical for suspensions. The nanoparticles, exfoliated
or not, behave as a filler – no surprise here.
Krishnamoorti et al. also carried out preliminary studies on the flow behaviour of
CPNC with PA-6 as matrix. More information on the topic was given in the
350
Rheology
Figure 93 Predicted by the Marrucci’s domain flow theory (a) apparent reduced
viscosity and (b) relative domain size versus shear rate. See text.
following publication [Krishnamoorti and Giannelis 1997]. Flow of three resins

from Ube was studied. These contained 0, 2 and 5 wt% of organoclay. The authors
also measured the dynamic flow behaviour for CPNC of poly-ε-caprolactone (PCL)
with up to 10 wt% organoclay. For the latter system validity of the time-temperature
superposition was reported. The Arrhenius plot of the frequency shift factor, aT
versus 1/T did not depend on the clay loading. Thus, excepting the apparent yield
behaviour at low frequencies, the matrix polymer dominated the flow.
Both these systems with PA-6 or PCL as a matrix were prepared by
polymerisation in the presence of intercalated clay, which engendered direct
bonding between the MMT surface and the macromolecules – a hairy clay platelet
(HCP) structure. The authors labelled these systems as ‘end-tethered polymer
layered silicate nanocomposites’. The G´ and G´´ moduli were found to increase
with clay loading. Their power law dependence in the terminal zone was different
from that observed for homopolymers. At low frequencies (ω < 10 rad/s) the
351
Figure 94 Zero-shear viscosity of CPNC of dimethyl ditallow ammonium MMT

dispersed in diphenyl dimethyl siloxane (intercalated) and in PDMS (exfoliated).
Data [Krishnamoorti et al. 1996].
Figure 95 The data from Figure 94 re-plotted as ηr versus φ. The exfoliated

clay has higher aspect ratio hence higher [η] and less particle-particle interaction
than the intercalated one. Data [Krishnamoorti et al., 1996].
352
Rheology
initial slope of G´ and G´´ was found to decrease with increasing concentration
of organoclay. Thus for 0, 2 and 5 wt% loading:
g´´ ≡ (d log G´´/d log ω)ω < 10 = 0.93, 0.80 and 0.70, respectively.
These values should be compared to the expectations: for neat polymer g´ = 2
and g′′ = 1, for the LCP domain flow g´´ = 1/2, while for systems with yield stress
g´´ = 0. Thus, these CPNC behaved like a solution of LCP in a molten polymer,
and not like filled melts with yield stress. At high strains the platelets may be
aligned, which would greatly reduce the rheological response. In short, these
end-tethered systems behaved differently than could be expected from diluted
suspensions (see also: Section 3.2.7).
A slightly different approach was used by Wagener and Reisinger [2003].
Instead of using the initial slope of G´ and G´´ the authors calculated the ‘shear
thinning exponent’ from the initial slope of the complex viscosity versus frequency
dependence: n ≡ d logη*/d log ω. Evidently, the parameter is a reflection of the
3D structure. There are many mechanisms responsible for such effects (e.g.,
compatibilisation of immiscible mixture of polymers [Utracki, 2002a]), but in
CPNC, when other factors are constant, the exponent n may reflect the degree of
platelet dispersion. Indeed, for PBT with 4 wt% organoclay, empirically n
correlated with Young’s modulus: Y(GPa) ≅ 2.5 – 1.2n.
It is to be expected that the rheological behaviour of the end-tethered systems
will differ from that where such direct bonding is missing [Hoffmann et al.,
2000a]. The authors prepared two types of CPNC based on PS. In the first, the
clay was intercalated with phenyl-ethyl amine, and then dispersed in PS, while in
the second the clay was exfoliated with amine-terminated PS. A plot of the storage
shear modulus, G´ versus reduced frequency ωaT for the neat PS and PS with
intercalated clay nearly superimposed one on top of the other – addition of
organoclay did not change the basic flow properties of the PS matrix. By contrast,
the exfoliated, end-tethered CPNC (with amine-terminated PS) showed large
increases of G´ at low ω, indicating a network formation.
In the next publication, the melt flow behaviour of two exfoliated CPNCs
was studied. Two types of clay: synthetic fluoromica, FM, and mineral MMT,
were used [Hoffmann et al., 2000b]. First, the clays were intercalated using either
protonated ω-amino dodecanoic acid (ADA) or water, then dispersed in ADA,
which in turn was polymerised into PA-12. The use of ADA-intercalated clay
resulted in the formation of end-tethered CPNC with platelets chemically bonded
to the matrix, but with surprisingly small interlayer spacing, d001 ≤ 2 nm. The use
of water as a swelling agent resulted in exfoliated nanocomposites, but without
the chemical bonds between clay and the polymer chains.
A stress-controlled rheometer was used in the parallel plate geometry at
ω = 1 to 25 rad/s assuring linear viscoelastic behaviour. Comparison of the neat
PA-12 matrix flow with those for the two CPNC showed significant differences.
The presence of a superstructure was deduced from the low frequency behaviour.
The slopes of G´´ in the terminal region were: g´´ = 0.4 to 0.6 for the end-tethered
and 0.9 for the not-tethered CPNC, thus lower than those of PA-12 with similar
molecular characteristics. Furthermore, flow of CPNC with exfoliated but non-
tethered clay platelets, was dominated (at least up to 4 wt% organoclay loading)
by the matrix behaviour, with only a minor contribution from clay. Tethering
dramatically enhanced the storage and loss shear moduli, by one and by one-half
decade, respectively. This observation is particularly important since XRD showed
353
that the end-tethered CPNC reached only a moderate level of intercalation.

Evidently, the end-tethering has stronger influence on flow than exfoliation. During
injection moulding of these CPNC the clay platelets became oriented in the
injection direction [Kim et al., 2001b].
There is also evidence that significant modification of the flow behaviour (in
comparison to classical filled systems) is possible without end-tethering of the
matrix macromolecules. One of the examples comes from Ren et al. [2000]. The
authors dispersed up to 9.5 wt% MMT (intercalated with 2M2ODA) in a matrix
of polystyrene-b-polyisoprene (PSIR, Mw = 17.7 kg/mol). Linear viscoelastic flow
was studied at T = 80-105 °C. The t-T superposition required simultaneous
horizontal and vertical shifting of the shear moduli: bTG´ and bTG´´ versus aTω.
While aT for all compositions followed the same WLF dependence, bT did not –
there was a dichotomy between the matrix copolymer and CPNC sets of data,
indicating different macromolecular structure engendered by the organoclay. XRD
indicated intercalation with d001 expanded from 2.25 nm (in organoclay) to
3.45 nm. Thus, these nanocomposites are neither end-tethered nor exfoliated.
The stress relaxation data in the terminal zone (see Figure 96) showed a solid-
like behaviour of these CPNC samples. The effect was particularly pronounced
at ≥ 6.7 wt% organoclay, resembling that observed for the exfoliated end-tethered
nanocomposites. The solid-like behaviour was evident plotting G´ versus ω – at
low frequencies the storage modulus was nearly constant with g´ ≅ 0. The authors
attributed this behaviour to the presence of stacks of intercalated clay platelets,
each stack randomly oriented, but forming a 3D network. A large-amplitude
oscillatory shear was able to orient these structures and reduce the solid-like
behaviour. However, that explanation may be partial. Dispersion of the same
organoclay (MMT-2M2ODA) in polyisoprene (IR) did not change d001; hence
there was no diffusion of IR macromolecules into the interlamellar galleries.
Evidently, during the dispersion of MMT-2M2ODA in PSIR it was the PS block
that diffused into the interlamellar galleries, expanding them by Δd001 = 1.2 nm.
This intercalation may suggest that there is a certain degree of interaction between
Figure 96 Stress relaxation, G(t), for PSIR and its CPNC. The solid lines were
computed from dynamic moduli, G´ and G´´.
Reprinted with permission from [Ren et al., 2000]. Copyright 2000 American
Chemical Society.
354
Rheology
MMT and the aromatic rings of PS. As discussed above, the non-tethered clay
platelets in the PS matrix showed limited influence on the CPNC flow. The
dramatic modification of the rheological behaviour shown in Figure 96 suggests
that in the copolymer clay is preferentially dispersed in PS-block domains, phase
separated from those of IR-blocks.
The data in Figure 96 also illustrate that the simple relation developed by
Ferry [1980] for a single component melt is also valid in these rheologically
complex systems:
G(t ) t =1 / ω = G ′(ω ) − 0.4G ′′(0.4ω ) + 0.014G ′′(10ω ) (113)
Sometimes, the end-tethering may be replaced by strong interactions between polar
groups and the clay surface. Schmidt et al. [2000, 2002a] measured birefringence
and small angle neutron scattering (SANS) during Couette shear flow of clay
suspensions in aqueous polymer solution. Thus, 3 wt% of synthetic hectorite (FH;
platelets with diameter d = 30 nm and thickness h ≅ 1 nm) was dispersed in an
aqueous solution of 2 wt% polyethylene glycol (PEG, Mw = 103 kg/mol) at pH = 10
and a NaCl concentration of 1 mmol/L. The birefringence indicated mechanical
coupling between clay platelets and PEG. At low rates of shear, γ˙ < γ˙ critical ~ 30 s −1 ,
birefringence was dominated by the clay platelets, but at high by the polymer
chains stretched in the flow direction. SANS data indicated that at γ˙ > γ˙ critical the
flow was strong enough to induce chain orientation. The clay platelets (within
aggregates with diameter d = 32-233 nm) were oriented in the flow direction with
the surface normal in the neutral (not radial) direction. In a later publication the
authors used SANS to study the effects of shear on clay platelet orientation [Schmidt
et al., 2002b]. As the rate of shear increased the clay platelets progressively oriented.
At the highest flow rates the macromolecules became stretched in the flow direction.
Lim and Park [2000; 2001] prepared CPNC by dispersing up to 10 wt% of
MMT (intercalated with 2M2HT; Cloisite® 6A) in either PS or in PS-co-MA
(containing 7 wt% MAH). Compounding in an internal mixer increased d001
from 2.94 nm (Cloisite) to 3.45 and 3.37 nm for PS and PS-co-MA, respectively.
In spite of the small difference of the interlayer spacing the low frequency dynamic
moduli showed large differences, viz. G´(10% clay, ω = 0.02) ≅ 0.1 and 6 kPa,
with the corresponding differences in the initial slope of g´ = 0.59 and 0.24,
respectively. Shearing these highly loaded samples at γ = 120%, ω = 1 rad/s for
30 min reduced the effects of association, but did not eliminate them entirely.
The cited examples demonstrate that instead of a sharp distinction between
the classical, filler-like influence of organoclays and the effects assigned to the
end-tethered CPNCs, there is a continuous spectrum of rheological behaviour.
The rheological response is associated with the ability of dispersed particles or
aggregates to interact with each other. In the presence of electrostatic interactions
in aqueous media the platelets readily form edge-face ‘house-of-cards’ structures,
even at low loading of ca. 5 wt%. However, in organic media there is a double
layer of semi-solid organic molecules that shields the silicate surfaces. Here, the
formation of 3D structures is possible by two mechanisms – crowding, as in
classical composites, or by entanglements. In the latter case the strongest effects
are to be expected when the terminal groups directly bond macromolecules to
the clay surface. However, entanglements may also be promoted by the use of
block copolymers or by forming associations between the clay surface and polar
groups of the polymer chain. Further examples of the effects of tethering will be
found in the following parts.
355
3.3.6 Fourier-Transform Rheology of CPNC

Application of the Fourier transform methods in rheology is at least 30 years old
[Wapner, 1971; Wapner and Forsman, 1971]. While the authors were interested
in extracting the true linear viscoelastic response from vibrating reed experiments,
their approach was general, incorporating all possible modes. During the last
few years Fourier-transform rheology (FTR) has gained more prominence mainly
as a tool for the analysis of non-linear viscoelastic response in polymeric systems
subjected to large amplitude oscillatory shear (LAOS). FTR is capable of detecting
and measuring the higher harmonics that in the past were only qualitatively
characterised by, e.g., the Lissajou stress-strain loops [Wilhelm, 2002].
In view of the complex rheological behaviour of CPNC it seems that
application of this method may provide a suitable tool for the characterisation of
the non-linear viscoelastic response in CPNC as well as for measurements of the
kinetics of orientation effects.
FTR analysis starts with writing the absolute magnitude of the shear rate in
the dynamic flow field, with frequency ω and strain amplitude Ao, as:
γ˙ (t ) = ωAo cos ωt (114)
The Fourier transform of this dependence yields an expression with only even
harmonics:
γ˙ (t ) ∝ ao + a1 cos 2ωt + a2 cos 4ωt + K (115)
Thus, the stress being a product of rate of shear and shear-dependent viscosity is
expressed as a sum of odd harmonics:
σ ∝ A1 cos ωt + A3 cos 3ωt + A5 cos 5ωt + K (116)
The simplest method for the analysis of the FTR signal is to plot the relative
magnitude of the odd harmonic peaks divided by the first: Rn(ω) = I(nω)/I1(ω),
with n = 3, 5, 7, … For the linear viscoelastic fluids Rn(ω) = 0, whereas for non-
linear materials Ri(ω) = 1/n, thus the strongest third harmonic, R3(ω), contains
all the important information.
Wilhelm demonstrated that the strain dependence of R3(ω) follows two simple
relations:
[ { }]
R3 (ω ) = R 1 − exp −( γ − γ L ) / k ; γ > γ L (117)
⎡ ⎤
1
R3 (ω ) = R ⎢1 − ⎥; γ > γ L (118)
⎢ 1 + ( Bγ )C ⎥
⎣ ⎦
In these relations R is a measure of the maximum intensity, γ is the applied strain,
γL is the maximum strain for the linear viscoelastic response, while k, B and C
are parameters characterising the relative intensity change of the 3rd harmonic
peak. The former relation, Equation 117, has been used to determine the limit of
the viscoelastic linearity, whereas the latter provides a better fit to data within
the full range of strains.
3.3.7 Rheology of CPNC with PA Matrix

Krishnamoorti et al. [1996] studied the flow of two end-tethered CPNCs prepared
by in situ polymerisation (in the presence of pre-intercalated MMT) of
356
Rheology
ε-caprolactone (PCL) and ε-caprolactam. In these systems the polymer chains

were end-tethered to the silicate surface via cationic intercalants. The linear
viscoelastic properties, the large amplitude oscillations and orientation were
examined. Unfortunately, the molecular weight varied with silicate loadings which
made evaluation of the data a bit difficult. The t-T superposition principle was
found to be valid and the master curves could be prepared in the whole range of
concentration (up to 10 wt% clay). The authors reported that the nanocomposites
were readily aligned at large amplitude oscillatory shear. The alignment resulted
in a change of slope within the terminal zone as well as in reduction of the dynamic
moduli by about one order of magnitude. Furthermore, a steep increase of the
complex viscosity, η*, was reported during strain sweeps at low frequencies, ω = 1
or 3 rad/s. Since the tanδ = G´´/G´ was reduced, the effect was related to increases
of G´, caused by enhanced interactions between the flow domains.
The industrial production of CPNC started with commercialisation of PA-6
nanocomposites by Ube (on a license from Toyota). In spite of thirty-odd years
of technology developments there have been relatively few publications dedicated
to melt flow studies of these systems. By contrast, several processes for the
manufacture of PA-6 nanocomposites have been published [Okada et al., 1988;
Deguchi et al., 1992; Okada and Usuki, 1995; Ube Ind., 2000]. The Toyota/Ube
process involves high temperature ring-opening polymerisation of ε-caprolactam
in the presence of MMT pre-intercalated with ω-amino dodecanoic (lauric) acid
(ADA). The molecular weight of the PA-6 matrix is about Mn = 22 kg/mol and
the organoclay content 2 wt%. The composition and properties of natural MMT
may vary with geographical location and local strata. However, an idealised Na-MMT
unit cell can be written as:
Triple layer sandwich of two silica

](
− 0.67 )
tetrahedron sheets and a central [ Al
3.33 Mg0.67 Si8 O20 (OH )4
octahedral sheet with 0.67 negative
charge per unit cell
c
Aqueous interlamellar layer containing

0.67 Na+ cations per unit cell (n × H2 O) Na0+.67
Thus, the molecular weight of a MMT unit cell is Mu = 734 + water. The cation
exchange capacity of the idealised MMT is CEC = 0.915 meq/g, with Na+ spaced
ca. 1.2 nm apart.
Assuming that every clay plate and every cation on its surface is available for
the exchange reaction of Na+ for ADA and that each lauric acid group starts the
polycondensation, leads to the conclusion that near the clay platelets the end-
tethered PA-6 chains are densely packed. Since the molecular weight of PA-6 is
Mn = 22 kg/mol, the resulting clay content of the fully grafted hairy clay platelets
(HCP) should be 4.74 wt%. As the clay platelets are 0.96 nm thick and their
aspect ratio is p = 287 (see below), each platelet would have about 140,000 end-
tethered macromolecules, i.e., Mn ≅ 3×106 kg/mol of a single HCP. Thus,
polycondensation that involves every Na+ on the Na-MMT surface results in
formation of an entity that resembles a star-branched or dendritic macromolecule
357
of a very high molecular weight. Near the clay surface the macromolecules are
crowded and immobilised.
Polycondensation results in CPNC containing exfoliated clay particles with
PA-6 macromolecules tethered to their surface. For the reason of dyeability these
CPNC need to be diluted with about twice the amount of neat PA-6. Alternatively,
the grafting efficiency of the clay platelets may be reduced and HCP with Mn ≅ 1
to 3×106 kg/mol are produced. To form these materials, standard processing
methods, e.g., extrusion or injection moulding, may be used. The improvement
of the rigidity, tensile and flexural strength, heat distortion temperature and gas
barrier properties over neat PA-6 have been rationalised on the basis of the surface
effects, change in crystallinity as well as by the orientation effects imposed by the
processing flow field.
Kojima et al. [1994] studied the orientation and crystallinity of extruded PA-6
CPNC calendered films containing 0.18, 0.46 and 0.74 vol% of clay. XRD, TEM
and DSC measurements were carried out. It was found that clay platelets as well
as the γ-crystals of PA-6 had planar orientation. The orientation direction was
independent of the clay content, but the degree of orientation increased with it.
It seems that during the flow through a T-die followed by subsequent stretching
between chilled rolls the clay platelets became in-plane oriented, then the matrix
polymer crystallised with the chain axes parallel to the clay surface. The γ-form
of PA-6 has four monomeric units in the monoclinic unit cell with hydrogen
bonding between parallel chains. This form is often associated with the formation
of extended chain crystals during processing involving elongational flow.
In the following paper the authors reported on the orientation engendered by
injection moulding of CPNC into an end-gated, 3 mm thick mould cavity [Kojima
et al., 1995]. Here the MMT content was 2.2 vol%. XRD and TEM measurements
were carried out. In Figure 97 the 002-reflection peak intensity of γ-PA-6 versus
injected bar thickness, z, is shown. Three regions of orientations are evident:
skin with in-plane orientation for the PA-6 macromolecules as well as for the
clay platelets, intermediate with chains perpendicularly oriented to the clay
platelets and the flow direction, and the centre layer where the macromolecular
chain orientation is perpendicular to the clay surface, and clay platelets are
primarily oriented perpendicular to the flow direction.
It is interesting that during the flow through rolls that engenders film stretching
or during fountain flow in the mould cavity the macromolecular chains of PA-6
get oriented in-plane and crystallise with the chain axis parallel to the clay surface.
However, at lower stresses the lamellae are oriented along the clay surface with
chains oriented perpendicular to it. Kojima et al. speculated that this is the natural
behaviour of PA-6 chains, highly crowded near the clay surface caused by the
high grafting density.
More recently, Medellin-Rodriguez et al. [2001] studied SAXS/WAXS
orientation of the same Ube CPNC during steady-state shearing between parallel
plates at γ˙ = 60 s-1, and T = 240 °C for up to 20 min. Compression moulded film
specimens, 0.25 mm thick and containing 0, 2, and 5 wt% of MMT were used.
At this relatively low shear rate and at a temperature near the melting point there
was a gradual change of clay platelet alignment (see Figure 98). Owing to the
vorticity component in the shear stress matrix, the end-tethered clay platelets are
expected to tumble with the period given by Equation 105. The increasing
scattering intensity (in the direction perpendicular to the shear field) indicates
358
Rheology
Figure 97 XRD peak intensity of γ-PA-6 versus injected bar thickness, z. Three
regions of lamellar orientation are shown: skin with in-plane orientation,
intermediate with perpendicular orientation and central (see text).
Data [Kojima et al., 1995].
Figure 98 MMT platelet orientation in PA-6/MMT-ADA nanocomposites with 0, 2

and 5 wt% of MMT-ADA as a function of the steady-state shearing time at
γ˙ = 60 s -1, and T = 240 °C. Data [Medellin-Rodriguez et al., 2001].
359
progressive orientation in the shear vector. Evidently, at φ < φmax the tumbling
motion of the clay platelets continues, but since the motion is periodic with long
residence time in the preferred direction the overall platelet orientation is in the
flow direction (e.g., see Goldsmith and Mason [1967]). The authors also reported
that randomisation of the clay orientation after cessation of shear is slow,
substantially slower than the relaxation of polymer chains. Thus, at T = 240 °C
it takes at least 12 min to randomise the platelets, whereas the PA-6 relaxation
time is about 0.4 s. In consequence, crystallisation during normal processing
conditions is bound to preserve the flow-induced clay orientation in the product.
3.3.7.1 Effects of Moisture

The Ube PA-6 and PANC containing 0 and 2 wt% organoclay, respectively, were
thoroughly studied in dynamic and steady-state shear flow [Utracki and Lyngaae-
Jørgensen, 2002]. Prior to compounding or testing the material was dried for
48 h at 80 °C under vacuum. As shown in Figure 99, these conditions were
sufficient to achieve about 97% of the equilibrium complex modulus, G*. The
two commercial resins were blended in proportions of: 0, 25, 50, 75 and 100 wt%
PANC. The studied samples (two ‘as received’ and five extruded) are listed in
Table 52.
The rheological properties of polyamides are known to depend on the
measurement time, e.g., see [Khanna et al. 1996] and references cited therein.
This reversible change is related to the variation of the moisture content and
changes of molecular weight associated with it, i.e., to reversibility of the
polycondensation-hydrolysis reaction. For these reasons, first the time sweeps
were measured under a blanket of N2 at T = 240 °C, frequency ω = 6.28 red/s and
strains γ = 10 and 40% for 1 h. After testing, the specimens did not show signs of
oxidative reactions – they remained off-white, indicating that the increase of the
Figure 99 Complex shear modulus as a measure of the PA-6 drying time under
vacuum at 80 °C. Data [Utracki and Lyngaae-Jørgensen, 2002]. The line follows
the exponential dependence: log G* = ao – a1 exp{-a2/t} with ao = 2.87 ± 0.01;
a1 = 0.43 ± 0.01; a2 = 1.4 ± 0.1 and the standard deviation σ = 0.02; r2 = 0.99995.
360
Table 52 Polynomial fit parameters for the time sweeps. The first five samples were re-extruded or compounded,
the last two 'as received'. Data [Utracki and Lyngaae-Jørgensen, 2002]
PANC wt% G′′0 G′′1 G′′2 rG′′ G′′′′0 G′′′′1 G′′′′2 rG′′
0 (PA-6) 39.39 0.04082 0.0000 0.99996 1926.9 0.55258 -4.5154e-05 0.99983
25 82.29 0.06113 0.0000 0.99993 2194.0 0.48794 -3.1387e-05 0.99977
50 152.9 0.07995 -2.6699e-06 0.99987 2560.4 0.50421 -3.4721e-05 0.99970
75 242.6 0.09321 -3.8080e-06 0.99978 2898.0 0.44210 -2.7627e-05 0.99939
100 (PANC) 321.3 0.09600 -4.2305e-06 0.99971 3133.3 0.37305 -2.2062e-05 0.99859
0 (PA-6) 35.84 0.04744 0.0000 0.99995 1918.2 0.65015 -4.9298e-05 0.99958
100 (PANC) 559.7 0.1774 -1.0141e-05 0.99962 3773.2 0.54600 -2.8488e-05 0.99888
361
Rheology
shear moduli was caused by polycondensation. The response was found to be

independent of frequency (ω = 0.1 to 100 rad/s) and strain (γ = 10 or 40%). The
data were fitted to a second order polynomial, with t being the sweep time (in sec):
G ′ = Go′ + G1′t + G2′ t 2 ; R ′ ≡ dG ′ / dt = G1′ + 2G2′ t
(119)
G ′′ = Go′′ + G1′′t + G2′′t 2 ; R ′′ ≡ dG ′′ / dt = G1′′+ 2G2′′t
In spite of the fact that before loading into a rheometer the specimens were well-dried,
during the 1 h in the rheometer the shear moduli, G´ and G´´, increased by a factor of
2 to 5 and 1.4 to 1.8, respectively. From these changes the rates of G´ and G´´ increase,
R´ and R´´, were calculated (see Equation 119, Table 52 and Figure 100).
As shown in Figure 100, the rates R´ and R´´ are both positive hence the two
moduli increase with time, but increasing the organoclay content caused an increase
of R´ and a decrease of R´´. In other words, addition of organoclay accelerates the
time-induced increase of G´, but it slows down that of G´´. This dual effect is
indicative of two parallel mechanisms: (1) polycondensation and (2) interaction
between the hairy clay platelets (HCP). Owing to the presence of the residual low
molecular weight amines (introduced during the intercalation and/or polymerisation
steps) an addition of organoclay slows down polycondensation. As the concentration
of clay in CPNC increases, the interactions between the HCPs increase as well.
Since these time effects were independent of the test conditions, it was concluded
that the explored variables had negligible effects on orientation – the effects were
chemical and thermodynamic in nature. As a consequence, the parameters listed in
Table 52 were used to recalculate all the subsequent rheological data to the initial
time. In consequence, the strain sweep, frequency sweep and other data reported
below are freed of these time effects.
Figure 100 Concentration dependence of the initial rate (data extrapolated to

t = 0) of G´ and G´´ changes. Lines represent the least-squares fit. Data [Utracki
and Lyngaae-Jørgensen, 2002].
362
Rheology
3.3.7.2 Strain Effects

