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MULTISCALE FIBER REINFORCED COMPOSITES USING A CARBON
NANOFIBER/EPOXY NANOPHASED MATRIX: PROCESSING, PROPERTIES,

AND THERMOMECHANICAL BEHAVIOR
by
KEITH JAMAHL GREEN
DERRICK R. DEAN, COMMITTEE CHAIR

J. BARRY ANDREWS
UDAY K. VAIDYA
A THESIS
Submitted to the graduate faculty of the University of Alabama at Birmingham,

in partial fulfillment of the requirements for the degree of
Masters of Science
BIRMINGHAM, ALABAMA
2007
MULTISCALE FIBER REINFORCED COMPOSITES USING A CARBON
NANOFIBER/EPOXY NANOPHASED MATRIX: PROCESSING, PROPERTIES,
AND THERMOMECHANICAL BEHAVIOR
KEITH JAMAHL GREEN
MATERIALS ENGINEERING
ABSTRACT
Fiber-reinforced polymer composites (FRCs) have shown great promise as high
strength structural materials due to their high stiffness to weight ratio and their ease in
processing. They have found extensive use in aerospace, automotive, construction, and
recreational equipment material applications. Research in polymer-based
nanocomposites (PNCs) has shown explosive growth in the past decade with much
emphasis focused on PNC using thermosetting polymer matrices. Modifying
conventional FRCs with a PNC matrix result in the emergence of a hybrid composite
material termed multiscale fiber-reinforced composites (M-FRCs).
The current research addresses carbon nanofiber (CNF) surface modification,
carbon nanofiber/epoxy polymer nanocomposite (CNF/PNC) development and M-FRC
fabrication. Vacuum assisted resin infusion molding (VARIM) is used to produce M-
FRC. The materials used in this research are surface modified and modified CNFs,
aerospace grade high temperature epoxy resin, and plain-weave E-glass fiber preforms.
The VARIM process used to produce M-FRC is explained in detail. The effects of using
a CNF/PNC nanophased polymer matrix is presented and thoroughly investigated.
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Flexural, thermomechanical, and rheological studies are presented on the
CNF/PNC nanophased matrix and compared with the neat epoxy resin. Flexural,
interlaminar shear strength (ILSS) and thermomechanical tests are presented for the 0.1
and 1 wt% M-FRCs and compared with the neat FRC.
Experimental results indicate that the glass transition temperatures (Tg) of the
CNF/PNC and M-FRC samples were higher than the neat epoxy resin and neat FRC
samples, respectively. Coefficients of thermal expansion (CTE) properties of the
CNF/PNC and M-FRC samples were lower than the neat epoxy resin and neat FRC,
respectively. Flexural studies indicated increases in flexural strength (16-20%) and
flexural modulus (23-26%) for M-FRC samples. The ILSS studies indicated increases in
ILSS (8-23%) for M-FRC samples. The improved Tg and CTE properties in the
CNF/PNC samples are believed to be due to achieving good nanoparticle dispersion.
While the increased properties in the M-FRC samples are believed to be due to
synergistic interactions between the CNF/PNC nanophased matrix and glass-fiber
interactions.
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DEDICATION
I dedicate this academic and professional achievement to my Lord and Savior
Jesus Christ. In addition, I dedicate this work to my grandparents Russell and Delores
McJett. I could not write enough words to express the depth of love that I have for the
both of you. Without your guidance and teaching I definitely would not be where I am
today, and I’m eternally grateful to God up above to have both of you in my life.
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ACKNOWLEDGEMENTS
The author would like to take this opportunity to sincerely express much gratitude
to those people who provided assistance and support during this academic endeavor.
First, I would like to express my appreciation to my advisor Dr. Derrick R. Dean, for his
bountiful guidance, and invaluable advice throughout my graduate career. I would like to
thank the members of my graduate committee, Dr. Uday K. Vaidya, and Dr. J. Barry
Andrews for their technical input and attentiveness that they put forth on my behalf.
I especially would like to thank my colleagues in the Polymers Research Group
(Mohamed A. Abdalla, Moncy V. Jose, Himani D. Deshpande, Ayesha Swarn, Brian W.
Steinert, John Tipton, Roberus S. McIntosh and Larry J. Harris) for their constant
encouragement and support during this endeavor. I would truly like to thank Dr. Selvum
Pillay and Dr. Haibin Ning for their assistance in performing flexural testing. I sincerely
appreciate the assistance of Mohamed A. Abdalla for his time in helping me obtain
greatly needed electron microscopy micrographs.
The financial support rendered from the NSF-NIRT (DMR 0404278) grant and
the ARL sponsored project on Thermoplastic Composites for Body Armor Applications.
Finally, I would like to thank my family, and true friends Everett D. Ingram, Peter
J. Spears Sr., Harry A. Lewis and Shavon L. Ford. The prayers, love, support, and
encouragement that you provided me has sustained me through many difficult times and
enabled me to fulfill my true destiny.
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TABLE OF CONTENTS
Page
ABSTRACT ........................................................................................................................ ii
DEDICATION ................................................................................................................... iv
ACKNOWLEDGEMENTS .................................................................................................v
LIST OF TABLES ........................................................................................................... viii
LIST OF FIGURES ........................................................................................................... ix
CHAPTER
1 INTRODUCTION .........................................................................................................1
Polymer Matrix Materials ..............................................................................................1

Epoxy Resin .............................................................................................................2
Modified Polymer Matrix Materials ..............................................................................7
Polymer Matrix Nanocomposites ............................................................................7
Fibers..............................................................................................................................8
Fiber-Reinforced Composites ......................................................................................10
Multiscale Fiber-Reinforced Composites ....................................................................11
Applications of Fiber-Reinforced Composites ............................................................12
2 LITERATURE REVIEW ............................................................................................13
3 EXPERIMENTAL .......................................................................................................22
Materials ......................................................................................................................22
Carbon Nanofiber Surface Modification Procedure ....................................................23
Epoxy-Carbon Nanofiber/Polymer Nanocomposite Synthesis ....................................24
Fabrication Procedure: Vacuum Assisted Resin Infusion Molding (VARIM) ............25
Dynamic Mechanical Analysis (DMA) .......................................................................27
Thermomechanical Analysis (TMA) ...........................................................................27
Thermogravimetric Analysis (TGA)............................................................................28
Rheology ......................................................................................................................28
X-ray Photoelectron Spectroscopy (XPS) ...................................................................28
Raman ..........................................................................................................................29
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Mechanical Test Methods ............................................................................................29
Flexural Testing (3-Point Bending) .......................................................................29
Short Beam Test (Interlaminar Shear Strength (ILSS)) .........................................31
Morphology..................................................................................................................32
Optical Microscopy (OM)......................................................................................32
High Resolution Scanning Electron Microscopy (Hi-Res SEM) ..........................32
4 RESULTS AND DISCUSSION ..................................................................................33
Carbon Nanofiber Characterization .............................................................................33

Raman ....................................................................................................................33
Thermogravimetric Analysis .................................................................................35
X-ray Photoelectron Spectroscopy ........................................................................29
Epoxy-Carbon Nanofiber/Polymer Nanocomposite Characterization.........................41
Dynamic Mechanical Analysis ..............................................................................41
Thermomechanical Analysis ..................................................................................48
Epoxy-CNF/PNC Processing Analysis ..................................................................52
Morphology............................................................................................................57
Multiscale Fiber-Reinforced Composite Characterization ..........................................63
Interlaminar Shear Strength Testing ......................................................................68
Dynamic Mechanical Analysis ..............................................................................71
Thermomechanical Analysis ..................................................................................74
5 CONCLUSIONS..........................................................................................................75
LIST OF REFERENCES ...................................................................................................77
vii
LIST OF TABLES
Table Page
1 Commonly used polymer matrix materials ......................................................................2
2 Comparison of fiber-reinforcements ................................................................................9
3 Properties of EPON 815C epoxy resin ..........................................................................22
4 Properties of PR-19-HT CNFs .......................................................................................23
5 D-peak/G-peak values from Raman spectrometry for

surface unmodified and modified CNFs ........................................................................35
6 Atomic concentration of C1s and O1s obtained from XPS spectra .................................39
7 List of samples and their corresponding codes ..............................................................41
8 Glass transition temperature from the tan delta peaks

a) HSM, b) HSU, c) MMM, and d) MMU.....................................................................45
9 CTEs (ppm/oC) of mechanically mixed specimens

(a) (1.0 & 0.1% wt/wt unmodified and modified CNF/PNCs) and
(b) high shear (1.0 & 0.1% unmodified and modified CNF/PNCs)
and neat epoxy resin.......................................................................................................49
10 Flow Rates and Shear Rates .........................................................................................53
11 Flexural strength and flexural modulus mechanical properties ...................................62
12 Flexural strength and flexural modulus mechanical properties ...................................63
13 Shear strength and flexural mechanical properties ......................................................68
14 Storage Modulus and Glass Transition Temperature...................................................73
15 CTEs (ppmC-1) of the neat, 0.1 & 1% samples............................................................74
viii
LIST OF FIGURES
Figure Page
1 Idealized chemical structure of an epoxide ring ..............................................................3
2 The cure chemistry mechanisms involving epoxy with

a) primary, b) secondary, and c) tertiary amines .............................................................4
3 Chemical structure of diglycidyl ether of bisphenol-A

(DGEBA) epoxy molecule ..............................................................................................5
4 Idealized cure chemistry of DGEBA epoxy resin and

primary amine curing agent ............................................................................................6
5 a) Mechanical Mixing and b) High Shear Mixing apparatuses ....................................25
6 Setup of VARIM process ..............................................................................................26
7 Experimental setup for 3-point bending test ..................................................................30
8 Raman spectra of a) unmodified CNFs b) modified CNFs, showing

peaks at 1363 and 1580, referred to as the D and G bands respectively........................34
9 TGA thermograms of surface unmodified and modified CNFs in nitrogen ..................37
10 TGA thermograms of surface unmodified and modified CNFs in air .........................38
11 XPS scan of the oxygen 1s peak of surface modified CNF .........................................40
12 Storage Modulus vs. Temperature curves of 0.1 wt%

a) high shear mixed b) mechanically mixed polymer nanocomposites .......................43
13 Tan delta vs. Temperature curves of the 0.1 wt%

14 Storage modulus vs. Temperature curves of the 1.0 wt%

15 Tan delta vs. Temperature curves of the 1.0 wt%
ix
16 CTE graphs of a) 1% samples b) 0.1% samples (pa = parallel),

(pd = perpendicular).....................................................................................................51
17 Unmodified CNF/PNCs ...............................................................................................54
18 Modified CNF/PNC samples .......................................................................................54
19 Overlay of All CNF/PNC samples...............................................................................55
20 Representative samples of a) 1% unmodified CNF/PNC

b) 1% modified CNF/PNC ...........................................................................................58
21 Flexural stress vs. strain of neat, 0.1 and 1% CNF/PNC samples ...............................60
22 Flexural stress vs. strain of neat, 0.1, 0.5, 1, 2, and

