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ORG
Effect of Particle Agglomeration and Interphase on the Glass Transition
Temperature of Polymer Nanocomposites
Rui Qiao,1 Hua Deng,1 Karl W. Putz,1 L. Catherine Brinson1,2
1
Department of Mechanical Engineering, Northwestern University, Evanston, Illinois 60208
2
Department of Material Science and Engineering, Northwestern University, Evanston, Illinois 60208
Correspondence to: L. C. Brinson (E-mail: cbrinson@northwestern.edu)
Received 3 December 2010; revised 16 February 2011; accepted 17 February 2011; published online 2011
DOI: 10.1002/polb.22236
ABSTRACT: In this article, we utilize finite element modeling to
investigate the effect of nanoparticle agglomeration on the glass
transition temperature of polymer nanocomposites. The case
of an attractive interaction between polymer and nanofiller is
considered for which an interphase domain of gradient prop-
erties is developed. This model utilizes representative volume
elements that are created and analyzed with varying degrees of
nanoparticle clustering and length scale of interphase domain.
The viscoelastic properties of the composites are studied using
a statistical approach to account for variations due to the ran-
dom nature of the microstructure. Results show that a monotonic
increase in nanofiller clustering not only results in the loss of
interphase volume but also obstructs the formation of a perco-
lating interphase network in the nanocomposite. The combined
INTRODUCTION Starting in 1994, a major focus of polymer
physics has centered on the dynamics of thin polymer films.
Early results demonstrated that the glass transition temper-
ature (Tg ) decreased dramatically in free-standing polymer
films (with two free interfaces), with a thickness below
50 nm.1 Supported polymer films, with one free interface and
a substrate interface, had deviations from the bulk Tg in
either the positive or the negative direction, depending on
the polymersubstrate interaction.2 Strongly attractive inter-
actions produced increases in Tg below 50 nm. In 2003, Ellison
et al. achieved a breakthrough using fluorescence to measure
the local dynamics of 14-nm sections of thin polymer films,
rather than average dynamics of the entire film.3 This work
was extended in 2007 to model nanocomposites with two
supported interfaces, indicating that changes in Tg could be
seen in films as thick as 500 nm in this geometry.4
Polymer nanocomposites have been the subject of much
research in the past decade and are becoming increasingly
important for applications due to their unique properties.
Experimental work has demonstrated that nanocomposites
can exhibit significant improvement in mechanical, thermal,
electrical, and other physical properties in comparison with
their parent polymer systems by judicious incorporation of
nanoparticles. The effect of nanofillers on the glass transition
2011 Wiley Periodicals, Inc.
740 JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS 2011, 49, 740748
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impacts lead to a remarkable decrease of Tg enhancement of
clustering nanofillers in comparison with a well-dispersed con-
figuration. Our simulation results provide qualitative support
for experimental observations that clustering observed at high
nanofiller concentrations negatively impacts the effects of the
nanofiller on overall properties. 2011 Wiley Periodicals, Inc.
J Polym Sci Part B: Polym Phys 49: 740748, 2011
KEYWORDS: agglomeration; clustering degree; filler reinforce-
ment; finite element modeling; finite element simulations; glass
transition temperature; interphase network; interphase percola-
tion; nanocomposites; particle distribution; polymer nanocom-
posites; viscoelastic properties
temperature (Tg ) of polymer nanocomposites has been studied
widely for the last decade. It has been reported that the devia-
tions from Tg of the pristine polymer can be as large as tens of
degrees in the nanocomposite system,2, 49 which is attributed
to the confinement effect of nanofillers. The attractive or
repulsive interactions between the nanofiller surface and local
polymer chain segments alters the mobility of the polymer
segments. Such perturbations in polymer molecular mobility
extend several radii of gyration and create regions of polymer,
the interphase, with properties and response different from
that of the host bulk polymer. Recent experimental and numer-
ical work revealed that Tg increased for the nanoparticles with
attractive interaction with polymer matrix in the interfacial
region,8, 10, 11 and decreased with repulsive polymernanofiller
interaction.2, 11
It is generally believed that a homogenous dispersion of
nanofillers in the polymer matrix enables these superior
properties to be reached at low concentration level with-
out sacrificing many advantages of the parent polymer.1215
For example, large deviations of Tg relative to the bulk poly-
mer were observed at very low nanofiller loadings (i.e., 0.05
wt % reported in ref. 16 and 0.75 wt % reported in ref. 17),
which is believed to be the result of the large extent of
interphase region penetrating through the nanocomposite and
 WWW.POLYMERPHYSICS.ORG
formation of a percolating altered polymer network. However,
nearly all of the relevant literature reveals that nanoparticle
agglomeration is a significant concern18 for several reasons