The strain sweeps were conducted in the range γ = 0 to 100% at ω = 6.28 rad/s
for about t ≤ 10 min. At this relatively high frequency the compositions containing
100, 75 and 50% of CPNC show viscoelastic non-linearity at strains of γ ≥ 12 to
20%. The strain effects on G´ and G´´ were well approximated by the KBKZ-type
non-linearity expression:
[ ]
G ′′(γ ) = Go′′ / 1 + G1′′γ 2f − G2′′γ 3f ; strain fraction : γ f + γ / 100 (120)
Knowing the parameters of this relation permits calculation of the strain
dependence of G´ and G″ for any composition (at ω = 6.28 rad/s). Evidently, the
largest strain effects are expected for the sample with the highest concentration
of clay, i.e., for PANC. However, even here at γ = 50% the reduction of G´ and
G″ is relatively small: 15 and 7.5%, respectively.
3.3.7.3 Dynamic Flow Curves

To determine whether CPNC obeys the t-T superposition principle, the samples
were first pre-sheared then scanned from ω = 100 to 0.1 rad/s at T = 230 to
260 °C. As shown in Figure 101, good superposition was achieved. Neglecting
the lowest frequency data for G´ (at the limit of the equipment sensitivity) the
slopes for G´ and G´´ are 1.18 and 0.90, respectively, hence already within the
power law region.
According to Ferry [1980] the frequency shift factor, aT, depends on the free
volume fraction, f:
⎡1 1 ⎤
log aT = B⎢ − ⎥ ; f ≈ h (121)
⎣f fo ⎦
Figure 101 Time-temperature superposition for Ube PANC at the four indicated
temperatures
363
where B is the equation constant, fo is the free volume fraction at a reference

temperature, To. It has been shown that f is well approximated by the Simha-
Somcynsky hole fraction, h. Under ambient pressure, the S-S coupled equations
yield the following dependence [Utracki and Simha, 2001a]:
h = −0.0921 + 4.89T˜ + 12.56T˜ 2 ; T˜ ≡ T / T*; r 2 = 0.99999 (122)

The value of the reducing parameter for CPNC in Table 46 is: <T*> = 11307 ± 54.
Substituting Equation 122 into Equation 121 gives:
⎡ 1 1 ⎤
log aT = B⎢ − 2 ⎥
˜ ˜
⎢⎣ −0.0921 + 4.89T + 12.56T
2 ˜ ˜
−0.0921 + 4.89To + 12.56To ⎥⎦ (123)
(
or log aT = ao + a1 / 1 + a2 T + a3 T 2 )
It is noteworthy that for a2T >> 1 (i.e., well above the glass transition temperature),
the dependence leads to the Arrhenius equation.
Substituting numerical values into the Equation 123 (B = 0.3817 was used)
gives the prediction shown as a dotted curve in Figure 102. Both dependencies
(the experimental and calculated) seem to follow the Arrhenius dependence with
the activation energy of flow:
ΔHη = R[d log aT/d (1/T)] = 18 kJ/mol.
Figure 102 Temperature dependence of the frequency shift factor for PANC (see
Figure 101). Comparison between the experimental and computed (from Equation
123) dependencies.
364
Rheology
The highest value of log aT corresponds to T = 230 °C, i.e., about 10 °C above
Tm(PA-6) = 220 °C, thus some pre-crystallisation and/or stress-induced structural
change is to be expected.
The frequency dependence of the dynamic viscosity (η´ = G´´/ω) is shown in
Figure 103. The frequency sweeps were conducted at T = 240 °C, strains γ = 40%,
from ω = 0.1 to 100 or from 100 to 0.1 rad/s. For PA and the mixture containing
25 wt% PANC, the shear moduli did not depend on the scan directions. Thus,
scanning by either increasing or decreasing frequency, or scanning in the same
direction but starting from different frequency, produced different rheological
responses and the observed differences increased with clay loading. These shear
history effects were well reproduced within ± 2% by two operators who used
two rheometers and a variety of specimens. A Newtonian plateau was observed
only for PA and the mixture containing 25% PANC – the higher is the clay
concentration the higher is the negative slope at ω < ωc. However, even for neat
PANC the slope is small, ca. –0.1, smaller than what could be expected for the
domain flow. Evidently there are interactions between HCP in this region, but at
a clay loading of 0.64 vol% their strength and/or intensity are relatively low.
To analyse the frequency dependence of G´´ the data at γ = 10% scanned in
both directions and these at 40% scanned from 100 to 0.1 rad/s were fitted to the
Krieger-Daugherty type dependence, rewritten for dynamic flow [Utracki, 1988]:
− m2
[ ] ( )
′ / ω 2 = ψ o ⎡⎢1 + G ′′ / Gψ ⎤⎥
− m1 2
η ′ ≡ Gcorr
′′ / ω = ηo 1 + G ′′ / Gη ; ψ ≡ Gcorr (124)
⎣ ⎦
The dependence was derived for linear viscoelastic, pseudoplastic systems; hence
it is unable to describe the yield stress. The least-squares fit of Equation 124 to
data is shown in Figure 103. Excepting PA all compositions showed some ‘solid-
like’ behaviour at ω < ωc ≅ 1.4 ± 0.2 rad/s. Thus, only data above ωc could be
used to determine the parameters of Equation 124 (see Table 53).
Figure 103 Frequency scans for extruded PANC/PA mixtures at 240 °C at γ = 40%
from 100 to 0.1 and from 10 to 0.1 rad/s (different specimens); points –
experimental, lines – Equation 124 [Utracki and Lyngaae-Jørgensen, 2002].
Reproduced with permission, copyright Springer 2002.
365
366
Table 53 Frequency effects for PA-6/PANC mixtures at T = 240 °C and γ = 40%.
Data [Utracki and Lyngaae-Jørgensen, 2002]
Parameter PA-6 25% PANC 50% PANC 75% PANC 100% PANC
ω
η′ = G′ ′ /ω
1. η′
η0 302±1 334±3 434±4 495±10 543±18
m1 0.121±0.251 0.1344±0.0567 0.124±0.033 0.136±0.046 0.150±0.056

log Gη 1.8404±0.0019 1.3947±0.0198 0.8321±0.0136 0.5411±0.0560 0.4672±0.0416
σ 0.00137 0.00161 0.00159 0.00230 0.00203
r2 0.9999998 0.9999997 0.9999998 0.999995 0.9999996
CD 0.993585 0.996715 0.999231 0.999078 0.999441

2
2. ψ = G′′/ω
log (ψ0) 0.00027±0.00323 0.3893±0.0122 0.912±0.024 1.494±0.053 1.864±0.069
m2 0.2277±0.0096 0.2577±0.0103 0.702±0.030 0.752±0.025 0.816±0.026
log Gψ 1.2471±0.0298 0.6876±0.0532 0.421±0.085 -0.143±0.118 -0.3892±0.134
σ 0.00759 0.0209 0.025106 0.0282760 0.036663
r2 0.99816 0.99423 0.997888 0.9990709 0.998994
CD 0.996539 0.9928 0.99511 0.996069 0.995322

Rheology
The presence of the critical frequency, ωc, at which the HCP associations
vanish, is worth commenting. The transition is independent of the clay content.
Thus, it is related to the relaxation time of the aggregates, or by analogy to the
LCP-type flow, to the domain size. The effect is associated with the formation of
a structure that, at the selected level of T and γ, breaks at ω = ωc. This corresponds
to the relaxation time of τaggr = 4.5 s, i.e., significantly longer than that for PA-6:
τPA = 0.2 s. Identifying ωc with the transition from Region I to Region II of the
LCP-type behaviour and using the Marrucci [1984] relation:
γ˙ ≅ K / ao2 ηequil (125)
with the elastic constant K ≅ 10 (N), leads to the estimated value of the domain
-11
size for the three compositions (PANC, 75 and 50%) of ao = 310 nm. This may
be a coincidental agreement, but as will be shown below the aspect ratio, p =
296, was calculated from the barrier properties and suspension viscosity – the
value gives the bare platelet diameter d = 275 ± 9 nm, quite close to the domain
size in CPNC flow.
It can be shown that for incompressible, linear viscoelastic liquids there is an
interrelation between G´ and G´´ through the relaxation spectrum, H(λ):
∞
λH (λ )dλ ∞
H (λ )dλ
G′ / ω 2 = ∫ 1 + (ωλ )
0
2
; G ′′ / ω = ∫ 1 + (ωλ )
0
2
(126)
Since these functions are valid in the whole range of relaxation times, they are
also valid within narrow ranges inside this interval, say from λ = t to (t + Δ), thus:
()ξH ξ
(G ′ / ω ) = Δ 1 + ωξ
2
= ξ (G ′′ / ω ); t ≤ ξ ≤ t + Δ (127)
( )
2
The mean value theorem only requires that the integrals be continuous and the
interval Δ small, hence the proportionality between the two moduli should be
valid in the full range of the relaxation time and frequency. For Maxwell fluids
this means that:
(G ′ / ω ) = λ(G ′′ / ω )
2
or ψ (ω ) = λη ′(ω ) (128)
where λ is the main relaxation time. Thus, the simple Maxwell model represents
the flow behaviour for fluids in which the ratio of parameters in Equation 124:
m2/m1 = 2. A similar prediction can be obtained using other fluid models proposed
by, e.g., Oldroyd, Spriggs, Bird-Carreau, Bogue, Meister, and others. However,
as the data in Table 53 show, this condition is approximately observed only for
PA-6 and the 25% PANC mixture – for the other systems m2/m1 ≅ 5.5, hence
these systems are rheologically complex.
The deviation from linear viscoelastic behaviour at ω < ωc ≅ 1.4 ± 0.2 rad/s is
dramatically evident in Figure 104, where the ratio: G´/G´´ is plotted as function
of G´´. The plot is suggested by the Doi and Edwards [1978] theory predicting
that the log G´/G´´ versus log G´´ dependence for ‘well behaving’ liquids should
follow a straight line with the slope of 1:
ln(G ′ / G ′′) = ln G ′′ + ln(6Me / 5 ρRT ) (129)
367
Figure 104 Inverse loss tangent versus G´´ for PA/PANC mixtures at T = 240 °C
and ω = 0.1 to 100 rad/s. Solid symbols for γ = 10%, open symbols for g = 40%.
The predicted slope = 1 is also shown. [Utracki and Lyngaae-Jørgensen, 2002].
Reproduced with permission, copyright Springer 2002.
Figure 104 displays the log G´/G´´ versus log G´´ relations for all PA/PANC
compositions, frequencies and strains. The predicted dependence is close to the
observed only for neat PA-6. For the clay-containing samples the deviation from
the expected linearity increases with the nanoparticle content, hence it most likely
originates from the interparticle interactions that more strongly affect the storage
than the loss modulus. In simple words, addition of tethered clay particles to a
PA-6 matrix results in higher values for the stored energy than expected from a
second order fluid.
3.3.7.4 Apparent Yield Stress

The increasing value of G´´ as the frequency decreases below ωc = 1.4 ± 0.2 rad/s is
related to the formation of a 3D structure, that may be treated as an apparent
yield stress. One can extract the yield function: Y ≡ η’exp/η’lin = G´´exp/G´´lin, from
which the apparent yield stress can be calculated as: σy(ω) = (Y - 1)G´´lin. Some
years ago, for compatibilised polymer blends, a theory for the dynamic yield
stress was proposed [Utracki 1989]. The conceptual model assumed formation
of dynamic aggregates of the dispersed drops. The strength of the drop-to-drop
interaction was σ yo , the relaxation time of the dynamic aggregate was τy, and the
exponent u accounted for the aggregate polydispersity:
[ {
σ y (ω ) = σ yo 1 − exp −τ yω }]
u
(130)
This model may be also applied to CPNC. For end-tethered CPNC the interacting
entity is the HCP. Here the polydispersity of size is related to polydispersity of
the aspect ratio, which for CPNC is narrower than that found in polymer blends
hence u ≅ 1 may be postulated.
368
Rheology
The yield stress function at ω < ωc is presented in Figure 105. The data are
well represented by Equation 130 with σ yo = σy(φ), τy = 0.59 ± 0.03 and u ≅ 1.
The solid-like structure formation starts at about 20 wt% PANC reaching a
maximum value of σ yo = 23 Pa for neat PANC. It is noteworthy that the onset of
the yield stress takes place at a MMT concentration of about 2.5 times lower
than that calculated for the platelet maximum packing fraction. Thus, the 3D
structure formation originates from the presence of the end-tethered
macromolecules – it is of the chain entanglement type.
3.3.7.5 Zero-Shear Viscosity and the Clay Aspect Ratio

The zero-shear viscosities (ηo) in Table 53 are a function of the (computed from
PVT data) hole fraction, h. The dependence (see Figure 106) follows the general
relation [Utracki, 1983; Utracki and Simha, 2001b; Utracki, 2002a]:
ln ησ = ao + a1Ys ; YS ≡ 1 / ( a2 + h) (131)
where: ησ indicates constant stress viscosity, ai are parameters and h is the hole
fraction in the Simha-Somcynsky eos. For n-paraffins a1 = 0.79 ± 0.01 and a2 = 0.07
was found. For CPNC analysis the parameter a2 (which is only needed to linearise
the dependence) was assumed to be zero. The data in Figure 106 show about the
same rate of viscosity increase with decrease of h for CPNC as that found for
n-paraffins.
The values of ηo have been also used to determine the intrinsic viscosity from
Equation 104. Its value, [η] = 105.5 ± 22.5 (k1 = kH = 0.52 ± 0.058, and the
measures of fit: σ = 0.0674 and r2 = 0.9983) were then used to calculate the
aspect ratio, p for the MMT from Equation 107, p = 287 ± 9. The value is in
good agreement with that calculated from the relative permeability for oxygen, p
= 286 for the PANC resin.
Figure 105 Frequency dependence of the yield stress function Y ≡ η’exp/η’lin = G´´exp/G´´lin
for PA/PANC mixtures at T = 240 °C. Lines computed from Equation 130.
[Utracki and Lyngaae-Jørgensen, 2002], copyright Springer 2002.
369
Figure 106 Constant stress dynamic viscosity of PANC mixtures with PA as

functions of the (computed from PVT) hole fraction – see text. The zero-shear
viscosity as well as dynamic viscosity at constant stress (G´´ = 50 MPa) show
similar behaviour.
3.3.7.6 Flow-Induced Orientation

At frequency ω > ωc and strain γ = 10% the rheological signals were the same for
scans up or down the frequency. This however was not the case for γ = 40% – at
these higher strains the orientation effects became important. The highest degree
of orientation was expected at the highest frequency where all the flow curves
for CPNC collapsed into a single dependence.
To verify these expectations TEM was used on two PANC specimens, one
dynamically sheared at ω = 100 rad/s and γ = 40% for 15 min, and another also
inserted into a rheometer, but not sheared (see Figure 107). To determine the clay
orientation, the specimens were microtomed close to the disc border (maximum
shear strain) in the planar and circumferential directions of the moulded disc
[Perrin, 2002]. In the first specimen the clay platelets (uniformly dispersed, about
1 nm thick) were found oriented parallel to the disc thickness (the lowest resistance
to the dynamic shearing). In addition to single platelets, small stacks of 2 to 3
platelets were also observed – in the micrographs these resembled tree branches
with a single Y- or a double ψ-branching, which may suggest a crystallographic
fault of the mineral clay. The slices microtomed parallel to the surface showed
mainly cross-cuts of the MMT platelet and few in-plane platelets (average size:
470 x 220 nm) suggesting that platelets were not perfectly aligned. The TEM of
a not-sheared specimen showed a random orientation. Characteristically, in this
compression moulded specimen most of the MMT were bent – more so than
those in the sheared specimen.
The orientation plays a major role at the start-up of rheological tests, e.g., in
a steady-state or dynamic shearing. At low deformation rates (see Figure 108
(a)), e.g., γ˙ = 0.003 or 0.01 initially there is a rapid increase of the shear stress
follow by a moderate increase caused by polycondensation. At higher deformation
370
Rheology
Figure 107 TEM of PANC from Ube shows ‘in plane’ orientation of MMT
platelets. Orientation in not sheared specimens was random, with many bent clay
platelets [Perrin, 2002].
rates (Figure 108 (b)) the signal goes through a local minimum followed by the
polycondensation effect.
As was the case for LCP, interrupted stress growth studies have also been
carried out on these CPNC systems. The work is usually performed in three
stages: (1) pre-shearing; (2) allowing the system to rest for a specific time; (3)
shearing either in the same or the opposite direction. The most interesting results
are obtained within the Onogi-Asada plateau Region II.
Figure 109 shows the stress growth functions for two PANC specimens. Both
were identically pre-sheared for 300 s at γ˙ = 0.1 s-1. Next, the shearing stopped
for either 600 s (specimen (1)) or 1200 s (specimen (2)), and then they were
sheared for 300 s, at γ˙ = 0.1 s-1, but in the opposite direction. The data were
fitted to a distribution curve:
η = ηequil + ao t b ( a1 )
t
(132)
The parameter b provides a measure of the breath of distribution: tw/tn = 1 + 1/b
or tz/tn = 1 + 2/b, etc. The parameter ao is a measure of the orientation effect,
while a1 is a measure of the rate with which the overshoot dissipates, i.e., the
platelets re-align with the field. The dependence very well described the observed
curves – it is difficult to distinguish the experimental points from the computed
lines. The maximum values from the stress overshoot experiments are plotted
versus the rest time in Figure 110. The quality of fit as well as the fitting parameters
are listed in Table 54.
Differentiating Equation 132 provides the conditions for the local extremum
of the function at tmax, from which a simple relation for the incremental increase
of shear viscosity is obtained:
( )
ln Δη ≡ ln η − ηequil = ln ao + b(ln tmax − 1); tmax = − b / ln a1 (133)
Thus, for rest times of trest = 0, 600 and 1200 s, values of Δη = 0, 124 and 171
were obtained. As shown in Figure 110, the data follow a single exponential
dependence. As the peak height increases it becomes narrower, thus the value of
b increases and the dispersion parameter, tw/tn decreases.
371
Figure 108 Stress growth function of PANC at T = 240 °C and at γ˙ = 0.01 (a) or
0.1 (b). In the first case shearing in the cone-and-plate tooling was for 10 s only, in
the second for t = 1000 s.
3.3.7.7 Steady-State Flow Curves – Shear History Effects

During the dynamic flow studies it was noted that the rheological responses varied
not only with strain and frequency, but also with the frequency scanning direction.
Since the effects of polycondensation were extracted prior to data plotting, these
additional variations reflected changes in orientation and domain size.
372
Rheology
Figure 109 Two PANC specimens pre-sheared at γ˙ = 0.1 s-1 for 300 s: (1) relaxed
for 600 s then sheared for 300 s, at the same rate, but in the opposite direction; (2)
had the rest time twice as long. The curves computed from Equation 132 are
virtually indistinguishable from the experimental dependence.
Figure 110 The incremental increase of shear viscosity for PANC versus the rest
time after pre-shearing. As shown, the increase follows a single exponential.
The steady-state shearing at γ˙ ≤ 10 s-1 was carried out in a cone-and-plate

geometry, increasing the shear rate from the initial value with ‘wait time’ between
the consecutive data acquisition of Δt = 360 s. Starting at γ˙ = 0.001 s-1, initially
the viscosity increased, then it decreased to the plateau value before reaching the
power law dependence. When the sweep started at γ˙ = 0.01 s-1 the viscosity values
373
Table 54 Interrupted stress growth functions with flow reversal for

PANC at T = 240 °C. Data [Utracki and Lyngaae-Jørgensen, 2002]
Parameter Sample (1); rest 600 s Sample (2); rest 1200 s
Pre-shearing Recovery Pre-shearing Recovery
Std. Dev., σ 0.673 3.78 1.423 1.670
Corr.Coeff. 0.999999 0.999960 0.999994 0.999992

Sq., r2
Coeff. 0.99959 0.99041 0.99878 0.99881

Determin.
ηequil 544.1±0.1 557.7±0.3 538.3±0.1 557.0±0.1
ao 51.29±0.30 36.82±1.25 67.91±0.66 20.35±0.40
a1 0.9663±0.0001 0.9641±0.0005 0.9708±0.0002 0.9594±0.0002
b 0.4689±0.0027 0.6467±0.0147 0.4085±0.0043 0.9459±0.0078
tw/tn=1+1/b 3.133 2.546 3.448 2.057
immediately started to decrease toward the plateau then power law regions.
However, it is important to note that in these two cases the plateau levels were
different by about 10%. Apparently, the initial shearing of the specimen in the
first experiment for 1975 s more than in the second one was responsible for the
development of larger domains yielding a higher plateau value. This effect was
additional to that of the time-dependent polycondensation.
Next, the flow curves were determined starting at the same γ˙ = 0.01 s-1, but
changing the wait time between data points, Δt from 0 to 540 s (see Figure 111).
The flow behaviour systematically varied with Δt. The slower was the sweep
time, the better defined and the higher was the Region II plateau. As the figure
illustrates, similarly well-defined plateaux were found by plotting N1/ γ˙ versus γ˙
for these five rate sweeps. It is noteworthy that proportionality between N1 and
γ˙ was observed for LCP at low deformation rates for a concentrated LCP solution
in cresol [Kiss and Porter, 1980; Moldenaers and Mewis, 1992]. Proportionality
between N1 and γ˙ was also observed for colloidal suspensions, block copolymers
(especially those with higher molecular weight blocks) and multi-branched star
polymers [Kotaka and Watanabe, 1987; Masuda et al., 1987]. The Larson and
Doi [1991] theory for polydomain flows predicts that:
( ) ( )( )
−1 / 2
N1 / σ 12 = 2 λ2 − 1 ; λ = pd2 + 1 / pd2 − 1 (134)
where λ is a characteristic ‘tumbling’ parameter given by the domain aspect ratio,
pd. For thermotropic LCP the value of this parameter is λ = 1.01 to 1.05 indicating
that N1 > σ12 [Ugaz et al., 2001]. This is not the case for CPNC in Region II
where the ratio N1/σ12 < 1 and consequently λ = 4.4, hence the equivalent ellipsoid
aspect ration pd ≅ 1.6. At the higher shear rates, in the beginning of the power
374
Rheology
Figure 111 (a) Shear viscosity and (b) a ratio of the first normal stress
difference and the deformation rate, N1/ γ˙ , for PANC at 240 °C. A series of the
indicated wait time between the data points, Δt = 0 to 540, was used. See text.
law Region III, for LCP negative first normal stress was observed; this behaviour
was not found in CPNC.
It has also been reported that in solutions of hydrophobically modified alkali-
soluble emulsions G´ is nearly a linear function of ω, and in concentrated
suspensions of non-colloidal spheres N1 is proportional to γ˙ [Brady and Bossis,
1985; English et al., 1997]. Proportionality of N1 to σ12 (with the proportionality
375
factor being characteristic of the system) was also reported for the latter system
[Zarraga et al., 2000].
3.3.7.8 Fourier Transform Analysis of CPNC