4 % CNF/PNC samples................................................................................................61
23 Flexural stress vs. strain of neat, 0.1 and 1% M-FRC samples ...................................64
24 Hi-Res SEM micrographs of a) 0.1% and b) 1% M-FRC samples .............................66
25 Hi-Res SEM micrographs of 1% M-FRC samples a) 4000X b) 4500X ......................67
26 Shear strength vs. strain of neat, 0.1 and 1% M-FRC samples ....................................69
27 Cross-sectional fracture surface optical micrographs of

a) neat, b) 0.1% c) and 1% M-FRC samples................................................................70
28 a) Storage modulus vs. temperature curves and

b) tan delta vs. temperature curves of neat, 0.1, and 1% M-FRC samples ..................72
x
CHAPTER 1
INTRODUCTION
Polymer Matrix Materials
The matrix component of composite material can be a thermosetting, a
thermoplastic or a modified matrix resin. The matrix component in composite materials
plays a minor role in tensile load-carrying capacity of a composite structure. While the
fibers are principal load-carrying members, the matrix is responsible for:
1. Keeping the fibers in the desired location and orientation.
2. Acting as a load transfer medium transmitting mechanical loads from the matrix
to the fibers.
3. Providing lateral support against possible fiber buckling caused by compressive
loading.
4. Protecting from an adverse chemical environment.
5. Broadening the transmission of stress concentration from broken to intact fibers.
6. Controlling interfacial bond failure between the fiber and matrix ahead of the
crack (and normal to the crack) blunts the crack and absorbing additional energy.
The table below shows some commonly used polymer matrix materials.
1
Table 1. Commonly used polymer matrix materials
Thermosetting resins Thermoplastic resins

Epoxy Polyether ether ketone (PEEK)
Phenolic Polyether imide (PEI)
Polyester Polyphenylene sulfide (PPS)
Polyimide Polysulfone
Vinyl ester
In general, thermoplastic polymer composites are more advantageous to process
and in addition they show better toughness than their brittle thermoset counterparts (1).
On the other hand, thermoplastics have some undesirable properties such as creep
resistance. This is due to the non cross-linked nature of many linear thermoplastics.
Epoxy Resin
In particular, epoxy resin is a very attractive and popular thermosetting polymer
matrix because of its widespread usage (i.e., aerospace industry, automotive industry,
marine industry, construction materials & sporting goods, etc.). Epoxy resins represent
some of the highest performance resins of those available at this time. In general, they
out-perform most other resin types in terms of mechanical properties and environmental
degradation resistance which leads to their exclusive use in the aerospace industry. One
of the most advantageous properties of epoxy resin is their low shrinkage during curing
which minimizes internal stresses. They have excellent adhesive strength and high
mechanical properties which are also enhanced by high electrical insulation and good
2
chemical resistance. They find uses as adhesives, caulking materials, sealants, and
varnishes, as well as laminating resins for an array of industrial applications.
The term ‘epoxy’ refers to the epoxide functional group consisting of an oxygen
atom bonded to two adjacent bonded carbon atoms forming a three-member ring. The
idealized chemical structure of an epoxide ring is shown in Fig. 1 and is easily identified
in complex epoxy molecules.
H2 C CH2
Figure 1. Idealized chemical structure of an epoxide ring
The three-member epoxide ring is quite reactive toward various reactants or cross-linking
agents. The properties of a final thermoset depend not only on the structure of the epoxy
resin but also on the type and the amount of curing agent. The speed of cure of an epoxy
system is governed by the curing process, the type and concentration of the curing agent,
and the chemistry of polymerization. For this reason, epoxy resins can easily and quickly
be cured at any temperature from 5 oC to 150 oC (1, 2). For instance, aliphatic amine
curing agents can cure at room temperature, while aromatic amine curing agents need
high temperatures to cure properly. If the curing agent is a primary or secondary amine,
the cure reaction will proceed as an addition reaction where one nitrogen-hydrogen group
reacts with one epoxy group (3). Reactions that involve tertiary amines result from the
unshared electron pair on the nitrogen. Since secondary hydroxyl groups are not
generated on the product side of the reaction, the resin homopolymerizes forming
3
polyether (3). When epoxy reacts with a primary amine curing agent, a secondary amine
and secondary hydroxyl group are formed. When epoxy reacts with a secondary amine
curing agent, tertiary amine and secondary hydroxyl groups are formed. In both cases
with epoxy resin reacting with primary and secondary amine curing agents, secondary
hydroxyls are formed and are believed to catalyze the reaction (3). The cure chemistry
mechanisms involving epoxy with primary, secondary, and tertiary amines are shown
below in Fig. 2.
H H
O
R NH2 H2C CH CH2 B R N CH2 C CH2 B
a)
primary amine epoxide secondary amine OH
secondary hydroxyl
H
O
b) R2 NH H2C CH CH2 B R2 N CH2 C CH2 B
secondary amine epoxide tertiary amine OH

secondary hydroxyl
H
O
c) R3 N H2C CH CH2 B R3 N CH2 C O
n
tertiary amine epoxide
CH2 B
quaternary ammonium polyether
Figure 2. The cure chemistry mechanisms involving epoxy with a) primary, b)

secondary, and c) tertiary amines; where (B) represents the polymer chain
One of the unique qualities of diglycidyl ether of bisphenol-A (DGEBA) epoxy molecule
is that it contains two ring groups at its center which enable the molecule to absorb
mechanical and thermal stresses better than linear groups and provide tremendous
4
stiffness, toughness and heat resistant properties (1, 2, 4). The chemical structure of the
DGEBA epoxy molecule is shown in Fig. 3 below.
O CH3 O
CH2 CH CH2 O C O CH2 CH CH2
CH3
Figure 3. Chemical structure of diglycidyl ether of bisphenol-A (DGEBA) epoxy
molecule.
The position of the epoxide rings in the epoxy molecule is an additional important factor
in the determination of epoxy reactivity. The chemistry of this reaction means that there
are usually two or more epoxy sites binding to each amine site. Both the number and
distance between reactive groups can affect the material’s performance. The idealized
cure chemistry of DGEBA epoxy resin and a primary amine curing agent can be seen
below in Fig. 4 (4). This reaction is responsible for forming the three-dimensional
molecular structure.
5
O O
R O CH2 CH CH2 CH2 CH CH2 O R
NH2
NH2
O O
OH OH
OH OH
Figure 4. Idealized cure chemistry of DGEBA epoxy resin and primary amine curing
agent.
6
Modified-Polymer Matrix Materials
Polymer Nanocomposites
A nanocomposite can be defined as a composite material that has one or more of
its constituents with nanoscale dimensions (i.e., on the scale of 1 billionth of a meter).
Polymer nanocomposite research has attracted international interest since the late 1980s
due to their unique property enhancements relative to the virgin polymer. The
incorporation of nanoscale constituents into polymer matrices leads to novel or modified
property enhancements significantly greater than that attainable using conventional fillers
or polymer blends. Improvements in mechanical strength, fracture toughness, thermal
(i.e., thermal stability, decomposition, and coefficients of thermal expansion (CTE)), and
physical (i.e., permeability, optical, dielectric) properties have been observed depending
on the type of nanoparticle (i.e., CNT, CNF, layered silicate, etc.). A key feature of
polymer nanocomposites is that such enhancements are achievable at very low volume
fractions of 2-5% “nanoconstituent.” Where in conventional reinforcing composites the
polymer matrix may account for as much as 50% by weight and typical structural
reinforcements may be as high as 60% by volume. Such low volume fractions offer a
potential for incorporating nanoconstituents into existing polymer resins without
significantly modifying existing processing techniques, and increases the tailor-ability
options for advanced composite matrices. Hence, polymer nanocomposites provide the
opportunity to explore new behaviors and functionalities beyond those found in
conventional materials.
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Fibers
The fibers are the principal load-bearing members in FRCs. The proper selection
of the type, amount, and orientation of the fibers are very important since it influences the
following composite laminate characteristics:
1. Density.
2. Tensile and compressive strength.
3. Fatigue strength and fatigue failure mechanisms.
4. Electrical and thermal conductivity.
5. Cost.
The fibers in FRCs have specific roles such as:
1. They support all main loads.
2. Limit deformations.
3. Increase overall mechanical properties (i.e., strength, toughness, and stiffness).
4. Decrease corrosion, creep, and fatigue.
The principal fibers in commercial use are various types of glass (i.e., E-glass, S-glass,
and C-glass) (1, 2), carbon fiber (i.e., pitch-based, or PAN-based) (1), boron (1, 2),
silicon carbide (SiC) (1, 2), ceramic fiber (i.e., alumina-based (Nextel)) (1), polymer-
based (i.e., aramid (Kevlar 49, Nomex), and polyethylene (Spectra, Tekmilon) (1).
Fibers used in FRCs for structural applications are mostly used in laminate form. This is
achieved by stacking a number of fiber preforms and matrix and then consolidating them
to a desired thickness. Fiber orientation in each layer and stacking sequence can be
8
controlled to obtain desired physical and mechanical properties. Table 2 below shows a
comparison of various fiber-reinforcements.
Table 2. Comparison of fiber-reinforcements
Density, ρ Tensile Strength, Tensile Modulus, Poisson’ CTE, α