including high surface tension during material processing,19
incomplete exfoliation of nanoparticles,20 and van der Waals
attractions between nanoparticles.21 Complete control of clus-
tering has not yet been achieved, though a wide variety
of processing methods and functionalization strategies12, 22, 23
have been applied resulting in systems with wide ranges of
degrees of nanopaticle agglomeration.
Clustering of nanoparticles has been correlated with a reduc-
tion in the advantages afforded to nanocomposite and under-
mines the potential enhancements.4, 6, 2426 Evidence of the
mechanical ramification of the interphase was shown, to
disappear on aggregation in functionalized nanotubes in
polystyrene, in the work done by Putz et al.24 In case of
glass transition temperature, the relative change of Tg to
the bulk polymer decreases or even disappears when severe
agglomeration of nanoparticles occurs in nanocomposites.4, 6
Ramanathan et al.6 reported that the enhancements in the
Tg values of graphite/PMMA composite initially increased
at low filler concentration but declined from the maximum
value with increasing concentrations. Rittigstein et al.4 also
observed a drop of Tg at high filler loading in silica/P2VP and
silica/PMMA nanocomposites. These phenomena are hypoth-
esized to result from decreases in nanoparticle dispersion
achieved at higher loadings. Cho and Daniel25 demonstrated
that the glass transition temperature of a composite increased
only modestly with nanotubes which were somewhat agglom-
erated, while the Tg was increased by 39 C in a composite
where better nanofiller dispersion was achieved by using a
dispersant. However, direct evidence and understanding are
lacking due to difficulties in quantifying dispersion in exper-
imental samples. As there are few ways to accurately assess
and control details of the dispersion and interphase domains
of a polymer nanocomposite sample, modeling can be used to
bridge the gap between knowledge of thin polymer films and
that of nanocomposites. As was previously noted, until 2003,
dynamics of thin polymer films could only be investigated as
a whole, obscuring the heterogeneity in the dynamics. In a
previous article, Qiao and Brinson,27 numerical simulations
demonstrated that homogenous interphase layers in polymer
nanocomposites were inadequate to replicate the experimen-
tally observed shifts in Tg of polymer nanocomposites. Much
as is observed in thin polymer films, a gradient of properties is
necessary to produce the gradual, rather than binary, Tg shifts.
In this article, we develop a numerical approach based on finite
element simulations to understand the effect of nanoparticle
agglomeration on the formation of the interphase network and
on the glass transition temperature of nanocomposites. The
systems also introduced a gradient interphase model, in which
the relaxation time in interphase domain decays away from the
inclusion/polymer interface, to describe the viscoelastic prop-
erties in the interphase region. We implement this model as a
double layer in which the relaxation time of each layer is a con-
stant, which captures the essential features of the interphase
regime. We also validate this discrete approximation with a
continuous gradient model. It is noted that only attractive
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FIGURE 1 (a) The black circle with radius of rcl represents the
cluster region and six particles with radius of R are randomly
distributed inside of the cluster. (b) Schematic of unit cell with
inhomogeneous microstructure. The large black dashed circles
and small blue empty circles are replicas of cluster regions and
nanoparticles to illustrate periodic geometry of the unit cell. The
inhomogeneity,
cl , of this unit cell is 30%. See text for details.
interfacial interaction that leads to Tg enhancement is consid-
ered in this article, but the method is also directly applicable
to the case of the repulsive interaction between nanoparticles
and polymer chains.
MICROSTRUCTURE DEVELOPMENT AND FINITE
ELEMENT MODEL
A two-dimensional plain strain model is adopted to examine
the effect of the interphase and nanoparticle clustering on the
viscoelastic behavior of polymer nanocomposites. The two-
dimensional approach simplifies the computational require-
ments, and although it represents explicitly the case of aligned
nanotubes, the trends in the results on time dependent prop-
erties are generalizable to other 3D configurations. To study
the influence of nanotube agglomeration on the formation of
the interphase network and further the glass transition tem-
perature of nanocomposites, inhomogeneous microstructures
of clustered materials must be generated. Herein, a particle
distribution similar to a method in literature28 for sphere
reinforced ductile-matrix composite is selected in which the
microstructure of the clustered nanoparticles is idealized as
an isotropic, random dispersion of circular regions with radius
rcl , which represent the clusters. Inside each cluster region, a
fixed number of nanotubes, np , are randomly generated [see
Fig. 1(a)]. Thus, the inhomogeneity of the microstructure can
be described by a parameter defining the local volume frac-
tion of nanotube in each cluster,
cl . Obviously, the degree of
inhomogeneity can be controlled by tuning rcl , thus, changing

