Perspective

pubs.acs.org/Macromolecules

Polymer/Nanoparticle Interactions: Bridging the Gap

Yogendra Narayan Pandey, George J. Papakonstantopoulos, and Manolis Doxastakis*,

Department of Chemical and Biomolecular Engineering, University of Houston, Houston, Texas 77004, United States

Global Materials Science Division, The Goodyear Tire & Rubber Company, Akron, Ohio 44316, United States

ABSTRACT: Materials created by dispersing nanoparticles in a

polymer matrix strive to meet the promise of enhanced and often
unique properties at a reduced cost. The availability of structure
property relationships and predictive modeling are deemed necessary to
tailor materials according to our needs. However, the road from detailed
information at the atomistic level to macroscopic properties has been
severely segmented due to diverse experimental, theoretical, and
modeling methods employed to study polymerparticle mixtures,
each with their own advantages and limitations. In this Perspective, we
focus on seemingly simple polymernanoparticle mixtures where
nanoparticles are bare or grafted with chains of the same chemical
constitution as the matrix. We present a number of studies that attempt to quantitatively identify where complete miscibility is
achieved. As we discuss, features pertaining to the nanoscale dimensions of particles continue to challenge our fundamental
understanding on polymerparticle interactions. However, through a concerted approach of theory, experiments, and
simulations, recent studies signicantly expand our knowledge on the morphological behavior of these systems. Most
importantly, our discussion demonstrates how new developments bridge knowledge of microscopic interactions with
thermodynamic behavior, an achievement that has far more reaching implications in the area of polymerparticle mixtures.

INTRODUCTION
Polymerparticle mixtures represent an exemplary manifes-
predict such interactions in the absence of experimental input.
We tactically refrain from referring to important developments
that pertain i.e. to particle shape, multicomponent matrices,
tation of the persistent and critical link between structure and
self-assembly, dynamics, metastable states, and other features of
property in synthetic materials oering improved mechanical,
particle mixtures; each of these subjects deserves their own
electrical, barrier, re-retardant, and optical properties. Our
independent survey and is beyond the scope of this Perspective.
knowledge accumulated over many decades of research in
However, despite our focus on the miscibility point, the studies
composite materials continues to be challenged by recent
presented are anticipated to have far more reaching
progress in manipulating structure at the nanoscale.1 Prescrib-
implications on our ability to tailor dispersion and properties
ing design rules to achieve the desired morphology is based on
of the resulting material.

our fundamental understanding of polymerparticle interac-
tions and our ability to predict thermodynamics a priori to the
synthesis of the material. To this extent, molecular theories and
modeling have made large contributions in recent years, and
our purpose herein is to provide selected examples of exciting
developments in characterizing such interactions that drive
macroscopic behavior. In addition, results presented highlight
persisting limitations and opportunities for future research.
Several reports in the literature provide comprehensive
reviews of developments in the area of nanocomposites15 or
target selected subjects, such as modeling methods, pertaining
to the interest and expertise of the readers and authors.610 In
this Perspective, we present a selected small number of studies
driven by the same aim as our own research endeavorsto
advance fundamental knowledge and establish predictive routes
that link chemical detail to macroscopic properties. More
specically, we report on several recent intriguing ndings,
mainly within the past three years, that attempt to address how
polymerparticle interactions change as we transition from the
colloidal limit (or at surface) to the nanoscale, the impact of
such eects on the miscibility point, and nally how can we
SIGNIFICANCE OF POLYMERNANOPARTICLE
INTERACTIONS
Molecular theories have made paramount progress in
predicting equilibrium phase behavior and macroscopic proper-
ties of polymer nanocomposites. A diverse range of theoretical
methods that include integral equation theory, density
functional theory, and self-consistent mean-eld theory are
continuously developed and applied to broaden our knowl-
edge.1118 As an example, complete phase diagrams, such as
shown in Figure 1a, are capable of describing the thermody-
namics of nanoparticles within a polymer matrix as a function
of interfacial attraction strength in units of thermal energy.
Explicit in these diagrams are the boundaries of a miscible
phase between depletion-governed aggregation and bridging
states.