Fiber
(g/cm3) σ (GPa) E (GPa) s ratio, υ (10-6 K-1)
E-glass 2.55 1.5-2.5 70 0.2 5
Carbon 1.75 2.7 250 0.2 -1
Kevlar 1.45 3.6 125 0.35 -2
Boron (W) 2.7 3.8 393 0.2 5
Al2O3 3.95 1.9 379 0.2 7.5
Of all of the principal fibers in use in FRCs, glass-fibers are the most common
selection for polymer matrix composite (PMC) materials. A major factor for the use of
glass-fibers in commercial applications is due to their relatively low cost when compared
to other commercial fibers. They have CTE properties (2-5 (10-6 K-1), which are lower
than many metallic fibers or filaments (i.e., steel, aluminum, titanium, nickel, gold, etc.).
Two types of glass fibers used in polymer FRCs are E-glass and S-glass. E-glass has the
lowest cost of all commercially available fibers, which is the reason for their widespread
use in FRC materials. The letter ‘E’ is used because of their original use in electrical
applications. S-glass was originally developed for aerospace applications (i.e., aircraft
components and missile casings). The letter ‘S’ is used due to their use where high
tensile strength properties are desired. At room temperature S-glass is 10-15% stronger
than E-glass, and can withstand higher in-use temperatures (1, 2). Another type of glass
9
fiber, known as C-glass, is used in chemical applications that require greater resistance to
chemical attack than is supplied by E-glass.
Fiber-Reinforced Composites
The history of fiber-reinforced polymer composites date back to work started in
the USA in the 1940s (1). It refers to a material that contains high strength and modulus
fibers embedded in a matrix with distinct interfaces or interphases between them. The
fibers and matrix retain their physical and chemical identities, yet produce a combination
of properties unattainable by either constituent. Fiber-reinforced composite materials
have shown great promise as high strength materials due to their potential benefits of low
density, high strength, high stiffness-to-weight ratio, economic feasibility, good corrosion
resistance, low CTE, high thermal damping capacity, excellent durability, design
flexibility and excellent in-service applications. They have found use in construction,
aerospace, automotive, and recreational equipment material applications. The main
advantage of most FRC materials is in the weight savings.
Incorporating CNFs in the polymer matrix used in making FRCs can have some
added benefits such as increased strength and fracture toughness. Carbon nanofibers
(carbon fibers with dimensions on the scale of 1 billionth of a meter) are currently being
used in various approaches to provide functional (thermal, electrical and magnetic
conductivity etc.) and structural property enhancement to polymer based materials
including composites (5). They have exceptionally high thermal and electrical
10
conductivity which make them excellent candidates for polymer nanocomposites in
applications demanding heat dissipation and thermal shock resistance. They also offer
the opportunity to create FRCs with multifunctional properties. Meaning that FRCs
would be able to perform mechanically, but also be able to conduct electrically or heat.
The potential of carbon based nanocomposites as the matrix material in FRC structural
composite materials has not been fully exploited. Carbon nanofiber usage is growing due
to their low cost and increased performance in a variety of applications as polymer
nanomaterials in the automotive and aerospace industries. Fiber-reinforced composites
with multifunctional properties show great potential for use in future automotive,
aerospace, and marine applications.
Multiscale Fiber-Reinforced Composites
Synergistically polymer nanocomposites with conventionally filled composites
(i.e., glass-fiber, carbon-fiber) have resulted in the multiscale composite materials that
possess unique properties. Multiscale composites possess a hierarchal microstructure
ranging from nanoscale fibers to micron size fibers. There is a strong need to balance the
multiple demands of performance, weight, risk and life-cycle cost in selecting new
structural materials. However, multiscale fiber reinforced composite materials (M-FRC)
offer a route of creating materials that exhibit multifunctionality (i.e., enhanced thermal
stability, lower CTE, high thermal and electrical conductivity, etc.) without sacrificing
performance.
11
Applications of Fiber-Reinforced Composites
Boeing’s 787 Dreamliner is the first aircraft to have its fuselage made entirely
from polymer composite matrix composite materials, and Airbus’ A380 is the largest
commercial passenger aircraft ever built and is comprised of 25 weight-percent of
composite materials, specifically with polymer composite materials in the fuselage, wings
and tail sections. Both Boeing and Airbus are revolutionizing the aircraft building
industry by introducing polymer composite materials as the primary structural
components in their aircraft, making the aircraft more fuel efficient than ever before.
Epoxy resins have found use in the marine industry for building boats because of their
excellent adhesive properties as a laminating resin and resistance to water degradation (2,
4, 6). Currently epoxy resins are supplanting use of polyester resins as the polymer
matrix material in the boating industry because of the environmental degradation caused
by water. In the space shuttle, for example, the total weight savings with FRCs is 2688 lb
per vehicle (2). Thermoset polymers, such as epoxy resins, and polyesters have
widespread commercial use for making FRCs due to their ease of processability. They are
often used in high performance, high temperature aerospace applications.
12
CHAPTER 2
LITERATURE REVIEW
Carbon nanofibers (CNFs) have been recognized as a promising constituent in
polymer nanocomposites (PNCs) because they exhibit characteristics similar to their
carbon nanotube (CNT) counterparts, such as excellent electrical, thermal, and
mechanical properties (7, 8). Carbon nanofibers typically have a larger average diameter
(100 ~ 300nm) than CNTs (1 ~ 50nm), and CNFs have a slightly lower modulus of only a
few tens of GPa, and are more inexpensive to produce compared to CNTs (8-11). Carbon
nanofibers have a one-dimensional morphology consisting of sp2-bonded graphitic
carbon oriented along an axis parallel to the basal plane. Carbon nanofibers as a
nanofiller in PNCs are quite useful in applications which employ CNTs because CNFs,
like their CNT counterparts, exhibit a high aspect ratio (length/diameter, L/D > 100), an
interfacial area which can reach 100-1000 m2/g, and chemical inertness (10).
Investigations are underway exploring the nature and thermal behavior of PNCs (7-12).
One of the major technological issues limiting widespread use of epoxy
CNF/PNCs is processability, where CNF dispersion or alignment is crucial to CNF/PNC
performance. For example, one of the problems is that CNFs have a tendency to
aggregate together, resulting in poor dispersion throughout the polymer matrix. Carbon
nanofiber aggregation is due to Van der Waals interactions. If CNF-polymer matrix
13
adhesion is poor, the CNF/PNC may fail at the interface, leading to mediocre mechanical
property enhancements (13). A key in PNC processing, is nanofiller/polymer interfacial
chemistry. Recent studies suggests that coupling the dispersion of the nanoconstituent
into polymer host and controlling the interfacial chemistry between the polymer host and
the nanoconstituent can provide a sufficient means of creating such multi-functional
materials (7, 9, 10, 12, 14). In systems employing silicates and CNTs, it has been
suggested that modifying their chemical surfaces increases their overall miscibility into
polymer hosts and provide increased thermomechanical and bulk properties (7, 9, 10, 12,
14-20). The chemical nature of the surface modifying molecules has proven that they
will affect the ease with which CNFs can be homogeneously dispersed in the epoxy resin.
Modifying the surfaces of the CNFs plays a vital role in disrupting the aggregating nature
of CNFs and simultaneously enhancing the solubility of CNFs within the polymer matrix
which can have a profound effect on the load transfer in the nanocomposite.
Recent studies have shown that CNF surface modification aids in the dispersion
of CNFs into the polymer matrix and leads to increased mechanical properties (9, 10, 14).
Rice et al. reported a 34-percent increase in strength and a 130-percent higher modulus
with a 4 weight percent CNF loaded epoxy CNF/PNC (14). Thus, good CNF-polymer
adhesion can promote interactions between the CNF and polymer matrix which should
produce desirable mechanical properties. Toebes et al. reported that the hydrophobic and
inert nature of CNFs are unfavorable for some applications, but by introducing the CNFs
to an oxidizing acid such as sulfuric/nitric acid (H2SO4/HNO3) can produce CNFs with
oxygen-containing surface groups and enhance the CNFs affinity for polar solvents (13).
Glasgow and co-workers reported that surface oxygen levels as high as 25 atom % can be
14
achieved from using the (H2SO4/HNO3) oxidation surface treatment (12). The oxygen on
the surfaces of the CNFs will be in the form of carboxylic acids. Other studies have
reported CNF surface treatments that consist of 1:3 (H2SO4/HNO3) (12, 13, 19) , air (12),
peracetic acid (12), and cold oxygen plasma treatment (21), with (H2SO4/HNO3) yielding
the best results. Recent studies reported that Thermogravimetric analysis (TGA) can be
used to quantitatively determine the degree of surface functionalization of fullerenes and
single-walled carbon nanotubes (SWNTs) in an argon atmosphere (22, 23). Sayes et al.
investigated the functional density dependence of SWNT cytotoxicity in vitro (23). They
functionalized SWNTs with three different solvents. Each solvent provided
functionalization of the SWNT surfaces from the least to the most surface coverage of
functional groups. The degrees of functionalization for three samples were 80, 41, and
18 for the least, medium, and most functionalized SWNT respectively.
Thermoplastic (TP) CNF/PNCs have been reported for polymers based on
systems employing isotatic polypropylene (iPP), polycarbonate (PC),
polyetheretherketone (PEEK), polymethylmethacrylate (PMMA), polyphenylene sulfide
(PPS) and nylon as polymer matrices (9, 10, 12, 13, 20). Thermoplastic CNF/PNCs as
electrostatic discharge materials are needed for electronic packaging purposes, for
garments, work benches, and personnel working in an electronic packaging facility (20).
Lozano et al. reported electrical resistivity on iPP-CNF/PNCs which showed that as CNF
loading increased from (0 to 40 wt.%), the electrical resistivity decreased 10-fold,
suggesting that the CNFs can increase conductivity and increase the electrostatic
dissipation properties of TP-CNF/PNCs (20). Other studies have reported thermoset (TS)
PNCs using CNFs employing different epoxy resins (low viscosity, high viscosity, room-
15
temperature, and high temperature) and bismaleimides (BMIs) as polymer matrices (9,
10, 12, 14, 16). Both Gauthier et al. (10) and Choi et al. (16) studied epoxy CNF/PNCs.
Choi et al. reported strength improvements with 5% CNF loadings (16). Gauthier et al.
reported higher strength improvements with strain to break increasing 100% and 160%
increase in stress (10). The strain to break significantly increased for Gauthier et al. but
when compared to Choi et al. study, the strain to break was relatively moderate. This
indicates that the data from both cases studying the mechanical properties of epoxy
CNF/PNCs are different from one another due to differences in the epoxy resin
composition. The vastly improved enhancement seen in Gauthier et al.’s study indicates
strong CNF and polymer matrix interactions are present.
Studies by Patton et al. (9) and Choi et al. (16) investigated the effects of using
epoxy resins with different viscosities (i.e., high viscosity, low viscosity) in making
CNF/PNCs. Patton and co-workers reported that the flexural modulus increased from 2.3
GPa to 8.74 GPa as the CNF loading increased from (0 to 35.5% vol/vol (Vf)) and
increased flexural strength up to 20% as the Vf increased to 15% vol/vol and decreased
at higher volume fractions for their low viscosity epoxy CNF/PNC (9). The decrease in
flexural mechanical properties in their high volume fraction CNF/epoxy samples is due to
increased void content and poor dispersion. Choi et al. reported increased glass transition
temperatures (Tg) of 26 oC with 20 wt.% CNF loading with low viscosity epoxy resin and
a decrease in Tg with 20 % CNF loading with high viscosity resin (16). This suggests
that the high loaded CNF/epoxy samples made with high viscosity epoxy resin showed a
decrease in Tg presumably due to poor dispersion. In a study investigating thermal
degradation of CNF/PNCs, Choi et al. reported that the samples began to decompose at
16
approximately 260oC (first stage), and were completely decomposed at around 640oC,
720oC, 730oC, and 735oC (third stage) for pure epoxy, epoxy/5 wt.%, 10 wt.%, 20 wt.%
CNF nanocomposite respectively (16).
The thermal conductivity measurements for the epoxy resin and CNFs are
inherently different with epoxy resin and CNFs showing typical thermal conductivity
measurements at ~0.1 W/mK, and 1950 W/mK respectively (9). CNFs have low
electrical resistivity ~55 µΩcm (9), while epoxies on the other hand have very high
electrical resistivity and are known to be insulators (16). A thermal conductivity study by
Chen et al. on epoxy CNF/PNCs showed that as CNF concentration increased from (2-
52% vol/vol) that thermal conductivity increased from zero to 695 W/mK respectively
(15). In a study on electrical resistivity of epoxy CNF/PNCs Choi et al. show that as the
CNF volume fraction increases; the electrical resistivity decreases in both the low and
high viscosity epoxy CNF/PNC systems, with the low viscosity epoxy CNF/PNC
samples showing greater sensitivity (16). The use of a low viscosity epoxy resin in
making epoxy CNF/PNCs suggests that the CNFs should disperse better throughout the
polymer matrix and possibly produce multifunctional polymer nanocomposites with the
ability to pass electric current.
Most of the data reported on CTE, thermal conductivity, electrical resistivity and
thermal properties have been on unmodified CNF reinforced epoxy CNF/PNCs while
little data exists on modified CNF reinforced epoxy CNF/CNFs. Abdalla et al. studied
the effect of layered silicate (LS) loading on the CTE properties of PMR-15/layered
silicate nanocomposites (24). Their 2.5% PMR/layered silicate sample exhibited a
reduction of 26% in the CTE property relative to their neat sample (24). Chen and co-
17
workers reported as CNF concentration increased from (2-52% vol/vol) the CTE of
epoxy CNF/PNCs decreased from 31.29 ppmK-1 to -0.11 ppmK-1 respectively (15). A
similar study by Sullivan et al. investigated the CTE properties ceramic
nanoparticle/polyimide PNCs, and they noted as the ceramic nanoparticle loading
increased from (0 to 6 wt.%) the resultant CTE values decreased, with the 3 wt.% sample
showing 18% reduction in CTE property (25). A recent study investigating nanoparticle
alignment using uniaxial magnetic fields paid close attention to CTE behavior and
showed reduced CTE values in the direction of the maximum layered silicate alignment
(26, 27) has led our group to investigate similar behavior with our PNCs.
A critical challenge for M-FRC is the integration, control, and exploitation of
nanoparticle-enabled properties within a hierarchal structural composite made with
commercially processing methods. Nanoparticles can be incorporated in a multitude of
different ways within traditional composite materials, (i.e., within a fiber, thin films, part
of the polymer matrix, etc.). Many of the limitations of fabricating M-FRC is directly
related to achieving a homogenous distribution of the nanoparticles throughout the bulk
of the composite (14, 28-35). For example, in a FRC fabrication process such as
vacuum-assisted resin infusion (VARIM), nanoparticles are sometimes filtered and can
lead to a inhomogeneous microstructure (33, 36). In order to take full advantage of the
unique mechanical properties of nanoparticles (i.e., CNTs, CNFs, etc.), much effort is
needed to improve processing techniques to achieve high-performance M-FRCs with
fully integrated and well dispersed nanoparticles. Control of the dispersion of the
nanocomposite matrix is extremely critical in achieving property enhancements and
making the M-FRC a multifunctional material.
18
Bekyarova et al. (28) and Qui et al. (33) used CNTs as the nanoconstituent in
fabricating M-FRC. Bekyarova et al. studied the effect of electrophoretically dispersing
0.25 wt% functionalized CNTs into carbon fiber preforms and fabricating M-FRC using
the VARIM process and showed 30% enhancement in interlaminar shear strength (ILSS)
(28). The 30% increase in ILSS is suggestive of improved matrix dominant properties in
the M-FRC. In a study investigating the epoxy/CNT/glass fiber M-FRC, Qui et. al
reported a 16% and 27% increase in tensile strength and modulus, respectively for their 1
wt% functionalized CNT M-FRC sample (33). The mechanical property enhancements
in their study were due to the use of functionalized CNTs amplifying the dispersion
throughout the polymer matrix and strengthening CNT-polymer matrix interactions.
Dean et al. (30), Haque et al. (31), Chowdury et al. (29), and Kornman et al. (32)
investigated the effects of using LS as the nanoconstituent in fabricating M-FRC. Dean
et al. investigated the effect that the LS loading had on mechanical properties of VARIM
processed multiscale fiber-reinforced nanocomposites (30). They reported enhancements
of 24% and 31% in flexural strength and modulus, respectively for their 2 wt% M-FRC
sample. Improvements in flexural strength and modulus in the 2 wt% sample are due to a
homogenous dispersion of the LS and low viscosity of the 2 wt% epoxy/LS
nanocomposite. Rheological characterization by Dean et al. show that their 2 wt%
nanocomposite is well within the range of fabricating FRCs using the VARIM process
and is suggestive that its low viscosity can lead to better wetting of the fibers and
dispersion of the nanoparticles. The effect of LS loading on the flexural and
thermomechanical properties of VARIM processed epoxy/LS/carbon fiber M-FRC was
studied by Chowdhury et al. (29). Chowdhury and co-workers reported a 25%, 14%, and
19
30% enhancement in flexural strength, modulus and ILSS, respectively. The increased
mechanical properties are attributed to enhanced polymer-nanoparticle-fiber interfacial
interactions. Haque et. al studied the effect of LS loading on the improvement of
mechanical and thermal properties of VARIM processed epoxy/LS/S2-glass M-FRCs
(31). They showed by dispersing 1 wt% LS that the resultant epoxy/LS/S2-glass M-FRC
exhibited an enhancement of 24%, 14%, and 44% in flexural strength, modulus, and
ILSS. It is to be noted that ILSS is the matrix dominant property and such improvements
in ILSS of M-FRC is mostly due to the improved property of the epoxy/LS
nanocomposite. The mechanical property enhancements in strength, modulus and ILSS
are due to increased interfacial areas, bond characteristics and unique phase morphology
of epoxy/LS nanocomposites. Kornman et al. studied the effect of LS loading on
VARIM processed epoxy/LS/glass-fiber M-FRCs (32). They reported improvements of
27% and 6% in flexural strength and modulus for their 10 wt% LS M-FRC sample. The
flexural strength and modulus improvements were due to the presence of the LS at the
surface of the glass fiber which improved the interfacial bonding between the epoxy/LS
nanocomposite matrix and glass-fiber.
In a study investigating the dimensional stability of epoxy/CNT/glass-fiber M-
FRC, Qui et al. (33) reported that their 1 wt% M-FRC sample exhibited a 25% reduction
in CTE relative to their neat sample. The CTE reduction was suggestive to having well
dispersed the CNTs throughout the M-FRC. Dean et al. (30) and Haque et al. (31)
reported very small increases in Tg in their VARIM processed M-FRC samples. On the
contrary, Qui et al. (33) reported a 11 °C reduction in Tg of their 1 wt% M-FRC sample
relative to the neat FRC sample. The Tg reduction was suggestive that the cross-link
20
topology decreases due to interference of the functional groups on the CNTs during
curing. As a result, the presence of the functionalized CNTs disrupts the optimized
epoxy resin-curing agent ratio in the curing reaction.
Kornmann et al. studied the effect of LS on moisture properties of VARIM
processed epoxy/LS/glass-fiber composites (32). They were able to show that their 10
wt% sample exhibited greater sensitivity to moisture uptake at 50°C and is the cause for
the apparent decrease in Tg. Studies by Bekyarova et al. (28) and Qui et al. (33) used 4-
Point probing to investigate the in-plane and out-of plane electrical conductivity in the
M-FRC samples. Bekyarova et al. (28) reported a 30% increase in out-of-plane electrical
conductivity for their epoxy/MWNT/carbon fiber and a 200% increase in out-of-plane
conductivity in the SWNT M-FRC samples. The substantial increase in the SWNT was
due to a network of interconnected SWNT bundles forming conducting paths in narrow
polymer regions. The differences in the electrical conductivity measurements can be
attributed to differences in sample thickness, but may also differ because of the
differences between SWNT and MWNT morphologies (28). In the study by Qui et al., a
nominal enhancement was exhibited in their functionalized 1 wt% M-FRC sample, but
not as significant as of using pristine SWNTs (33). The nominal electrical conductivity
enhancement was due to the functionalization disrupting the CNT electronic properties
which led to decreased electrical properties. Differences between both studies may also
be due to the type of fiber reinforcement used during fabricating M-FRCs. For example,
carbon fibers possess excellent electrical conductive properties; while on the contrary,
glass-fibers behave as insulators.
21
CHAPTER 3
EXPERIMENTAL
Materials
The materials used in this investigation were, EPON 815C (Modified diglycidyl
ether of bisphenol A (DGEBA) Epoxy resin) and EPICURE W curing agent (Aromatic
diamine) were purchased from the Miller-Stephenson Chemical Company. The epoxy
resin and curing agent were mixed in the ratio of 100:20 and cured at 150 oC for 2-hours.
Table 3 below shows the properties of EPON 815C epoxy resin system.
Table 3. Properties of EPON 815C epoxy resin
Property Value Units