cl correspondingly.
The glass transition temperature of nanocomposite was
obtained by a finite element analysis of a representative
volume element (RVE) with periodic boundary conditions.
A square unit cell with edge length equal to L containing
a random dispersion of nonoverlapping identical circles is
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generated to simulate the in situ configurations of nanoparti-
cles embedded in polymer matrix. Uniaxial loading condition
is applied, and simulations are performed by ABAQUS to
predict the tan  of the nanocomposites. In this study, the
inhomogeneous dispersion of nanotubes is created with a sim-
ilar algorithm but composed of two steps. In the first step,
the centers of ncl clusters are generated based on random
sequential adsorption algorithm (RSA)2729 that ensures all
cluster regions are impenetrable, nonoverlapping circles with
the same radius, rcl . In the following step, the positions of
np particles within each cluster are generated using the same
RSA algorithm, so that the particles are also nonoverlapping
and randomly distributed inside of each cluster. Given a uni-
form radius, R, of all particles, the local volume fraction of
nanoparticles
cl can be calculated by the equation

2
R

cl = np ,
rcl
where we let R be one unit length and np be 6 in this study so
that
cl is the function of only one variable, rcl . As we assume
each cluster has the same radius and equal quantity of par-
ticles, the local volume fraction is identical for all clusters in
the unit cell. In remaining of this article,
cl is used to dis-
tinguish the difference of inhomogeneity for models with the
same volume fraction of nanoparticles, f . It is worth noting
that due to the limitation of the RSA algorithm, the clusters
with radius rcl larger than the jamming limit cannot be gen-
erated without applying additional strategies. Therefore, the
method described in ref. 29 is utilized to construct the unit
cell with large rcl (thus small
cl ). In this study, the models
with
cl < 10% were generated by this method. Two different
volume fractions of nanoparticles are studied here, f = 3.8%
and f = 5.4%. Given the edge of RVE equal to 70R (area
A = 4900R2 ), the corresponding numbers of particles inside
RVEs (N) are 60 and 90, respectively.
Periodic boundary conditions are applied to the RVE to repli-
cate an infinite but repetitive configuration to represent the
continuum properties of the composite with many inclusions.
To properly enforce the periodic boundary conditions, the
geometry of the unit cell must be periodic such that particles
intersecting the edges have the counterparts on the oppo-
site edges and the intersections must be identical. To fulfill
this requirement, the inclusions close to or intersecting the
edges of the unit cell are duplicated and shifted to the oppo-
site edge by a distance of edge length L [see Fig. 1(b)]. To
impose the restriction that the clusters are nonoverlapping,
we enforce the distance between any two cluster centers to
be greater than 2rcl , including the repetitive clusters outside
of the unit cell. Once the cluster positions are determined, the
nonoverlapping requirement for particles is automatically sat-
isfied regardless of periodic condition because these particles
can only be generated inside of each cluster. In addition to the
inhomogeneous microstructure, a homogeneous microstruc-
ture is also created for comparison. For the homogeneous
system, the nanoparticles are randomly dispersed inside of the
corresponding unit cells with RSA algorithm taking account
into periodic conditions.
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FIGURE 2 Schematic of composite configuration showing the
interphase region, which is modeled by two concentric annuli
surrounding the nanoparticle (in black). Interphase layers are
merged in the overlapping regions.
The interphase region in the polymeric composites is modeled
as an annulus surrounding the particle and perfect bonding
between matrix and inclusions is assumed. The ratio of thick-
ness of the interphase to the diameter of the particle, defined
as , is a parameter to describe the interphase volume around
particles. For the composites with nanoscale fillers, this ratio
is expected to be 110 or even larger depending on the
dispersion of particles and interaction between polymer and
particles.14
Considering experimental data on ultrathin polymer films on
an attractive surface,3 the polymer mobility changes in a gra-
dient fashion away from the polymer-surface interface. To take
this gradient into account, we divide the interphase region into
concentric layers with modulated properties. In the examples
chosen here, a simple gradient of two layers is chosen (see
Fig. 2), which has been shown to capture important features
of overall response.27 We also validate this discrete model with
a continuous gradient model. Two different ratios are adopted
in this article, for the lower volume fraction case (f = 3.8%),
 = 3, whereas for the higher volume fraction (f = 5.4%),
 = 2. It is noted that as this model is dimensionless, for the
case of (Tg ) shift in thin films [O(100 nm)] filled with multi-
walled carbon nanotubes (2050 nm), the ratio of interphase
thickness to the diameter of particle being 23 is very reason-
able. We use a smaller ratio for the higher volume fraction
sample due to easier formation of a percolated interphase
network in the sample with more particles. Decreasing the
interphase thickness can lead to a more pronounced transi-
tion from a discrete interphase network to a percolated one