Received: March 1, 2013
Revised: May 14, 2013
Published: June 4, 2013

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Macromolecules
Figure 1. (a) Nanoparticle volume fraction at spinodal phase
separation predicted by PRISM theory for hard spheres in a freely
jointed chain polymer melt as a function of the strength of exponential
interfacial attraction. The depletion and bridging induced phase
separated regimes bracket a window of miscibility at intermediate
interfacial cohesion strength. The type of polymer-mediated nano-
particle organization is schematically indicated. Reproduced with
permission from ref 16. Copyright 2010 Elsevier. (b) Three-
dimensional representation of domains of high-shear modulus for a
solid nanocomposite. Reproduced with permission from ref 20.
Copyright 2007 the American Physical Society.
A critical part of theoretical methods is the ability to
quantitatively describe interfacial layers surrounding nano-
particles, regions with distinct properties from the bulk polymer
phase. Kim et al. using contrast-matching small-angle neutron
scattering characterized such interfacial layers by measuring
partial collective structure factors in stable concentrated ternary
solutions of short-chain polymers, nanoparticles, and solvent.19
It was demonstrated that predictions by the microscopic
polymer reference interaction site model (PRISM) theory were
in quantitative agreement with experimental data. PRISM
theory employs a freely jointed chain and an exponential
monomerparticle interfacial attraction as the only adjustable
parameter to extract information on the overall spatial
organization of the mixture. One intriguing prediction made
was that in the case of particles of nanoscale size in the miscible
region, lowering interfacial interactions toward the depletion
aggregation boundary should make the composite material
stier.15,19 In general, theoretical modeling oers explicit
knowledge of the introduced parameters and approximations
made and is often the most versatile and ecient technique to
rationalize experimental behavior. Nevertheless, echoing Hall et
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Perspective
al., it is imperative to couple predictions with computer
simulations to create necessary benchmark tests for the
structure and properties that are free of unavoidable statistical
mechanical approximations present in theoretical modeling.16
Computer simulations can characterize dispersion, uctua-
tions, and heterogeneities in mechanical properties, provided
that judicious measures of interfacial segmentparticle
interactions are introduced. As an example, Papakonstantopou-
los et al. have used molecular simulations to quantify
mechanical heterogeneities in a polymer nanocomposite.20,21
They explicitly identied regions of high-shear modulus
domains in lled and unlled systems and the morphological
behavior of these mechanical heterogeneities (Figure 1b) in
addition to the distribution of the llers in their systems. A
propensity of high modulus domains was found close to llers
of favorable interactions to the polymer and also between such
llers. When dealing with such systems of even simplied
models of particlepolymer mixtures, adequate sampling
remains a challenge, and application of Monte Carlo strategies
that assist to overcome connectivity limitations is critical for
equilibration purposes.2225
Clearly, the accuracy of theoretical predictions and computer
simulations depends on our ability to quantitatively characterize
interfacial interactions. In fact, even the presence and the extent
of a polymer layer with altered characteristics from the bulk
material continues to be a subject of experimental investigation.
Often contradictory ndings are reported depending on sample
preparation, technique employed, and system studied.2628 We
briey add that the optimum dispersion state for reinforcement
does not necessarily translate to overall improved material
characteristics.1 Most importantly, it was recently shown that
for the same nanocomposite material spatial dispersions that
optimize properties are sensitive to state (melt versus glass).29
Such ndings stress our need for modeling that accurately
accounts for the overall eective polymerparticle interactions
(as they emerge by the interplay of enthalpic and entropic
contributions) and provides unequivocal guidance to materials
design. To support our view, we selectively discuss recent
progress made on our understanding and modeling of such
interactions at the nanoscale and how they impact the
miscibility state point in a polymerparticle mixture.
INTERFACIAL INTERACTIONS AND GRAFTED
NANOPARTICLE SYSTEMS
Grafting is a common method to alter the interactions between
the polymer matrix and the dispersed nanoparticles.1,30 In some
cases, controlled grafting can be exploited not only to achieve
miscibility but also to tailor the shape of aggregates formed in
the immiscible regime of the phase diagram.3133 Concepts of
polymer brushes have long been explored by seminal
contributions in the eld of polymer science,3446 and the
reader interested in theoretical and simulation aspects is
referred to a comprehensive review by Binder and Milchev.47
We consciously restrict ourselves to recent ndings on the
autophobic eect as it applies in nanoparticle systems.