The FTR method was used to analyse the rheological signals from an ARES
rheometer for the two resins from Ube, PA-6 and PANC, at 240 °C. The following
independent variables were used: strain, γ = 20-70%; frequency, ν = 0.1, 1.0 and
10 Hz; and the shearing time, t ≤ 1100 s. For the analysis the computer program
developed by Manfred Wilhelm was used. Within this range of variables PA-6
was found to follow linear viscoelastic principles, thus the tests focused on the
PANC resin. Figure 112 shows the raw data for PANC as a function of frequency.
The imposed test frequency was ν = 10 Hz. As evident from the figure, the intensity
of the first peak, I1, is about 100 times stronger than that of the third harmonic,
I3. From such plots the relative intensity, R3(ω) = I(3ω)/I1(ω) was calculated. The
resulting map is shown in Figure 113.
The dependence shown in Figure 113 will not be a surprise to rheologists – it
has been known that non-linearity increases with strain and frequency (note that
for CPNC at 0.1 Hz the non-linearity was so small that I3 was difficult to measure).
However, the value of FTR is in quantification of these influences, as well as in
showing the influence of the shearing time on the evolution of 3D structure. In
nanocomposites as in LCP, the term ‘structure’ encompasses two types of
contribution: orientation and association. The time dependence of R3 shown in
Figure 113, most likely originates from the latter effects.
3.3.8 Rheology of CPNC with PO Matrix

Lim and Park [2001] studied the dynamic flow behaviour of exfoliated (according
to XRD) CPNC with PE as the matrix. The system was prepared by mixing in an
internal mixer poly(ethylene-g-maleic anhydride) with up to 10 wt% of Cloisite®
6A (MMT-2M2HTA) for 10 min at 210 °C. The PE-MA resin had MW = 212 kg/mol
and contained 0.8 wt% MA. The dynamic flow data showed systematic increases
of the dynamic moduli as well as of their slopes within the terminal region. As
shown in Figure 114, the ratio G´(CPNC)/G´(matrix) strongly increases with
clay loading and decreases with test frequency.
The authors also oriented the CPNC (with 10 wt% organoclay), shearing it at
γ = 120% (LAOS). The tests were conducted until a plateau was achieved. The
results for the PE-MA system were compared with those obtained for PS and PS-MA
with the same amount of Cloisite® 6A. The principal difference between these
three CPNC systems was the degree of exfoliation – at 5 wt% organoclay loading
PE-MA was exfoliated whereas the other systems were intercalated with d001 =
3.45 and 3.37 nm, respectively.
The time to reach the plateau in the LAOS experiments with PE-MA was tplat
= 7200 s, whereas for PS and PS-MA system it was four times shorter. Furthermore,
the frequency scan after alignment showed that G´ for PS-system approached the
matrix dependence, whereas for PS-MA the G´ versus ω dependence was
intermediate between that for non-aligned CPNC and that of the matrix. The
authors also reported that G´ in aligned or non-aligned CPNC with PE-MA as
the matrix showed a similar dependence, especially at low frequency. As the
frequency increased, the dependence slowly drifted toward that for the matrix.
Judging by the relatively fast alignment of the two styrenic CPNCs, it seems that
376
Rheology
Figure 112 Fourier transform rheology, FTR, data for PANC at 240 °C, after 600
s of shearing at 70% strain with imposed frequency of 10 Hz. The harmonic peak
(I3) at 30 Hz is evident.
Figure 113 Relative intensity of 3rd harmonic peak, I3/I1, for PANC at 240 °C.
The plot illustrates how the non-linearity varies with strain, frequency and
shearing time.
377
Figure 114 Relative storage moduli of PE-MA with Cloisite® 6A at T = 210 °C.
Curves for frequency ω = 0.12 and 119 rad/s are shown. Data [Lim and Park,
2001].
in spite of high clay content the dispersed assemblies were relatively large and
had low aspect ratio. The high value of tplat agrees with the image of delaminated
platelets hindered in their rotation by crowding of the encompassed volumes.
Furthermore the observed drift of G´ versus ω dependence after alignment toward
that of the matrix indicates that alignment is easier at higher frequencies than at
ω = 1 rad/s, which was used in LAOS. Considering the long period of platelet
rotation (see Equation 105) the frequency most likely affected the extent of
interaction between platelets without forcing them to rotate.
Similar CPNCs, containing PE-MA and silicates of different aspect ratios,
were studied by Wang et al. [2002]. The PE-MA was LLDPE grafted with
0.85 wt% MAH. The silicates were two organoclays (Cloisite® 20A, C20A and
Laponite® SCPX2231, SCPX) and a synthetic SiO2. The organoclays were both
intercalated with 2M2HTA and had the nominal aspect ratio, p = 100 to 200
and 20 to 30, respectively. The silica had spherical particles with diameter of ca.
1.8 μm. XRD did not show diffraction peaks down to 2θ = 2°; hence d001 > 4.4 nm.
As it is to be expected, the initial slope, g´ = d lnG´/d lnω, a measure of deviation
from linear viscoelasticity, decreases with nanofiller content and aspect ratio.
Note that the matrix alone showed a lower value than that expected for a linear
viscoelastic liquid (g´ = 2), indicating that the system is phase segregated, with
MA domains acting as local crosslinks.
The data in Figure 115 indicate that g´ decreases with clay aspect ratio and
concentration. Other factors, such as the degree of exfoliation and potential
association of the intercalated clay platelets have also been identified [Lepoittevin
et al., 2002a,b]. Association is suspected in the system containing MMT
intercalated with MT2EtOH (Cloisite® 30B).
378
Rheology
Figure 115 The initial slope of the storage modulus versus frequency dependence,
g′≡ (∂lnG′/∂lnω)T for LLDPE-MA with two organoclays C20A and SCPX (with
aspect ratio: p ≅ 100-200, and 20-30, respectively) and with silica (p = 1). Data
[Wang et al., 2002].
While the end-tethered CPNC with PA-6 as a matrix showed rheological behaviour
similar to LCP, other CPNC may show behaviour resembling that of filled
polymers with yield stress. The review by Giannelis et al. [1999] provided several
examples of such behaviour. For example, the steady-state shearing of a
poly(dimethyl0.95 diphenyl0.05 siloxane) containing up to 35 wt% of MMT
intercalated with 2M2HTA (Cloisite® 6A) showed a steep increase of low-shear
viscosity with clay loading [Krishnamoorti et al., 1996]. In this case exfoliation
(suppressed at high loadings) seems only to intensify the known filler effects.
However, the authors also studied end-tethered PCL and PA-6 nanocomposites
with exfoliated MMT. Judging by the reported log G´ versus log ω plots, at a
MMT loading of 1 to 3 wt% the behaviour resembled that described in the
preceding parts for PA-6 based CPNC (LCP-type), but at a clay loading of 5 and
10 wt% the CPNC behaved as a filled-system. Note that at these high loadings
the platelets are crowded, unable to tumble along the flow lines.
Galgali et al. [2001] prepared CPNC by melt blending PP (82-97 wt%;
MFI = 3 and Mw = 300 kg/mol) with maleic anhydride grafted PP (PP-MA,
Polybond 3200) as compatibiliser and Cloisite® 6A (MMT-2M2HTA). The ratio
of PP-MA to organoclay was either 0:1 or 1:1. The mixtures were characterised
by TEM and XRD at T = 200 °C. Dynamic flow measurements were performed
at T = 200 °C and ω = 0.06 to 100 rad/s on samples annealed in a controlled
stress rheometer for t = 0 to 3 h. The ‘terminal’ slope of log G´ versus log ω at the
lowest frequencies, ω = 0.06 to 1 rad/s, depended on the compatibiliser and clay
content as well as on annealing time (see Figure 116). The data were analysed
using the linear function:
go′ ≡ lim ( d log G ′ / d log ω ) = ao + a1 w PP− MA + a2 wclay + a3 t (135)
ω →0
379
Figure 116 The initial slope of the storage modulus versus frequency
dependence, g′≡ (∂lnG′/∂lnω)T for PP/PP-MA/ Cloisite® 6A. Upper line for CPNC
without compatibiliser (PP-MA), lower for PP-MA content the same as that of
Cloisite® 6A. Data from [Galgali et al., 2001].
The data fit generated the following set of parameters:

ao = 1.48 ± 0.09; a1 = -0.085 ± 0.013; a2 = -0.043 ± 0.015; and a3 = -0.028 ± 0.027 with
the standard deviation σ = 0.15 and the correlation coefficient squared, r2 = 0.986.
Evidently, the dependence is dominated by PP-MA then by the organoclay content,
but (within the statistical error) not by the annealing time. This strong variation
of the terminal slope is noteworthy considering that, according to XRD, the
system was only intercalated with d001 = 3.3 nm. On the other hand, TEM showed
the presence of large clay aggregates, probably along with a few exfoliated
platelets. Since addition of PP-MA did not change the interlayer spacing, the
compatibiliser most likely coated the exterior of the intercalated stacks of MMT
platelets. Thus, the reduction of the terminal G´ slope is most likely related to the
formation of interactive 3D structures, but not to LCP-like behaviour.
Next, creep experiments were carried out at T = 200 °C. For CPNC with
9 wt% MMT, changing the shear stress from σ12 = 10 to 2000 Pa reduced the
viscosity by nearly four decades – in the vicinity of σ12 = 1 kPa. The latter value
was identified as an apparent yield stress – apparent, since even at the lowest
imposed stress the viscosity was measurable (η ≅ 107 Pas). This behaviour is
consistent with a 3D structure formed with interacting domains, forming
aggregates with their own relaxation times (see Equation 130).
Creep measurements were also carried out at σ12 = 10 Pa (for 3% and 6%
clay) and 50 Pa (for 9% clay). The data were collected every 15 min for a period
of 3 h during which the sample was annealed inside the rheometer. The creep
compliance was significantly lower for CPNC specimens containing MA-PP. For
the specimens containing 6 and 9 wt% of PP-MA and organoclay the effect
increased with the annealing time. Evidently some structure build up was taking
place under the low stress creep. It is noteworthy that dynamic yield stress has
380
Rheology
been observed for compatibilised blends that, prior to compatibilisation, showed

a regular pseudoplastic behaviour with an upper Newtonian plateau. The
mechanism responsible for the CPNC dynamic yield stress may be similar to that
for blends – enhanced interactions between the dispersed domains that formed a
dynamic, percolating 3D network.
Extracted from the creep data the zero shear viscosity, ηo, increased with the
PP-MA and clay content by two to three orders of magnitude over that of the
matrix resin, but the activation energy of flow, Eη = 33.4 kJ/mol, was found to be
unchanged. The compatibilised CPNC also showed a solid-like response that
apparently originated from the interactions between compatibilised clay
aggregates. The presence of MA-PP increased the probability of 3D structure
formation (the solid-like rheological response) similar to that observed for the
end-tethered chains.
Solomon et al. [2001] reported on the linear and non-linear rheology of CPNC
with PP as the matrix. The samples were prepared by melt mixing of organoclay, PP
(Mw = 246 kg/mol and Mw/Mn = 6.1), and compatibiliser (PP-MA, Mw = 92 k g/mol,
Mw/Mn = 2.6 MA = 0.43 wt%). The weight ratio of organoclay to compatibiliser
was 1:3. The organoclay was prepared by cation exchange of
Na-MMT (d001 = 1.1 nm) with stearyl amine (C-18), tri-decyl amine (C-13), or
di-tri-decyl amine (2C-13). The inorganic content in these CPNCs was varied
from 1.30 to 6.17 wt%. Melt mixing was carried out in an internal mixer under
N2 at T = 175 °C for 40 min. XRD measurements indicated that intercalation
about doubled the original interlayer spacing in Na-MMT (from d001 = 1.1 to
about 2.3 nm), but compounding with PP and PP-MA induced only small changes.
As shown in Table 55, at a loading of 4.8 wt% clay, depending on the
intercalant the interlayer spacing changed by Δd001 = 0 to 0.8 nm. Addition of
clay significantly increased G´ and G´´, but the time-temperature superposition
principle was found to be obeyed with the same horizontal shift factors (aT) as
those for PP. Evidently, increasing the amount of organoclay increased the
magnitude of the dynamic moduli. Furthermore, as one might have expected, the
rheological response depended on the type of intercalating onium salt, but it is
surprising that (see Figure 117) the increase correlates so well with the interlayer
spacing. It is difficult to comprehend how such a small change of the interlayer
spacing (Δd001 ≤ 0.9 nm!) could be responsible for the 40-fold increase of G´,
especially since these systems were only ‘mildly’ intercalated. It may be that at
the high loading (4.8 wt% inorganic clay) the interactions between clay and
Table 55 Interlayer spacing of neat organoclays and in mixtures

with PP/PP-MA. Data [Solomon et al., 2001]
Intercalant Interlayer spacing, d001 (nm)
ammonium salt of: organoclay CPNC
C-13 1.9 2.2
2C-13 2.5 2.5
50/50 C-18/2C-13 2.6 2.8
C-18 (ODA) 2.1 2.9
381
Figure 117 Storage shear modulus at constant frequency (G´ at T = 180 °C and ω
= 10 rad/s) versus interlayer spacing, d001, for PP with 4.8 wt% MMT intercalated
with (from the bottom left) tri-decyl amine (C13), di-tri-decyl amine (2C13), a
mixture of these (C13+ 2C13), and stearyl amine (C18). Data [Solomon et al., 2001].
intercalant parallel those between intercalated stacks in the PP matrix – the latter
are responsible for the rheological response.
To study the viscoelastic non-linearity Solomon et al. used shear flow reversals.
First, a CPNC specimen was sheared for 300 s at γ˙ = 0.005 to 1.0 s-1 recording
the value of the shear stress (σ12), then the flow was stopped for a time, trest, and
the specimen was re-sheared at the same rate of shear, but in the opposite direction.
As has been observed for LCP and CPNC with PA-6 as the matrix, the magnitude
of the stress overshoot (σmax) increases with trest. The authors constructed master
curves by plotting: (σmax/σ∞ - 1)/c versus trest (where σ∞ is the value of σ12 at long
time and c is MMT loading). The linear scaling with c indicates that during non-
linear deformation the stress response originates in the individual clay domains,
thus the network is destroyed by deformation. The stress overshoot is related to
the distribution of particle orientations in CPNC and the stress-induced destruction
of the network. Furthermore, the linear scale suggests that the domain size is
independent of loading. It is interesting to note that, not unexpectedly, the
magnitude of the stress overshoot depended on the rate of shearing (see
Figure 118). The anisometric structure of the CPNC was considered responsible
for the non-linear flow behaviour.
CPNC of PP with organoclay and PP-MA was prepared by melt compounding
[Li et al., 2003]. The ratio of compatibiliser (containing 0.31 wt% of MAH) to
organoclay was 3. Strong non-linear viscoelastic behaviour was observed at
organoclay loadings exceeding 2 wt%, i.e., 8 wt% of organoclay + PP-MA. The
interlayer spacing only slightly expanded from that of neat organoclay, viz. from
d001 = 3.5 to 4.2 nm. The strong non-linearity in the dynamic response indicated
the formation of a 3D structure readily altered by pre-shearing. Similarly, as for
PA-based CPNC, (see Figure 109 and Figure 110) stress overshoot was observed.
382
Rheology
Figure 118 The ratio of the maximum stress overshoot to its plateau value
versus the rate of shear, γ˙ . Data [Solomon et al., 2001].
Considering the low degree of clay dispersion, it is unlikely that the origin of the
observed non-linearity is the platelet/platelet interaction. Similarly, since the degree
of PP-MA maleation was low, it is doubtful that it phase-separated from the PP
matrix. Thus, the most probable structure responsible for the non-linear
viscoelastic behaviour is the interaction between domains of organoclay tactoids
embedded in a cloud of the compatibiliser, the latter bonded to the clay platelets.
Okamoto et al. [2001a,d] studied the rheology of CPNC with PP-MA as the
matrix. The system was prepared by melt compounding at T = 200 °C maleated-
PP (PP-MA, 0.2 wt% MAH) with 0, 2, 4 and 7.5 wt% of MMT intercalated
with stearyl ammonium ion (ODA). TEM showed fine dispersion of the silicate
stacks ca. 193 to 127 nm long and about 5 to 10.2 nm thick, respectively.
According to XRD the interlayer spacing of the organoclay increased from only
d001 ≅ 2.31 to 3.24, 3.03 and 2.89 nm, respectively. The PP crystalline lamellae
thickness and spherulite diameter did not depend on clay content. For the
rheological study the rotating clamps, Meissner-type elongational RME rheometer
was used at T = 150 °C and Hencky strain rates ε̇ = 0.001 to 1.0 s-1.
The stress growth function in elongational flow, log η E+ versus log ε̇ for the
three CPNC compositions showed strain hardening (SH). The latter function is
defined as a logarithm of a ratio of the stress growth function in elongation to
three times that for the linear viscoelastic response in shear, with both values
taken at the same deformation time, t, viz.:
(
SH ≡ log η E+ / 3ηS+ ) t
(136)
SH has been observed for entangled polymers (e.g., LDPE), for highly
polydispersed resins (e.g., some LLDPE where Mw/Mn = 10 to 50) as well as for
the new bimodal metallocene PO. Partial crosslinking as well as dissolution of
ultrahigh molecular weight polymer into its standard resin are also known to
induce SH. The phenomenon is essential for several processing operations, viz.
383
foaming, film blowing, blow moulding, wire coating, etc. As exemplified in

Figure 119 by data for the branched polycarbonate of bisphenol-A, PK, for a
single-phase polymer, plot of SH versus Hencky strain, ε = ε˙t , does not depend
on the strain rate and the value of its slope is characteristic for the material.
There is a striking difference in the SH behaviour for a single-phase polymer
and CPNC. In the latter case (see Figure 120) only the high strain rate results
follow the customary straight-line dependence. However, even in this range there
is no superposition of data taken at different Hencky strain rates, ε̇ . For lower
rates of straining the SH is significantly higher – it almost seems that for each
strain rate there is a specific polymeric system with its own structure and
rheological response. A cross-plot of SH at constant Hencky strain versus strain
rate gives a simple dependence: SHε=const = ao + a1log ε̇ . One may speculate that
the flow disrupts a network of interacting domains, and then it orients them.
A similar enhancement of SH was reported by Kotsilkova [2002] for CPNC
of PMMA with 10 or 15 wt% of smectite pre-intercalated with methyl diethyl
propylene glycol ammonium ions. The nanocomposites were prepared by radical
polymerisation of MMA in the presence of organoclay. The elongational viscosity
and birefringence were measured at 180 °C, using a rotating clamp, optorheometer
designed by Kotaka at strain rates, ε̇ = 0.01 to 1.0 s-1 at Hencky strains ε = 0.8 to
3. The author noted a correlation between SH and birefringence – as the former
increased so did the latter.
Owing to disturbance of the stress distribution pattern by suspended solid
particles, the extensional flow of classical composites shows not SH, but its
opposite, strain softening [Takahashi, 1996]. The SH reported by Okamoto et
al. for CPNC signalled the basic difference in rheological behaviour between
macro- and nanocomposites. Evidently, the nanosize of clay platelets may be one
of the elements that differentiate these systems, but the end-tethering (engendered
by interactions between clay and maleic anhydride moieties) might also play a
role. Furthermore, as the authors observed, there are significant structural changes
during flow. At low extensional or shear flow rates, e.g., ε̇ = γ˙ = 0.001 s-1, a
‘house-of-cards’ structure was observed under TEM. At high extensional flow
rate, ε̇ = 1.0 s-1, the platelets were found oriented perpendicularly to the stretch
direction. Formation of either structure requires energy input; hence increased
viscosity is to be expected.
Another important observation of Okamoto et al. is that the linear viscoelastic
envelope of the stress growth function in shear was about one decade lower than
that measured in elongation. This type of behaviour is expected from multiphase
systems with yield stress [Utracki, 1995]. Furthermore, unlike single-phase
polymer melts, the low deformation rate ( γ˙ = ε̇ = 0.001 s-1) stress growth functions
of CPNC (in shear or elongation) increase with test time, t ≤ 300 s, not showing
a tendency to reach a steady-state. The authors concluded that flow-induced
internal structure is different in shear than in elongation.
3.3.9 Foaming of CPNC

It has been recognised that SH stabilises flow during the processing steps that
involve elongational flows, particularly during extrusion foaming. Owing to the
poor SH of classical isotactic PP, the resin was difficult to foam. The CPNCs of
PP-MA (with 0, 2, 4 and 7.5 wt% organoclay) discussed above were autoclave-
foamed with supercritical CO2 at P = 10 MPa and T = 130.6 °C to 143.4 °C,
which was well below the melting temperature of CPNC and PP-MA [Okamoto
384
Rheology
Figure 119 Typical strain hardening plot for a single-phase polymer, viz. for
branched PC at 270 °C [Utracki and Sammut, 2000; unpublished].
Figure 120 Strain hardening parameter, SH, versus Hencky strain at indicated rates
of extension, ε̇ , for CPNC of PP-MA with 4 wt% of C18-MMT (d001 = 3.03 nm).
Data [Okamoto et al., 2001]. The absence of superposition of data for constant values
of ε̇ indicates the presence of a 3D network of interacting organoclay particles.
385
et al., 2001a, d; 2002; Nam et al., 2002]. The foams of PP-MA and CPNC with
2 wt% organoclay had closed cell structures with pentagonal and/or hexagonal
faces. For the higher clay concentrations, the cells had closed spherical structure.
The foamed CPNCs had a high cell density of 107-108 cells/ml, the homogeneity
of cell size was in the range of 20-120 μm, the cell wall thickness was 5-15 μm,
and the low mass density was 0.05-0.3 g/ml. Within the cell walls clay particles
were biaxially aligned along the cell boundary. TEM showed that MMT platelets
were oriented parallel to the wall surface. In the junction of three adjacent cells
the platelet orientation near the walls was parallel to the proximate one with a
random orientation in the centre of the three-cells junction.
However, it seems that SH is not the only mechanism responsible for enhanced
foamability of nanocomposites – it has been shown that CO2 foaming of either
PMMA-based CPNC or neat PMMA geometrically constrained 75-100 μm thick
films follows a similar mechanism and leads to a decrease of cell size and increase
of cell density [Siripurapu et al., 2002].
The batch foaming of PP-based CPNC (clay content 2, 4, and 7.5%) was
carried out in a high-pressure cell equipped with a microscope and high-speed
digital video recording camera [Taki et al., 2003]. Significant reduction of the
bubble size (from 155 to 34 μm) and increase of cell density (from 2.5 to 220 cells/nL)
has been observed. Furthermore, the foam compression modulus increased by a
factor of 6.These observations were confirmed in the sequel publications. Thus,
preparation of micro- and nanocellular foams in PLA-based CPNC has been
accomplished [Fujimoto et al., 2003; Ray and Okamoto, 2003]. Foaming of
PLA/organoclay nanocomposites has been conducted using supercritical CO2.
Compared to neat PLA foam, the CPNC foam showed smaller cell size and higher
cell density, confirming that the dispersed silicate particles acted as nucleating
sites for cell formation and the increase in SH stabilised the bubble growth. The
biaxial flow-induced alignment of the platelets along the cell boundary also had
a positive effect on the strength of the bubble wall, hindering coalescence. PC-
based CPNC were also successfully foamed [Mitsunaga et al., 2003]. The relatively
easy foamability of CPNC with supercritical CO2 to give materials with small
cell diameter (nanofoams with 200 nm diameter bubbles have been produced)
may be in part due to the high solubility of CO2 in most polymers. Even in the
case of insolubility (e.g., PEG swells but does not dissolve in CO2) its presence
increases the free volume content, thus macromolecular mobility, which on the
one hand leads to the expansion of interlayer spacing [Zhao and Samulski, 2003]
and on the other to higher foaming rates.
As recent events demonstrate, CPNC foaming is close to commercialisation.
For example, PU-based CPNC foams with submicron size cells combining
exceptional mechanical, thermal, and barrier properties have been identified as
prime candidates for high efficiency insulation in refrigerators [Domszy, 2004].
The patenting activities also reflect the high expectations from this technology.
For example, a general patent for foaming CPNC was applied for [Lee et al., 2003].
Its claims are quite broad, specifying a diversity of polymers (PS, PMMA, PP, PA,
PU, elastomers, and their blends), of organoclays (of MMT, HT, FH, saponite,
laponite, and beidellite), incorporated in amounts ranging from ≤ 0.5 to ≤ 20 wt%,
and using from ≤ 1 to ≤ 7 wt% of a blowing agent (supercritical CO2). The resulting
closed or open cell foams should have cells with diameter ranging from 15 to
20 μm, and cell density from 106 to 109 cells/ml. Extrusion or batch foaming quality
depends on the CO2 content, melt temperature, and pressure drop rate.
386
Rheology
3.3.10 Rheology of CPNC with PS and Styrenics Matrix