Viscosity 5-7 Poise
Density 1.13 g/cm3
Tensile Strength 60 MPa
Tensile Modulus 2.0 GPa
Coefficients of Thermal Expansion 80-90 ppm/K
Electrical Resistivity Insulator µΩ-cm
Thermal Conductivity 0.230 W/m-K
22
The CNFs (heat treated grade PR-19-HT) were kindly provided by (Pyrograph III™ from
Applied Sciences Incorporated). Table 4 below shows the properties of PR-19-HT CNFs.
Table 4. Properties of PR-19-HT CNFs
Property Value Units

Fiber Diameter 100-200 nm
Density 2.1 g/cm3
Tensile Strength 7.0 GPa
Tensile Modulus 600 GPa
Coefficient of Thermal Expansion -1.0 ppm/K
Electrical Resistivity 55 µΩ-cm
Thermal Conductivity 1950 W/m-K
Carbon Nanofiber Surface Modification Procedure
The CNFs were refluxed in methylene chloride (CH2Cl2 ) at 35oC over a duration
of 7 days. Following refluxing they were vacuum filtrated and washed with distilled
water to remove any surface residue. Immediately following washing, they were placed
into a large volumetric flask containing 3:1 concentrated sulfuric acid/ nitric acid
(H2SO4/HNO3), and sonicated in a water bath for three hours at ambient temperature.
Next, the CNF’s were vacuum filtrated and washed with excessive amounts of distilled
water until no residual acid was present. The resulting CNFs were collected and dried in
an oven at 120oC overnight. After drying, the CNFs were ground into powder form.
23
Epoxy-Carbon Nanofiber/Polymer Nanocomposite Synthesis
Epoxy CNF/PNCs were prepared using 2-dispersion methods. In the first
dispersion method the appropriate amount of CNFs (0.1, or 1.0 wt %) were dispersed into
epoxy resin and mixed with a mechanical mixer for 30 min. The appropriate amount of
curing agent was added to the epoxy resin/CNF mixture and mixed for an additional 5
minutes. The nanodispersed prepolymer was poured into a steel mold, and degassed
under vacuum to remove trapped air bubbles, followed by curing in an oven at 150oC for
2 hours. Fig. 5a below shows the mechanical mixing apparatus.
In the second dispersion method (high shearing), the appropriate amount of CNFs
(0.1, or 1.0 wt %) were dispersed into the epoxy resin. The epoxy resin/CNF mixture
was poured into a cylindrical syringe with a small orifice, followed by high shear mixing,
in which the polymer/CNF mixture is sheared under high pressure through the small
orifice. The appropriate amount of curing agent was added and additionally sheared for
7-10 times. The high shear mixing apparatus is shown in Fig. 5b. The nanodispersed
prepolymer was poured into a steel mold, and degassed under vacuum to remove trapped
air bubbles, followed by curing in an oven at 150oC for 2 hours.
24
a) b)
Figure 5. a) Mechanical Mixing and b) High Shear Mixing apparatuses
Fabrication Procedure: Vacuum Assisted Resin Infusion Molding (VARIM)
Vacuum assisted resin infusion molding (VARIM) is a very attractive, cost
effective and environmentally friendly method of processing composites. The dry fabrics
(E-glass plain weave) were cut into plies and stacked several layers to form the dry
preform. During the stacking, the weft and warp fibers were carefully aligned so that
each layer preserves the same directions of reinforcement. The fabric was placed in an
open mold with a peeling cloth between the fabric and the mold surface. After laying up
the desired number of fabric layers, another peeling cloth and distribution mesh was
25
placed over the preform. One resin-suction line and one resin-injection line were
attached to the mold surface. The resin-suction line was connected to a resin trap that
was connected to a vacuum pump. A vacuum bag was placed over the open mold to
enclose all the contents on the mold surface. A typical setup of the VARIM process is
illustrated in Fig. 6 below.
Figure 6. setup of VARIM process
The epoxy resin and curing agent were mixed according to the prescribed 100:20 ratio.
Prior to resin injection, the vacuum was applied to the mold for thirty minutes to debulk
the preform. Debulking is done to remove any air within the VARIM setup. After
debulking, the resin was infused via vacuum (28.5 to 30 inch mercury) to completely
“wet out” the reinforcements and eliminate all air voids in the laminate structure. The
26
resin flowed and wetted the preform in-plane and through the thickness of the preform.
After the preform was completely wetted by the resin, the resin-injection line was
clamped and blocked off and the preform was left under vacuum at room temperature for
one hour. Uniform wettability was attained. The preform was then removed from the
VARIM setup, consolidated with a Carver hydraulic hot press and cured at 150 oC for 2
hours.
Dynamical Mechanical Analysis (DMA)
The glass transition temperature (Tg) of the CNF/PNC samples were obtained
using a TA Instruments 2980 Dynamical Mechanical Analyzer. To find the Tg of the
materials, the temperature was ramped from ambient to 200 oC at a rate of 5 oC min-1.
The Tg was determined by the corresponding peak of the tan delta (tan δ) curve.
Thermomechanical Analysis (TMA)
CTE measurements of the CNF/PNC samples were obtained using a TA
Instruments Q400 Thermomechanical Analyzer. To find the CTE of the materials, the
temperature was ramped from ambient to 200 oC at a rate of 10 oC min-1 and under a load
of 0.5 N. The CTE measurement was taken below the Tg of the material.
27
Thermogravimetric Analysis (TGA)
The thermal stability of the CNFs was studied using a TA Instruments 2950
Thermogravimetric Analyzer. The procedure involved a temperature ramp from ambient
to 1000 oC at a rate of 20 oC min-1 in air and nitrogen.
Rheology
Rheological experiments were performed on the nanodispersed prepolymers using
a TA Instruments AR 2000 Rheometer. Time sweeps were performed at a strain rate of
0.1% and frequency of 1 Hz.
X-ray Photoelectron Spectroscopy (XPS)
X-ray photoelectron spectroscopy (XPS) was used to characterize the effect of
chemical surface modification of the CNFs. The surface chemistry was studied with a
Surface Science Instruments (SSI) M-probe XPS instrument operated at a base pressure
of 8 x 10-10 torr. Binding energy positions were calibrated using the Au 4f7/2 peak at
83.93 eV, and the Cu 3s and Cu 2p3/2 peaks at 122.39 and 932.47 eV, respectively.
28
Raman Spectroscopy
Raman spectroscopy was used to characterize the effect of chemical surface
modification of the CNFs. Raman spectroscopy was carried out using a backscattering
geometry. The wavelength of 422 nm line of Kimmon Electric’s HeCd laser was used to
excite the sample. The laser beam with a nominal power of 80 mW was focused onto a
spot 5 µm in diameter.
Mechanical Test Methods
Flexural Testing (3-Point Bending)
Flexural properties of neat and CNF/PNCs, and the multiscale FRCs were
measured using a SATEC Apex T5000 mechanical testing instrument. A crosshead
speed of (1.15 mm min-1) and a span length of (48 mm) was used according to ASTM
D790. The ASTM D790 method was used to determine the flexural strength of the
CNF/PNCs and multiscale FRCs. The support span to depth ratio (L/d) was 16 to 1. The
experimental setup for the three-point bend is illustrated in Fig. 7 below.
29
Figure 7. Experimental setup for 3 point bending test
Flexural strength, σ f is determined for three-point bending from the relationship:
3PL
σf = (1)
2bd 2
where:
σ f = flexural strength, MPa (psi)