In the special case where grafted chains and polymer matrix
are of identical chemistry, no disparity in enthalpic interactions
between segments of these components exists. At intermediate
grafting density, the phase behavior of the nanoparticle
polymer mixture is governed by the mixing entropy of free
chains exploring the additional volume within the grafted layer
and the elastic free energy cost of stretching for the grafted
chains. The key parameter is then the ratio between the length
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Macromolecules Perspective

of grafted chains (N) and free chains (P): R = N/P.48,49 When

free chains are shorter, they are able to penetrate into the
grafted layer leading to a wet brush. As a result, particles can
be well-dispersed into the matrix. In contrast, for short grafted
chains, free polymer molecules are expelled, the brush becomes
dry, and particles aggregate. The wetting region is bound by
two grafting density limits: a lower * and a higher **. A
theoretical phase diagram for this autophobicity as calculated
for a at surface (or particles with low curvaturecolloidal
limit) is shown in Figure 2a with * scaling as P1/2 and **,
characterizing the boundary of a second-order autophobic
transition, similar to P1/2 or P3/2.44,48
The application of this wet-to-dry transition to control the
dispersion of silica nanoparticles grafted with polystyrene (PS)
chains in a PS matrix was recently studied by Chevigny et
al.4951 A combination of neutron scattering with contrast
variation was employed to extract the conformation of the
grafted brushes in the matrix while X-ray scattering and
microscopy assessed the dispersion state. While it was evident
that tuning the length of the grafted chains provides a unique
tool to tailor dispersion, the exact boundaries of this transition
did not conform to theoretical predictions. Nanoparticles were
well-dispersed for values of R = N/P > 0.24, suggesting that
aggregation required much longer free polymer chains. This
mismatch was attributed to processing kinetics, chains
polydispersity eects, or surface curvature.49
At the nanoparticle limit, the increased curvature of the
grafted particle reduces the crowding of grafted chains,
eectively assisting free molecules to wet the brush. Self-
consistent eld theoretical calculations by Trombly and
Ganesan studied the limit of nanoparticles showing explicit
changes in the width of the grafted polymerfree polymer
interface as a function of R and curvature.13 Calculations
supported that curved systems are less sensitive to grafting
densities than what may be expected from considerations
pertaining to at surfaces. In addition, the matrix molecular
weight has to be increased further than the corresponding at
surface in order to induce a dewetting transition. These
advantages of highly curved nanoparticles were also brought
forward in a molecular dynamics simulation by Smith and
Bedrov, employing a beadspring model for short grafted
chains (N = 10) and free polymer molecules (P = 10140).54
Signicantly longer beadspring models (above the entangle-
ment threshold) were studied by Kalb and co-workers55
employing connectivity-altering algorithms (N = 501, P =
1000) and variable grafting density. Surprisingly, after detailed
comparison to theoretical scaling laws, no signature of
dewetting phenomena was observed, a feature attributed to Figure 2. (a) Theoretical phase diagram in terms of the grafting
the nite size of melt chains studied which displayed density and the length of the chains of the polymer melt P for a
comparable size to the interface width. In addition, ends of constant graft length of N = 200.48 Reproduced with permission from
tethered chains presented a higher probability to reside in ref 48. (b) Phase diagram for 10 nm PS-g-silica nanoparticles dispersed
proximity to the nanoparticle surface compared to earlier in PS matrices as determined by X-ray scattering and transmission
theoretical predictions.55 The latter nding provides an electron microscopy. Reproduced with permission from ref 52. (c)
Phase diagram for suspensions of 10 nm PEG-g-silica nanoparticles in
example of the necessity to complement theoretical predictions polymeric hosts. Black symbols represent well-dispersed systems, red
with accurate numerical calculations. A subsequent study with symbols denote completely phase-separated systems, and orange
similar models (N = 30, 60, P = 10140) supported that while symbols denote partially phase-separated systems. Lines correspond to
the interface for a single nanoparticle does not provide any theoretical predictions for dewetting based on at surfaces.
signature of autophobic dewetting in a regime where such a Reproduced with permission from ref 53.
