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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 impacts lead to a remarkable decrease of Tg enhancement of
investigate the effect of nanoparticle agglomeration on the glass clustering nanofillers in comparison with a well-dispersed con-
transition temperature of polymer nanocomposites. The case figuration. Our simulation results provide qualitative support
of an attractive interaction between polymer and nanofiller is for experimental observations that clustering observed at high
considered for which an interphase domain of gradient prop- nanofiller concentrations negatively impacts the effects of the
erties is developed. This model utilizes representative volume nanofiller on overall properties. © 2011 Wiley Periodicals, Inc.
elements that are created and analyzed with varying degrees of J Polym Sci Part B: Polym Phys 49: 740–748, 2011
nanoparticle clustering and length scale of interphase domain.
The viscoelastic properties of the composites are studied using KEYWORDS: agglomeration; clustering degree; filler reinforce-
a statistical approach to account for variations due to the ran- ment; finite element modeling; finite element simulations; glass
dom nature of the microstructure. Results show that a monotonic transition temperature; interphase network; interphase percola-
increase in nanofiller clustering not only results in the loss of tion; nanocomposites; particle distribution; polymer nanocom-
interphase volume but also obstructs the formation of a perco- posites; viscoelastic properties
lating interphase network in the nanocomposite. The combined

INTRODUCTION Starting in 1994, a major focus of polymer temperature (Tg ) of polymer nanocomposites has been studied
physics has centered on the dynamics of thin polymer films. widely for the last decade. It has been reported that the devia-
Early results demonstrated that the glass transition temper- tions from Tg of the pristine polymer can be as large as tens of
ature (Tg ) decreased dramatically in free-standing polymer degrees in the nanocomposite system,2, 4–9 which is attributed
films (with two free interfaces), with a thickness below to the confinement effect of nanofillers. The attractive or
50 nm.1 Supported polymer films, with one free interface and repulsive interactions between the nanofiller surface and local
a substrate interface, had deviations from the bulk Tg in polymer chain segments alters the mobility of the polymer
either the positive or the negative direction, depending on segments. Such perturbations in polymer molecular mobility
the polymer–substrate interaction.2 Strongly attractive inter- extend several radii of gyration and create regions of polymer,
actions produced increases in Tg below 50 nm. In 2003, Ellison the interphase, with properties and response different from
et al. achieved a breakthrough using fluorescence to measure that of the host bulk polymer. Recent experimental and numer-
the local dynamics of 14-nm sections of thin polymer films, ical work revealed that Tg increased for the nanoparticles with
rather than average dynamics of the entire film.3 This work attractive interaction with polymer matrix in the interfacial
was extended in 2007 to “model nanocomposites” with two region,8, 10, 11 and decreased with repulsive polymer–nanofiller
supported interfaces, indicating that changes in Tg could be interaction.2, 11
seen in films as thick as 500 nm in this geometry.4
It is generally believed that a homogenous dispersion of
Polymer nanocomposites have been the subject of much nanofillers in the polymer matrix enables these superior
research in the past decade and are becoming increasingly properties to be reached at low concentration level with-
important for applications due to their unique properties. out sacrificing many advantages of the parent polymer.12–15
Experimental work has demonstrated that nanocomposites For example, large deviations of Tg relative to the bulk poly-
can exhibit significant improvement in mechanical, thermal, mer were observed at very low nanofiller loadings (i.e., 0.05
electrical, and other physical properties in comparison with wt % reported in ref. 16 and 0.75 wt % reported in ref. 17),
their parent polymer systems by judicious incorporation of which is believed to be the result of the large extent of
nanoparticles. The effect of nanofillers on the glass transition interphase region penetrating through the nanocomposite and

© 2011 Wiley Periodicals, Inc.