CPNC with PS or a styrene copolymer as a base have been prepared by
polymerisation (in solution, suspension or bulk) or by melt processing methods.
Because of the amorphous matrix these CPNCs are advantageous as models for
studies of, e.g., mechanical or barrier properties, without the complications due
to crystallinity. However, as will be evident from the few cases discussed below,
exfoliation of clay in a PS matrix is difficult and it requires careful consideration
of chemistry. Furthermore, as discussed in Section 3.2, the work with PS
nanocomposites is seriously complicated by the thermal decomposition of the
quaternary intercalant, which in the presence of oxygen leads to formation of
peroxy radicals that in turn cause degradation of the PS matrix. Thus, in spite of
extensive academic studies these systems are not commercialised.
Hoffmann et al. [2000a] prepared two types of CPNC by intercalating synthetic
fluoromica (FM; Somasif ME-100; CEC = 0.7-0.8 meq/g) with either amine-terminated
PS (ATPS; Mn = 5.8 kg/mol) or 2-phenyl-ethyl amine (PEA; Mn = 121 g/mol).
The intercalation was carried out in a THF/H2O solution at 40 °C. The dried
organoclays were compounded with the PS at 200 °C in a microcompounder for
5 min. According to XRD, the interlayer spacing of FM, d001 = 0.95 nm expanded
after intercalation with PEA to 1.4 nm and with ATPS to > 4 nm. TEM of the
CPNC showed the presence of large clay aggregates in CPNC with PEA (C-
PEA), and full exfoliation in CPNC with ATPS (C-PS). In the latter system it was
estimated that the clay platelets of ca. 1 nm thick were about 600 nm long and
100 nm wide. The dynamic rheological measurements showed a sharp difference
in behaviour between these two systems. The presence of 5 wt% clay in C-PEA
caused G´ = G´(ω) to parallel the dependence of the matrix, with only a slight
increase caused by the presence of organoclay acting as filler. In the exfoliated C-
PS system the low frequency slope in the terminal zone was about 0.5 (instead of
2, as in the former case). The authors concluded that in the presence of ATPS the
clay platelets formed a network. The observed large difference in behaviour was
ascribed to the length of the intercalating compound. Accordingly, one may control
the degree of intercalation/exfoliation by varying the chain length of the intercalant
chain.
A more recent publication [Meincke et al., 2003] extended this work to a
series of compositions containing 0 to 10 wt% of FM pre-intercalated with either
PEA or ATPS. For either system good time-temperature superposition was
obtained, with virtually identical WLF c1 and c2 constants as those for the PS
matrix. Analysis of the dynamic data showed a dramatic change in the van Gurp
plot (plot of arctan G´´/G´ versus G*) – the dependencies for PS and for PS with
FM-PEA were virtually identical, quite different from that of FM-ATPS.
Furthermore, it was observed that the plateau modulus follows the dependence:
GN0 ∝ 1 / φ PS
n
, where φPS is the PS matrix volume fraction, and the exponent n = 0
when FM-PEA was used, and n = 2 when FM-ATPS was incorporated. The hairy
platelet model (HCP) was postulated.
This experimental finding confirms the theoretical conclusions (see
Section 3.1.5) by Balazs and her colleagues [1999; 2000]. Their theoretical analysis
of clay dispersed in a mixture of polymer with its functionalised homologue
showed that the most promising strategy for developing an exfoliated system is
by using long-chain end-functionalised compatibiliser. Its chain length should be
smaller but comparable to that of the matrix polymer.
387
The rheology of CPNC with a di-block copolymer of PS and IR (PS-IR; Mw =

17.7 kg/mol; 44 wt% PS) was of interest to Ren et al. [2000]. The authors dispersed
organoclay (MMT with CEC = 0.90 meq/g, intercalated with a dimethyl
dioctadecyl ammonium ion, 2M2ODA) in a toluene solution of PS. The five
CPNCs had clay content ranging from 0 to 9.5 wt%. According to XRD,
intercalation increased the interlayer spacing of MMT from d001 = 0.95 to 1.3 nm,
whereas solution blending of PS or PS-IR increased it further to d001 = 2.1 to
2.5 nm, independently of the clay content. Thus, these CPNCs were only
intercalated. Dynamic shear tests indicated that to achieve time-temperature
superposition both horizontal (aT) and vertical (bT) shifting was necessary. While
a plot of aT versus T was common for all compositions, a similar plot for bT
degenerated into two dependencies: for PS-IR and for CPNCs. The authors also
reported significant difference in the rheological responses for specimens oriented
or not.
Considering the small degree of interlayer expansion, at first it is surprising
that the dynamic data show concentration dependence of the G´ and G´´ slopes
in the terminal zone. However, the reported observations indicate that only the
PS part of the copolymer can be inserted into the interlamellar galleries, with the
PI block being outside. Thus, the structure of these CPNCs is of stacks of MMT
platelets intercalated with 2M2ODA and PS-blocks surrounded by IR-blocks.
Formation of the 3D structures responsible for the rheological behaviour in the
terminal zone is due to the interaction between IR clouds. This situation very
much resembles that of compatibilised immiscible polymer blends. Finally, it is
worth recalling that, as shown in Figure 96, the stress relaxation data computed
from the dynamic moduli span five decades and still follow the simple Ferry’s
relation.
The work was extended to systems containing up to 5 wt% of an organoclay,
either a fluorohectorite (FH) modified with 3MODA, MMT intercalated with
2M2ODA, or laponite intercalated with 2M2ODA. According to XRD the degree
of dispersion increased in the order of decreasing aspect ratio – from FH to
MMT to laponite. Similarly, as for PA-6 systems [Utracki and Lyngaae-Jørgensen,
2002], here also the critical frequency, ωc, was observed – at ω < ωc viscoelastic
non-linearity was observed.
Fu and Qutubuddin [2000, 2001] started their work by preparing a
polymerisable intercalant, vinyl-benzyl-dimethyl dodecyl ammonium
(2MVBDDA), which was ion-exchanged with either Na-MMT or Ca-MMT (d001
= 4.62 and 4.0 nm, respectively). The purified and dried organoclay was dispersed
in styrene and copolymerised. XRD and TEM of the samples indicated full
exfoliation. However, only limited data on the rheological and mechanical
behaviour were reported. The samples had a viscous gel structure with yield
stress and shear thinning behaviour.
Okamoto et al. [2000] used Na-MMT (CEC = 0.866 meq/g) intercalated
either with oligo(oxy-propylene) diethyl methyl-ammonium chloride,
[(C 2 H 5 ) 2 (CH 3 )N + (O ¯ iPr) 25 ]Cl - , or methyl- trioctil-ammonium chloride,
[CH3(C8H17)3N+]Cl-. The intercalated clays (SPN and STN, respectively) were
dispersed in MMA or styrene (St) via ultrasonication at 25 °C for 7 h then the
monomer was polymerised. The organoclay content was 10 wt%. The mean
interlayer spacing of the neat organoclays was: d001 = 4.20 and 1.81 nm for SPN
and STN, respectively. The spacing expanded in monomer suspension. However,
polymerisation in a MMT matrix resulted in PMMA/STN nanocomposite with
388
Rheology
d001 = 2.66 nm, smaller by about 0.3 nm from the value in monomer suspension.
SPN suspended in MMT was fully exfoliated, while PMMA/SPN nanocomposite
showed a small shoulder at d001 ≅ 4.55 nm. For the St/SPN suspension, a small
shoulder was found at d001 ≅ 3.85 nm, i.e., reduction of the interlayer spacing of
neat SPN. The PS/SPN nanocomposites showed strong diffraction peaks,
demonstrating that in this case polymerisation leads to ordered intercalated
nanocomposites.
The frequency sweeps for the suspensions showed two types of rheological
behaviour. The suspensions of intercalated MMA/STN and St/SPN systems
indicated solid 3D, gel-like behaviour with frequency-independent dynamic
moduli. By contrast, the exfoliated MMA/SPN suspension showed strong
frequency dependence. The data indicate that at 10 wt% loading in the monomer
the expanded, intercalated clay stacks strongly interact with each other. However,
surprisingly, the exfoliation into individual platelets seems to eliminate the
interactions. For the polymerised CPNC systems only a viscoelastic temperature
sweep was carried out.
Kim et al. [2002] emulsion polymerised PS in the presence of Na-MMT highly
swollen in water. CPNC containing 0, 2, 5 and 10 wt% of clay were prepared.
Polymerisation increased d001 from 1.195 nm determined for dry Na-MMT to
1.511 nm measured for the three CPNCs. Thus, in these nanocomposites the
interlamellar galleries of MMT were expanded to h = 0.55 nm hence slightly
larger than estimated from the Flory diameter of the paraffinic chain (0.45 nm),
but significantly smaller than that of PS (0.83 nm). As a result, the clay was
poorly dispersed in the PS matrix. The flow curves, log η versus log γ˙ , showed a
simple pseudoplastic behaviour, following the dependence:
η = ηo ⎡1 + (λγ˙ ) ⎤
1− n
(137)
⎣⎢ ⎦⎥
Here, ηo is the zero shear viscosity, λ is the longest relaxation time, and n is a
power law exponent. From the values of ηo the intrinsic viscosity listed by the
authors, [η] = 112 and the aspect ratio p = 270 was calculated. Thus, the assemblies
of intercalated MMT platelets are highly anisometric. In consequence, scans
conducted by increasing and decreasing the rate of shear resulted in a hysteresis
loop, with the former scan data forming the upper and the latter scan data forming
the lower part of the loop. The size of the loop increased with clay concentration.
Three PS grades from Nova Chem with Mw = 310, 270, and 230 kg/mol were
melt compounded in a TSE (T = 200 °C, screw speed of 200 rpm, feed rate of
5 kg/h) with 1 to 20 wt% of Cloisite® 10A (MMT-2MBHTA) [Tanoue, et al.,
2003b]. It was found that each re-extrusion of CPNC reduced the zero-shear
viscosity, ηo, by about 30%. This is particularly interesting since increasing the
residence time in a TSE by a factor of up to 10 did not reduce further the CPNC
matrix viscosity. Similarly, extrusion of neat PS had only a small (ca. 2%) effect
on ηo. Thus, the combination of oxygen, temperature and organoclay was
responsible for the degradation of PS.
The rheological properties of these CPNCs were measured in the steady shear
and dynamic mode at 160, 200 and 240 °C. The time-temperature (t-T)
superposition was found valid, with the horizontal and vertical shift factors being
nearly independent of the organoclay content and PS grade. The extrapolated
zero-shear viscosity and zero-shear storage modulus slightly increase with
organoclay content. According to the results of strain sweeps (γ = 0~100%,
389
T = 200 °C, ω = 6.28 rad/s) for γ > 40%, the storage and loss moduli of all
specimens (including PS) decreased with strain. The frequency sweeps showed
that the storage and loss modulus increase with organoclay content. At low
frequency (ω < 0.1rad/s), the initial slopes of the log G´ or log G´´ versus log ω (g´
or g´´, respectively) decreased with organoclay content, e.g., for 0 to 10 wt%
organoclay g´ decreased from 1.9 to 1.6, and g´´ from 0.99 to 0.95. In steady-
state shear flow tests in a capillary rheometer, the power law index of the shear
viscosity decreased with increasing organoclay content. The extensional flow
behaviour of the PS matrix and the CPNC were also studied. It was found that
incorporation of the degraded organoclay resulted not in strain hardening, but
in a small strain softening effect, similar to that observed by Takahashi [1996]
for polymeric composites with solid particles.
Sohn et al. [2003], studied PS with Cloisite® 25A (MMT-2MHTL8). A solvent
(chloroform) casting method was used to prepare CPNC with 0, 2 and 10 wt%
of organoclay. Upon mixing with PS the organoclay interlayer spacing increased
from d001 = 1.94 to 3.27 nm. The dynamic flow measurements were carried out
at 200 °C. In spite of the achieved expansion of the interlamellar galleries, the
rheological data show small increases of both, G´ and G´´ moduli – a behaviour
typical to composites, but not nanocomposites. Thus, similarly as in the work by
Ren et al. [2000], here also only a monolayer of PS could be inserted into the
organoclay gallery space.
As these studies on PS-based CPNC indicate, preparation of CPNC with PS
as the matrix has been largely unsuccessful. The exceptions are the systems where
amine-terminated PS was used as intercalant (as in publications from Friedrich’s
or from Qutubuddin’s laboratories), to directly bond to the clay surface and to
form a miscible blend with the matrix. Evidently, PS is immiscible with alkyl-
intercalants. The macromolecular diffusion into interlamellar galleries most likely
originates in the tendency of aromatic molecules (i.e., benzene rings) to complex
with surface cations. However, once the first macromolecule is inserted, on the
one hand the attractive sides are shielded and on the other the interaction between
benzene side groups and clay expose the paraffinic chain. As a consequence, the
intercalated stacks of organoclay particles phase-separate from the matrix. The
situation is worse when during melt compounding the intercalant decomposes
and bare clay platelets re-aggregate into stacks with mineral clay spacing, e.g.,
d001 ≈ 1.4 to 1.7 nm.
3.3.11 Rheology of CPNC with Other Polymer Matrix Types

Owing to solubility in water and polarity of statistical segments, polyethylene
glycol (PEG), poly-ε-caprolactone, polyacrylics, polyvinyl esters and their
hydrolysed versions, e.g., poly(ethylene-co-vinyl alcohol), have been frequently
used for the preparation of CPNC in aqueous media. Recently, interest in these
systems was sparked by their potential application as solid-state electrolytes.
Hyun et al. [2001] studied the flow behaviour of PEG/MMT. The authors
prepared these systems by solvent casting. Three organoclays: Cloisite® 15A
(C15A; d001 = 2.96 nm), Cloisite® 20A (C20A; d001 = 2.47 nm), and Cloisite®
25A (C25A; d001 = 2.02 nm) comprised MMT (CEC = 0.95 meq/g; d001 = 1.23 nm)
modified with either 2M2HTA (32% excess in 15A and no excess in 20A) or
2MHTL8 (25A – stoichiometric). XRD showed that dispersion of these organoclays
in PEG resulted in expansion of the interlayer spacing by Δd001 = 0.52, 1.2 and
1.03 nm, respectively. Thus the resulting CPNCs were intercalated, but not
390
Rheology
exfoliated – concentration had only a small effect on d001. TEM showed highly
anisometric aggregates, ca. 200 nm thick and several micrometres long.
Rheological properties of these systems were measured in the steady-state
and dynamic shearing modes in parallel-plate geometry at 120 °C. The steady-
state data were fitted to the generalised Carreau-Yasuda equation:
2 (
1− n ) / 2
η = ηo ⎡1 + (λγ˙ ) ⎤ (138)
⎣⎢ ⎦⎥
During steady-state shearing the systems showed a pseudoplastic behaviour.
Addition of organoclay increased the shear viscosity – the strongest effects were
observed for C15A, then C20A and the weakest for C25A. Evidently, increasing
the concentration of organoclay also increased the strength of the rheological
signal. From the cited values of ηo for the CPNC with C25A, the intrinsic viscosity
[η] = 44 and the aspect ratio, p = 155 were calculated, confirming the TEM
observations of anisometric aggregates. Shearing while increasing and then
decreasing the deformation rate produced hysteresis loops, with the maximum
loop height observed for the highest hs material near the rate of shear: γ˙ ~ 1/λ.
The concentration dependence of the relative shear viscosity was fitted to the
Krieger-Daugherty [1959] equation:
[ ][]
− η φmax
ηr ≡ η / ηφ →0 σ 12 = const = 1 − φ / φmax (139)
For the multiphase systems, this relation must be taken at constant stress, σ12 = const.
For monodispersed particles, the maximum packing volume fraction, φmax, has a
unique, theoretically predicted value. For polydispersed suspensions, its value
depends on the polydispersity of size, shape and orientation of the dispersed
particles, thus it has to be treated as an adjustable parameter.
Dynamic measurements were carried out to analyse the CPNC structure within
the linear viscoelastic region at strain γ = 0.03. G´ and G´´ were measured for
nanocomposites containing C25A at clay content 0 to 17 wt%. The moduli
showed a monotonic increase at all frequencies. The initial slope of the storage
modulus, g´ ≡ d log G´/d log ω < 2 was observed for all concentrations (including
neat PEG). A solid-like behaviour was particularly pronounced at w ≥ 9 wt% of
organoclay. This may indicate that within this region, the clay aggregates are
unable to rotate hence they are prevented from relaxing. It was reported that
organoclay enhanced thermal stability of the nanocomposites.
Gelfer et al. [2002] prepared CPNC by melt blending commercial organoclays
with either poly(ethylene-vinylacetate) (EVAc; 3.1 and 8.15 mol% VAc) or
neutralised poly(ethylene-methacrylic acid) (PEMA; 3.1 mol% methacrylic acid).
The reason for using these copolymers originated from the observation that
organoclay is easier to disperse in highly polar polymers. Thus, EVAc and PEMA
were used as models for studying the structure, property and processing
relationships in CPNC. The organoclays were: Cloisite® 6A (C6A; d001 = 3.59 nm),
Cloisite® 20A (C20A; d001 = 2.47 nm), and Nanomer I30 E (I30). They all contain
MMT intercalated with (1) 2M2HTA (6A and 20A) or (2) N-tallow alkyl
trimethylene diamine chloride (?) (I30 usually comprises MMT-ODA). The
intercalant content was 45 wt% in C6A, and 30 wt% in C20A and in I30. XRD
of the CPNC indicated intercalation with d001 = 2.1 to 4.1 nm. In all systems, Tm
and crystallinity were not significantly affected by the presence of organoclays,
391
suggesting that clay particles were shielded from the matrix by the intercalant
molecules and predominantly confined to the amorphous phase.
Small strain oscillatory experiments were carried out at constant strain
amplitude (γ = 0.06), frequency 0.1 < ω < 100 rad/s and T = 120-200 °C (above
Tm). Under these conditions the specimens remained stable for t < 30 min. The
CPNC with EVAc as a matrix showed solid-like behaviour at small-strain
oscillatory shear, but it was able to yield and flow under a steady shear – the
characteristic performance of physically crosslinked systems. In contrast, the
CPNC with PEMA as matrix exhibited a melt-like rheological behaviour, with a
minimal contribution by the organoclays. The controlled stress rheometer was
used to determine the yield stress. The authors speculated that the carbonyl groups
of VAc in EVAc interact with the clay surface, resulting in physically crosslinked
structures. By contrast, the interactions between PEMA and the clay were
considered weak (due to repulsion between carboxyl anions and the negatively
charged clay surface) preventing the formation of structures in these systems.
The extrapolated ηo versus T showed an upswing at T > 200 °C, indicating physical
crosslinking. The time-temperature superposition has not been discussed, but
judging by the reported rheological data, its applicability to the studied systems
is dubious.
3.3.12 Rheology of CPNC – A Summary

In summary, the rheological studies of CPNC in shear and elongation demonstrate
that even at low clay loading the flow is frequently complex. One source of
complication that seldom is even considered by rheologists are the chemical
changes within the system, caused by the decomposition of intercalant, which in
turn affects the interlayer spacing and thermomechanical degradation of the matrix
polymer.
As discussed on the preceding pages, CPNCs show a range of performance
that starts with the traditional behaviour of filled systems and ends with end-
tethered nanocomposites showing quite distinct flow characteristics. For the end-
tethered CPNC, at low or moderate concentration of clay platelets, the shear
flow may be interpreted using the LCP theories. Following Onogi and Asada
classification, three regions of flow can be clearly identified:
(1) At low deformation rates – a solid-like yield stress behaviour, caused by a
3D structure.
(2) At middle strain rates assemblies of clay platelets undergo either a tumbling
(in shear) or stretching (in elongation) motion.
(3) At high rates of deformation, the platelets become oriented in the shear
direction, which causes the shear viscosity to decrease nearly to the level of
the matrix (the effect is particularly evident in the steady-state flow).
The end-tethered systems show the formation of 3D structures at a concentration
of about 0.5 vol% clay. These structures are responsible for the non-linear
viscoelastic flow behaviour, characterised by classic rheological tests or Fourier
transform rheology [Wilhelm, 2002; Debbaut and Burhin, 2002]. This method is
particularly well suited for quantification of the non-linear effects as a function
of composition, strain rate, strain, temperature, etc.
The unique character of CPNC is evident in the extensional flows. The studies
on these flows lead to the conclusion that the presence of exfoliated clay platelets
392
Rheology
able to interact with the matrix (e.g., end-tethered systems) results in significant
enhancement of strain hardening. This effect agrees very well with the ‘hairy clay
platelet’ (HCP) model of CPNC. Thus, in analogy to improved processability of
some resins by blending them with branched homologues (e.g., common industrial
blends of LLDPE with LDPE) one may use CPNC technology to improve film
blowing, blow moulding or foaming (and microfoaming) of difficult to process
resins. At high extensional flow rates, the platelets may be oriented perpendicular
to the stretch direction, which causes the transient viscosity to move into the
strain hardening region. Both effects are stronger for the end-tethered than the
free platelets systems, especially at higher clay loading.
393
394
Nucleation and Crystallisation
3.4
Nucleation and
Crystallisation
3.4.1 Introduction
Polymers may crystallise when: (1) their molecules have sufficiently regular
structure and mobility, (2) the temperature is: Tg < T < Tm, (3) there are nuclei
present and (4) the rate of crystallisation is sufficiently high.
Nucleation is the initial stage of the phase separation during which a new
phase is formed on a minute amount of substance that acts as a nucleus for
subsequent phase growth. In Nature, fog, rain or snow are formed through this
process. Nucleation of crystals requires seed crystals, viz. self-formed nuclei, dust
particles or nucleating agents. Thus, crystallisation may take place via a
homogeneous crystallisation mechanism, where the molecules self-assemble into
ordered entities having critical size for the crystal growth, or via a heterogeneous
crystallisation mechanism, where the molecules assemble on the surface of a
foreign body. In polymer technology, especially for injection moulding, the desired
high crystallisation rates often require the addition of nucleating agents.
A nucleating agent is a substance that forms nuclei for the growth of crystals
in a supercooled polymer melt. Virtually any solid body with a high energy surface
may act as a nucleating agent. However, for efficient nucleation it is necessary
that the crystalline structure of the nucleating agent closely matches the crystalline
structure of the polymer [Vesely, 1996]. Several specific crystalline or crystallisable
substances have been developed, viz. 4-biphenyl carboxylic acid, aluminium salts
(benzoate, phenyl-acetate, tert-butyl-benzoate), antimony compounds (trioxide,
phosphates), sodium salts (4-methyl-valerate, benzoate, β-naphthoate, caproate,
cinnamate, succinate), pigments, etc. These substances generate from 2 to
20 million nuclei per 1 mm3.
The nucleating agents may preferentially induce a specific crystallographic
form of the polymer. For example, addition to isotactic-PP of either 1,2,3,4-bis-
(3,4-dimethyl-benzylidene sorbitol) or N,N´-dicyclohexyl-2,6-naphthalate
dicarboxamide, preferentially generate α-iPP or β-iPP, respectively. The nucleating
efficiency depends on several independent variables, such as temperature, pressure,
stress, part thickness as well as the presence of other processing additives. For
this reason, during the last few years combinatorial methods have been used to
study polymer nucleation and crystallisation.
As stated above, an efficient nucleating agent must have a high-energy surface
– the larger the specific surface, the more efficient it is expected to be. Nucleation
involves initial adsorption of macromolecules on the surface. The process is
particularly efficient if the foreign body is able to provide an energetic matrix for
the formation of thermodynamically favourable crystalline forms. Alternatively,
the crystalline cell type and size of the nucleating agent may induce a transitory
crystalline polymer form that upon annealing transforms into a stable form of
395
higher packing density. Several researchers have reported this behaviour for CPNC
with PA-6 as the matrix.
The nucleating efficiency, ϕ, may be expressed in terms of the energy ratio
required to generate a nucleus in a heterogeneous nucleation over that in a
homogeneous one [Dobreva and Gutzow, 1993]. The authors assumed that
nucleation is the rate-determining step, while the extent of crystallinity is constant.
Thus, the nucleation rate, r, depends on the degree of supercooling, ΔTp = Tm - Tc:
{ }
r = A exp − En / ΔTp2 ; En = ωσ 3 Vm2 / nk B Tm ΔSm2
(140)
ϕ ≡ En (hetero) / En (homo) T ≈Tm
where En is the energy required to form a nucleus, ω is a geometrical factor, σ is the
specific surface energy, Vm is the molar volume of the crystallising substance, ΔSm
is the melting entropy, n is the Avrami exponent and kB is the Boltzmann constant.
According to Equation 140, the nucleating activity factor (ϕ) is given by the ratio
of the slopes of ln r versus 1/ΔTp2. Note that 0 ≤ ϕ ≤ 1, with ϕ = 0 indicates the
highest activity of the nucleating agent and ϕ = 1 indicates total lack of it.
Nanofillers such as clays may have strong nucleating effects. The wide variety
of intercalants, intercalating methods and compatibilisers may form a barrier
between the high-energy clay surface and the semicrystalline polymer matrix. In
this section the recorded effects of nanoclay on the crystallinity of CPNC will be
summarised. Since CPNC with PA and PP matrices are of great academic and
industrial interest the focus will be on these two classes of nanocomposites.
3.4.2 Fundamentals of Crystallisation