feature is expected, matrix-induced depletion attractions from
free chains on a pair of nanoparticles dominate the free energy chains. This is even more signicant at low-grafting densities
prole at intermediate separations.56 Thus, while aggregation where it was recently shown that grafted particles can self-
remains entropic in origin, it is essential to consider collective assemble to anisotropic shapes.31 At this limit, favorable
anities to form clusters in the presence of long free polymer particleparticle interactions compete with the polymer brush
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Macromolecules
free energy; redistribution of the brush favors aggregation at the
point diametrically opposite to the rst contact. As a result,
interactions between the particles become eectively aniso-
tropic. Formation of self-assembled structures provides an
additional level of control to the structure and properties of the
polymerparticle mixture.29 We believe that a quantitative
characterization of such many-body eects by calculations of
free energy changes to form shapes in an explicit polymer
matrix would contribute to our understanding of the miscibility
limit and identication of metastables states.
New additional experimental studies continue to supply data
on the thermodynamics of grafted nanoparticles in a polymer
matrix forming complete phase diagrams. Sunday et al.
employed X-ray scattering and microscopy to study silica
nanoparticles grafted with PS chains (PS-g-silica) in a PS
matrix.52 As shown in Figure 2b, the P/N ratio for certain
grafting densities could reach values up to 4.3 before
aggregation was observed. The power laws extracted follow
* P0.54 and ** P0.71. A dierent report for
poly(ethylene glycol) (PEG) tethered silica nanoparticles
dispersed in PEG hosts53 presented a phase diagram that
bears some similarities to the data by Sunday et al. Specically,
Srivastava et al. argued that while indeed the P/N ratio can be
as high as 5 maintaining a well-dispersed state, above a certain
threshold (required to ensure screening of attractive forces)
dispersion becomes independent of grafting density. However,
a low particle diameter to size of grafted chains (D/Rg) ratio
was necessary in order to maximize curvature eects at the
small particle limit. Furthermore, by summarizing the results
from previous studies (Figure 2c), it was argued that the phase
diagram is independent of polymer chemistry.53 We note that
theoretical modeling has stressed the role of particle size and, in
addition, new simulations suggest that polydispersity eects can
alter these boundaries.57,58
Accounting for polymer chemistry remains a daunting task
for computer simulations. Studies are limited to a single or a
pair of particles at most, immersed in oligomers.59,60 Ndoro
studied atomistic models of PS-g-silica (N = P = 20),
conrming geometric eects (higher available volume around
a small nanoparticle) as discussed earlier.61 Peters et al.
performed atomistic simulations with silica particles grafted
with linear hydrocarbon chains (N = 9, 17, 35) in explicit
solvents (P = 10, 24, 48 and a branched solvent),62 and
Ghanbari et al. built coarse-grained (CG) models of PS and
silica to extend the work of Ndoro to N = 80 and P = 20
160.63 The last two studies have shown evidence of free chain
migration out of the interfacial region which do support a wet-
to-dry transition. We clarify though that lengths reported in
these works correspond to repeat units and not Kuhn segments.
So the chains are shorter than in the systems employed by Kalb
and co-workers.55
Brute-force atomistic modeling will remain severely limited
within the foreseeable future in addressing truly polymeric
systems. Long relaxation times restrict sampling in the vicinity
of the initial state and hinder our ability to quantify
thermodynamics of mixing. However, chemically specic CG
models provide signicant promise depending on the ability of
simplied representations to reproduce the target structure
including interfacial layers. Coupling such models with
advanced simulation methods can expand the range of
molecular weights studied. For example, Spyriouni and co-
workers modeled bulk CG PS systems up to P = 100064
through connectivity-altering Monte Carlo (MC) methods. It is
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Perspective
also worth noting that our past work has demonstrated how we
can apply preferential sampling schemes, focusing computa-
tional eort in proximity to the surface and enhancing further
sampling.24 This technique is particularly benecial when large
systems are considered, necessary to avoid nite-size eects due
to periodic boundary conditions.