P= failure load, N (lbf)
L= support span of beam, mm (in)
b= width of beam tested, mm (in)
d= depth of beam tested, mm (in)
It should be noted that the above equation applies directly to materials for which the
stress is linearly proportional to strain up to the point of rupture and for which the strains
are small. Since this is not the case in reality, a slight error will arise when the equation
is used. It yields an apparent strength based on homogenous beam theory.
30
Short Beam Test (Interlaminar Shear Strength Test (ILSS))
The ASTM D 2344 test method was used to determine the interlaminar shear
strength of the neat and CNF/PNC multiscale FRCs. A crosshead speed of (1.00 mm
(0.05) min-1) was used. The support span to depth ratio (L/d) was 4 to 1. As shown in
Figure 7, this test method involves loading a beam under a three-point bending fixture
with a span to depth ratio (L/d) selected such that interlaminar shear failure is induced
rather than failure due to bending. For short beam shear test, the apparent ILSS, F sbs is
determined from the relationship:
3P
F sbs = (2)
4bd
where:
F sbs = flexural strength, MPa (psi)

P = failure load, N (lbf)
b = width of beam tested, mm (in)
d = depth of beam tested, mm (in)
It should be noted that proper precautions were taken to prepare the samples for testing.
A water-lubricated saw was used to obtain the samples final dimensions and the samples
were free of undercuts, notches, delaminated surfaces, and rough surfaces.
31
Morphology
Optical Microscopy (OM)
Optical microscopy was used to characterize the fracture surfaces of FRC samples
to confirm that delamination of the glass fiber laminates occurred at the glass fiber
laminate-resin interface during the ILSS test. Optical micrographs of the M-FRC
samples were taken using a AXIOPLAN 4MP stereomicroscope.
High Resolution Scanning Electron Microscopy (Hi-Res SEM)
High resolution scanning electron microscopy was used to analyze the
microstructure of the fracture surfaces of the CNF/PNCs and FRCs. This technique
provides an excellent view of the topology of fracture surfaces. SEM micrographs of a
freeze fracture surface of CNF/PNC and FRC samples were taken using a JEOL-7000F
with a 10-15 kV accelerating voltage.
32
CHAPTER 4
RESULTS AND DISCUSSION
Carbon Nanofiber Characterization
Raman Spectroscopy
The effect of CNF surface oxidation was investigated using Raman spectroscopy,
because Raman spectroscopy offers useful information concerning the structural changes
of CNFs, especially changes due to sidewall modification (37, 38). Fig. 8 shows the
Raman spectra of the (a) surface modified CNFs, as well as the (b) surface unmodified
CNFs. The peak at 1363 cm-1 is related to the disordered density of the sp3-hybridized
carbon atoms of the nanofiber and is designated as the D band, whereas the peak at the
1580 cm-1 is related to the ordered graphitic structure of sp2-hybridized carbon atoms of
the nanofiber and is designated as the G band. The D/G band ratio would then represent
the amount of sp3-hybridized carbon defects in the nanofiber due to the presence of
functional groups.
33
5500
5000
Intensity (Counts)
4500
4000
3500
1100 1200 1300 1400 1500 1600 1700 1800 1900

-1
R a m a n S h if t ( c m )
a)
6500
6000
Intensity (Counts)
5500
5000
4500
4000
3500
1100 1200 1300 1400 1500 1600 1700 1800 1900

-1
R a m a n S h ift ( c m )
b)
Figure 8. Raman spectra of a) unmodified CNFs b) modified CNFs, showing peaks at

1363 and 1580, referred to as the D and G bands respectively.
34
These defects (or functional groups) on the CNF now become potential reactive sites for
bonding with the polymer matrix. Thus, an increase in the D band intensity is indicative
of adding functional groups on the surfaces of the CNFs. Table 5 shows the D/G values
for both surface unmodified and modified CNFs. From these values it can be presumed
that the surface modification is due to the carboxylic acid oxidation that occurred.
Table 5. D-peak/G-peak values from Raman spectrometry for surface unmodified and
modified CNFs
Sample D Peak intensity G Peak intensity D/G value

Unmodified 239 1377 0.1735
Modified 566 2545 0.2223
Thermogravimetric Analysis
Thermogravimetric analysis (TGA) measures the amount and rate of change in
the weight of a material as a function of temperature or time in a controlled atmosphere.
Measurements are used primarily to determine the composition of materials and to
predict their thermal stability at temperatures up to 1000°C. The technique can
characterize materials that exhibit weight loss or gain due to decomposition, oxidation, or
dehydration. The total weight loss from the TGA experiments showed the effect that
carboxylic acid surface modification had on the CNFs results in a nitrogen atmosphere
was shown in Fig. 9 and results for tests in air are shown in Fig.10. The surface
unmodified CNFs showed no weight loss up to 777oC in nitrogen and suffered only a
0.07% weight loss up to that temperature. The surface modified CNFs showed a 1.35%
35
weight loss up to 820oC in air. The surface modified CNFs in nitrogen exhibited a 5%
weight loss on heating to 632oC. Interestingly, the surface modified CNFs in air
exhibited a 7% weight loss up to 769oC. The surface modified CNFs in both atmospheres
exhibited lower thermal stability than the unmodified CNFs suggestive of the
introduction of the carboxylic acid surface modification. The lower thermal stability of
the modified CNFs can be attributed to the functionalization moieties from the CNFs
surface.
TGA is useful for quantitatively determining the degree of functionalization of
CNFs. Sayes et al. used TGA to quantitatively determine the degree of surface
functionalization of fullerenes and SWNTs in an argon atmosphere (22, 23). To
Wl Wi -Wl
determine the degree of functionalization, this method uses the ratio: : ,
Wmol WC
where Wl is the weight loss of the grafted molecule, Wmol is the molecular weight of the
grafted functional group, Wi is the initial weight of the modified CNF and WC is the
molecular weight of carbon. The weight loss of the grafted molecule and the initial
weight of the modified CNF values are taken from the TGA thermogram. The molecular
weight of the carboxyl functional group is 45 g/mol, and the molecular weight of carbon
is 12 g/mol. The degree of functionalization was determined using TGA from 80oC to
600oC under a nitrogen atmosphere. The weight loss for surface modified CNFs was
5.082%. The weight loss of surface unmodified CNFs was 0% under the same
conditions. The degree of functionalization of (carbon/carboxyl functional group ratio)
for the surface modified CNF was determined to be 70. The degree of functionalization
is suggestive of one carboxyl functional group per every 70 carbon atoms on the CNF
surfaces.
36
105
495.33°C
99.93%
777.79°C
100
z z z z z z z z z z
z

z
397.14°C 632.06°C

95 97.07% 887.33°C
92.92%
z
Weight (%)

90 z

z
744.39°C
87.75%
85

z
––––––– CNF unmodified
80 – – –
– CNF modified

75
0 200 400 600 800 1000
Temperature (°C)
Figure 9. TGA thermograms of surface unmodified and modified CNFs in nitrogen
37
120
565.91°C
98.65%
100 z z 820.38°C
z z

z z z z z z
z
769.03°C

566.22°C z
80 92.97%
862.24°C
z
58.10%
Weight (%)
60
z

816.54°C
40 52.36%
z

z

20
z

0 z
––––––– CNF unmodified z

––––––– CNF modified
-20
0 200 400 600 800 1000
Temperature (°C)
Figure 10. TGA thermograms of surface unmodified and modified CNFs in air
38
X-ray Photoelectron Spectroscopy
X-ray photoelectron spectroscopy is extremely useful in studying the effects of
chemically surface modified nanoparticles. This technique is based on the observation of
electrons being emitted by atoms undergoing x-ray radiation. The energy of the emitted
electrons yields the binding energy of the electron from a particular atom. The energies
measured are characteristic of the elements and are sensitive to the electronic
environment of the atom. This technique is very useful in quantifying the chemical
species on the surface of nanoparticles. XPS was conducted to investigate the effect of
surface modification on the CNFs. The surface unmodified and modified CNF atomic
concentrations obtained from XPS are listed in Table 6.
Table 6. Atomic concentration of C1s and O1s obtained from XPS spectra
Sample C1s spectra O1s spectra
Unmodified 98.223 1.777