740 JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS 2011, 49, 740–748

The large black dashed circles glass transition temperature.24 In case of inhomogeneous microstructure. nearly all of the relevant literature reveals that nanoparticle agglomeration is a significant concern18 for several reasons including high surface tension during material processing. a In this article. Cho and Daniel25 demonstrated that the glass transition temperature of a composite increased only modestly with nanotubes which were somewhat agglom. 740–748 741 . It is noted that only attractive a random dispersion of nonoverlapping identical circles is WWW. 24–26 Evidence of the FIGURE 1 (a) The black circle with radius of rcl represents the mechanical ramification of the interphase was shown. As there are few ways to accurately assess viscoelastic behavior of polymer nanocomposites. To study dynamics of thin polymer films could only be investigated as the influence of nanotube agglomeration on the formation of a whole. but the method is also directly applicable silica/PMMA nanocomposites. the inhomogeneity of the microstructure can agglomeration on the formation of the interphase network and be described by a parameter defining the local volume frac- on the glass transition temperature of nanocomposites. Obviously. 23 have been applied resulting in systems with wide ranges of degrees of nanopaticle agglomeration. Qiao and Brinson. Rittigstein et al. inclusion/polymer interface. to describe the viscoelastic prop- erties in the interphase region.4. 1(a)]. cl . However.ORG FULL PAPER formation of a percolating altered polymer network. MICROSTRUCTURE DEVELOPMENT AND FINITE erated. and although it represents explicitly the case of aligned bridge the gap between knowledge of thin polymer films and nanotubes. Thus.19 incomplete exfoliation of nanoparticles. a gradient of properties is microstructure of the clustered nanoparticles is idealized as necessary to produce the gradual. the effect of the interphase and nanoparticle clustering on the imental samples. (b) Schematic of unit cell with polystyrene. thus. the trends in the results on time dependent prop- that of nanocomposites. until 2003. cl . while the Tg was increased by 39 ◦ C in a composite ELEMENT MODEL where better nanofiller dispersion was achieved by using a dispersant. direct evidence and understanding are A two-dimensional plain strain model is adopted to examine lacking due to difficulties in quantifying dispersion in exper. rather than binary. regime. We implement this model as a The glass transition temperature of nanocomposite was double layer in which the relaxation time of each layer is a con. though a wide variety of processing methods and functionalization strategies12. distribution similar to a method in literature28 for sphere tally observed shifts in Tg of polymer nanocomposites. are randomly generated [see element simulations to understand the effect of nanoparticle Fig. obscuring the heterogeneity in the dynamics. Ramanathan et al.COM JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS 2011.4 also interfacial interaction that leads to Tg enhancement is consid- observed a drop of Tg at high filler loading in silica/P2VP and ered in this article. Clustering of nanoparticles has been correlated with a reduc- tion in the advantages afforded to nanocomposite and under- mines the potential enhancements. erties are generalizable to other 3D configurations. we develop a numerical approach based on finite fixed number of nanotubes. in the work done by Putz 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.POLYMERPHYSICS. which captures the essential features of the interphase volume element (RVE) with periodic boundary conditions. random dispersion of circular regions with radius rcl . the degree of systems also introduced a gradient interphase model. Herein. modeling can be used to ments. to cluster region and six particles with radius of R are randomly disappear on aggregation in functionalized nanotubes in distributed inside of the cluster. obtained by a finite element analysis of a representative stant. np .21 Complete control of clus- tering has not yet been achieved. See text for details. We also validate this discrete approximation with a A square unit cell with edge length equal to L containing continuous gradient model.20 and van der Waals attractions between nanoparticles. 6 inhomogeneity. inhomogeneous microstructures demonstrated that homogenous interphase layers in polymer of clustered materials must be generated. of this unit cell is 30%. achieved at higher loadings. which represent the clusters. Much reinforced ductile-matrix composite is selected in which the as is observed in thin polymer films.27 numerical simulations perature of nanocomposites. However. 49. the relative change of Tg to and small blue empty circles are replicas of cluster regions and the bulk polymer decreases or even disappears when severe nanoparticles to illustrate periodic geometry of the unit cell. 6. 22.MATERIALSVIEWS. As was previously noted. The tion of nanotube in each cluster. The agglomeration of nanoparticles occurs in nanocomposites. Tg shifts. In a the interphase network and further the glass transition tem- previous article. The two- and control details of the dispersion and interphase domains dimensional approach simplifies the computational require- of a polymer nanocomposite sample.4. Inside each cluster region. changing the relaxation time in interphase domain decays away from the cl correspondingly. to the case of the repulsive interaction between nanoparticles esized to result from decreases in nanoparticle dispersion and polymer chains. WWW. in which inhomogeneity can be controlled by tuning rcl . an isotropic. a particle nanocomposites were inadequate to replicate the experimen. These phenomena are hypoth.