POLYMER-SEGMENT/PARTICLE INTERACTIONS:
ACCOUNTING FOR CHEMICAL DETAIL
Polymer chemistry relies on an ever-growing gallery of chemical
repeat units to synthesize materials with desired properties. The
majority of the theoretical and modeling results presented
earlier require input or introduce approximations at the level of
polymer-segment/particle interactions. Thus, a question that
pertains to our discussion is whether interfacial phenomena
between nanoparticles and polymers can be predicted without
experimental characterization. Toward this aim, the eld of
quantum mechanics has made signicant progress in the past
decade.65 We anticipate that overcoming challenges associated
with translating results from electronic calculations to polymer/
particle interactions will be in the center of future modeling
eorts. We refer readers to a recent article that provides an
excellent overview of the challenges faced66 and detail selected
important points. Quantum calculations targeting interactions
between small compounds and surfaces predict dierent
absolute energies depending on the method employed.
Nevertheless, it is the relative energies between adsorption
sites and the monomer states that are important. Such energies
need to be reproduced by classical force elds introduced in
molecular simulations. This is veried by performing distance-
dependent scans as well as lateral- and orientation-dependent
evaluations.66 These tests are critical to ensure that a
representative ensemble of congurations as a function of a
multitude of order parameters is retrieved by force-eld
simulations. Figure 3 depicts interaction energies between a
single PS monomer and a gold surface as calculated by density
functional theory.67 Johnston and Harmandaris stressed the
need to introduce a Morse functional form in classical modeling
to simultaneously capture both distance and orientation
dependent interaction energies. These potentials were sub-
sequently employed in classical molecular dynamics simulations
to study the properties of short polystyrene chains conned
between two gold surfaces.67 It is noted that a building-block
approach, where interactions of a specic segment extracted by
electronic calculations are treated in an additive approach to
model macromolecules on surfaces,6871 remains highly
nontrivial. A large challenge in these methods is the interplay
of enthalpic contributions with nonlocal entropic eects that
are dicult to account for in original electronic calcula-
tions.66,72 We note, therefore, that translating chemically
specic segment interactions to polymeric molecules is an
area that requires particular development.
Challenges discussed in bridging quantum calculations to
classical atomistic force elds pertain to methods available to
systematically derive CG models.73,74 However, signicant
progress has already been made, and it is now feasible to build
polymersegment interactions based on input from atomistic
simulations with classical force elds. As mentioned earlier, PS-
g-silica nanoparticles in a PS matrix were studied by Ghanbari
and co-workers employing such a scheme.63 In their study, Si
atoms served as the centers of interaction sites with a polymer
CG segment and pairwise interaction potentials were
determined through the iterative Boltzmann inversion (IBI)
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Figure 3. Adsorption energy of PS monomer as a function of the
distance from a gold surface. The density functional theory results
(symbols) are compared to the results from the pair potentials (lines)
obtained from an optimization procedure using (a) Lennard-Jones and
(b) Morse nonbonded potentials. Reproduced with permission from
ref 67. Copyright 2012 The Royal Society of Chemistry.
method.75 A thorough test of this technique for bulk systems
appeared in the literature recently.76 Note that in the study by
Ghanbari and co-workers challenges in matching the bare
nanoparticlepolymer density persisted with CG polymer
segments forming density layers of higher packing than the
corresponding results from atomistic simulations.63 Moving
back to atomistic representations resulted to a better agreement
to atomistic models, supporting that discrepancies are due to
fundamental dierences between an atomistic and the spherical
CG representation of beads in a PS segment. In another recent
study, Khounlavong et al. determined the polymer-segment/
particle eective potential that acts between the center of mass
(COM) of a nanoparticle and a CG polymer bead.77 This
method presents additional computational advantages due to
reduction to a single interaction site for each solid nano-
particle.78 Simulations with the extracted CG representations of
polymer revealed the need for additional correction terms to
the nanoparticlenanoparticle potential as a side eect of the
CG polymer representation. Similar ndings were reported by
Hong et al. for bare and grafted silica nanoparticles dispersed in
poly(ethylene oxide) oligomers.79 Thus, it is clear that further
development and testing of the ability of coarse-graining to
capture connement eects is needed. For nanoconnement
between at surfaces, a test of IBI with polyamide-6,6 between
graphene was presented by Eslami and co-workers.80 While
there were some deviations in the total density prole, the
peaks observed in the atomistic simulations were captured by
the simpler CG model. However, the surface was again
represented by a collection of CG beads as in the study of
Ghanbari and co-workers. While retaining interactions sites for
surface atoms could result to potentials that are curvature-
independent, this is not necessarily the case when a single
interaction potential as a function of distance from the surface
5101
Perspective
or the COM of the particle is considered. In fact, the anity of
polymer segments to track the curved nanoparticle surface
depends on particle curvature.24 As we will show herein, we can
extract coarse-grain curvature-dependent potentials based on
atomistic simulations with at surfaces that are computationally
less demanding.