Modified 86.696 13.304
An XPS scan of the surface modified CNFs is shown in Fig. 11. The oxygen 1s peak is
broadened due to the presence of two types of oxygen bonded on to the CNF surface
(12). The 1s oxygen peak typically is due to doubly bonded oxygen (C=O), and single
bonded oxygen (C-O). The magnitude of the peak is proportional to the number of
surface atoms of each type. The percentage of oxygen on the CNF surfaces increased by
7.5 times due to surface modifying the CNFs with 3:1 H2SO4/HNO3. The atomic oxygen
on the surfaces of the CNFs is in the form of carboxylic acid (COOH) groups. Similar
39
studies by Glasgow (12) and Lakshminarayanan (39) use XPS to quantify the atomic
amounts of oxygen and other atoms on the surface of CNFs. Their findings show that
chemically modifying the CNFs with an oxidizing acid led to increased oxygen levels on
the surfaces of the CNFs.
3000
2500
2000
Counts
1500
1000
500
0
541 536 531 526 521
Binding Energy (eV)
Figure 11. XPS scan of the oxygen 1s peak of surface modified CNF
40
Epoxy-Carbon Nanofiber/Polymer Characterization
Dynamic Mechanical Analysis
Dynamic mechanical analysis (DMA) is used to determine the mechanical
properties (i.e., modulus and damping of viscoelastic materials) over a spectrum of time
(frequency) and temperature. DMA can detect molecular motions enabling the
development property-structure-morphology relationships. DMA was conducted to
investigate the effect of CNFs on polymer nanocomposite relaxation behavior. Plots of
the storage modulus (E’) versus temperature for the 1% CNF compositions and
dispersion methods are shown in Fig. 12. Table 7 shows the compositions of polymer
nanocomposites and their corresponding codes. The glass transition temperature can be
determined from the peak of the tan delta curves shown in Fig. 13 and the values are
listed in Table 8. Plots of E’ versus temperature for the 0.1% CNF compositions and
dispersion methods are shown in Fig. 14.
Table 7. List of samples and their corresponding codes
Sample Code
Neat Neat
Mechanical Mixed Surface Unmodified MMU
Mechanical Mixed Surface Modified MMM
High Shear Mixed Surface Unmodified HSU
High Shear Mixed Surface Modified HSM
41
Starting with the lowest CNF concentration of 0.1 wt%, the curves show essentially no
difference in the glassy state. However, as the temperature increases to the transition
region, the curves for both the HSM and MMM extend to higher temperatures than the
neat resin and unmodified sample, suggestive of higher glass transition temperatures
(Tgs). The values of the plateau modulus are also increased. The Tg for the MMM 0.1%
sample is higher than the HSM 0.1% sample as illustrated in the tan delta curves in Fig.
13 (see Table 8). When the CNF content is increased to 1%, more dramatic relaxation
behavior is observed, as shown in Fig. 14. While no significant difference is observed in
the glassy state, a marked difference in the slopes of the E’ decrease is observed in the
transition region. In addition, the plateau modulus increases by a few tens of MPa. Both
of these effects can be attributed to a reduction in molecular mobility, presumably caused
by enhanced epoxy-CNF interactions. The tan delta curves shown in Fig. 15 provide
additional insight into the relaxation behavior. Of particular note are the curves for the
1% modified samples. Both the MMM and HSM exhibit a first peak which is shifted to a
higher temperature relative to the neat and unmodified CNF samples, followed by a
second, higher temperature peak. The presence of the higher temperature peak in the
modified samples relative to the unmodified samples clearly suggest that there is an
interaction between the surface modified CNFs and the epoxy resin. It is also noted that
the magnitude of the tan delta peaks for the MMM and HSM samples is lower than that
for the neat epoxy and the MMU and HSU. The lower tan delta value is due to the more
elastic nature of the resin caused by the presence of the CNFs and the enhanced epoxy-
CNF interactions.
42
10000
z
––––––– Neat
– – –
– HSM 0.1%
z

z z z

––––– · HSU 0.1%
z

Storage Modulus (MPa)
z
1000

z

z

100
z

z

z
10 z z z z
1
20 40 60 80 100 120 140 160 180 200
Universal V4.2E TA Instruments
a) Temperature (°C)
10000
z
––––––– Neat
– – –
– MMM 0.1%
z z z z

––––– · MMU 0.1%
z

z
1000
z

z

100
z

z

z
10 z z

z z
1
20 40 60 80 100 120 140 160 180 200
Universal V4.3A TA Instruments
b) Temperature (°C)
Figure 12. Storage Modulus vs. Temperature curves of 0.1 wt% a) high shear mixed b)
mechanically mixed polymer nanocomposites
43
1
z

z
z

z
z

z

0.1 z

Tan Delta
z
z
z z z z z

z z
z

z z
z

zz
z
z
zz z
0.01 z
z zz
z
––––––– Neat
– – –
– HSM 0.1%

––––– · HSU 0.1%
0.001
20 40 60 80 100 120 140 160 180 200
1
z

z
z

z
z

z
0.1
z

Tan Delta

z
z

z z z z z

z
z
z

z z

z
zzz
z

zz z
0.01
z
z zz
z
––––––– Neat
– – –
– MMM 0.1%

––––– · MMU 0.1%
0.001
20 40 60 80 100 120 140 160 180 200
Figure 13. Tan delta vs. Temperature curves of the 0.1 wt% a) high shear mixed b)
44
Table 8. Glass transition temperature from the tan delta peaks a) HSM, b) HSU, c)
MMM, and d) MMU.
(a) HSM
CNF loading (%) Peak 1 (oC) Peak 2 (oC)

0 117 N/A
0.1 119 N/A
1.0 128 155
(b) HSU

0 117 N/A
0.1 117 N/A
1.0 126 N/A
(c) MMM

0 117 N/A
0.1 123 N/A
1.0 126 154
(d) MMU

0 117 N/A
0.1 115 N/A
1.0 126 N/A
45
10000
z
––––––– Neat
– – –
– HSM 1%
z

z
z z

––––– · HSU 1%
z

z

1000
z

z

100
z

z

z
10 z z z z
1
20 40 60 80 100 120 140 160 180 200
10000
––––––– Neat
z
– – –
– MMM 1%
z
z
z
z

––––– · MMU 1%

z
z
1000

z

z
100
z

z

z
10
z
z
z

z
1
20 40 60 80 100 120 140 160 180 200
Figure 14. Storage modulus vs. Temperature curves of the 1.0 wt% a) high shear mixed
b) mechanically mixed polymer nanocomposites
46
1
z
z
z

z
z

z
0.1 z

Tan Delta

z
z

z z z z z
z z

z
z z
z zz
z
z

zz z
0.01 z
z zz
z
––––––– Neat
– – –
– HSM 1%

––––– · HSU 1%
0.001
20 40 60 80 100 120 140 160 180 200
1
z

z
z

z
z

z
0.1
z

Tan Delta

z

z

z z z z z
z z
z
z z
z
zzz
z
zz z
0.01 z
z zz
z
––––––– Neat
– – –
– MMM 1%

––––– · MMU 1%
0.001
20 40 60 80 100 120 140 160 180 200
Figure 15. Tan delta vs. Temperature curves of the 1.0 wt% a) high shear mixed b)
47
Thermomechanical Analysis
Thermomechanical analysis (TMA) is used to measure the dimensional change
(i.e., CTE) in materials as a function of time, temperature and force in a controlled
atmosphere. TMA was conducted to investigate the effect that the CNFs had on CTE of
the polymer nanocomposites. The CTEs for the high shear samples were measured in
two directions, parallel and perpendicular to the shear direction to investigate if the effect
of alignment on CTE. The CNFs in the mechanically mixed samples are assumed to have
no orientation preference and no specific emphasis was made to investigate any
alignment effects. The CTE values of all of the PNC samples are listed in Table 9. The
neat epoxy resin sample had a CTE value of 85 ppmC-1. The 1 and 0.1% HSM
CNF/PNCs (parallel to the shear direction) samples showed the best property
enhancements with CTEs of 67 and 59 ppmC-1 respectively. The 1 and 0.1% HSM
CNF/PNCs (perpendicular to the shear direction) exhibited CTEs of 72 and 77 ppmC-1
respectively. The anisotropic CTE behavior observed suggests that the surface modified
CNFs play a significant role in lowering the CTE of the epoxy resin matrix. The CTE
values of the mechanically mixed samples fell in between the values of the high shear
samples and the neat epoxy resin sample. The nominal property enhancement for the
mechanically mixed samples is presumably due to poor dispersion and CNF aggregation
(9). Due to the entangled and curved nature of CNFs, processing thermoset polymer
nanocomposites using mechanical mixing may not be the best dispersal method in
disrupting CNF aggregation. The effect of surface modified CNFs on the CTE of the
CNF/PNCs is shown in Fig. 16. The samples made with surface modified CNFs have
48
better CTE properties relative to the samples made with surface unmodified CNFs, for
both mixing methods.
Table 9. CTEs (ppm/oC) of mechanically mixed specimens (a) (1.0 & 0.1% wt/wt
unmodified and modified CNF/PNCs) and (b) high shear (1.0 & 0.1% unmodified and
modified CNF/PNCs) and neat epoxy resin.
(a) Mechanical Mixed specimens
CNF loading (%) Unmodified Modified

0 85 85
0.1 82 (-3) 71 (-14)
1.0 81 (-4) 71 (-14)
(b) High Shear Mixed specimens
CNF loading (%) Unmodified Modified

0 85 85
0.1 (perpendicular) 66 (-19) 77 (-8)
1.0 (perpendicular) 75 (-10) 72 (-13)
0.1 (parallel) 65 (-20) 59 (-24)
1.0 (parallel) 69 (-16) 67 (-18)
Chen et al. observed that adding large amounts (2-52% vol/vol) of CNFs reduced the
CTE in their CNF/epoxy composites (15). The CNF/epoxy composites were fabricated
by stacking plies of CNF mats followed by infusion of epoxy resin into the plies and
compression molding. Chen and co-workers reported as CNF concentration increased
from (2-52% vol/vol) that the CTE of epoxy CNF/PNCs decreased from 31.29 ppmK-1 to
-0.11 ppmK-1 respectively (15). However, our 1 and 0.1 wt% HSM PNC samples
49
showed a 21 and 31% decrease respectively when compared to the Neat. The 1 and 0.1
wt% MMM PNC samples showed a 16.5% decrease when compared to the Neat sample.
The CTE decrease in our surface modified CNF/PNC samples is very significant
considering that we have a much lower volume fraction (0.54% vol/vol = 1 wt%) and
(0.054% vol/vol = 0.1 wt%), which is 4 times less than the Chen et al. reported 2%
vol/vol sample.
Interestingly, the 1 and 0.1% surface modified CNF/Epoxy PNCs made by both
methods show property enhancements relative to the neat epoxy resin sample indicating
that only small amounts of modified CNFs are needed to alter the dimensional stability of
the resultant polymer nanocomposites. Creating PNCs for high performance applications
will need maximum synergistic efforts between the processing approach and surface
modified nano-reinforcements.
50
1%
95
90
85 Neat
80 MMU
CTE (ppm/oC)
75 HSU pd
HSM pd
70 MMM
HSM pa
65 HSU pa
60
55
50
45
40
35
30
a)
0.1 %
100
95
90
85 Neat
MMU
80
CTE(ppm/oC)
HSM pd
75
MMM
70
65 HSU pd HSU pa
60 HSM pa
55
50
45
40
35
30
b)
Figure 16. CTE graphs of a) 1% samples b) 0.1% samples (pa = parallel), (pd =
perpendicular)
51
Epoxy-CNF/PNC Processing Analysis
Rheology is extremely useful in investigating the viscous (fluid), elastic (solid),
and viscoelastic (behaves both as a fluid and solid) states of matter. This technique is
used to determine the mechanical properties i.e., modulus and damping of fluid, solid and
viscoelastic materials over a spectrum of time (frequency) and temperature, detect
molecular motions and develop property-structure or morphology relationships.
A schematic of the device used to disperse the CNFs was shown in Fig. 4 in the
experimental section. Shearing through the syringe results in flow that can be described
8Q
by Pouiselle’s equation: ΔP = μ L , where ΔP is the pressure drop, µ is the viscosity,
π R4
Q is the flow rate, R is the radius, and L is the length. The shear rate for Newtonian
. 4Q
fluids can be described by: γ = , where Q is the flow rate. For non-Newtonian
π R3
fluids, the shear rate is an apparent shear rate (40). The shear rate can be determined by
using the experimental volumetric flow rate. Based on the inner orifice diameter (id)
0.202 cm the flow rate of the neat epoxy resin is 11.73 mLs-1 and the calculated shear rate
is 14495 s-1. The flow rates and apparent shear rates for the CNF/PNCs were calculated
and are listed in Table 10. As the CNF loading increased from 0 to 1% the flow rates
showed a decrease from 11.73 to 10.44 mLs-1. This change in flow rate was due to the
CNFs disrupting flow through the orifice. The apparent shear rates for the CNF/PNC
samples were lower than the shear rate of the neat epoxy resin, and can be attributed to
the CNFs obstructing flow through the orifice. A flow study was conducted to correlate
the rheological behavior of the fluid to the conditions experienced during flow. This was
measured by applying a steady shear flow to the samples.
52
Table 10. Flow Rates and Shear Rates
Sample Flow Rate (mLs-1) Shear Rate (s-1)