occurring as the agglomeration reduces. The properties of the
first interphase, that closest to the nanotube is denoted as
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FIGURE 3 Effect of number of RVEs on the mean and COV of
predicted Tg .
Interphase-1, whereas the properties of the second inter-
phase, closest to the bulk matrix is denoted as Interphase-2.
Note that any overlapped interphase regions are merged to
form a union, and the area is only counted once.
The material properties of polycarbonate (PC) were measured
by dynamic mechanical analysis.30 Mastercurve of the matrix
polymer in frequency domain is then approximated by a 28-
term Prony Series using a program developed in this group.31
The nanoparticles are assumed to be elastic with Youngs mod-
ulus of 100 GPa and Poissons ratio of 0.3. The properties of
Interphase-1 are determined by shifting the PC master curve
two decades lower in the frequency domain, representative of
strong positive interactions between the nanoparticle and the
host matrix material. For Interphase-2, the properties are also
derived from bulk PC but are shifted only one decade in fre-
quency, thereby simulating the decay of the restriction toward
that of the matrix material. By running steady-state dynamic
simulations on Abaqus, the complex modulii of the composites
are retrieved and the corresponding tan  as a function of fre-
quency are obtained. For the temperature domain calculation,
simulations are performed at one particular frequency value
(1 Hz in this work) for different temperatures. Then the glass
transition temperature (Tg ) of the nanocomposite is measured
as the location of the tan  peak in the temperature domain
calculation.
NUMBER OF DISTRIBUTION AND RVE SIZE
As the interphase regions may overlap, for unit cells with
the same volume fractions and inhomogeneity of nanoparti-
cles, it can be expected that different specific distributions of
particles will lead to different predictions of glass transition
temperature of the composites. Therefore, for given f and
cl ,
a statistical approach is used in which number of RVEs with
different particle distributions are generated and calculated to
obtain the mean value and the standard derivation of Tg . It is
believed that as the number of RVEs approaches infinity, the
coefficient of variation (COV) of the prediction becomes con-
stant, and the finite size model can represent the real material
behavior.32, 33 However, in practice, we have to determine the
minimum required RVEs for practical consideration.
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A unit cell containing 60 particles (N = 60) with f = 3.8%,
 = 3, and
cl = 10% is selected to study the minimum num-
ber of RVEs required for this simulation. ABAQUS scripting
language is utilized to rapidly create multiple models, which
meet all requirements and differ only by the particle distribu-
tion. In total, 50 distributions are investigated, and the mean
value and COV of predicted Tg are shown in Figure 3 as a func-
tion of RVE number. From this figure, we can see both mean
value and COV of the predicted Tg become constant when the
number of RVEs is more than 20. Thus, 20 RVEs are suffi-
cient to have a statistically meaningful representation of the
microstructure. Therefore, in the remainder of this paper, Tg
for all distributions is calculated by averaging predictions of
20 RVEs.
In addition to the number of RVEs, the size of RVE also has
important influence on the predictions. To confirm the proper
size of the model, two RVEs with the same volume fractions
as before, f = 3.8 and 5.4%, but larger area of the unit cells,
A = 14700R2 , are investigated. In both cases, the highest clus-
tering degree generated in this work,
cl = 30%, is selected as
the example to study the size effect. The mean and COV of the
predicted Tg of those two cases are computed and listed in
Table 1. It can be seen that the mean value changes by less
than 0.056% for the larger system. Therefore, we assume that
the specimen with the area A = 4900R2 is sufficiently large,
and this size is used for all models in this study.
RESULTS AND DISCUSSION
Nanocomposite specimens containing 60 particles (f = 3.8%)
with  = 3 (where  is defined as the ratio of interphase thick-
ness to particle diameter) are first investigated. RVEs with six
different degrees of clustering (in order of increasing agglom-
eration
cl = 8, 10, 15, 20, 25, and 30%) as well as a RVE
for homogenous dispersions are constructed (Examples are
shown in Fig. 4). Because of the limitation of the particle gen-
eration algorithm, the lowest clustering degree generated in
this study is 8%. In each microstructure, the glass transition
temperature is calculated by averaging predictions of 20 RVEs,
and the results are plotted in Figure 5. It can be seen that the Tg
decreases as the degree of clustering increases from homoge-
nous (no clustering) to moderate agglomeration (
cl = 30%).
The composites with
cl = 30% result in a Tg increase of only
2.3 C, nearly three times lower than the Tg increment for
composites with randomly dispersed particles.
TABLE 1 Mean Values and COVs of Predicted Tg for Different
Specimen Size
Specimen Size Mean Value COV (%)
Sample-1 A = 4,900R 2 155.32 0.371
f = 3.8%,  = 3 A = 14,700R 2 155.27 0.309
Sample-2 A = 4,900R 2 155.27 0.202
f = 5.4%,  = 2 A = 14,700R 2 155.19 0.202
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FIGURE 4 Three models showing the interphase morphology
for different clustering degree with f = 3.8%, (a) random, (b)