Interactions with implicit at surfaces can be computed by
integration of pairwise potentials over the atoms constituting
the solid slab; in the case of Lennard-Jones interactions this
results to 104 (single solid layer) or 93 (multilayer) power
law expressions for the repulsive and attractive part of the
potential.81 However, when the interaction of the COM of a
group of atoms with a at surface is considered, conformational
characteristics alter the shape of the corresponding eective
potential.82 The need to properly account for changes in the
ensemble of congurations of the group of atoms that are now
represented by a single site is also manifested when considering
changes in the resolution of the CG model. Such features in
theoretical modeling of melts in proximity to surfaces were
addressed by the work of de Pablo and co-workers.83,84
Khounlavong et al. suggested a recalculation of the eective
interactions with the nanoparticle which not surprisingly leads
to dierent (but still accurate) eective potentials.77
Given the growing application of chemically specic CG
models, we decided to independently assess the ability to
extract polymer-segment/nanoparticle potentials based on
atomistic simulations on a at surface. Our motivation was to
evaluate if features beyond the total density prole (as
conformations of chains in contact with the surface) are
captured accurately and whether we can eciently predict
changes with particle curvature. Following the literature, we
performed bulk simulations with a fully atomistic model of cis-
1,4-polyisoprene (PI)85,86 and employed the IBI method (with
pressure corrections as described by Wang et al.87) to extract
CG potentials for polymer segments centered along the bond
connecting consecutive repeat units (interactions were cuto at
1.5 nm).75,8890 All simulations were performed with a 24
repeat units PI to avoid chain-end eects present for lower
molecular weights.91,92 The next step of our quest included
atomistic molecular dynamics simulations of PI on an
amorphous silica slab and around a silica particle of radius 2
nm referred to as SIL-2.0 (as in our previous work24).
Simulations were performed with 400 chains of 24 repeat units)
for the slab (141 032 atoms) and 800 chains of equal length for
the single particle system (253 854 atoms) at T = 413 K and P
= 1 bar (semi-isotropic coupling for slab) using the software
Gromacs.93 Note that the generation of 50 ns trajectories for
these large systems (necessary to avoid nite size eects)
requires several months of computational time even with highly
ecient software as Gromacs. Subsequently, atomistic
trajectories were mapped to CG congurations created with
the fully atomistic potential. Figure 4a presents snapshots of
atomistic simulations where chains in contact with the surface
or the particle are depicted based on the CG representation
(single site for each repeat unit). The distribution of CG beads
as a function of distance from the surface extracted from the
atomistic trajectories is shown in Figure 4b (solid lines)
together with a decomposition to trains, tails, and loops based
on a distance criterion of 0.4 nm to dene a beadsurface
contact. The second step of our procedure was to extract a
wallCG bead potential via IBI targeting only the total density
prof ile (black line) and maintaining the same CG beadCG
bead and intramolecular polymer interactions determined from
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Macromolecules Perspective

Figure 4. (a) Rendered images from atomistic simulations of cis-1,4-PI on silica. Chains in contact with silica are explicitly depicted by spheres
according to the CG scheme utilized. (b) Radial distribution functions of CG beads and their decomposition as a function of distance from the slab
surface. The solid lines represent the distributions obtained from the atomistic trajectories mapped to CG sites, and symbols represent the data from
CG NVT simulations based upon derived eective potentials. (c) CG potentials extracted for dierent radii. For the slab system, IBI and atomistic
simulations were performed while for particles potentials were determined based on eective interactions of polymer segments with the at surface.
(d) Same as (b) with CG simulations of the SIL-2.0 particle system based on an estimate of the particlepolymer bead interaction.