The growth rate of lamellar crystal is controlled by the degree of undercooling,
ΔT = Tm - Tg and the macromolecular diffusion rate towards the crystal growth
front. A maximum rate of crystal growth takes place near Tmax ≈ (Tg + Tm)/2. In
other words, the rate of crystal growth, G, is governed by the activation energy
required to transport crystalline molecules across the solid-liquid interface (ΔE)
and the work necessary to form a critical nucleus (ΔF*). The crystallisation growth
rate is usually expressed as [Turnbull and Fisher, 1949]:
{ }
G = Go exp − ΔE / R(Tc − To ) exp{− ΔG * / k B T } (141)
where Go is a constant, To is the temperature at which motions necessary for the
transport of molecules through the liquid-solid boundary cease, and Tc is the
temperature of crystallisation. At low supercooling the growth rate is nucleation
controlled, while at high supercooling it is diffusion controlled.
Inherent to this model is an assumption that ΔG* depends on the size and
shape of the homogeneously formed nucleus. The crystallisation may take place
if the nucleus reaches a critical size [Hoffman et al., 1976]:
[
ΔG* = 32σ e σTm (Tm + T ) / 2Δh f (Tm − T )]
2
(142)
where σ and σe are the side and end free energies of the crystal, Δhf is the free enthalpy
of fusion and Tm is the equilibrium melting temperature. The critical size for
homogeneous nuclei is about 100 nm3, comparable to the macromolecular chain size.
Binsbergen [1973] considered the second type of nucleation, the heterogeneous
one. The author assumed that a foreign substance, e.g., a dust particle or a nucleating
agent, facilitates formation of a polymeric nucleus, similar to that formed in
396
homogeneous nucleation excepting the presence of a high energy solid surface that
lowers the magnitude of ΔG*. As a result the critical size of the nucleus is reduced,
which in turn leads to crystallisation at lower undercooling, thus:
[
ΔG* = 16σ ( Δσ )σ e Tm (Tm + T ) / 2Δh f (Tm − T ) ]
2
(143)
where Δσ is the specific interfacial free energy difference between the nucleus
and the nucleating agent. The overall crystallisation kinetics of blends is often
described by the Avrami equation [Avrami, 1939]:
{ }
α (t ) = 1 − exp − kt n (144)
α(t) is the weight fraction of a crystalline part at time t, whereas n and k are equation
parameters. The Avrami index (n) depends on the type and geometry of nucleation
and the crystal growth, thus it may be written as n = nnucleation + ngrowth. The Avrami
rate parameter k, is often expressed in terms of the crystallisation half-time, t1/2:
k = (ln 2) / t1n/ 2 (145)
Derivation of the Avrami equation is based on several assumptions, such as the
shape constancy of the growing crystal, the constant rate of radial growth, lack
of induction time, the uniqueness of the nucleation mode, complete crystallinity
of the sample, random distribution of nuclei, constant radial density, primary
nucleation process (no secondary nucleation) and absence of an overlap between
the growing crystallisation fronts. Furthermore, the often-cited form of the
dependence is simplified – as Ga ęski [1995] pointed out, the relation is only
valid for sporadic or instantaneous nucleation. The derived expressions are
different for crystallisation in films and in the bulk.
Pérez-Cardenas et al. [1991] developed a modified Avrami expression,
separating the primary and the secondary (subscripts ‘p’ and ‘s’, respectively)
crystallisation effects. Thus, the crystalline weight fraction, α, was written as:
α = αp + αs (146)
Accordingly, the crystallisation proceeds in three steps: (I) the initial primary
crystallisation, (II) mixed primary and secondary crystallisation and (III) pure
secondary crystallisation. The authors expressed the weight fraction of the polymer
crystallised by primary and secondary crystallisation as ζ. In consequence, the
crystallisation may be described by two equations:
⎡ t ⎤
( ) ⎢⎣ ∫ ( )
1 − α = exp − kt n − k ′t n′ ⎢kn(1 − ς ) xp kt n + k ′t n′ τ n−1 dτ + 1⎥ ; α ≤ ς (147)
⎥⎦
0
{ } { }
1 − α = (1 − ς ) exp k ′t * n′ exp k ′t n′ ; α > ς (148)
Now, six parameters are required to describe the process: k and n (the primary
crystallisation parameters) depend on crystallisation temperature, the nature of
primary nucleation and the fast growth; the secondary crystallisation parameters,
k´ and n´ depend on the conditions under which the slow crystallisation of the
remaining amorphous regions takes place, ζ, indicates the weight fraction of
material crystallised up to the moment the primary crystallisation ends and t*
indicates the start of the pure secondary crystallisation.
Furthermore, Avrami theory is limited to isothermal processes. Since polymer
processing is mostly non-isothermal, the theory has been extended by Ozawa
397
[1971] who considered the Avrami constant k to depend on temperature, k = k(T),

and the crystallisation time t as dependent on the cooling rate: t = Φ–m (m is the
Ozawa exponent).
A more general approach to non-isothermal crystallisation was developed by
Kamal and Chu [1983]:
⎧ t ⎫
α (t ) = 1 − exp ⎨− k (T )nt n−1 dt ⎬
∫
⎩ 0 ⎭
⎧⎪ T (149)
dT ⎫⎪
n −1
⎛T −T⎞
α (T ) = 1 − exp ⎨− k (T )n⎜ o
∫ ⎟ ⎬
⎝ R ⎠ R⎪
⎩⎪ o
T
⎭
where k(T) and n are Avrami’s isothermal parameters. For DSC scans the following
expression has been successful:
[α ′ (T
p p )] [ (
− Tons / β 1 − a p )] = (n − 1) − [ E(T
p )] [
− Tons / RTp2 ] (150)
where : Tp = Tons + βt and α ′p ≡ dα / dt = (1 − α )nkt (
n −1 )
where β is the heating rate, Tons is the onset temperature, Tp is the peak temperature
reached after time t, and E is the activation energy of the crystallisation process.
In a semicrystalline homopolymer, the change in free energy of melting per
mole of monomer is given by:
ΔGu(T) = ΔHu - TΔSu (151)
where ΔHu and ΔSu are the enthalpy and the entropy changes on melting,
respectively. For an infinitely thick crystal at equilibrium melting temperature
Tm, ΔGu(Tm) = 0 and:
T m = Δ Hu / ΔS u (152)
The value of Tm can experimentally be determined from Hoffman-Weeks plots,
where the experimental melting point is plotted as a function of the crystallisation
temperature, Tc. Extrapolation of experimental data to the Tm = Tc line gives the
equilibrium value of Tm.
Xu et al. [2001] studied the nonisothermal crystallisation kinetics of CPNC
with POM or with PP [2002] as the matrix. Two CPNC with POM were prepared
in a roller mill at T = 175 to 180 °C; the first comprised 5 wt% of Na+-MMT and
the second MMT-3MHDA. The interlayer spacing in these systems was d001 = 1.92
and 3.52 nm, respectively. The nonisothermal crystallisation kinetics were
investigated by DSC at 5 to 40 K/min cooling rate. The difference in the values of
the Avrami exponent n between POM and the nanocomposites suggests a
tri-dimensional growth with heterogeneous nucleation. At a given cooling rate
the crystallisation of neat POM was slightly slower than that of either
nanocomposite. The activation energies, 387, 330, and 329 kJ/mol were
determined for the nonisothermal crystallisation of POM, POM/Na+-MMT
nanocomposite, and POM/MMT-3MHD, respectively.
A similar process was used to prepare nanocomposites with PP with 3 wt%
MMT-3MHDA. A 3 mm thick sheet was compression moulded at 180 °C. The
interlayer spacing was d001 = 3.88 nm. The crystallisation rate increased with
increasing cooling rates for both PP and its nanocomposite. The crystallisation
rate of CPNC was higher by 40% at a cooling rate of 5 K/min, but virtually
398
identical at the fastest cooling rate of 40 K/min. The activation energies were
estimated as 189 and 156 kJ/mol for PP and nanocomposite, respectively. Thus,
incorporation of 3 wt% of organoclay into PP affected the matrix crystallisation
more than 5 wt% in POM.
General procedures for evaluating crystallinity in polymeric systems by XRD
and DSC have been developed, e.g., by Murthy and Minor [1990] and by Khanna
and Kuhn [1997], respectively. Additional information on the topic can be found
in [Mathot, 1994; Chan et al., 1995; Hammami et al., 1995], etc.
3.4.3 Effects of Clay on Crystallisation of PA-6 Matrix

Nucleating PA by means of standard nucleating agents (e.g., silica, talc, Na-phenyl
phosphate, etc.) leads to higher crystallinity that translates into higher modulus,
hardness, yield strength, HDT, improved abrasion and water absorbance, but
reduced elongation at break and impact strength. The characteristic properties
of PA-6 and PA-66 are listed in Table 56. Both these polymers are polymorphs,
the former crystallising mainly in α-form, γ-form and a metastable β-form.
Historically, PA-6 is more important for CPNC technology. There is a large body
of information in the patent and open literature for these systems. As far as the
effects of clay addition on crystallisation of PA-6 are concerned, the focus has been
on nucleation, crystalline structure and total crystallinity. In PA-6 the stable monoclinic
Table 56 Characteristic parameters of polyamides

Property PA-6 PA-66
Condition Value Condition Value
Glass transition Dry 320-330 Dry 351

temp., Tg (K) 50% RH 276-293 50% RH 308
Melting point Dry 493 Dry 542.2

(eq.), Tm (K)
Density, ρ Dry 1130 Dry 1220-1250

(kg/m3)
Typical Dry 50 Dry 40-60

crystallinity,
α (%)
Unit cell α-form 0.956×1.724×0.801 αI-form 1.57×1.05×1.73
dimensions γ-form 0.933×1.688×0.478 β-form 0.49×0.8×1.72
(nm)
Unit cell angles α-form 67.5 (4) αI-form 73 (9)

(# mers) γ-form 121 (4) β-form 77 (2)
Lattice all forms Monoclinic αI-form Monoclinic and

triclinic
β-form Triclinic
399
α-form has a planar zigzag chain conformation, the metastable (pseudo-) hexagonal
γ-form has a twisted chain, while the β-form is less well identified and often considered
to be an intermediate stage between the two others. The α-form is most common,
readily obtained during melt processing. A nearly pure α- and γ-form may be obtained
by, respectively, treating the specimen in superheated water vapour at 150 °C, and
by reversibly complexing it with iodine from KI aqueous solution [Penel-Pierron et
al., 2001a,b]. Uniaxial drawing increases the α-form content and reduces that of the
γ-form. The tensile strength is higher for the α-form, while the γ-form shows better
toughness. The solid/solid transition of α-crystal into γ-crystal, observed during heating
or cooling, is known as the Brill transition.
At the crystallisation temperature, Tc > 450 K PA-6 crystallises in a mixture
of α- and γ-forms, whereas above this limit essentially in nearly a pure α-form
[Privalko et al., 1979]. Thus, the α-form is more stable at higher temperatures.
The authors reported that addition of glass beads or aerosil to PA-6 did not
change the molecular mechanism of crystallisation. PA-66 crystallises in at least
six forms, of which the αI- and β-form dominate. Incorporation of organoclay
into PA-6 increases the nucleation density, the proportion of the γ-form in the
crystal as well as modifying the total crystallinity content. While the former two
effects are generally accepted the latter is more controversial – some authors
report enhancement, some others reduction while newer publications indicate
that both may be present within specific ranges of conditions, e.g., using a different
cooling rate or annealing method.
Kojima et al. [1994] used XRD and DSC to study orientation and crystallinity
of the exfoliated PA-6/MMT system. The platelets of MMT and the γ-form of
PA-6 crystallites were reported parallel to each other. The α-form was not detected.
Incorporation of 0.2 to 0.8 vol% MMT increased the degree of crystallinity of
PA-6 (to 31%) by 5 to 7%, but the effect did not depend on composition. In the
following publication it was reported that in injection moulded tensile bars the
orientation depended on the depth, but the γ-form of PA-6 still dominated the
crystalline phase [Kojima et al., 1995]. In the surface layer of the moulding,
MMT platelets and chain axes of crystalline PA-6 were parallel to the surface. In
the intermediate layer the MMT platelets remained parallel to the surface of
tensile bar, but the chain orientation rotated 90o (hence orienting perpendicularly
to both, bar surface and MMT). In the central layer the platelets were randomly
oriented along the flow axis with chain axes perpendicular to them.
Usuki et al. [1995] studied CPNCs of PA-6 containing ca. 5 wt% of MMT,
synthetic mica, saponite or hectorite (CEC = 1.2, 1.0, 1.0 and 0.5 meq/g,
respectively). Prior to reactive exfoliation in ε-caprolactam, the clays were
pre-intercalated with ω-amino lauric acid (ADA). Owing to end-tethering, the
concentration of –COOH macromolecular chain ends was about twice as large as
that of –NH2. The authors established correlations between the performance (e.g.,
tensile strength, modulus, HDT), the strength of the clay-polymer interaction
(determined by the 15N-NMR chemical shift, CP) and the degree of crystallinity, X
(wt%). The latter was calculated from the DSC-measured heat of fusion, taking
the literature value for the heat of fusion of PA-6 crystal as 188 J/g. Surprisingly, it
was found that X decreased upon incorporation of organoclay. At the same time,
the mechanical performance (e.g., tensile modulus) increased with CP from 1.11
for PA-6 to 2.02 GPa for CPNC with mica. These observations are summarised in
Figure 121 – note that excepting the degree of crystallinity, X (wt%), the other
performance characteristics for CPNC diverge from those of PA.
400
Liu et al. [1999] prepared CPNC by melt blending PA-6 in a TSE with 1 to
18 wt% of MMT (CEC = 1.0 meq/g) intercalated with ODA. After compounding
at T = 180 to 220 °C, the CPNC with more than 10 wt% of organoclay showed
intercalated structures with d001 increased from 1.55 to 3.68 nm. However, at
low MMT content the samples were exfoliated. In accord with the Usuki et al.
[1995] results, the authors observed a difference in crystallisability between PA-6
and its CPNC – addition of any amount of clay reduced the supercooling effect
to a common level, indicating enhanced nucleation. However, by contrast with
the Usuki et al. [1995] results, here all specimens (with 0 to 6.7 wt% MMT)
showed about the same crystallinity. The difference most likely originates in the
different internal structure of these CPNC – in the former work the reactive
exfoliation resulted in end-tethering, whereas compounding PA-6 with pre-intercalated
MMT generated exfoliated CPNC (at lower clay content), but without end-
tethering. XRD of PA-6 showed a virtually pure α-crystallographic form, whereas
the polymer in CPNC crystallised mainly in the γ-form.
Wu and Liao [2000] prepared CPNCs of exfoliated synthetic saponite in a
PA-6 matrix using the reactive route with a unique pre-intercalation step; synthetic
clay was dispersed in water/ε-caprolactam/phosphoric acid solution, then the
mixture was polymerised at T = 80 to 270 °C under pressure. The authors do not
provide information about the platelet dispersion. XRD and DSC were used to
study the effect of clay on crystallinity, which in turn was related to performance.
The specimens containing 0, 2.5 and 5 wt% clay were pressed into sheets at
240 °C, then either slowly cooled or quenched to room temperature. Slow cooling
Figure 121 Crystallinity, relative tensile strength, TS/TS(PA), and relative HDT
(expressed in Kelvin), HDT/HDT(PA) as functions of the 15N-NMR chemical shift,
CP. Systems: PA-6 with 5 wt% of exfoliated clay – see text. Data [Usuki et al.,
1995].
401
resulted in nearly pure γ-form crystals in the sample containing 2.5% clay, nearly
pure α-form in the sample containing 5 wt% clay and polymorphic crystals in
PA-6. By contrast, quenching yielded a nearly pure γ-form for the sample with
5 wt% clay, predominantly α-form for PA-6 and intermediate polymorphous
composition for the sample containing 2.5 wt% clay. To transform γ- into α-form
required 2 h heating at 210 °C. Addition of synthetic saponite increased the
crystallisation rate, but the crystallinity was not determined. The tensile modulus
and HDT showed significant improvements.
Akkapeddi [2000] used a melt compounding method for the manufacture of
PA-6 based CPNC. Thus, organoclay of MMT or hectorite was dispersed in PA-6
at a level of 2 to 5 wt% of clay. The author reported that clay platelets had
strong surface nucleation effects that promoted faster crystallisation and a higher
level of crystallinity in relation to that of neat PA-6 (particularly at the surface
and in thin-wall injection mouldings). For example, in 1 mm thick PA-6 injection
moulded bars the crystallinity was 16 to 18%, while in CPNC (4 wt% clay) the
crystallinity was 50% throughout the specimen. It is noteworthy that whilst in
PA-6 specimens the skin had lower crystallinity than the core, in CPNC the
situation was reversed.
Giza et al. [2000] reported enhanced crystallinity in spun fibres of PA-6/MMT
(from Ube). While the crystallinity content in drawn fibres of PA-6 was about
51%, in those containing 2 and 5 wt% clay it was 59 and 63%, respectively. Part
of the reason for the difference may be the higher drawing temperature for CPNC
(170 °C) compared with PA-6 (150 °C). Furthermore, the high-speed drawing
that produced the highest crystallinity was also instrumental in transforming the
γ-form into predominantly α-form. Increased crystallinity translated into higher
modulus, viz. the tensile modulus for CPNC with 0, 2, and 5 wt% clay was
about 8, 9 and 10 GPa, respectively.
Intercalated or exfoliated CPNC were prepared by extrusion compounding
of PA-6 with ca. 3 wt% of pre-intercalated MMT, Cloisite® 30B (C30B);
d001 = 1.8 nm or Cloisite® 6A (C6A); d001 = 3.6 nm [Varlot et al., 2001]. The
compounds were injection moulded into 4 mm thick bars, which subsequently
were characterised by XRD. In accord with Kojima et al. [1995], the authors
reported significant variation of crystalline morphology with depth. Thus in the
three specimens: PA-6, PA-6 + C30B, and PA-6 + C6A, the surface layer was rich
in γ-form. The central, bulk layer of the injection moulded bar of PA-6 showed
preponderance of α-form, whereas γ-form dominated the two other specimens.
The CPNC showed MMT platelets aligned with the flow direction. The average
distance between MMT platelets in a PA-6A sample was determined from the
SAXS spectra to be ca. 35 nm. The same value was calculated from the
composition, assuming perfect exfoliation and uniform distribution of the
platelets.
VanderHart et al. [2001] used solid-state proton and 13C NMR to study 17 CPNC
compositions based on PA-6, provided by Ube Ind. and SCP. Except three samples
that contained laponite clay, the CPNC comprised natural, pre-intercalated MMT
dispersed either by in situ polymerisation or by melt compounding. The clays
were found to promote growth of the γ-form of PA-6 in all CPNC samples, while
the α-form characterised the neat PA-6. The total crystallinity in neat PA-6 was
40% – all in α-form. In CPNC the crystallinity was ca. 33 to 45% with the α-
form ranging from 2 to 75% (after injection moulding and annealing). However,
most specimens annealed at Ta = 214 °C showed only a partial conversion of γ-form
402
to α-form (e.g., from 4 to 19%). The CPNC showed higher Tc and Tm than that
of PA-6. Since the main objective was to study paramagnetic effects there is little
more information on crystallinity.
To prepare CPNC with PA-6 as a matrix, Liu and Wu [2002a,b] used a three-step
method. Thus, Na-MMT (CEC = 0.8 meq/g) was intercalated with trimethyl
hexadecyl ammonium bromide (3MHDA). The precipitate of the reaction in H2O
was dried under vacuum then compounded in an internal mixer with the diglycidyl
ether of bisphenol-A (MW = 360 g/mol). In the last step the doubly intercalated
MMT was dispersed in molten PA-6 by means of compounding in a TSE at ca.
230 °C. The product containing 5 wt% clay was used in crystallographic studies
published in several articles, summarised below. More recently, the work was
extended to a PA-66/MMT system [Liu and Wu, 2002a; 2003]. A higher
crystallisation temperature for CPNC than that for neat PA-66 (Tc = 237 instead
of 226 °C), reduction of spherulite size, the presence of a γ-phase instead of an
α-phase were reported. Similar behaviour was observed for an exfoliated PA-66/MMT
system [Zhang et al., 2003].
The DSC and XRD studies on the influence of the cooling rate on the
crystallinity in PA-6 and CPNC demonstrated that the two materials behave
differently [Wu et al., 2001a]. Thus, as the cooling rate increases the rate of
crystallisation of PA-6 decreases while that of CPNC increases. In Figure 122
two separate sets of experiments are presented. The DSC data represent
experiments with well-defined cooling rates, whereas those measured by XRD
are plotted versus estimated ones. The dependencies are similar. The XRD data
show even stronger divergence of behaviour between PA and CPNC than DSC.
Furthermore, WAXS data indicated that PA-6 was highly polymorphous – only
at the slowest cooling rate was nearly pure α-form obtained. By contrast, the
Figure 122 Crystallinity versus cooling rate for PA-6 and PA-6 containing 3 wt%
of doubly pre-intercalated MMT. Two methods were used: DSC with well defined
cooling rates and XRD with roughly estimated cooling rates. Data [Wu et al.,
2001]. See text.
403
CPNC diffraction showed nearly pure γ-form – only at the slowest cooling rate
did the α2-peak-emerge.
A partial explanation for the diverse behaviour of PA-6 as a neat resin and as
a nanocomposite matrix can be gleaned considering the results of an annealing
experiment, displayed in Figure 123 [Liu and Wu, 2002a]. Granules of PA or
CPNC were placed between two glass slides, heated in an oil-bath up to 250 °C
for 10 min, and then quenched in liquid N2. The films were annealed in an oil-
bath at different Ta for 1 h, re-quenched and their crystallinity was determined
by XRD. In the Figure the α- and γ-form crystalline content is plotted versus Ta
– the total crystallinity is a sum of these two forms. During the compounding
and pelletising some crystallinity in PA-6 and CPNC certainly developed. However,
this crystallinity was to be eliminated by keeping the specimens for 10 min at
250 °C. Thus, the subsequent quenching generated 0 and 48% crystallinity in
PA and CPNC, respectively. The 1 h annealing of PA-6 at T ≥ 100 °C
characteristically formed g-crystals that subsequently converted to α-form. The
total crystallinity reached a maximum value of 36% at 180 °C. By contrast,
CPNC maintained ca. 49% of crystallinity in the γ-form up to ca. 130 °C. Above
this temperature γ- progressively converted to α-form – the latter reached its
maximum content of ca. 19% at 180 °C. Thus, the presence of organoclay
increased the total crystallinity of the PA-6 matrix well above the level observed
for the neat resin, and it had stabilised the γ-form to higher temperatures before
the onset of the solid-solid phase Brill transition from γ- to α-form. It is noteworthy
that the DSC-determined Tm of PA-6 and its CPNC was 223 and 219 °C,
respectively, in good agreement with the known melting points for the α- and γ-
crystals.
FTIR studies of PA-6 and CPNC led to the conclusion that the presence of
organoclay weakens the hydrogen bonding in PA-6. The γ-form was found
Figure 123 Determined by XRD crystallinity of PA and CPNC (containing 5 wt%

of doubly pre-intercalated MMT) as a function of the annealing temperature. The
α- and γ-form crystalline content is shown – see text. Data [Liu and Wu, 2002].
404
preferentially located near the clay platelets, whereas the α-one preferentially in
the bulk [Wu et al., 2002a].
Murase et al. [2002] used FTIR, XRD and DSC to study the structure of PA-6
with 2 wt% of either synthetic mica or natural MMT. The PA-6/mica was prepared
by melt polymerisation of ε-caprolactam while the PA-6/MMT was industrial
resin from Ube Ind. The films were prepared by pressing at 250 °C for 2 min
followed by quenching into an ice-water bath and then annealing at 110 °C for
6 h. In PA-6 only the α-form was found, in the Ube nanocomposite both α- and
γ-crystalline forms, and in the mica-containing CPNC only γ-form crystals were
detected. The latter composition also showed the highest degree of crystallinity
of about 58% followed by that of PA/MMT and PA-6 (37%). Judging by the
reported results, it seems that mica in the studied CPNC was only intercalated,
whereas MMT in the Ube nanocomposite was exfoliated. Thus, it is difficult to
speculate whether the observed difference in the composition of the crystalline
phase is due to the nature of these two clays or to the degree of exfoliation.
Kamal et al. [2002] studied the crystallisation kinetics of PA-6 and its CPNC
(Ube PA-1015B and –1015C2, respectively) under pressure P = 50 to 200 MPa.
Isobaric volume changes associated with the crystallisation process were
determined at constant T and P, from which the crystallinity was calculated as:
X(%) = 100(V0 – Vt)/(V0 – V∞) (153)
where V0 is the initial (melt) volume, Vt is the volume at time t, and V∞ is the
volume at the end of crystallisation. Isobaric heating or cooling was used to
determine the melting or crystallisation temperatures of PA-6 in its neat state
and in CPNC. The data were fitted to a linear dependence:
Tm,c(°C) = ao + a1P(MPa) (154)
The numerical values of the parameters ai, along with the correlation coefficient
squares, r2, are listed in Table 57. It is noteworthy that the Tm for both resins
follows the same dependence, whereas Tc of the CPNC is lower by about 6 °C
than that of neat PA-6. It is also interesting that within the experimental error of
these measurements, the pressure gradient of Tm and Tc, dTm,c/dP = a1, is about
the same for PA-6 and CPNC.
The kinetics of crystallisation were studied at constant T and P. For both
resins, the data plotted according to the linearised Avrami equation showed two
intersecting linear dependencies. Apparently, the crystallisation started with the
γ-form, and then proceeded to the α-form. Thus, within the first zone the γ-form
Table 57 Pressure dependence of the melting point, Tm °C, and the