In the examples intersecting the edges have the counterparts on the oppo. Two different as . that closest to the nanotube is denoted as 742 JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS 2011. In this study. of all particles.  = 3. the inhomogeneous dispersion of nanotubes is created with a sim- ilar algorithm but composed of two steps. 29 is utilized to construct the unit between matrix and inclusions is assumed. the local volume fraction of nanoparticles cl can be calculated by the equation  2 R cl = np . which has been shown to capture important features this requirement. rcl . for the be greater than 2rcl . the ratio of interphase nonoverlapping requirement for particles is automatically sat. FULL PAPER WWW. To in this article. f = 3. the centers of ncl clusters are generated based on random sequential adsorption algorithm (RSA)27–29 that ensures all cluster regions are impenetrable. To take To properly enforce the periodic boundary conditions. For the composites with nanoscale fillers. Considering experimental data on ultrathin polymer films on cate an infinite but repetitive configuration to represent the an attractive surface.8%). whereas for the higher volume fraction (f = 5. In the following step. Decreasing the ture is also created for comparison. impose the restriction that the clusters are nonoverlapping. In the first step. As we assume FIGURE 2 Schematic of composite configuration showing the each cluster has the same radius and equal quantity of par. The ratio of thick- cell with large rcl (thus small cl ). the corresponding numbers of particles inside dispersion of particles and interaction between polymer and RVEs (N) are 60 and 90. For the homogeneous interphase thickness can lead to a more pronounced transi- system. In addition to the sample due to easier formation of a percolated interphase inhomogeneous microstructure.8% particles. the local volume fraction is identical for all clusters in surrounding the nanoparticle (in black). including the repetitive clusters outside case of (Tg ) shift in thin films [O(100 nm)] filled with multi- of the unit cell. a simple gradient of two layers is chosen (see site edges and the intersections must be identical. f . Interphase layers are the unit cell.14 Periodic boundary conditions are applied to the RVE to repli. is a parameter to describe the interphase volume around volume fractions of nanoparticles are studied here. The interphase region in the polymeric composites is modeled erated without applying additional strategies. we enforce the distance between any two cluster centers to  = 2. chosen here. the this gradient into account. thickness to the diameter of particle being 2–3 is very reason- isfied regardless of periodic condition because these particles able. We use a smaller ratio for the higher volume fraction can only be generated inside of each cluster. Uniaxial loading condition is applied. the inclusions close to or intersecting the of overall response. first interphase.3 the polymer mobility changes in a gra- continuum properties of the composite with many inclusions. Therefore. particles. 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.ORG generated to simulate the in situ configurations of nanoparti- cles embedded in polymer matrix. which is modeled by two concentric annuli ticles. 49. In this study. a continuous gradient model. tinguish the difference of inhomogeneity for models with the same volume fraction of nanoparticles. It is noted that as this model is dimensionless. It is worth noting that due to the limitation of the RSA algorithm. the walled carbon nanotubes (20–50 nm). network in the sample with more particles. and simulations are performed by ABAQUS to predict the tan  of the nanocomposites. nonoverlapping circles with the same radius. Given the edge of RVE equal to 70R (area is expected to be 1∼10 or even larger depending on the A = 4900R2 ). interphase region. the clusters with radius rcl larger than the jamming limit cannot be gen. Given a uni- form radius. for the lower volume fraction case (f = 3. 1(b)]. rcl . R. this ratio and f = 5. dient fashion away from the polymer-surface interface. cl is used to dis. respectively.4%. so that the particles are also nonoverlapping and randomly distributed inside of each cluster. The properties of the into periodic conditions. the positions of np particles within each cluster are generated using the same RSA algorithm. Two different ratios are adopted site edge by a distance of edge length L [see Fig. defined with cl < 10% were generated by this method. the models ness of the interphase to the diameter of the particle. the as an annulus surrounding the particle and perfect bonding method described in ref.POLYMERPHYSICS.27 We also validate this discrete model with edges of the unit cell are duplicated and shifted to the oppo. a homogeneous microstruc. Once the cluster positions are determined. In remaining of this article. To fulfill Fig. 2). the nanoparticles are randomly dispersed inside of the tion from a discrete interphase network to a percolated one corresponding unit cells with RSA algorithm taking account occurring as the agglomeration reduces.4%). 740–748 . merged in the overlapping regions. we divide the interphase region into geometry of the unit cell must be periodic such that particles concentric layers with modulated properties.