bulk polymer simulations. The resulting numerical potential is
shown in Figure 4c with nal density proles contrasted to CG
beads proles from atomistic simulations shown in Figure 4b as
symbols. A major nding of our study was that subsequent CG
simulations with the derived potentials reproduced almost
quantitatively the conformational characteristics (trains, tails,
and loops) of the polymer layer in contact with the surface.
While it remains to be tested whether this is the case for other
polymers as well, it is particularly encouraging that CG
simulations meet successfully this challenge. We anticipate
that the quantitative representation of the total density prole
of the melt suces for melt systems; this CG scheme has been
applied for PS solutions,94 and certainly future research needs
to focus on blends and copolymers.
Within the main theme of our article we decided to examine
further the predictive ability to construct polymer-segment/
particle eective interactions for curved nanoparticles. An
explicit per surface site pairwise interaction can be recon-
structed using the CGslab potential calculated from the IBI
and the number density of silica sites using a procedure
outlined by Nielsen et al.82,95 Numerical integration of the per
site interaction over the nanoparticle volume within the cuto
distance allows the estimation of a single, pairwise, spherical
nanoparticlepolymer CG segment potential as a function of
5102
COM separation shown for dierent radii in Figure 4c. These
potentials can now serve to model single nanoparticles
immersed in CG representations of the polymer matrix and
extract density proles as performed previously for the at
surface. Figure 4d shows that our CG model, which accounts
for chemical stiness through bonded, angular, and dihedral
potential terms, is able to capture conformations in proximity
to the particle in excellent agreement with independent fully
atomistic simulations. Deviations are observed only at short
separations between the particle COM and the polymer beads,
an anticipated outcome given that roughness is increasingly
important for smaller particles24 and is not accounted for
explicitly in the single pairwise potential employed.
Finally, we investigated whether such models can capture
features beyond the mean density prole at a specic
separation. As discussed earlier, this is a critical test when
evaluating the performance of classical force elds with respect
to data from quantum calculations.66 Using our simple contact
criterion, we can examine changes in free energy along the
surface by calculating the probability to form a train segment of
consecutive CG beads of length S, Ptr(S). Simulations with
beadspring models recently demonstrated that the train size
distribution depends on the strength of the interaction between
polymer segments and the surface.96 Figure 5a shows that these
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Macromolecules
Figure 5. (a) Probability distributions for train segments from CG
simulations and atomistic simulations. (b) Normalized RMS bound
layer thickness as a function of particle size relative to polymer Kuhn
segment length. Data on particles immersed in polyethylene melts are
taken from our previous study.24
probabilities depend on curvature as we described in our
previous atomistic simulations.24 Most importantly, the CG
model developed herein for PI/silica systems appears to
accurately capture the distributions both for the slab and the
SIL-2.0 system. To the best of our knowledge, this is the rst
time where not only mean density proles are matched, but
uctuations on the surface are described faithfully and
throughout dierent curvatures. As a nal result, Figure 5b
shows that the interfacial layer thickness (normalized to the at
surface result) quantied for polyethylene on silica through
atomistic simulations reported previously24 presents excellent
agreement with our new CG PI data when the latter are scaled
with the corresponding Kuhn length (0.82 nm97). These results
provide a rst indication that the scaling of the layer follows a
universal behavior when polymer stiness is accounted for.
Overall, application of systematic CG techniques presents
signicant potential to capture curvature eects in polymer
nanoparticle interactions. We believe that further research with
dierent polymer chemical architectures, surfaces, many
particles, blends, and copolymers is required to establish the
capabilities and limitations of these simpler eective potentials
in capturing the behavior of polymerparticle mixtures.
OUTLOOK
Progress made in polymer synthesis and characterization
methods reveals that we are not far from tailoring dispersion
and morphology of nanoparticles within a polymer matrix.1
Despite extensive fundamental knowledge accumulated over
many decades on the thermodynamics of these systems, as we
move to the nanoscale, further challenges appear with features
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Perspective
previously unaccounted for. To support our view, we chose to
present herein studies in recent years that advanced our
knowledge regarding the eect of nanoscale dimensions on
interfacial interactions and complete miscibility in seemingly
simple systems, nanoparticles, grafted or bare, within a
homopolymer matrix.