crystallisation temperature, Tc °C, for PA-6 and its nanocomposite.
Data [Kamal et al., 2002]
Parameter PA-6 CPNC
Tm Tc Tm Tc
ao 214 184 214 178
a1 0.21 0.23 0.21 0.22
r2 0.986 0.997 0.989 0.996
405
was dominant while within the second zone the α-form dominated. The Avrami
exponent n for the γ-form was between 1.0 and 3.2 in PA-6 and between 0.9 and
2.6 in CPNC. Its value for the α-form was between 1.0 and 2.1 in PA-6 and
between 1.2 and 2.6 in PNC.
In Figure 124 and Figure 125 the crystallisation rate of, respectively, PA-6
and PANC is expressed as the crystallisation half-time, t1/2, versus the free volume
( )
parameter, h = h P˜ , T˜ , where P˜ , T˜ are reduced pressure and temperature,
computed for each resin from the Simha-Somcynsky eos. Evidently, the kinetics
of crystallisation not only depend on h, but on P as well. To more clearly see the
effects of the independent variables, the experimental data were fitted to a linear
dependence, t1/2 = t1/2(h, P). The correlation coefficient squared, r2 = 0.74 to 0.95
was obtained. At the same value of h and P, the rate of crystallisation of the
α-crystals is systematically slower (t1/2 larger) than that of the γ-crystals. PA-6 in
CPNC crystallises faster than in its neat form. Surprisingly, in these isothermal
and isobaric experiments the pressure seems to play a secondary role to h as far
as the crystallisation kinetics is concerned. This was not the case for the isobaric
scans (at constant scanning rate) where high pressure slowed down either melting
or crystallisation in PA and CPNC.
Bureau et al. [2002] reported on the crystallinity and mechanical properties
of compression moulded PA-6 and its CPNC (Ube Ind., PA-1015B and 1015C2).
Specimens were moulded at 250 °C for 90 sec at P = 0.7 MPa, then either cooled
to room temperature under pressure at a rate of ca. 30 °C/min, or quenched in
ice water. Some quenched specimens were subsequently annealed at 80 °C for
24 h under vacuum. It was expected that these procedures would produce
specimens containing, respectively: the α-form (cooled), amorphous PA-6
(quenched), and the γ-form (annealed).
The DSC scans of PA-6 specimens showed a crystallisation peak followed by
an α-form melting peak at Tm = 221 °C. The crystalline content was estimated
as: 31% (cooled), 7% (quenched) and 21% (annealed). DSC scans of cooled or
quenched CPNC showed a double melting point, Tm = 213 and 221 °C, indicating
a polymorph with either γ- (in the cooled sample) or α-form (in the quenched
sample) predominating. The crystalline content in both these two samples was
ca. 25%, thus lower for the cooled specimen (than that in neat PA-6) and
significantly higher in the quenched specimen, indicating rapid nucleation by
MMT. Identification of the a- or g-form was confirmed by XRD and FTIR.
The tensile test results are summarised in Table 58. There is strong correlation
between the mechanical behaviour and morphology. All PA-6 specimens showed
necking with strain at break varying between 120% and 670%, depending on
the moulding condition. For the cooled CPNC specimens, higher Young´s modulus
and yield stress (with brittle fracture without necking) was observed. The tensile
strength and the Young´s modulus of the CPNC were ca. 15% higher than those
of PA-6. 25% polymorphous crystallinity in CPNC yielded a higher tensile
modulus than PA-6 with a 31% α-form crystalline phase. The data indicate that
improvements of rigidity and strength caused by addition of MMT are related to
the reinforcing effects of the nanofiller and not to the increased γ-crystals content.
The effect of matrix molecular weight on the kinetics of isothermal and non-
isothermal crystallisation in a PA-6/MMT system was studied by Fornes and
Paul [2003]. Incorporation of ca. 0.5 to 1 wt% clay resulted in the highest PA-6
crystallisation rate. While for neat PA-6 the crystallisation rate decreases with
molecular weight, in the case of CPNC the maximum crystallisation rate was
406
Figure 124 Half-time for crystallisation of the γ- and α-forms in PA-6 versus the
free volume fraction parameter, h. Solid points are experimental, open are
computed from the linear fit to Equation 94. Data [Kamal et al., 2002]. See text.
Figure 125 Same dependence as in Figure 124 but for a CPNC sample of 2 wt%
organoclay in a PA-6 matrix (Ube PA-1015 C2). Data [Kamal et al., 2002]. See
text.
407
hardly affected by it. Furthermore, the largest enhancement of the crystallisation

kinetics was reported for systems with the highest molecular weight (the authors
postulate that this was related to the highest degree of exfoliation). However, the
degree of crystallinity decreased with the matrix molecular weight.
3.4.4 Clay Effect on Crystallisation of Other Polyamides

Kuchta et al. [2000] studied crystallisation of PA-11 in its CPNCs. The authors
prepared several compositions by in situ polycondensation or melt compounding.
To start with, MMT was pre-intercalated with ω-amino-undecanoic acid.
Polycondensation yielded CPNC with 2.4 to 19.7 wt% MMT, while compounding
of PA-11 with organoclay (10 min in a recirculating mini-TSE) yielded CPNC
with 1.7 to 31 wt% clay. TEM and synchrotron radiation indicated uniform
dispersion of MMT in the PA-11 matrix.
By contrast with PA-6 CPNC, where the γ-form has been observed already at
low clay loadings, in the PA-11 nanocomposites the α-form remained stable up
to 20 wt% MMT. In the sample containing 5.6 wt% MMT the α- to γ-form Brill
transition was observed at T ≅ 100 °C, the same as in neat PA-11. Thus, the
influence of MMT on the solid-solid transition in PA-11 is less significant than
that in PA-6. Heating PA-11 and its CPNC resulted in different extents of lamellar
thickening. While in neat PA-11 the lamella thickness at 180 °C is 72% higher
than that at room temperature, in CPNC the constraint by the MMT layers
reduced the increase to 17%. Reactively prepared CPNC showed a reduction of
crystallinity at MMT content above 20 wt%. The CPNC had enhanced thermal
stability, tensile modulus and increased elastic behaviour over a broader
temperature range than the neat resin. Zhang et al. [2004] used the same method
for the preparation of neat PA-11 and its CPNC containing 5 wt% MMT.
However, the γ-form of PA-11 was induced and stabilised by MMT. Furthermore,
the hydrogen bonding in neat resin and its CPNC was quite different.
The crystallisation behaviour of PA-1010 and its CPNC (containing up to
10 wt% MMT) were studied using DSC and the results were interpreted with
Avrami’s equation [Zhang and Yan, 2003]. Addition of 1 wt% MMT increased
Table 58 Summary of test results for PA-6 and CPNC.

Data [Bureau et al., 2002]
Material Molding Crystallinity Young's Yield stress, Strain at
conditions (%) modulus, E σY break, εb
(structure) (GPa) (MPa) (%)
PA-6 Cooled 31 4.0±0.3 93±1 140±40

(α-form)
Quenched 7 2.4±0.2 69±2 670±60

(amorphous)
Annealed 21 2.8±0.1 91±2 120±30

(γ-form)
CPNC Cooled 25 4.7±0.2 106±3 3.8±0.3

(γ- and α-form)
408
the crystallisation rate, but at higher loading (i.e., 6 and 10 wt% MMT) the rate
decreased. The thermograms for all specimens showed multiple melting peaks.
However, such crystallisation parameters as the Avrami’s exponent, n, the
crystallisation temperature, and the heat of crystallisation were virtually
independent of the MMT content. In the following publication [Liu et al., 2004],
CPNC of PA-1010 was prepared by melt compounding with up to 10 wt% of
MMT pre-intercalated with either methyl tallow dihydroxyethyl ammonium
(MT2EtOH) or trimethyl hexadecyl ammonium (3MHDA) salts. XRD showed
significantly better clay dispersion for the MT2EtOH series (than 3MHDA), which
in turn resulted in superior mechanical performance. At 7 wt% MMT loading
the glass-transition temperature increased by 8.5 and 1.0 °C for the specimens
with MT2EtOH and 3MHDA, respectively. Addition of the former organoclay
accelerated the crystallisation rate of the matrix and changed its crystallisation
behaviour.
Wu et al. [2002b] studied the nucleating effect of MMT on the crystallisation
of PA-1212. The exfoliated CPNC was prepared by melt compounding of pre-
intercalated MMT with PA-1212. The film (ca. 0.5 mm thick) was moulded at
10.0 MPa and 200 °C for a few minutes, then quenched. Non-isothermal
crystallisation and melting tests were conducted in a DSC under N2. The sample
was heated to 220 °C and kept at this temperature for 10 min, then cooled at a
rate of 5 to 40 °C/min to 50 °C, and then re-heated to 200 °C at a rate of 10 °C/min.
For PA-1212 and its CPNC, an increased cooling rate shifted the Tc to lower
temperatures, as well as reducing and broadening the Tc peak. Compared to PA-1212
the CPNC had narrower exothermic peaks at higher temperatures. In Figure 126
the peak crystallisation temperature of PA-1212 and its CPNC, Tc, is plotted
versus the cooling rate, r. The overall time of crystallisation, tc ≡ (Ti-Te)/r versus
r is also presented (the subscripts i and e indicate the initial and final temperature).
Thus, addition of organo-MMT shifts the Tc to a higher temperature and shortens
the crystallisation time, tc. Both these functions indicate enhanced nucleation.
The authors also calculated the time for the initiation of crystallisation (ti) as
well as the nucleating activity coefficient, ϕ = 0.71. As expected, these parameters
also indicate enhanced nucleation by MMT. Optical microscopy under polarised
light, POM, confirmed this conclusion – the spherulites in neat resin were about
15¯25 times larger than those in its nanocomposite.
3.4.5 Crystallisation of PO Matrix

PP has a complicated crystalline microstructure, which depends on the mechanism
and the rate of crystallisation. The four principal crystalline structures of PP are:
monoclinic (α), hexagonal (β), triclinic (γ), and smectic or quenched polymorphic.
The monoclinic α-form is usually obtained under typical industrial and laboratory
processing conditions. The β-form is thermodynamically less stable, and the shear
stress or specific nucleating agents enhance its formation. The other forms are
quite rare. The characteristic parameters of PP and HDPE are listed in Table 59.
When injection moulding thin-walled articles of PP, it is customary to add a
nucleating agent. The addition reduces the moulding cycle and improves optical
as well as mechanical properties. Inorganic compounds such as talc, silicates, clays,
and carbon black have poor nucleating ability. The preferred nucleating agents are
organic salts, viz. Na-succinate, Na-glutarate, Na-caproate, Na-(4-methyl) valerate,
Na-benzoate, Na- β-naphthoate, Al-benzoate, Al-tert-butylbenzoate, bis-
benzylidene sorbitol, etc. Pigments are also known to nucleate PP. For example,
409
Figure 126 Non-isothermal crystallisation of PA-1212 and its CPNC as a function

of the cooling rate from 220 °C. Data [Wu et al., 2002].
red pigment (Quinacridone) is an efficient a-crystal nucleating agent, while white

pigment (White PE MB) was found to nucleate the β-form.
By contrast with PP, PE crystallises rapidly, thus additives are rarely used to
nucleate it. However, K-stearate has been used to reduce spherulite size.
Nanocomposites with PE as matrix are still rare. Recently CPNCs, containing
PE-MA and silicates of different aspect ratios, were studied by Wang et al. [2002].
The PE-MA was LLDPE grafted with 0.85 wt% MAH. The –MA groups were
randomly placed along the LLDPE macromolecules. The silicates were two
organoclays (Cloisite® 20A, C20A and Laponite®SCPX2231, SCPX) and synthetic
SiO2. The organoclays were both intercalated with 2M2HTA and had the nominal
aspect ratio, p = 100 to 200 and 20 to 30, respectively. The silica had spherical
particles with diameter of ca. 1.8 μm. XRD did not show diffraction peaks down
to 2θ = 2°; hence d001 > 4.4 nm. Surprisingly, addition of any of these three
silicates reduced the total crystallinity, X, of PE-MA by an amount proportional
to the silicate volume fraction, φ: X(%) ≅ 41.5 - 120φ. Probably the reaction of
the randomly grafted –MA groups on the silicate surface disrupted formation of
the ordered macromolecular crystals.
Young´s modulus and yield stress increased with increasing crystallinity and
increasing α-form content, while elongation at break increased with increasing
β-crystal content [Mubarak et al., 2000]. Addition to PP of 0.05 wt% 1,2,3,4-
bis-(3,4-dimethyl-benzylidene sorbitol) or N,N´-di-cyclohexyl-2,6-naphthalate
di-carboxamide, generated the α- or β-form, respectively [Ellis et al., 2001].
Infrared microscopy has been used to study the crystalline morphology of these
two crystalline forms.
CPNC with PP as a matrix are more recent than these of PA [Kurokawa et al.,
1996; 1997]. The authors used an elaborate process involving pre-intercalation of
smectite clay with ammonium ion, polymerisation of di-acetone acryl amide on the
410
Table 59 Characteristic parameters of polyolefins

Property HDPE PP
Condition Value Condition Value
Glass transition Dry 140-150 Dry 280
temp., Tg (K)
Melting point Dry 419 Dry 459
(equilibr.), Tm
(K)
Density, ρ Dry 920-990 Dry 900-910
(kg/m3)
Typical Dry 35-90 Dry 50-70

crystallinity,
α (%)
Unit cell α-form 0.742×0.495×0.255 αI-form 0.667×2.08×0.65
dimensions β-form 0.809×0.479×0.253 αII-form 0.665×2.07×0.65
(nm) β-form 1.103×1.103×0.649
γ-form 0.854×0.993×4.241
Unit cell angles α-form - (4) α-forms 98.67 (3)
(# mers) β-form 107.9 (4)
Lattice α-form Orthorhombic α-forms Monoclinic

β-form Monoclinic β-form Hexagonal
γ-form Orthorhombic
organoclay, and then mixing the doubly intercalated clay with maleated-PP and finally
with PP. Exfoliated and well-dispersed clay platelets were observed under the TEM.
Kato et al. [1997] simplified this procedure by melt-mixing PP with oligopropylene
modified by MAH (PP-MA) and MMT intercalated with stearyl-ammonium salt
(ODA). CPNC with a high degree of exfoliation was obtained when PP-MA was
able to (1) bond to the clay and (2) be miscible with the PP matrix.
There are several variants of these procedures, with different amounts of the
PP-MA compatibiliser, of different structure, molecular weight and MAH-content.
Since these variables control the mutual miscibility of PP with PP-MA, this type
of CPNC shows a wide range of properties. For example, pre-intercalation and
compatibilisation may results in a system where the clay particles are shielded
from the matrix, preventing direct PP-clay contact, hence the matrix crystalline
structure entirely depends on the behaviour of the PP/PP-MA blend. In such a
CPNC the effect of clay on matrix crystallisation may be negligible.
There are two major differences between CPNC with PA and that with PO
matrix. (1) ω-Amino acid may be used to intercalate clay, thus after polymerisation
the clay is in full contact with the matrix. By contrast, owing to the strong
hydrophobicity of PO-macromolecules such a structure could not form in the
latter systems. (2) The crystallinity of PA rarely exceeds 50%, thus is significantly
411
lower than that in isotactic PP where X = 60 to 70% is often observed. Since the
intercalated clay platelets cannot enter the crystalline domains, they must be
concentrated in small pockets of the amorphous or meso-crystalline phase. This
means that the local concentration is about three times higher than the average,
thus (excepting low clay loading of ca. w ≤ 0.5 wt%) the platelets are unable to
freely rotate and form parallel stacks with local ordering – full exfoliation is
difficult to achieve.
The National Chemical Laboratories (NCL) in Pune conducted systematic
studies of clay effects on crystallisation of PP and the resulting performance of
the CPNC. Hambir et al. [2001] prepared PP-based CPNC with MMT (CEC =
1.35 meq/g) intercalated with octadecyl amine (ODA) and compatibilised with
maleated PP (MA-PP). XRD gave the interlayer spacing of d001 ≅ 2.5 nm. The
isothermal crystallisation of the PP and PP/MMT-ODA systems was carried out
by DSC. The thermograms indicated that the clay presence narrows the
crystallisation peak and reduces the crystallisation time hence it accelerates PP
crystallisation. As shown in Figure 127, crystallisation in neat PP and in its CPNC
may have different activation energy, but this conclusion hinges on the validity
of two data points at low temperatures (T = 100 and 136 °C) where reduced
chain mobility may already start slowing down the crystallisation rate. Optical
microscopy under polarised light showed a dramatic change of morphology –
large, well-defined spherulites in specimens crystallised at 122 °C PP, but
crystallites in the form of a fibrous mat in those crystallised at 142 °C CPNC.
In the following publication from the same laboratory [Kodgire et al., 2001]
PP was compounded in a single-screw extruder (SSE) with 12 wt% MA-PP and
4 wt% of commercial organoclay, either Cloisite® 6A (C6A; MMT, CEC = 1.4 meq/g
intercalated with 2M2HTA), or Nanomer I.30 (MMT, CEC = 1.35 meq/g
intercalated with ODA). The XRD-determined interlayer spacing in Na-MMT was
d001 = 1.2 nm, in C6A (two peaks) d001 = 1.2 and 1.8 nm and in I.30 d001 = 2.45 nm.
Figure 127 Crystallisation time as a function of crystallisation temperature in non-

isothermal DSC scans for PP and PP/MMT-ODA. Data [Hambir et al., 2001].
412
Compounding with PP increased d001-values, but the system containing C6A was
exfoliated only after compounding with MA-PP, while that with I.30 intercalated
(d001 = 2.75 nm). However, the enhancement of mechanical properties was similar
for either CPNC (hence independent of the degree of clay dispersion) – ca. 35%
increase in the tensile modulus and about a 10% increase in the tensile strength. In
accord with the results reported in the preceding publication, the Tc of PP increased
after addition of clay from 122 °C (for neat PP) to 142 °C. Furthermore, in CPNC
the crystallites formed a fibrous mat that coarsened with time, but did not transform
into spherulites. Thus, clay nucleated a very specific PP morphology.
Another publication from this laboratory provides additional information
[Hambir et al., 2002]. This time the ODA intercalated clay was prepared in
house and used along with C6A. Furthermore, three PP resins (Mw = 164, 241
and 362 kg/mol) and two MA-PP resins (Mw = 188 kg/mol, MAH = 1%; and
151 kg/mol, MAH = 0.64%) were used. The isothermal crystallisation of PP and
PP/clay was studied by DSC at Tc = 115 to 131 °C. The PP/clay systems showed
a sharper crystallisation peak than that of PP. Thus, crystallisation of PP was
accelerated by organoclays. Furthermore, the crystallisation half-time depended
on the organoclay content, Mw of PP as well as on the presence of MA-PP.
However, the change of Mw from 241 to 362 had a more pronounced effect than
addition of up to 4 wt% of organoclay. The crystallisation activation energy
seems to be more influenced by the Mw of PP than the other variables. Thus,
incorporation of organoclay resulted in enhanced nucleation and faster
crystallisation of the PP matrix. The clay also changed the macromorphology of
the crystalline phase – in CPNC instead of spherulites fibrillar structures have
been observed. However, since the authors did not calculate the unit cell, it is
unknown whether the addition of organoclay modified the crystal cell structure,
e.g., from the common α-monoclinic into the more desirable β-hexagonal one.
Saujanya and Radhakrishnan [2001] studied the crystallisation of PP in the
presence of calcium phosphate nanoparticles (CaP). These were prepared from
CaCl2 and Na3PO4 in a MeOH solution of PEG. Varying the concentration ratio
of PEG to CaCl2 from 0 to 32, resulted in reduction of β-ortho CaP (monoclinic)
particle diameter from d = 82 to 7 nm. It is noteworthy that in the presence of
CaP PP crystallises in spherulitic form with a monoclinic α-crystalline cell
structure. At 2 wt% CaP the t1/2 and the ultimate spherulite size decreased with
the particle size from 45 to 20 μm. The strong nucleation efficiency of CaP
originates in high surface energy and large surface area, viz.:
ln(G/Go)∝1/d (155)
where G is the crystallisation rate in the presence of CaP and Go without it. The
optical transparency of the PP/CaP-nanoparticles system was higher than that
containing conventional CaP at the same concentration. The DSC data showed
that incorporation of CaP increased the crystallisation temperature of PP from
110 to 114 °C and reduced the width of the crystalline peak as compared to PP.
The heat of fusion of neat PP was determined as 77.9 J/g whereas that of the
nanofilled PP as 132.9 J/g, indicating that in the presence of 2 wt% CaP the
crystallinity of PP nearly doubled. Such a large effect has not been observed for
compatibilised PP/organoclay systems. The most likely reason is the presence of
an organic phase around the clay particles. Since the intercalant molecules are
immiscible with PP, they form a barrier, separating the crystallisable matrix from
the high-energy clay surface.
413
3.4.6 Crystallisation of PEST Matrix

Several patents on the preparation of PET-nanocomposites claim that addition
of clay increases the crystallisation rate. When organoclay is used, the
crystallisation temperature and the melting point increase. Again, since there are
different methods for the preparation of these materials as well as different
intercalants, it is difficult to predict the extent of these effects.
Tsai [2000] grouped the processing methods described in the patent literature
into three categories: melt compounding with organoclay, polymerisation in
the presence of organoclay and polymerisation in the presence of synthetic, not
pre-intercalated clay (e.g., fluoromica dispersed in ethylene glycol prior to
polycondensation with p-terephthalic acid). However, in these publications
crystallinity has been of little concern.
The crystallisation process and crystal morphology in PET/organoclay CPNC
was studied by Ke et al. [1999]. The nanocomposites were prepared by in situ
polymerisation of PET in the presence of up to 5 wt% organoclay (MMT with
CEC = 0.7 to 1.1 meq/g intercalated by a ‘proprietary’ method). At low
magnification SEM and TEM showed a large number of solid particles. The
interlayer distance, d001 = 1.4 to 3.5 nm, was determined by TEM and XRD,
hence only intercalation was achieved. In consequence, while the modulus
increased with clay loading the stress at break decreased. The authors used the
Avrami equation for the analysis of non-isothermal crystallisation. The pertinent
information is summarised in Table 60. As observed for other CPNC systems,
also here addition of organoclay increased the crystallisation temperature and
the crystallisation rate. However, in the studied system, the melting temperature
and the heat of melting decreased with organoclay content. The most likely
explanation is an excess of the non-identified, intercalating agent. CPNC with
5% of clay had a broad distribution of particle sizes from ca. 10 to 1,000 nm,
with a maximum at about 80 nm. It was difficult to detect spherulites in these
PET/clay systems. The macromolecular chains diffused into the interlamellar
galleries.
A more recent publication focuses on poly(ethylene terephthalate-co-ethylene
naphthalate), PETN [Chang and Park, 2001a,b]. First, Na-MMT (CEC = 1.19 meq/g)
was intercalated with hexadecyl ammonium salt (HDA). PETN (92 mol% ethylene
terephthalate) was solution-blended with the organoclay then cast into film of
ca. 10 to 15 μm thick. The interlayer spacing, as measured by XRD, increased
Table 60 Crystallisation temperature, Tc, melting point, Tm,

crystallisation half-time, t1/2, and heat of fusion, ΔHm, for PET/MMT
systems. Data [Ke et al., 1999]
MMT (wt%) Tc (°C) Tm (°C) t1/2 (s) ΔHm (J/g)
0 174 259 108 50.0
0.5 201 258 – –
1.5 206 257 43 43.5
2.5 209 254 48 44.0
5.0 208 252 36 45.2
414
from d001 = 1.199 (for Na-MMT) to 2.596 nm (for MMT-HDA). The PETN
containing 2 to 4 wt% MMT-HDA was only intercalated (d001 = 3.104 nm).
Furthermore, as the concentration of the organoclay increased to 6 wt% the
interlayer spacing decreased to d001 = 2.662 nm, indicating that at higher
concentration the organoclay aggregates (also observed in SEM). DSC
measurements of these CPNCs have shown that the glass-transition temperature
(Tg), melting temperature (Tm), and heat of fusion (ΔHm) are nearly independent
of the organoclay loading (see Table 61). Thus, the total crystallinity of PETN
does not seem to be affected by MMT-HDA. The structure of these CPNCs is a
phase-separated matrix with intercalated, internally ordered organoclay domains
dispersed in it. Nevertheless, incorporation of the organoclay did enhance the
thermal stabilities and mechanical properties (maximum in the tensile strength
and modulus was obtained for 4 wt% loading).
Imai and his colleagues from AIST prepared PET-based CPNC by melt, and
then solid-state polymerisation in the presence of ca. 3.7 ± 0.2 wt% of clay [Imai et
al., 2003; Saujanya et al., 2003]. Fluoromica (FM), FM pre-intercalated with
triphenyl dodecyl phosphonium bromide (3PPC12), or FM pre-intercalated with
triphenyl di(methoxycarbonyl)phenoxy decyl phosphonium bromide (3PPPC10)
were used. The interlayer spacings were: d001 = 1.33, 1.82, and 1.86 nm, respectively.
For the crystallisation studies neat PET (PET-0), CPNC with FM (PET-1) and CPNC
with FM-3PPPC10 (PET-2) were used. The isothermal crystallisation tests showed
that the crystallisation rate, and crystallinity increase in the order from PET-0 to
PET-2; the opposite tendency was observed for the activation energy. The results
seem to indicate that, at least for the crystallisation of PET, the degree of dispersion
is more important than the surface energy of the dispersed clay. This observation
may explain the small effect of organoclay on PET crystallisation, reported by
Wang et al. [2003b; 2004], and by Ou et al. [2003].
Recently nanocomposites with poly(trimethylene terephthalate) (PTT) have
been prepared using the solution intercalation or melt compounding method,
and their crystallisation behaviour was studied [Ou, 2003; Liu et al., 2003]. The
first author used MMT pre-intercalated with cetyl-pyridinium chloride (CPC),
whereas the others used MMT-MT2EtOH. For both systems XRD indicated
Table 61 Glass transition temperature, Tg, melting point, Tm, and

heat of fusion, ΔHm, for PETN/C16-MMT nanocomposites.
Data [Chang and Park, 2001]
MMT-HDA (wt%) Tg (°C) Tm (°C) ΔHm (J/g)
0 76 236 32
1 74 237 31
2 73 238 31
3 75 238 30
4 75 238 32
6 74 236 30
415
intercalation with short stacks dispersed in the matrix. From the DSC thermograms
the authors concluded that organoclay behaves as a nucleating agent, enhancing
the crystallisation rate of PTT. As in other systems, here also a maximum
crystallisation rate was observed at relatively low organoclay loadings.
3.4.7 Crystallisation of Syndiotactic PS Matrix