cl = 10%, (c)
cl = 15%, and (d)
cl = 30%. It is clear that the inter-
phase forms a connective network in (a) and (b) while interphase
regions are discrete in (c) and (d). Interphase-1 is represented in
dark blue and Interphase-2 is in light blue.
FIGURE 5 The predicted Tg for two unit cells with different
nanoparticle concentrations, f = 3.8% and f = 5.4%. Columns
from left to right in each category are the Tg for random disper-
sion,
cl = 8, 10, 15, 20, 25, and 30%, respectively. The error bars
indicate the standard deviations of the predicted Tg .
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FIGURE 6 Relationship between mean value of predicted Tg and
averaging interphase volume for samples with (a) f = 3.8%,  = 3
and (b) f = 5.4%,  = 2. The numbers above symbols indicate
the clustering degree of each data point. The error bars in x and
y represent the standard deviations of the volume fractions of
interphase and the predicted Tg .
As agglomeration of nanoparticles leads to loss of interphase
volume as the interphase in agglomerate overlap, it is unsur-
prising that increased inhomogeneity weakens the influence
on Tg . However, examining the relationship between the mean
value of Tg and the average volume fraction of interphase of
the RVEs [see Fig. 6(a)], it can be seen that the predicted Tg
of composite is not strictly proportional to the interphase vol-
ume. Instead, the slope of the curve rises at the prediction
of unit cells with
cl = 10% and
cl = 10% but drops to the
initial value for samples with higher interphase volume. To
explain this phenomenon, we examine the microstructures of
the RVEs shown in Figure 4, where Figure 4(b) is an example
of
cl = 10% and Figure 4(c) is of
cl = 15%. It can be seen
that the interphase regions are percolated and form a connec-
tive network inside of matrix in Figure 4 (a,b) (random and

cl = 10%), while, the interphase domains remain discrete in
the model shown in Figure 4 (c,d) (
cl = 15% and
cl = 30%).
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A percolated interphase network has significant effect on the