Control over dispersion was brought forward by a series of
experimental studies that are now able to construct phase
diagrams and probe material structure with unprecedented
detail. Experiments continue to explore and propose structure
property relationships necessary to design improved materi-
als.29,98101 Theoretical modeling continues to oer the most
versatile and ecient route toward providing predictions and
establishing reasoning for experimental ndings. However,
given the underlying approximations, computer simulations
need to continue to test and challenge the accuracy of theory.
Our aim was to present that there is still progress to be made
on quantitatively characterizing the underlying factors that drive
the observed behavior. We have provided herein several
examples on the miscibility limits of grafted-nanoparticles
immersed in a matrix of similar chemical constitution to justify
this point of view.
While we acknowledge this critical role of modeling, it is also
important to recognize the prospect of hierarchical materials
design. Quantum calculations can now oer detailed
information on the interactions between polymer segments in
proximity to the surface, even for systems that are yet to be
realized in the laboratory. It is anticipated that an increasing
number of studies will focus on translating data from such
calculations to classical force elds with several challenges to be
met. Force-eld-based atomistic modeling suces to probe
ensembles of conformations in a specic environment and
major progress in systematically derived ecient coarse-grain
representations has already been made. It appears that it is now
feasible to employ such specic models to capture the structure
of interfacial layers at the nanoscale. An ambitious aim for the
future is to systematically develop a library of interaction
potentials for specic polymersurface chemistry which will
consolidate the eorts in predictive modeling of polymer
nanoparticle interactions. This will allow comprehensive tests
on the performance of these models by the community.
Futhermore, theoretical modeling will have the opportunity to
foster on eective interactions extracted and provide
predictions for the phase behavior without experimental
input. Multiscale modeling has long been conceived as the
only viable route toward predicting properties of nano-
composites;10,102 the recent progress in fundamental under-
standing of polymerparticle interactions is now bridging the
gaps and completing the realization of this ambitious aim.
AUTHOR INFORMATION
Corresponding Author
*E-mail: edoxastakis@uh.edu (M.D.).
Notes
The authors declare no competing nancial interest.
dx.doi.org/10.1021/ma400444w | Macromolecules 2013, 46, 50975106
Macromolecules
Biographies
Yogendra Narayan Pandey is a senior graduate student at the
department of Chemical and Biomolecular Engineering at the
University of Houston. Yogendra defended his PhD in April 2013.
He worked with Professor Manolis Doxastakis on modeling and
simulation of materials, e.g., polymernanoparticle systems, polymer
thin lms, and zeolites. Earlier, he received Bachelor of Technology (B.
Tech.) in Chemical Engineering and Technology from Institute of
Technology, Banaras Hindu University, Varanasi, India, in 2005.
Before joining graduate school in Fall 2008, he worked as a software
developer (20052008) with leading information technology
companies in India.
George Papakonstantopoulos received his Diploma in Chemical
Engineering from the National Technical University of Athens in
2002. He received his PhD in Chemical Engineering in 2007 from the
University of WisconsinMadison. He worked with Professors Juan J.
de Pablo and Paul F. Nealey in the areas of polymeric nanocomposites
and block copolymer self-assembly using molecular modeling
techniques. He worked for Arkema Inc. (20072010) in the Analytical
and Systems Research department as a Scientist, mainly investigating
the modication of the mechanical behavior of polymeric materials
with the aid of molecular modeling and microscopy techniques.
Currently he works for the Goodyear Tire and Rubber Company as a
Senior Scientist in the area of Multiscale Modeling of polymeric
composites and polymer blends.
5104
Perspective
Manolis Doxastakis received his Diploma in Chemical Engineering
from the National Technical University of Athens in 1996. He received
a masters in Materials Science and Ph.D. in Chemical Engineering
from the University of Patras in 2002. He worked with Professors
Doros N. Theodorou and George Fytas designing and performing
simulations and experiments on polymer melts, blends, and
copolymers. He moved to the University of Wisconsin in Madison,
working as a postdoctoral fellow with Professor Juan J. de Pablo in
2003, investigating polymerparticle mixtures and lipid membranes.
Since 2007, he is an assistant professor in Chemical and Biomolecular
Engineering at the University of Houston, studying interfacial
phenomena with molecular modeling.
ACKNOWLEDGMENTS
We acknowledge nancial support by the National Science
Foundation under Grant CBET-1067356 and The Goodyear
Tire and Rubber Company.
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