Wu et al. [2001] analysed the effects of MMT on the chain conformation and
crystallisation of syndiotactic polystyrene (sPS) using FTIR, XRD, and TEM.
The CPNC was prepared by solution dispersing of 5 wt% of MMT or organoclay
(MMT pre-intercalated with cetyl-pyridinium chloride, CPC) in a dichlorobenzene
solution of sPS at 140 °C for 24 h. For the first system TEM showed large
aggregates (dimensions from a few tenths to 100 nm), but a high degree of
intercalation (size 1-2 nm) in the second system: sPS/MMT-CPC.
sPS has four crystalline forms: α-, β-, γ-, and δ-, which can be divided into two
groups: (i) γ- and δ- forms possessing a helical trans-trans and gauche-gauche (TTGG)
chain conformation and (ii) α- and β- forms possessing a planar all-trans (TTTT)
‘zigzag’ conformation. Addition of clay changes the sPS chain conformation from
TTGG to TTTT. This phenomenon leads to a change in the mechanism of molecular
packing during melt-crystallisation. The clay plays a vital role in facilitating the
formation of the thermodynamically favoured all-trans β-crystal, particularly in thin
films. Crystallising the sPS/MMT system at a cooling rate of 1 °C/min from 320 °C
resulted in the highest absolute crystallinity of β-form of 56%. This is to be compared
with 49% obtained for sPS/organoclay and 42% for neat resin. Thus, clay may
significantly affect the chain conformation and crystallisation of sPS, but the effect
very much depends on clay surface energy. It is noteworthy that the effect of poorly
dispersed clay with significantly reduced surface contact area affected sPS more than
the finely dispersed cetyl-pyridinium covered clay platelets.
Another team of researchers [Wu et al., 2002a] confirmed these observations.
The nanocomposites were prepared by dispersing 0.5, 1 and 5 wt% organoclay
in sPS/xylene solution. The organoclay was MMT pre-intercalated with 3MHDA
and then treated with a mixture of monomers (styrene and methacrylate in the
ratio 4:1), which were then polymerised into copolymer having short PS blocks
on the outside. Both XRD and TEM showed exfoliation and random dispersion
of clay platelets in the matrix. XRD also indicated polymorphism of sPS, which
strongly depended on thermal history and clay content. Isothermal crystallisation
at higher Tc favoured formation of β-crystals. Thus, during the process the α-crystals
could be transformed into β-form. During crystallisation, the sPS chains achieved
better alignment at higher T c . In the presence of MMT or at lower T c
conformational defects may preclude perfect chain alignment.
At the present state of knowledge, it is impossible to make generally valid
statements about the influence of organoclay on the polymeric matrix crystallinity.
There are many factors that influence the outcome. The presence of a high-energy
clay surface most often leads to an enhanced crystallisation rate, which in turn
results in a different, less thermally stable crystalline form (viz. γ-form in PA-6,
β-form in PVDF [Priya and Jog, 2003], etc.) crystallising at higher Tc and melting
at higher Tm. Notwithstanding the higher crystallisation rates, the total crystallinity
content may increase or decrease with organoclay content. These effects are
controlled by the equilibrium thermodynamics (type and intensity of interaction)
as well as dynamics (orientation and annealing).
416
Mechanical Behaviour
3.5
One of the reasons for the interest in CPNC is enhancement of the mechanical
performance of the matrix polymer at low clay loading. For example, addition
of 2 wt% of organoclay to PA-6 increased the flexural modulus by 26%, and
tensile strength by 14% [Ube Ind., 2000]. Similarly, dispersion of 2 and 5 wt%
of vermiculite in PP increased the tensile strength by 18 and 30%, the tensile
modulus by 20 and 54%, and the storage modulus by 204 and 324%, respectively
[Tjong et al., 2002]. A thorough review of the theories of mechanical behaviour
in a multiphase polymeric system can be found in the PhD thesis of D. Colombini
[1999].
3.5.1 Micromechanics of CPNC

The assumed model of a nanocomposite is highly simplified, containing either
exfoliated clay platelets or intercalated short stacks, aligned with the stress tensor.
The particles are assumed to perfectly adhere to the matrix. The simplest model
of perfectly aligned large reinforcing particles leads to the volumetric rule of
mixtures for the tensile modulus in the stress and transverse direction:
in stress : Ec = Emφ m + f L E f φ f
(156)
transverse : 1 / Ect = φ m / Em + φ f / E f
where E is tensile modulus, φ is the volume fraction, φm = 1 - φf ; subscripts c, m
and f stand for composite, matrix and filler, respectively; and fL is the filler particle
length correcting factor. The dependence predicted by Equation 156 is presented
in Figure 128. Note that the predictions are supposed to be valid for infinitely
large filler particles with perfect adherence to the matrix. For the computations
the moduli ratio was assumed to be Ef /Em = 100 or 1000.
Several modifications of Equation 156 have been published:
Nicolais & Narkis : Ec = Em 1 − αφ bf ( )

( )
b
Faber & Farris : Ec = Em 1 − φ f
(
Kerner : Ec = Em 1 + ABφ f ) / (1 − Bφ ); f Gc / Gm = Ec / Em
A = (7 − 5ν m ) / (8 − 10ν m ) (157)
( )(
B = E f / Em − 1 / E f / Em + A )
(
Neilson : Ec = Em 1 + ABφ f ) / (1 − ΨBφ ); f Gc / Gm = Ec / Em
Ψ = 1 + [(1 − φ f ,max ) / φ ]φ
2
f ,max f
where νm is the Poisson’s ratio.
417
Halpin-Tsai (H-S) rigorously derived the tensile modulus in the stress direction,
Ec:
( )(
Ec / Em = 1 + 2 pκφ f / 1 − κφ f ) (158)
κ = ( Er − 1) / ( Er + 2 p); Er ≡ E f / Em
Here p is the aspect ratio defined in this book as p = (platelet diameter)/(platelet
thickness). For the modulus in transverse direction p = 1 may be assumed. For p
→ ∞ Equation 158 converts into Equation 156 with fL → 1. The predicted
behaviour is illustrated in Figure 129.
According to Brune and Bicerano [2002] the above relationships may be used
only for predicting the modulus of fully exfoliated CPNC with oriented, clay
platelets perfectly adhering to the matrix. When the clay platelets are only
intercalated then the variables: p, Ef, and φf obtained from fitting the equations
to data must be consider empirical. On the other hand, the authors derived the
following relationships between these variables for exfoliated and intercalated
(symbols with prime) systems:
[
p ′ = ( p / N ) / 1 + (1 − 1 / N )( s / t ) ]
[
φ ′ = φ 1 + (1 − 1 / N )( s / t ) ] (159)
Er + (1 − 1 / N )( s / t )
Er′ =
1 + (1 − 1 / N )( s / t )
In this relation the aspect ratio, p´, the volume fraction, φ´, and the tensile modulus,
E´, refer to the platelet stack composed of N-clay layers, each with thickness t
and the interlamellar gallery spacing, s ≅ d001 – 0.96 nm. However, since the
Figure 128 Relative tensile modulus for Ef /Em = 100 or 1000 in the stress and
transverse to it directions. See Equation 156.
418
Figure 129 Predictions of the Halpin-Tsai Equation 158 for relative modulus in
the stress direction for Ef /Em = 100 or 1000 and p = 10 or 1000.
dependence does not have the correct upper limit for the s/t ratio, the parameter
N in the dependence should be replaced by:
φ
N ′ = N + (1 − N )( s / t ) (160)
1−φ
Evidently, Equations 157 to 159 are valid for idealised, well-oriented CPNCs
where the platelets are perfectly bonded to the matrix. The important teaching
of this theory is the strong influence of the degree of dispersion on the relative
modulus, Ec/Em = E´/Em. In Figure 130 variation of the relative modulus for
intercalated CPNC is plotted as a function of the number of platelets in the stack,
N, and the size of the interlamellar gallery expressed as: s/t = (d001/t) – 1 ≅ d001 – 1.
The role of this parameter is to express the modification of the macromolecular
behaviour within the galleries. It is noteworthy that the steepest decline of
performance is predicted for stacks containing 2 to 3 platelets, i.e., for these
most often observed in CPNC. In other words, the modulus of a truly exfoliated
system is at least twice as high as that obtained for the most common ‘exfoliated’
ones.
Brune and Bicerano [2002] proposed a further refinement to the above
treatment for disk-shaped filler particles. The aim was to correctly predict the
effects of the aspect ratio. The derived equation is in a scaled form:
Ec ( p) − Ec ( p = 1) 2( p − 1) Ef
Es ≡ = ; Er ≡ (161)
Ec ( p → ∞) − Ec ( p = 1) ( Er − 1)(1 − φ f ) + 1 + 2 p Em
The relation virtually traces the prediction of the Halpin-Tsai relation (see
Figure 131). Within the customary range of the clay content, φf < 5 vol%, it is
insensitive to composition, but it strongly depends on Er and p. It is important to
note that when a high Er value is required, platelets with larger aspect ratio
ought to be used. Considering that E(clay) ≅ 170 GPa and the modulus of
unoriented, unfilled engineering plastic ranges from 2 to 4 GPa the clay platelets
419
Figure 130 Prediction of the Brune-Bicerano theory (see Equation 159) of the
relative modulus of intercalated CPNC versus the average number of platelets in
the stack for the interlayer spacing, d001 ≅ (s/t) + 1. For the most common value of
d001 ≅ 3 nm stacks of ca. three platelets show only 40% of the modulus expected
for exfoliated CPNC.
Figure 131 Scaled tensile modulus versus aspect ratio according to Halpin-Tsai (H-
T) and Brune-Bicerano (B-B) equations. Moduli ratio: Er = Ef /Em = 100 or 1000,
filler volume fraction, φf = 0.01 or 0.05. Both relations provide equivalent
dependence, insensitive to φf but sensitive to Er.
420
with p ≅ 200 would reach about 90% of the theoretically possible modulus. For
CPNC with more ductile polymeric matrices clay with still higher p should be
used.
Hui and Shia [1998] derived a simplified H-S theory for the tensile modulus
of oriented fibre or flake reinforced composites. The simplification involved the
assumption that the Poisson’s ratio, νm = 0.5, is the same for both components
and that there is perfect adhesion between filler and matrix. For flakes oriented
in the stress direction the modulus is given by:
−1
⎧⎪ φ ⎡1 3 ⎤ ⎫⎪
Ec = Em ⎨1 − ⎢ + ⎥⎬
⎪⎩ 4 ⎣ ξ ξ + Λ ⎦ ⎪⎭
ξ ≡φ+
1
+ 3(1 − φ )
(
(1 − g) − gp2 / 2 ) (162)
Er − 1 1 − p2
Λ ≡ (1 − φ )
( )
3 1 + 0.25 p2 g − 2
; g ≅ π / 2p
1− p 2
Predictions of Equation 162 are higher and are more sensitive to the aspect ratio
than those from Halpin-Tsai (H-T) Equation 158.
The Hui-Shia (H-S) theory was evaluated using the tensile modulus data for
CPNC with PDMS as the matrix [Shia et al., 1998]. The experimental results did
not follow the theoretical predictions of H-T and H-S theories. To explain the
discrepancy the authors postulated that the difference originates in imperfect
bonding between the matrix and clay. This introduced two ‘effective’ quantities
into the H-S model: the aspect ratio and clay volume fraction. Both were assumed
to depend on the interfacial shear stress, σi, determined by fitting the data to the
equation – the calculated σI-value was in the range of kPa. The interfacial shear
stress was further decomposed into an intrinsic and a frictional shear stress, the
former decreasing with the increasing volume fraction of the inclusion and the
latter increasing linearly with strain. For the CPNC studied, the effective friction
coefficient was calculated as 0.0932.
However, as shown in Figure 132, in the whole range of concentration the
data are well described by Brune-Bicerano Equations 159-161, with Ef = 170 GPa
and Em = 1 MPa. The numerical values of the remaining variables were taken
from Shia et al. [1998]. The least squares fit gave a reasonable value of the aspect
ratio, p = 239. The number of platelets in the stack increased from the initial
value of N = 2 to 4 at the highest concentration. The standard deviation and the
correlation coefficient squared were: σ = 0.18 and r2 = 0.995, respectively.
Ji et al. [2002] expanded Takayanagi’s two-phase model into three-phases:
the matrix (m), interphase (i), and filler (f), randomly distributed in the matrix.
The filler particles may be spherical, cylindrical or lamellar. The incorporation
of an interphase is particularly important for the nanoparticles. According to the
model, the three phases are connected to each other in series and in parallel. The
realistic representation of a filled system is then reduced to three idealised regions,
A, B, and C connected in series. The general form of the derived relation is:
1 1− β β −ϕ ϕ
= + + (163)
Ec Em (1 − α )Em + αEBi (1 − α )Em + (α − λ )ECi + λE f
421
Figure 132 Relative modulus versus clay content for CPNC with PDMS as the
matrix. Experimental data [Shia et al., 1998] and theoretical prediction from
Brune-Bicerano (B-B) theory. See text.
where α, β, ϕ and λ are idealised dimensions of the interphase and filler regions
determining the volume fraction of each of the three components, viz. Vf = λϕ; Vi
= αβ – λϕ; and Vm = 1 – Vf - Vi. The moduli of the composite, matrix and filler
are given as: Ec, Em, and Ef. The interphase modulus is defined for the model
regions B (in series) and C (in parallel) as EBi and ECi , respectively. When particles
are relatively large the interphase contribution is negligible, Vi → 0 and
Takayanagi’s equation is recovered.
The principal advantage of this theory is incorporation of the interphase
contribution. As stated before, the authors consider two types of interphases
connected to other phases either in parallel or in series. In the case of CPNCs
these may be treated as the interphase inside the stack of clay platelets, and that
between the stacks and the matrix. The two types depend on the distance from
the filler surface respectively, linearly and exponentially:
1 ln( E0 i / Em ) (164)
E Bi
=
E0 i − Em
[ ]
; ECi = E0 i + Em / 2 with : E0 i / Em ≡ k
where E0i is the interphase modulus on the filler surface at τ = 0 and k is one of
the model parameters. The platelet and the interphase shapes were assumed to
be square, thus:
α=β= [2(τ / t ) + 1]V f ; ϕ = λ = Vf (165)

Substituting these relations into Equation 164 yields:
422
1 1−
=
[2(τ / t ) + 1]V f
+
[2(τ / t) + 1]V − V
f f
Ec Em ⎧1 −
⎨
⎩
[2(τ / t) + 1]V ⎫⎬⎭E + [2(τ / t ) + 1]V (k − 1)E
f m f m / ln k
Vf
+
⎧1 −
⎨
⎩
[2(τ / t) + 1]V ⎫⎬⎭E
f m
⎩
[ ]
+ ⎧⎨ 2(τ / t ) + 1 V f − V f ⎫⎬( k + 1) Em / 2 + V f E f
⎭
(166)
For CPNC the controlling parameters are: the dispersed particle size: t << ϕ = λ,
thickness of the interfacial region (τ), filler-to-matrix modulus ratio (Ef/Em), and
a parameter (k) describing a linear gradient change in modulus between the matrix
and the surface of the particle. Since t and Ef/Em are in principle known, the
model has two adjustable parameters: τ and k; validity of the model can be judged
by the ‘reasonableness’ of these parameters computed from fitting Equation 166
to the experimental data.
To test their model, Ji et al. [2002] prepared CPNCs of PA-6/MMT and measured
the tensile properties. The experimental data were fitted to the theoretical
dependence with τ = 7 nm and k = 12. It is worth recalling (see Section 3.1.7) that
the thickness of the solidified layer of organic compounds on the surface of clay
platelets as determined in the surface force analyser (SFA) ranges from ca. 3 to 12
nm, with most of the values centred near 6 nm. For polymers the layers with
reduced segmental mobility stretched to a distance of about 100 nm. However,
these measurements were taken in a liquid not solid state. In the model the two
parameters, τ and k characterise the interphase: τ its thickness and k its rigidity.
The computed value of τ = 7 nm well agrees with the thickness of the PA-6 layer
that is adsorbed on the clay surface and solidified in the molten state, e.g., at
240 °C. Evidently, this is a highly satisfactory outcome! As shown in Figure 84,
the solidification was found to significantly reduce the free volume in molten
polymer. Reduced free volume should translate into higher modulus, thus k > 1
would be expected. The experimental value of k = E0i/Em = 12 is high (especially
since Ef/Em = 40 was assumed), but it may be reasonable (the ratio of the crystalline
to the amorphous modulus for the same polymer ranges from 2 to 6 [Ferry, 1980]).
In this book there are several tables listing the tensile modulus versus clay
loading (inorganic part). These values were used to generate Figure 133. The aim
was not to prove or disprove any of the listed theories, but to show how the best
CPNC performs in an amorphous polymer matrix (PS), in a semicrystalline end-
tethered exfoliated matrix (PA-6), and in a semicrystalline not tethered matrix
with a compatibiliser (PP). For these systems MMT was used with an average
aspect ratio p = 200 to 300. The results indicate that independently of the matrix
the CPNC modulus doubles at clay content of about 5 wt%. CPNC comprising
fluoromica (FM) instead of montmorillonite (MMT) has lower modulus, most
likely caused by lower aspect ratio, p. Lower modulus is also observed for systems
with poorly dispersed clay platelets.
In dilute systems the tensile modulus linearly increases with clay loading
following the relation:
[]
E R ≡ E / Em = 1 + η φ = 1 + aw ; w ≤ 8wt% (167)
423
Figure 133 Relative tensile modulus versus clay content for CPNC of PA-6, PP,
PLA and PS with montmorillonite (MMT), as well as for PP with fluoromica
(FM). See text.
Here the reinforcing factor [η] is the hydrodynamic volume, for monodispersed
hard spheres (p = 1) it is equal to the Einstein value of 2.5. The parameter
[]( ) []
a = η / 100 ρ f / ρ m ~ η / 314 . The lowest predicted value for hard spheres is a
= 0.008. For poorly exfoliated PP, PA-6 and polylactic acid (PLA) the values of
ER increase with the slope a = 0.07. Substituting the equivalent value of [η] into
Equation 107, gives the aspect ratio: p = 93. On the other hand, fully exfoliated,
best performing systems follow the dependence with a = 0.20 equivalent to p = 200.
The latter value is close to that expected for the commercial organoclays with
MMT. It is noteworthy that the values for PP reinforced with FM can also be
approximated by Equation 167 with a = 0.13 equivalent to p = 150. This value is
close to p = 132 calculated from data by Zilg et al. [1999a].
It has been universally accepted that the values measured for CPNC following
well-established procedures for polymeric specimens represent the inherent material
behaviour. However, the same PS/organoclay or PP/organoclay/compatibiliser
system tested in two laboratories resulted in not only different values, but also
different tendencies for increasing clay content. Part of the answer can be found
in the recent work by Uribe-Arocha et al. [2003]. The authors prepared CPNC
of PA-6 (with 0 and 5 wt% clay) by injection moulding the specimens with
thickness of 0.5, 0.75, 1.0 and 2.0 mm. These were subsequently tested by DMA
and in a tensile tester. Both methods showed only a small effect of thickness on
the performance of PA-6. However, the effects for CPNC with 5 wt% clay were
severe. As an example, Figure 134 displays the dependence of the tensile modulus
(E) on specimen thickness (t). The data indicate that increasing t from 0.5 to
2 mm does not affect the tensile modulus of neat PA-6, while it reduces E(CPNC)
by ca. 25%. Similarly, for PA the stress at 2% strain ranged from ca. 46 to52 MPa,
whereas for CPNC specimens with thickness: t = 0.5, 0.75, 1.0 and 2.0 mm the
stress at 2% strain was: 84, 84, 72 and 61 MPa, respectively. Other measured
parameters showed similar dependencies.
424
Figure 134 Tensile modulus versus specimen thickness for PA-6 and its CPNC
with 5 wt% clay. Data [Uribe-Arocha, 2003].
Explanation for this behaviour rests in the skin-core structure of injection moulded
specimens. The data show only limited effect of skin on PA-6 behaviour – the
molecular alignment near the mould surface was not too severe. In the case of
CPNC, the orientation of clay platelets near the wall causes significant
improvement of modulus. It is noteworthy that theoretically the ratio:
E(perfect orientation)/E(random orientation) = 1/2
thus the observed decrease by 50% is reasonable. Specimens with thickness
t ≤ 0.75 mm had similar stress-strain dependence, whereas there is significant
reduction of yield stress, σy, for thicker specimens. SEM of these specimens tested
under uniaxial loading showed multiple voiding in the core. After this initial
stage (evidenced by necking) the skin with aligned clay platelets maintained the
load – the specimen failed when the skin broke.
During the last few years a new method of computation of mechanical
properties of nanocomposites has been developed. This multiscale approach is
most advanced for systems containing carbon nanotubes [Odegard et al., 2002].
The method consists of three-steps: (1) atomic/molecular dynamics (MD)
modelling of the nanoparticle and its interactions; (2) construction of a
representative volume element (RVE); and (3) computation of macroscopic
behaviour of the nanocomposite from RVE, using either classical continuum
expressions or a finite element method (FEM). The latter method was used by
Sheng et al. [2004]. For CPNC the authors applied a multiscale modelling strategy
assuming that: (1) at a length scale of millimeters, the structure is one of high
aspect ratio particles within a matrix; (2) at micron-scale, the clay particles are
either exfoliated or in the form of intercalated stacks; (3) at a nanoscale the
interactions between the matrix and nanoparticles must be computed. In addition,
the matrix may be amorphous or semicrystalline. In the latter case the effects of
425
polymer lamellae orientation and transcrystallisation must be accounted for.