viscoelastic properties of polymer composite, particularly on
the loss modulus and Tg . The increase of clustering degree
leads not only to loss of interphase volume but also to disap-
pearance of an interphase network in the matrix. Thus, in the
prepercolation regime [Figure 4(c,d)], the effect of changes
in agglomeration have a modest impact on the predicted Tg
(lower slope at lower volume fractions of interphase in Fig. 6).
In the percolation regime where percolating paths are being
formed [Fig. 4(b)], the changes in Tg due to small changes in
agglomeration are more pronounced even with small changes
in volume fraction of interphase (higher slope at intermediate
volume fractions of interphase in Fig. 6). In the postpercolation
regime, with the percolated paths saturated, the small change
in volume of interphase due to small changed in agglomera-
tion again produce modest Tg increments (lower slope at high
volume fractions of interphase in Fig. 6).
A similar phenomenon is also observed in the unit cells with
higher f [Fig. 6(b)]. In the case shown here, the effect is
not as pronounced as in Figure 6(a) both because of small
interphase/nanofiller ratio,  and high volume fraction of
nanoparticles. The smaller interphase/nanofiller ratio causes
the interphase to play a smaller role compared with the first
example with a larger . Moreover, although the RVEs have
the same agglomeration degrees in both examples, the num- FIGURE 7 Microstructures for different volume fraction of
ber of clusters in the unit cell is larger for the higher volume nanoparticles (f = 3.8% in the left figure and f = 5.4% in the
fraction case because the clusters are randomly dispersed right one) with cluster degrees
cl = 10% and
cl = 15%. It is clear
in the matrix. The particles and interphase are more uni- that the interphase/nanoparticle ratio is smaller and the parti-
formly distributed, resulting in a smaller average distance cles are more uniformly distributed in the higher volume fraction
between particles and stronger interaction between isolated case f = 5.4% (right column), which diminishes the interphase
interphase regions (Two examples are shown in Fig. 7). There- percolation effect.
fore, the interphase percolation effect is diminished in the
second example [Fig. 6(b)] with higher nanoparticle volume
fraction. media is much lower than that of the disc shape in 2D media
These results can qualitatively explain the experimental obser- considered here.39 Thus, in typical composites with randomly
vations in some nanocomposites that the enhancement of Tg oriented nanotubes or nanofibers, the interphase regions
is not a monotonic function of nanofiller loading.4, 6, 34, 35 At will form a connective network at lower thresholds. In such
higher loadings of nanofiller, self-attraction of nanoparticles real nanocomposites with 3D morphology, the destruction
leads to more prevalent nanoparticle clustering36, 37 which of interphase network due to clustering can be observed in
then undermines the enhancement of the thermal properties compositions with a lower loading of nanoparticles and fewer
caused by the interphase in the composites. As shown above, interphase regions than the situations considered here.
the clustering can have a compounding effect due to loss of Interparticle distance is often used to quantify the particle dis-
interphase percolation. persion.33, 40, 41 Here, the Delaunay triangulation is applied to
The material properties of interphase used in this work measure the interparticle distance in nanocomposites, which
are assumed to be one or two decades shift of relaxation is similar in spirit to the Voronoi tessellation of space that
time of neat PC in frequency domain and the corresponding makes each particle at the center of a minimally closed poly-
glass transition temperatures are 162.4, 156.4, and 153 C for gon (Fig. 8). To diminish the edge effect, the microstructure
Interphase-1, Interphase-2, and pure PC, respectively. There- was replicated and copied along x and y axis in both direc-
fore, the maximum increase of Tg relative to pristine polymer tions with the length of the unit cell. Only those ligaments
is 9.4 C, which can be achieved only if Interphase-1 satu- with at least one end inside the unit cell were taken into
rated the matrix. In contrast, experimental and numerical account for measuring the interparticle distance. The rela-
studies demonstrated that the attractive interaction between tionship between interparticle distance and predicted Tg for
nanofillers and polymer chain can significantly restrict the both samples with f = 3.8% and f = 5.4% is plotted in
mobility of polymer chain and thus increase Tg by tens of Figure 9. The interparticle distance data are quite scattered
degrees.2, 5, 9, 38 In such systems, the agglomeration of nanopar- due to small size of the unit cell. However, we can observe
ticles will have even more pronounced effect. It is also noted a trend that the interparticle distance increases as cluster-
that the percolation threshold for particles or nanotubes in 3D ing degree increases, leading to a decrease of predicted Tg

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of nanocomposites. This behavior agrees well with the exper-

imental observation by Bansal et al.,40 showing that larger
interparticle spacing has a negative impact on the Tg change of
the bulk polymer caused by nanoparticles and provides addi-
tional evidence that agglomeration of nanoparticles can reduce
the Tg enhancement in nanocomposites.