Neat 11.73 14495
0.1% unmodified CNF/PNC 10.68 13206
0.1% modified CNF/PNC 11.18 13813
1% unmodified CNF/PNC 10.50 12975
1% modified CNF/PNC 10.44 12907
Fig. 17 and Fig. 18 show the viscosity as a function of shear rate for the neat
sample and CNF/PNC samples based on unmodified and modified CNFs. The viscosity
of the neat epoxy resin is independent of frequency, consistent with behavior exhibited by
a Newtonian fluid. As the nanoparticle content increases, the behavior changes to that of
a complex fluid, with shear thinning behavior being exhibited at higher shear rates. The
low frequency range is useful for discerning differences in the structure of the systems.
As can be seen, the 1% unmodified and modified CNF/PNC samples exhibit high
viscosities at low shear rates. This behavior has been observed for other carbon based
nanoparticles dispersed in epoxy resins, including spherical particles and CNTs (41, 42).
The effect of surface modification on the flow behavior is examined by overlaying the
flow curves for the CNF/PNCs containing unmodified and modified CNFs, as shown in
Fig. 19. Both systems exhibit higher viscosities than the neat epoxy resin.
53
100.0
Unmodified 1% CNF/PNC
Umodified 0.1% CNF/PNC
Neat
viscosity (poise)
10.00
1.000
0.1000 1.000 10.00 100.0
shear rate (1/sec)
Figure 17. Unmodified CNF/PNCs
100.0
Modified 1% CNF/PNC
Modified 0.1% CNF/PNC
Neat
viscosity (poise)
10.00
1.000
0.1000 1.000 10.00 100.0
shear rate (1/sec)
Figure 18. Modified CNF/PNC samples
54
100.0
Modified 1% CNF/PNC
Unmodified 1%CNF/PNC
Modified 0.1% CNF/PNC
Unmodified 0.1% CNF/PNC
Neat
viscosity (poise)
10.00
1.000
0.1000 1.000 10.00 100.0
shear rate (1/sec)
Figure 19. Overlay of All CNF/PNC samples
55
Moreover, the 1% modified and unmodified CNF/PNC samples exhibit approximately
the same viscosity with respect to the other CNF/PNC samples. However, at high shear
rates the 1% modified CNF/PNC sample has a higher viscosity, suggestive of a highly
dispersed system and stronger epoxy resin-CNF interactions. On the other hand, the 1%
unmodified CNF/PNC sample exhibited more distinct shear thinning behavior, suggestive
that the CNFs are restricting resin flow at low shear rates, but at high shear rates the
CNFs do not restrict resin flow leading to the resin exhibiting shear thinning behavior,
indicative of CNF having poor dispersion. The behavior observed in this study has been
observed in studies using MWNTs (41, 43). Abdalla et al. studied the effect of interfacial
chemistry on molecular mobility and morphology of multi-walled carbon nanotubes
epoxy nanocomposite (43). The surfaces of the MWNT were functionalized with
fluorine and carboxylic acid groups. They report data similar to what is observed in this
study. It is interesting to note that their 0.1 and 1% COOH-MWNT samples exhibited
approximately the same viscosities at low shear rates. They show as the MWNT content
increases, that the viscosity increases. In both modified and unmodified CNF/PNC
samples in our study, similar behavior occurred. The studies by Kim et al. and Abdalla et
al. attributed the increase in viscosity is due to the presence of strong interfacial
interactions (41, 43). The high viscosity at low shear rates can be attributed to the
formation of a percolated structure by the CNFs. As the shear rate increases, the
percolated structure breaks down and results in all of the CNF/PNCs showing similar
viscosities at high shear rates. In light of this, shearing followed by curing allows the
well dispersed morphology to be locked in before aggregation can occur.
56
Morphology
High-Resolution SEM was used to characterize the dispersion of the CNFs in the
epoxy resin matrix. Representative samples of the 1% unmodified and modified
CNF/PNCs are shown in Fig. 19. The Hi-Res SEM images in Fig. 20a and Fig. 20b
shows fracture surfaces for the 1% unmodified CNF/PNC and 1% modified CNF/PNC
samples, respectively. Circles are used to show some regions where CNFs are present.
Fig. 20a shows that agglomerates are visible, indicative of a poor dispersion of the CNFs
within the epoxy resin matrix. Fig. 20b shows that the some CNF agglomerates are
present but the overall CNF dispersion is good in the epoxy resin matrix.
57
a)
b)
Figure 20. Representative samples of a) 1% unmodified CNF/PNC b) 1% modified

CNF/PNC
58
Flexural Testing (3-Point Bending)
3-point bending tests were conducted on the CNF/PNCs to investigate the effect
of the CNFs on the flexural properties of the epoxy polymer matrix. A plot of flexural
stress vs. strain for the neat, 0.1 and 1% CNF/PNCs are shown in Fig. 21. The flexural
strength of the 0.1 and 1% CNF/PNC samples decreased by 33.75 and 14.43%
respectively, relative to the neat sample. The flexural moduli of the 0.1% CNF/PNC
sample decreased by 8.23% while the 1% CNF/PNC sample increased by 11.92%,
relative to the neat sample. The decreased flexural strength is suggestive that possible
flaws or defects are present in the CNF/PNC samples. The decreased flexural modulus in
the 0.1% CNF/PNC sample is suggestive that the CNFs were not homogeneously
dispersed, leading to inefficient load transfer within the CNF/PNC. The flexural modulus
increase in the 1% CNF/PNC sample is suggestive that the CNF concentration is high
enough to provide more efficient load transfer.
Additional 3-point bending tests were conducted on 0.5, 2, and 4% CNF/PNC
samples to observe if varying CNF concentrations would show mechanical property
enhancements. A plot of stress vs. strain for neat, 0.1, 0.5, 1, 2, and 4 % CNF/PNC
samples are shown in Fig. 22. The results of flexural testing of all CNF/PNC samples are
listed in Table 11. All CNF/PNC samples show decreased flexural strength properties.
There is a 12.01% increase in flexural modulus in the 0.5% CNF/PNC sample relative to
the neat sample, followed by 11.92% and 5.81% increases in the 1% and 4% respectively.
The 20.92% decrease in flexural modulus for the 2% CNF/PNC sample is suggestive of
inhomogeneous CNF dispersion throughout the sample. The decreased flexural strength
is suggestive that possible flaws or defects are present in the CNF/PNC samples.
59
Figure 21. Flexural stress vs. strain of neat, 0.1 and 1% CNF/PNC samples
60
Figure 22. Flexural stress vs. strain of neat, 0.1, 0.5, 1, 2, and 4 % CNF/PNC samples
61
A similar effect has been shown by others, and generally has been attributed to poor
dispersion of the nanoparticles. Strength is very sensitive to flaws or defects within a
sample, and the inhomogeneous nanoparticle dispersion can be considered as flaws. In
addition, variations in crosslink topology can lead to molecular scale defects, such as
dangling chains which would result in strength decreases (16, 30, 44). Flaws and defects
can lead to inefficient load transfer within the CNF/PNC and subsequent premature PNC
fracture.
Table 11. Flexural strength and flexural modulus mechanical properties
Flexural Strength % Gain/Loss in % Gain/Loss in

Sample Modulus (GPa)
(MPa) Strength Modulus
Neat 118.5 (+/-10.7) 0 2.84 0
0.1% 78.5 (+/-9.2) -33.75 2.60 -8.23
0.5% 87.9 (+/-10.8) -25.82 3.18 12.01
1.0% 101.4 (+/-6.7) -14.43 3.18 11.92
2.0% 62.7 (+/-16.2) -47.08 2.23 -20.92
4.0% 37.8 (+/-3.1) -68.01 3.00 5.81
62
Multiscale Fiber-Reinforced Composite Characterization
Flexural Testing (3 Point Bending)
3-Point bending tests were conducted on M-FRC to investigate the effect of the
nanophased polymer matrix on the FRC. A plot of stress versus strain for the neat, 0.1
and 1% M-FRC samples are shown in Fig. 23. The results of flexural testing results of
the neat, 0.1, 1% M-FRC samples are listed in Table 12.
Table 12. Flexural strength and flexural modulus mechanical properties
Flexural Strength % Gain/Loss in Modulus % Gain/Loss

Sample
(MPa) Strength (GPa) in Modulus
Neat 336.8 (+/-6.5) 0 17.4 (+/-0.3) 0
0.1% 392.7 (+/-5.1) 16.61 21.05 (+/-1.1) 23.43
1.0% 404.2 (+/-18.6) 20.02 22.02 (+/-0.5) 26.44
The flexural strength of the 0.1 and 1% M-FRC samples increased by 16.61 and 20.02%
respectively, relative to the neat FRC sample. The flexural modulus of the 0.1 and 1%
M-FRC samples increased by 21.05 and 22.02% respectively, relative to the neat FRC
sample. The increased mechanical properties are suggestive of enhanced nanophased
polymer matrix-glass-fiber interfacial interactions. Qui et al. (33) studied
epoxy/MWNT/glass-fiber M-FRC using the VARIM process. They attributed the
observed mechanical property enhancements to enhanced polymer-nanoparticle-fiber
interfacial interactions.
63
Figure 23. Flexural stress vs. strain of neat, 0.1 and 1% M-FRC samples
64
Fig. 24a and Fig. 24b show Hi-Res SEM micrographs of the fracture surfaces of
0.1 and 1% M-FRC samples. Both M-FRC samples show that the fibers are embedded
within the matrix. It is obvious that the interfacial bonding between the nanophased
polymer matrix and glass fiber was so strong that the nanophased polymer matrix
deformed significantly during fracture. The embedded glass-fiber remains in the
nanophased polymer matrix until the fiber broke creating a fracture surface. Since the
breaking of the fiber consumed a significant amount of energy, the failure method
achieved an efficient load transfer between the reinforcing constituent (glass-fiber) and
the nanophased polymer matrix, which improved the mechanical properties of the M-
FRC samples. At higher magnification, the 1% M-FRC sample shown in Fig. 25a and
Fig. 25b, show that CNFs are pulled out of the matrix during fracture. In Fig. 25a, many
CNFs are visible in the nanophased polymer matrix. Some CNFs experience fiber
pullout due to the M-FRC undergoing fracture and other CNFs remain embedded within
the nanophased polymer matrix. In Fig. 25b, some CNFs experience fiber pullout and lay
adjacent to the micron-sized glass-fibers. At high magnification, similar behavior was
not observed for the 0.1% M-FRC sample. This was due to a combination of two
limitations; the low concentration of CNFs and the brittle fracture behavior of the
nanophased polymer matrix.
65
a)
b)
Figure 24. Hi-Res SEM micrographs of a) 0.1% and b) 1% M-FRC samples
66
a)
b)
Figure 25. Hi-Res SEM micrographs of 1% M-FRC samples a) 4000X b) 4500X
67
Interlaminar Shear Strength Testing
Interlaminar shear strength (ILSS) testing was conducted on the M-FRC to
understand the failure mechanism within the M-FRC samples. The high performance
capability of glass-fiber FRCs is certainly related to the wettability of its surface by the
matrix resin. A plot of shear strength vs. strain of the neat, 0.1 and 1% M-FRC samples
is shown in Fig. 26. The results of interlaminar shear strength testing of all M-FRC
samples are listed in Table 13.
Table 13. Shear strength and flexural mechanical properties
Interlaminar Shear Strength