Starting with the structural parameters (extracted from XRD and TEM) and
platelet modulus obtained from MD, a layer of matrix surrounding the
nanoparticle was modelled. Next, numerical or analytical models based on the
‘effective clay particle’ were used to calculate the CPNC elastic modulus. The
new model correctly predicted the elastic moduli for CPNC with MXD6 or PA-6
matrix. The model predicted only a moderate increase in the overall modulus for
exfoliated clay as compared to that comprising stacks of intercalated clay. Sheng
et al. even speculated that experimentally (due to curving of clay platelets) full
exfoliation might not result in the highest modulus.
3.5.2 Prediction of Tensile Strength

Prediction of the tensile strength, σ, for composites or nanocomposites is more
difficult than that for modulus. Strength involves transmission of stresses through
the tested specimen. Thus, strength must depend on the degree of exfoliation, the
type of bonding between clay platelets and the matrix, as well as on the
compatibiliser. The simplest case is for continuous particles that perfectly adhere
to the matrix. The tensile strength in the stress direction is expected to follow the
volumetric rule of mixtures:
σ c = σ mφ m + σ f φ f
σ R ≡ σ c / σ m = 1 + φ f (σ r − 1) (168)
σr ≡ σ f / σm
where, as before, the subscripts c, m and f stand for composite, matrix and filler,
respectively. An example of experimental findings is shown in Figure 135. In the
figure, the relative tensile strength versus volume fraction of organoclay is shown.
Figure 135 Relative tensile strength for a biodegradable polyester of glycol +

butanediol + succinic + adipic acids (Mw = 60 kg/mol) with Cloisite® 30B (circles)
and Cloisite® 10A (squares). Data Lee et al. [2002b].
426
The CPNC contained a biodegradable polyester of glycol + butanediol + succinic

+ adipic acids (Mw = 60 kg/mol) as a matrix in which either Cloisite® -30B or -10A
(C30B or C10A, respectively) were dispersed [Lee et al., 2002]. XRD data indicated
that the former system was well dispersed, especially at high clay concentration.
By contrast, the system with C10A was intercalated with d001 = 3.25 nm. Evidently,
the hydroxyl group in C30B provided superior interaction between the intercalated
organoclay and the matrix, while the benzyl of C10A failed. As a result the
tensile strength of the C30B system followed the volumetric rule of mixtures up
to at least 10 vol%, while the C10A system followed it only up to ca. 4 vol%.
The latter type of behaviour with a local maximum is most common. The secret
of success is to find at which composition the maximum performance is reached
and optimise the process to obtain reproducible performance.
According to Equation 168, the slope of the straight line in Figure 135 provides
a low value for the relative strength: σr = σf/σm = 6.39, giving σf = 6.39 × σm
= 83 MPa. By analogy to well described micas, the flexural strength of clay platelets
should also depend on the aspect ratio, p. The tensile strength of mica with
p = 100 is about σf = 240 MPa [Milewski and Katz, 1987], i.e., about three times
higher than the value calculated for the clay platelets. The reduced tensile strength
(as well as moduli) of the reinforcements may originate from: stress concentration
at the edges, imperfect alignment with the stress direction, imperfect spacing in
the matrix, imperfect interaction between platelets and the matrix, interaction
between the flakes, etc. Furthermore, the failure can take place by diverse
mechanisms, e.g., by fracturing the flake or by pulling it out.
The full reinforcing effect can be reached only if the width of the reinforcing
platelet, W, is [Clegg and Collyer, 1986]:
W>Wc = tσf /σfm (169)
where t is flake thickness and σfm is the interfacial shear strength between clay
platelet and matrix. These considerations lead to revision of Equation 168 into:
σ c = σ mφ m + FRσ f φ f ; σ R = 1 + φ f ( FRσ r − 1)
⎡ tanh(u) ⎤
FR = ⎢1 − ⎥ 1 − sec h(u) (170)
⎢⎣ u ⎥⎦
[ (
u = p Gmφ f / E f 1 − φ f )]
where Gm is the matrix shear modulus, Ef is the flake tensile modulus and FR is
the filler strength reducing factor. For the aliphatic polyester (APES)/clay system
[Lee et al., 2002b] the calculated value of FR = 0.667 leads to a value for the
tensile strength of clay platelets σf = 125 MPa, approaching the expected strength,
but still smaller by a factor of about 1.8. It should be noted that the definition of
FR in Equation 170 predicts that: 0.666 ≤ FR ≤ 0.900.
Kerner’s composites theory provides the following relation for the tensile
strength:
( )( )
σ c = σ m 1 + ABφ f / 1 − Bφ f ; where :
A = (7 – 5ν m ) / (8 − 10ν m ) (171)
( )(
B = σ f /σm −1 / σ f /σm + A )
427
The dependence is identical to that shown in Equation 157 with strength (σ)
replacing the modulus (E).
Finally, an interesting relation was proposed by Turcsáyi et al. [1988]. The
authors corrected for the decreasing load bearing cross-section of a specimen
and for the effects of the interfacial interactions:
( )( ) { }
σ R ≡ σ c / σ m = 1 − φ f / 1 + 2.5φ f exp Bφ f ; where :
(172)
B = (1 + A ρ l ) ln(σ / σ )
f f i m
In Equation 172 Af and ρf are the specific surface area and density of the reinforcing
particles, while l and σi are the thickness and strength of the interphase. It is
worth noting that B < 0 for σi < σm – the other variables only scale the effect. The
dependence predicted by Equation 172 is illustrated in Figure 136. For the yield
stress of composites to be about equal to that of neat polymer the value of the
B-parameter should be about 3. Substituting the largest possible values (Af =
750 m2/g; ρf = 5000 kg/m3 and l = 100 nm) indicates that this condition would be
met if σi > 1.01σm. Thus, for nanocomposites able to adsorb and solidify the
macromolecules one may expect that the tensile strength will increase with loading
of clay platelets.
3.5.3 Fatigue Resistance of CPNC

Properties such as modulus and strength provide information on the material
behaviour at relatively low deformation under steady-state loading. In particular,
the modulus (measured as the initial slope of the stress-strain curve) reflects the
initial structure of the material. The other type of mechanical testing addresses
the ultimate properties – how the material breaks. The three principal test methods
Figure 136 Relative tensile strength of CPNC as a function of the clay platelet
volume fraction and the interaction parameter B from Equation 172 [Turcsáyi et
al., 1988].
428
used by fracture mechanics are impact tests, steady-state deformation (at stresses
exceeding the strength of the material) and fatigue [van der Giessen and
Needleman, 2002].
In the latter case the fatigue crack grows when the stress intensity (cycling
between σmin and σmax) is much smaller than that needed for crack growth under
steady-state loading. The cycling causes failure at stresses well below the tensile
strength level. Analysis of this behaviour is done by determining the stress versus
number of cycles to failure (S-N diagram) curves, usually followed by studies of
the mechanism of crack propagation and determination of the fracture energy.
Fatigue crack growth will take place if and only if the following three conditions
are met: (1) the stress amplitude, σa = σmax – σmin exceeds a critical value; (2) the
maximum stress intensity σmax exceeds its critical value; and (3) there is an energy
dissipation process during the cycle (fatigue fracture cannot occur in a fully elastic
system without memory). Above the threshold stress value, the crack growth
rate, ∂l/∂N, is a function of the stress amplitude, σa. To generate an S-N diagram
the specimen may be subjected either to constant stress amplitude or to the mean
stress, respectively defined as [Moet, 1986]:
σa = σmax – σmin; σmean = (σmax + σmin) / 2 (173)
Construction of the S-N curve is time consuming since for statistically valid results
ca. 10 samples have to be tested at each stress level.
In Figure 137 a schematic S-N plot for PS is shown [Sauer et al., 1976]. The
specimens were tested at a frequency of 1600 cycles/min at constant maximum
stress, σmax = 17.25 MPa, systematically varying sa from about 4.75 to 17.25 MPa.
There is a substantial difference in the material behaviour when cycling is done at
the same level of stress amplitude, but either fully in tension, e.g., σmin = 0 and σmax
= 17.25 MPa, or in tension and compression, e.g., σmin = -8.62 and σmax = +8.62 MPa
Figure 137 Schematic representation of the S-N plot for PS at 500 Hz. After [Sauer
et al., 1976].
429
– the corresponding lifetime is N = 100 and 30 k-cycles, respectively. Thus, stress

reversal has a deleterious effect on the specimen endurance. As shown in
Figure 137, at σa ≅ 6 MPa there is a change in the slope of the S-N plot, suggesting
two different mechanisms of fracture below and above this limit. Since the usual
requirement is that the material survives 107 to 108 cycles, here the ‘endurance
limit’ is about 4.4 MPa.
The main difference in fatigue behaviour between metals and polymers is the
sensitivity to test frequency. While metals are insensitive to frequency, polymers
with high energy dissipation and low thermal conductivity are. Depending on
the material characteristics (e.g., internal friction coefficient and thermal
conductivity), frequency, ν, and stress amplitude, σa, two mechanisms have been
identified. The boundary between these two is determined by the rate of energy
input: (∂E/∂t) ∝ν × σa. At low rates (∂E/∂t) < (∂E/∂t)crit the material is able to
dissipate the energy of deformation, thus the temperature rises only to a specific,
dynamic level. Under these conditions, the fatigue fracture proceeds by the
conventional fatigue crack initiation and propagation (FCP) mechanism. However,
when the rate of energy input exceeds the critical value, there is an unbounded
temperature increase. Under these circumstances FCP cannot proceed and the
specimen fails by the thermal fatigue failure (TFF) mechanism [Crawford and
Benham, 1975]. These authors developed an empirical relation between the critical
value of the stress amplitude, σa, crit, and frequency, νcrit:
(∂E / ∂t ) = (∂E / ∂t )crit ⇒ σ a, crit = (c1 − c2 log ν crit ) A/V (174)
where ci are material parameters, while A and V are specimen surface area and
volume, respectively.
The data schematically shown in Figure 138 are based on the reversed load
fatigue tests of polyoxymethylene (POM or acetal) at different levels of frequency:
ν = 0.167 to 10 Hz and stress amplitude, σa. At low frequency and low σa the
conventional FCP fracture mechanism was observed and the data followed the
FCP-type dependence, shown in Figure 137. However, when the frequency and
stress amplitude exceeded the critical values for POM, the number of cycles to
failure, N, dramatically decreases forming TFF-branches, each for a specific
frequency. Evidently, the two mechanisms lead to significantly different
morphology of the fractured surfaces. Stress concentration caused by a notch
reduces the critical value of the energy rate, thus it increases the probability of
the TFF mechanism.
The FCP mechanism often starts by craze formation which, depending on the
material and test conditions, leads either to cracks or shear banding, which in
turn proceed to the crack propagation stage. The crack opens either in a single
craze or shear band. The initiation is best described in terms of the fracture
mechanics stress intensity factor, σth ∝ l / r where l is the crack length and r its
radius of curvature. Growth of the crack length with the number of cycles during
the fatigue test was found to be proportional to the amplitude of the stress
concentration factors in the tensile mode, σKI = σI, max – σI, min:
∂l / ∂N = co Δσ lm (175)
where co and m are characteristic constants of this ‘Paris law’ equation. Continuum
theories that assume that the crack growth rate is proportional to the crack opening
displacement predict the exponent value: m = 2. Nguyen et al. [2001] have
430
Figure 138 S-N plot for two mechanisms of failure in POM: thermal fatigue failure
(TFF) and fatigue crack propagation (FCP). After [Crawford and Benham, 1975].
developed a finite element model to simulate the fatigue behaviour of a specimen

under plane strain. The material was characterised by a continuum plasticity
model, with a combination of isotropic and kinematic hardening, a cohesive law
that progressively softens and has loading-reloading hysteresis, which results in
the crack tip blunting. The numerical calculations of the fatigue crack growth
rate predicted m ≈ 3, confirmed with the experimental data for aluminium. The
damage accumulation models predict the exponent value, m = 4, frequently
observed for polymeric systems.
The effect of exfoliated clay on fracture and fatigue behaviour has seldom
been studied. For example, PA-6 and CPNC of PA-6 containing 2 wt% of
organoclay (Ube resins: PA-1015B and -1015C2, respectively) were dried and
injection moulded [Bureau et al., 2001; Gloaguen and Lefebvre, 2001]. The former
authors measured the tensile and fracture toughness using either dried or
conditioned at 50 RH specimens. The tensile properties were determined in the
machine direction, while the fracture tests with a notch were carried out in the
transverse direction. The tensile modulus, E, tensile strength, σy, elongation at
break, εb, stress intensity factor in mode I, KIc, and the fracture energy parameter
(composed of two parts, elastic and plastic: Jc = Jel + Jpl) were determined. The
parameter Jc is a measure of an internal energy change per unit crack length. It
characterises the fracture toughness prior to the onset of stable crack extension.
Its value is independent of the in-plane dimensions.
Selected results from Bureau et al. [2001] are listed in Table 62. Note that the
mechanical properties of semicrystalline reinforced polymers depend on
crystallinity and reinforcement. Addition of clay to PA-6 induces formation of
the γ-crystalline form, which during annealing may convert to the more stable
α-form (more information on the topic is in Section 3.4.2). Furthermore, injection
moulded PANC specimens have skin dominated by the α-form and core by the
431
γ-form. In these nanocomposites the level of crystallinity is also higher than that
in neat PA-6, which in part accounts for the increased values of E and σy as well
as for the reduction of εb.
The data in Table 62 show that addition of 2 wt% of organoclay (equivalent
to 0.64 vol% of MMT) has a large effect on the tensile (Young´s) modulus, E,
especially when the matrix is plasticised by the moisture. There is also a significant
increase of the yield (or ultimate) strength, σy. However, the elongation at break,
εb, is reduced – the dry CPNC specimens are particularly brittle. From the fracture
test data the stress intensity factor, KIc, and the fracture energy, Jc, were computed.
For CPNC the values of these parameters are also below those for neat resin.
Noteworthy is the difference in the moisture effect on the fracture mechanics of
PA and CPNC – while for PA the humidity changes linear-elastic behaviour into
an elastoplastic one; for CPNC linear-elastic behaviour is observed for both, dry
and conditioned specimens.
These results are in good agreement with data reported by Gloaguen and
Lefebvre [2001], who also studied the Ube material. The authors carried out
tensile tests at constant strain-rate of 10-3 s-1, recording the stress, linear strain,
and volume strain (a specific video-extensometer was used). CPNC showed brittle
behaviour at room temperature (εb = 5-7%). At T = 80 °C (above the glass
transition temperature, Tg) the elongation at break for PANC was higher than
that for PA-6 (εb = 900 versus 800%). The authors also reported large volume
expansion during tensile tests; about twice as large for CPNC as that for the
matrix polymers, PA-6 or PP. The cavitation in CPNC was large and orientation-
dependent, similar to that observed in HIPS. In the authors’ opinion, the cavitation
originates in local damage at the polymer/clay interface, and thus in an unspecified
nanoscale defect (crystalline organisation in the vicinity of the clay platelet,
localised necking and fibrillation, nanoscale interfacial cavitation, etc.).
The recent publication by Bellemare et al. [2002] describes fatigue test results
for the same two Ube resins (PA-1015B and PA-1015C2). The measurements
Table 62 Mechanical properties at room temperature of PA-6 and its

CPNC with 2 wt% organoclay (Ube Ind. PA-1015B and 1015C2,
respectively). Data [Bureau et al., 2001]
Property PA CPNC CPNC/PA
Symbol Units Dry Cond.1 Dry Cond. Dry Cond.
E GPa 2.7 0.8 4.1 1.8 1.5 2.25
σy MPa 74 39 100 52 1.35 1.33
εb % 175 700 <10 600 <0.06 0.89
KIc MPa m1/2 4.9±0.1 – 1.8±0.2 3.0±0.2 0.37±0.3 –
Jc kJ m-2 8.1±0.4 20.4±0.25 0.75±0.18 4.5±0.57 0.91±0.6 0.22±0.2
Note: 1 Cond. indicates that these specimens were conditioned at room

temperature in a 50% relative humidity environment
432
were conducted at constant stress ratio, σmax/σmin = const, at maximum stress

σmax = 75 or 57 MPa, and at frequency ν = 5 Hz. The authors found that the
fatigue resistance of both resins, PA-6 and PANC, is similar. However, in the
latter material the crack initiations occurred within the specimen, near an inorganic
particle. The authors speculated that some inorganic, micron-sized contaminants
of the clay were responsible for the fracture initiation. However, the mechanism
of crack propagation in PA-6 and CPNC was quite different. The latter material
had a higher tendency to follow the thermal fatigue fracture mechanism (TFF).
After a similar number of cycles, N = 104 to 105, there was an onset of volume
expansion in CPNC, but volume reduction in PA-6. The critical maximum cyclic
stress for PA-6 and CPNC was determined as, respectively, 60 and 78 MPa. The
fractured surfaces indicated a three-step process – an initial zone of crazing,
followed by fatigue crack propagation, and a rapid final fracture. The initiation
started at or near large, micron size particles containing variable concentrations
of Si, Mg, Ca and Al – most likely mineralogical contaminants.
Kim et al. [2001b] prepared CPNC from synthetic fluoromica (FM, Somasif
ME-100) intercalated with ω-amino-dodecanoic acid (ADA). The organoclay
was dispersed in ADA, which was then polymerised. The injection moulded
specimens were microtomed then inserted into a high voltage electron microscope
(HVEM). The microtomed slices, ca. 500 nm thick, were deformed in situ, in
HVEM. The intercalated clay platelets formed local stacks in the PA-12 matrix.
The local morphology of CPNC results in remarkable differences in the
deformation processes. During the deformation of CPNC the stacks tilt
perpendicular to the direction of the applied load. The localised damage at the
polymer/clay interface induced cavitation and fibrillation. The main
micromechanical deformation consists of microvoid formation inside the stacked
silicate layers. Depending on the orientation of the stacked layers, a different
amount of energy is dissipated by splitting, sliding or opening of the stack. This
enhances the CPNC toughness well above that of PA-12 matrix polymer. Since
the microvoids are surrounded by bonded clay platelets that make the system
rigid, the CPNC modulus is increased. The high specific surface area of the clay
and covalent bonding of the PA-12 chains to the clay surface noticeably alter the
local chain dynamics.
Studies of the fracture mechanics of CPNC with a PO matrix are very rare
[Chen et al., 2003]. The CPNC was prepared by compounding PP-MA with up
to 50 wt% of MMT-ODA (Nanomer I.31PS) in a TSE at 210 °C. Re-compounding
was used to homogenise the system, but TEM and XRD showed poor dispersion
of clay platelets, especially after injection moulding. Tensile strength and modulus
increased with the clay loading, but the J-integral fracture resistance decreased
with an increase in the clay content, viz. from ca. J1c = 1.2 to ca. 0.2 kJ/m2 at 10
and 50 wt% organoclay, respectively.
Tensile stress-strain and fatigue behaviour of CPNC with either PA-6 or PP
have been measured [Mallick and Zhou, 2003]. The specimens produced by RTP
contained 3 and 5 wt% MMT, respectively. The standard S-N tests were conducted
at ν = 1 Hz and T = 21.5 °C. Fatigue fracture of CPNC with PA-6 as the matrix
that required high stresses (60 to 70 MPa) was caused by thermal failure, while
at lower stresses the FCP mechanism was observed. PP-type nanocomposites
fractured at σ < 40 MPa only by the FCP mechanism.
Cavitation was also observed in CPNC with a glassy epoxy matrix [Zerda
and Lesser , 2001]. XRD showed that in the post-cured samples the MMT was
433
only intercalated (d001 = 3.21 nm). With increasing clay loading the modulus
slightly increased (ca. 15% at 12.5% loading), while the values of σy and εb were
reduced, which is consistent with a particulate-reinforcement mechanism. In
compression tests the presence of clay had marginal effects on the stress-strain
behaviour. Results of the fracture toughness measurements were expressed in
terms of the stress intensity factor, KIc, and the energy release rate, GIc, which is
a measure of the new surface energy, ν1. Both these parameters reached a local
maximum at a clay loading of about 3.5 wt%. At this clay concentration the
value of KIc and GIc was higher by about 68 and 170% than those of the matrix,
respectively. Atomic force microscopy in the tapping mode was used to determine
the surface area after fracture, ΔA = Ameasured/Aprojected. Plotting the energy per
surface area (GIc = 2 × surface energy):
GIcreduced = GIc / (1 + ΔA) (176)
as a function of the clay content showed that GIcreduced is about constant. Therefore,
the primary mechanism for toughening in the intercalated systems is the creation
of new surfaces. The authors expressed the opinion that intercalation affords
property improvements that are unavailable to fully exfoliated systems.
Incorporation of organoclay into rubbers leads to materials with a new set of
properties, viz. high stiffness, tensile strength, reasonable elongation at break
and tear strength [Nah et al., 2001]. In their preliminary report the authors stressed
the unique fracture surface morphology of CPNC with NBR as the matrix. At
15 phr loading of organoclay the tear strength, Gc, was nearly 4-times higher
than that of the matrix and comparable to that of carbon black (CB) filled rubber.
At the same time the modulus of CPNC was at least twice as large as that of
CB-filled rubber.
In summary, it seems that in CPNC (with clay particles intercalated or
exfoliated, end-tethered or not), fracture proceeds by a crazing-and-cracking
mechanism, frequently with large volume expansion during the fracture. To date
pure shear banding fracture without volume expansion has not been observed
for CPNC. The initiation may indeed be a mineral contaminant or a nanoscale
defect at the polymer/clay interface. According to Bureau et al. [2001] the internal
energy change per unit crack length, Jc, is significantly lower in CPNC than in
the neat polymer.
434

Clay Containing Polymeric NanoComposites, Volume 1, L.A. Utracki

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Clay-Containing

Rapra Technology Limited

Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom

Rapra Technology Limited

©2004, Rapra Technology Limited

All rights reserved. Except as permitted under current legislation no part

Typeset, printed and bound by Rapra Technology Limited

recognised variability of composition, the secondary concerns focus on the

polar monomers or oligomers (e.g., amino acids or glycols). However, preparation

To provide condensed information on the essential elements of CPNC technology,

Part 2 Basic Elements of Polymeric Nanocomposite Technology

Part 3 Fundamental Aspects

Part 4 Technology of Clay-Containing Polymeric

Part 6 Closing Remarks

1.2 NCs with Ceramic or Metallic Matrix

1.2.1 Metallic Nanoparticles in Amorphous Matrix

1.2.2 Magnetic Oxides in Silica Nanocomposites

1.2.4 Summary on Non-Polymeric NC

1.3 NCs with Polymeric Matrix

Table 1 NCs with either a ceramic or metallic matrix

α-Fe R2Fe14B Magnetic properties

ZrO2 Al2O3 Pore structure stability

γ-Al2O3 Amorphous SiO2 Reaction sintering

γ-Fe2O3 Ag Negative magnetization

Si3N4 20 vol% SiC Strength, structure, properties

1. Addition of nanoparticles, especially anisometric ones, viz. nanofibres,

et al., 1995; Lichtenhan, 1996; Haddad and Lichtenhan, 1996; Lichtenhan

1.3.1 PNC Definitions

Exfoliated layered material: individual platelets (of an intercalated layered

1.3.2 Methods of Characterisation of CPNCs

1.3.2.1 X-Ray Diffraction (XRD)

Iα = K´wα Ineat α (5)

intensity decreases. Parallel with these changes there is an enhancement of the

1.3.2.2 Small Angle Neutron Scattering (SANS)

Figure 3 Interlayer spacing of n-butyl ammonium vermiculite vs. volume fraction

Figure 4 TEM of intercalated organoclay in PS matrix: (a) magnification 150k, (b)

1.3.2.4 Fourier Transform Infrared Spectroscopy (FTIR)

1.3.2.5 Nuclear Magnetic Resonance Spectroscopy (NMR)

provide information on the preponderance of α- and γ-crystalline phases of PA-6

1.3.2.6 Other Methods

1.3.3 Determination of PNC Properties

1.3.4 PNC Types and Methods of their Preparation

1.3.5 PNCs of Commercial Interest

Poly(2-oxazoline) Au-nanoparticles Polymerisation on functionalised Au [Jordan et al., 2001]

Polyaniline (PANI) TiO2 Polymerisation in the presence of [Su and Kuramoto,

Polyacrylonitrile or CdS Synthesis under gamma radiation [Qiao et al., 2000

Polyimine NiO For magnetic properties [Castro et al., 2000]

A polymer α-RuCl3 [Wang et al., 2000]

Polyacrylamide Ni Synthesis under gamma radiation [Liu et al., 2000]

Polyethylene (PE) Au or Ag nanoparticles Optical anisotropy [Dirix et al, 1999a,b]

PCL Tetraethoxysilane Chemical synthesis of a biocompatible [Tian et al., 1999]

PVC Cellulose whiskers Mechanical performance [Dubief et al., 1999]

Polymer solution Fe Nanocomposites by reduction of Fe2+ [Yu et al., 1999]

PET Intercalated clay Polycondensation [Frisk and Laurent,

Aromatic PA Aromatic PA fibers Polymer blending [Akita and

Styrene-maleic anhydride TiO2 Covalently bonded, stable 3D [Wang et al., 1999]

A polymer Mn-Zn ferrites Room temperature synthesis [Mathur et al., 1999]

Poly(maleic monoester) Fe2O3 Thin films [Lee and Kang, 1998]

Polycarbonate-co-poly(p-ethyl CdS Enzyme-catalysed synthesis [Wang et al., 1999]

A polymer NbSe2 Superconducting polymers [Tsai, 1997]

A polymer LiMoO3 Encapsulative precipitation [Wang et al., 1997]

Polyacrylamide Ag Synthesis under gamma radiation synthesis [Zhu et al., 1997]

PMMA or PS Au Radical polymerisation [Gonsalves et al.,