VALIDATION OF DOUBLE LAYER INTERPHASE MODEL

It can be seen that the double layer interphase model can be

regarded as an approximation of a continuous gradient model,
where the relaxation time of the interphase decays as a func-
tion of the distance from the particle/polymer interface. To
validate this approximation, simulations based on a continu-
ous gradient model are made for different particle clustering
degrees (random, 10, 20, and 30%). This gradient model is
implemented in ABAQUS using the user subroutine UTRS by
manually defining the shift factor for each element in models.
We determine the shift function F(d) in the continuous gra-
dient model by using the analog between the glass transition
temperatures in polymer nanocomposites and polymer thin
films. We hypothesize that, in nanocomposites, the Tg changes
in the same way as that in thin films, thus, the empirical model
developed for thin films4 is used to estimate the Tg derivation
of the interphase region in nanocomposites


 
A
Tg (d) = Tg (bulk) 1 + , (1)
d

FIGURE 9 Relationship between interparticle distance and pre-

dicted Tg for samples with (a) f = 3.8%,  = 3 and (b) f = 5.4%,
 = 2. The error bars in x and y indicate the standard deviations.

where d is the distance of the element to its nearest particle,

FIGURE 8 An example of measuring interparticle distance for the
model with
cl = 10%, f = 3.6%. The microstructure has been
replicated both along x and y direction to diminish the edge
effect. The circles in black denote the particles within the com-
posite. Only the edges in solid blue are taken into account for the
average of interparticle distance.
A and  are both material parameters (A = 0.05 and  = 0.79
were used here). It is to be remarked that the form in eq
1 has been altered to account for the attractive attraction
between particles and polymers. On the basis of this relation
between Tg and distance, we derived the shift factor func-
tion aT [Fig. 10(a)]. Also the values of A and  were chosen
to make sure that the two shift factors (i.e., 2 and 1) in the
double layer interphase model are equivalent to the shifting
function aT (d) in the continuous gradient model, in the sense
of integral over the interphase area. Because of the computa-
tional demands of this calculation, for each clustering degree
only one configuration is considered. Comparing the predicted

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FIGURE 10 (a) shift factor as a function of distance away from
polymer/particle interface in the gradient interphase model and
shift factors in the double layer interphase model; (b) predicted Tg
for the these two models. Except for the extreme case where parti-
cles disperse completely randomly, the predicted Tg s of gradient
models fall into the error bars of double layer models.
Tg of the gradient model with that of the statistical results of
double layer model, it is found that the value of the gradient
model falls into the range of error bars in the double layer
model, except for the extreme case where particles are dis-
persed randomly [Fig. 10(b)]. This result provides us a good
support that using double layer interphase model is a good
approximation to the continuous gradient model. For further
accuracy while still remaining computationally lean, a three-or
four-layer model could be used.
CONCLUSIONS
The effect of nanoparticle agglomeration on the formation of
interphase network and the glass transition temperature of
nanocomposites are studied numerically in this work. The
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microstructures of agglomerated nanoparticles are created
by generating randomly dispersed cluster domains and then
randomly distributing particles inside of each cluster region.
The degree of inhomogeneity is controlled by the local vol-
ume fraction of nanoparticles inside of the clusters, which is
varied from 8 to 30%. In each case, 20 models are created
and calculated to obtain statistically average results for vis-
coelastic properties with a focus on the RVE Tg value. Our
simulations suggest that the agglomeration of nanoparticles
remarkably reduce the volume fraction of interphase and,
moreover, impede the formation of a percolating interphase
network inside the polymer matrix. Therefore, the -relaxation
dynamics of nanocomposites with clustered nanoparticles
show less change from the pure polymer relative to nanocom-
posites with well-dispersed nanoparticles. These predictions
provide additional evidence to aid the interpretation of exper-
imental observations regarding the enhancement in Tg in
nanocomposites with varying degrees of dispersion. In addi-
tion, they provide additional insight into cases in which Tg
improvements decay above a threshold volume fraction of
nanofillers.
Although our numerical simulations based on 2D models
successfully aid the interpretation of current experimental
observations, 3D finite element modeling is necessary to bet-
ter study the properties of nanocomposite. Three-dimensional
simulation will be helpful for a quantitative comparison
between the numerical and experimental results and also the
percolation thresholds in 3D differ significantly from those in
a 2D configuration. We will also build 3D models with inclu-
sions of different shapes on some of our previous results,42
where we characterized the effects of CNT aspect ratios on
overall properties.
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