Sample % Gain/Loss in Strength
(MPa)
Neat 35.49 (+/-1.8) 0
0.1% 43.85 (+/-1.0) 23.55
1.0% 38.48 (+/-2.5) 8.42
The 0.1% M-FRC sample shear strength showed a 23.55% increase relative to the neat
FRC sample. Interestingly, the 1% M-FRC sample shear strength showed a nominal
increase 8.42% relative to the neat FRC sample. The small increase in the 1% M-FRC is
suggestive of an inhomogeneous dispersion of the CNFs within the nanophased polymer
matrix and/or inhomogeneous wetting of the glass-fibers with the nanophased polymer
matrix. This is caused by the CNFs being filtered by the glass-fiber preforms during M-
FRC fabrication using the VARIM process. The cross-sectional fracture surfaces of the
neat, 0.1 and 1% M-FRC samples representative optical micrographs are shown in Fig.
27a, Fig. 27b, and Fig. 27c, respectively.
68
Figure 26. Shear strength vs. strain of neat, 0.1 and 1% M-FRC samples
69
a)
b)
c)
Figure 27. Cross-sectional fracture surface optical micrographs of a) neat, b) 0.1% c) and
1% M-FRC samples
70
All of the M-FRC samples fail in shear. In Fig. 27a, the neat FRC shows that the crack
begins at the matrix-glass-fiber interface and propagates through the matrix and is
blunted by the glass-fiber. In Fig. 27b, the 0.1% M-FRC sample shows that the crack
propagates along the nanophased polymer matrix-glass-fiber interface. In Fig. 27c, the
1% M-FRC sample shows that the crack propagates into the cross-section of glass-fiber
tow. The increase in ILSS is suggestive that the surface modified CNFs do not
compromise the epoxy resin ability to effectively wet the glass-fibers. Dean et al. (30)
Haque et al. (31) and Kornmann et al. (32) used LS as the nanoconstituent in their
nanophased matrix and glass-fibers as the reinforcement component to fabricate M-
FRCs. They observed substantial improvements in ILSS, and concluded that the ILSS
improvements were due to efficient load transfer between the nanophased polymer matrix
and the reinforcing component.
Dynamic Mechanical Analysis
Dynamic mechanical analysis was conducted to investigate the effect of the
nanophased polymer matrix on the M-FRC relaxation behavior. A plot of storage
modulus (E’) vs. temperature and tan delta vs. temperature is shown in Fig. 28a and Fig.
28b respectively. The results from dynamic mechanical analysis of all M-FRC samples
are listed in Table 14.
71
1.000E10 0.1% FRC sample
1% FRC sample
Neat
G' (Pa)
1.000E9
1.000E8
25.0 50.0 75.0 100.0 125.0 150.0 175.0 200.0
temperature (°C)
a)
1.000 0.1% FRC sample
1% FRC sample
Neat
tan(delta)
0.1000
0.01000
25.0 50.0 75.0 100.0 125.0 150.0 175.0 200.0
temperature (°C)
b)
Figure 28. a) Storage modulus vs. temperature curves and b) tan delta vs. temperature
curves of neat, 0.1, and 1% M-FRC samples
72
Table 14. Storage Modulus and Glass Transition Temperature
Storage Modulus in Glass Transition

Sample % Tg Improvement
glassy region (GPa) Temperature (oC)
Neat 4.24 78 0
0.1% 4.97 103 32.05
1.0% 4.43 103 32.05
The 0.1 and 1% M-FRC sample showed an increase in E’ in the glassy region of 17 and
4.5% respectively, relative to the neat FRC sample. The increase in E’ in the M-FRC
samples is suggestive that M-FRC samples have a well dispersed nanophased polymer
matrix and enhanced interfacial bonding. However, as the temperature increases to the
transition region, the curve for both 0.1 and 1% extend to higher temperatures than the
neat sample, suggestive of higher Tgs. The Tgs were obtained from the maximum of the
tan delta peak in Fig 28b. Interestingly, the Tgs of 0.1 and 1% M-FRC samples increased
by 25 oC, relative to the neat FRC sample. However, when the CNF content increased
from 0.1 to 1%, no significant increase in Tg was observed. The Tg increase observed in
the M-FRC samples relative to the neat FRC sample is suggestive of an increase in
crosslink density, mechanical reinforcement arising from a percolated CNF morphology,
and/or restriction of segmental relaxation of chain segments near the CNFs. Enhancing
the nanophased polymer matrix relaxation behavior allows for enhancing the M-FRC
relaxation behavior.
73
Thermomechanical Analysis
Thermomechanical analysis was conducted to investigate the effect of the
nanophased polymer matrix on the CTE of M-FRC. The CTE values of all FRC samples
are listed in Table 15.
Table 15. CTEs (ppmC-1) of the neat, 0.1 & 1% samples
Sample CTE value (ppm/oC) % Reduction

Neat 71 0
0.1% 44 37
1.0% 33 53
The neat FRC sample had a CTE value of 71 ppmC-1. The 0.1 and 1% M-FRC samples
show CTE values of 44 and 33 ppmC-1 respectively. In light of this, the 0.1 and 1% M-
FRC samples show a 37 and 53% decrease respectively, relative to the neat FRC sample.
Interestingly, both M-FRC samples show that substantial property enhancements relative
to the neat sample are obtainable with small amounts of surface modified CNFs. This
suggests that small amounts of CNFs significantly alter the dimensional stability of the
nanophased polymer matrix, and as a result will significantly affect the dimensional
stability of M-FRC.
74
CHAPTER 5
CONCLUSIONS
We have studied the processing-property relationships of M-FRCs with a
hierarchal microstructure ranging from nanoscale fibers to micron size fibers have been
studied. Surface modification of the CNFs promoted dispersion of the CNFs in the epoxy
resin and led to enhanced relaxation behavior (Tg) and thermal dimensional stability
(CTE) in the CNF/PNC nanophased matrix. Enhancing the CNF/PNC nanophased
matrix properties allows for the development of M-FRCs with improved properties.
Addition of the CNF in the epoxy resin results in a nominal increase in resin viscosity,
and is within the desired range for VARIM processing. Multiscale fiber-reinforced
composites were prepared using a combination of VARIM and compression molding.
The Tgs of the M-FRC samples increased (25oC) for both 0.1 and 1% M-FRC
samples respective to the neat FRC sample. The CTE properties improved (37-53%) for
both M-FRC samples respective to the neat FRC sample. The resulting 0.1 and 1% M-
FRCs exhibited a maximum flexural strength and modulus enhancement (16-20%) and
(23-26%) respectively. The 0.1% M-FRC sample showed a 23% increase in ILSS, while
the 1% M-FRC showed a nominal increase in ILSS (8%). The small increase in ILSS for
the 1% M-FRC sample is due to an inhomogeneous dispersion of the CNF/PNC
nanophased matrix within the M-FRC caused by filtering of the CNFs by the glass-fiber
75
preforms during VARIM processing of M-FRC. The enhanced relaxation behavior,
thermal dimensional stability and mechanical properties in the 0.1 and 1% M-FRCs may
be due to synergistic interfacial interactions between the CNF/PNC nanophased matrix
and glass-fibers.
The M-FRCs thermomechanical and mechanical property enhancements attained
with very low filler loaded-nanophased matrices coupled with the ease of production
makes them a very promising new class of materials. The unique combination of their
key properties and potential low production costs paves the way for their usage in an
array of potential applications. The very low filler amount needed to result in property
enhancements make them competitive with other materials.
76
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MULTISCALE FIBER REINFORCED COMPOSITES USING A CARBON

NANOFIBER/EPOXY NANOPHASED MATRIX: PROCESSING, PROPERTIES,

KEITH JAMAHL GREEN

DERRICK R. DEAN, COMMITTEE CHAIR

Submitted to the graduate faculty of the University of Alabama at Birmingham,

KEITH JAMAHL GREEN

Fiber-reinforced polymer composites (FRCs) have shown great promise as high

recreational equipment material applications. Research in polymer-based

emphasis focused on PNC using thermosetting polymer matrices. Modifying

material termed multiscale fiber-reinforced composites (M-FRCs).

The current research addresses carbon nanofiber (CNF) surface modification,

carbon nanofiber/epoxy polymer nanocomposite (CNF/PNC) development and M-FRC

fabrication. Vacuum assisted resin infusion molding (VARIM) is used to produce M-

a CNF/PNC nanophased polymer matrix is presented and thoroughly investigated.

and 1 wt% M-FRCs and compared with the neat FRC.

samples, respectively. Coefficients of thermal expansion (CTE) properties of the

respectively. Flexural studies indicated increases in flexural strength (16-20%) and

CNF/PNC samples are believed to be due to achieving good nanoparticle dispersion.

synergistic interactions between the CNF/PNC nanophased matrix and glass-fiber

I dedicate this academic and professional achievement to my Lord and Savior

I especially would like to thank my colleagues in the Polymers Research Group

(Mohamed A. Abdalla, Moncy V. Jose, Himani D. Deshpande, Ayesha Swarn, Brian W.

greatly needed electron microscopy micrographs.

enabled me to fulfill my true destiny.

LIST OF TABLES ........................................................................................................... viii

LIST OF FIGURES ........................................................................................................... ix

Polymer Matrix Materials ..............................................................................................1

2 LITERATURE REVIEW ............................................................................................13

4 RESULTS AND DISCUSSION ..................................................................................33

Carbon Nanofiber Characterization .............................................................................33

LIST OF REFERENCES ...................................................................................................77

1 Commonly used polymer matrix materials ......................................................................2

2 Comparison of fiber-reinforcements ................................................................................9

3 Properties of EPON 815C epoxy resin ..........................................................................22

4 Properties of PR-19-HT CNFs .......................................................................................23

5 D-peak/G-peak values from Raman spectrometry for

7 List of samples and their corresponding codes ..............................................................41

8 Glass transition temperature from the tan delta peaks

9 CTEs (ppm/oC) of mechanically mixed specimens

10 Flow Rates and Shear Rates .........................................................................................53

11 Flexural strength and flexural modulus mechanical properties ...................................62

12 Flexural strength and flexural modulus mechanical properties ...................................63

13 Shear strength and flexural mechanical properties ......................................................68

14 Storage Modulus and Glass Transition Temperature...................................................73

15 CTEs (ppmC-1) of the neat, 0.1 & 1% samples............................................................74

1 Idealized chemical structure of an epoxide ring ..............................................................3

2 The cure chemistry mechanisms involving epoxy with

3 Chemical structure of diglycidyl ether of bisphenol-A

4 Idealized cure chemistry of DGEBA epoxy resin and

5 a) Mechanical Mixing and b) High Shear Mixing apparatuses ....................................25

6 Setup of VARIM process ..............................................................................................26

7 Experimental setup for 3-point bending test ..................................................................30

8 Raman spectra of a) unmodified CNFs b) modified CNFs, showing

9 TGA thermograms of surface unmodified and modified CNFs in nitrogen ..................37

10 TGA thermograms of surface unmodified and modified CNFs in air .........................38

11 XPS scan of the oxygen 1s peak of surface modified CNF .........................................40

12 Storage Modulus vs. Temperature curves of 0.1 wt%

13 Tan delta vs. Temperature curves of the 0.1 wt%

14 Storage modulus vs. Temperature curves of the 1.0 wt%

15 Tan delta vs. Temperature curves of the 1.0 wt%

16 CTE graphs of a) 1% samples b) 0.1% samples (pa = parallel),

17 Unmodified CNF/PNCs ...............................................................................................54

18 Modified CNF/PNC samples .......................................................................................54