From this figure. the size of RVE also has important influence on the predictions.  = 3 A = 14.3.32. 50 distributions are investigated. the lowest clustering degree generated in simulations are performed at one particular frequency value this study is 8%.371 coefficient of variation (COV) of the prediction becomes con- f = 3.31 the specimen with the area A = 4900R2 is sufficiently large.309 stant. It can be seen that the Tg as the location of the tan  peak in the temperature domain decreases as the degree of clustering increases from homoge- calculation. ABAQUS scripting language is utilized to rapidly create multiple models. the example to study the size effect.4%.ORG FULL PAPER A unit cell containing 60 particles (N = 60) with f = 3. nous (no clustering) to moderate agglomeration (cl = 30%). are investigated. two RVEs with the same volume fractions “Interphase-1. By running steady-state dynamic eration cl = 8.900R 2 155. thereby simulating the decay of the restriction toward different degrees of clustering (in order of increasing agglom- that of the matrix material.  = 3. 740–748 743 .8%) host matrix material. we have to determine the f = 5.8%. It is believed that as the number of RVEs approaches infinity. RVEs with six quency.27 0. for unit cells with the same volume fractions and inhomogeneity of nanoparti- cles. For Interphase-2.MATERIALSVIEWS. 10.3 ◦ C.700R 2 155. eration algorithm. and the mean value and COV of predicted Tg are shown in Figure 3 as a func- tion of RVE number. In both cases. Therefore. Tg for all distributions is calculated by averaging predictions of FIGURE 3 Effect of number of RVEs on the mean and COV of 20 RVEs.900R 2 155.” A = 14700R2 .  = 2 A = 14. than 0. in practice. As the interphase regions may overlap. cl = 30%.8%.8 and 5. TABLE 1 Mean Values and COVs of Predicted Tg for Different a statistical approach is used in which number of RVEs with Specimen Size different particle distributions are generated and calculated to Specimen Size Mean Value COV (%) obtain the mean value and the standard derivation of Tg . 20. the glass transition (1 Hz in this work) for different temperatures. but larger area of the unit cells. the highest clus- Note that any overlapped interphase regions are merged to tering degree generated in this work. 33 However. ness to particle diameter) are first investigated. 25. which meet all requirements and differ only by the particle distribu- tion. and the finite size model can represent the real material Sample-2 A = 4.202 minimum required RVEs for practical consideration.700R 2 155. Therefore. and the area is only counted once. The composites with cl = 30% result in a Tg increase of only NUMBER OF DISTRIBUTION AND RVE SIZE 2. the properties are also with  = 3 (where  is defined as the ratio of interphase thick- derived from bulk PC but are shifted only one decade in fre.” whereas the properties of the second inter- as before. 4).202 behavior. ulus of 100 GPa and Poisson’s ratio of 0. 20 RVEs are suffi- cient to have a statistically meaningful representation of the microstructure. 49. In total. 15. we can see both mean value and COV of the predicted Tg become constant when the number of RVEs is more than 20. In addition to the number of RVEs. The properties of Interphase-1 are determined by shifting the PC master curve RESULTS AND DISCUSSION two decades lower in the frequency domain.4%. and cl = 10% is selected to study the minimum num- ber of RVEs required for this simulation. The mean and COV of the The material properties of polycarbonate (PC) were measured predicted Tg of those two cases are computed and listed in by dynamic mechanical analysis.19 0.27 0.COM JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS 2011.30 Mastercurve of the matrix Table 1. phase. WWW. In each microstructure. we assume that term Prony Series using a program developed in this group. nearly three times lower than the Tg increment for composites with randomly dispersed particles. predicted Tg . and 30%) as well as a RVE simulations on Abaqus. and this size is used for all models in this study. for given f and cl .32 0. WWW. representative of strong positive interactions between the nanoparticle and the Nanocomposite specimens containing 60 particles (f = 3. For the temperature domain calculation. To confirm the proper size of the model.056% for the larger system. closest to the bulk matrix is denoted as “Interphase-2. transition temperature (Tg ) of the nanocomposite is measured and the results are plotted in Figure 5. is selected as form a union. the Sample-1 A = 4. f = 3. It can be seen that the mean value changes by less polymer in frequency domain is then approximated by a 28. The nanoparticles are assumed to be elastic with Young’s mod. Thus.POLYMERPHYSICS. Because of the limitation of the particle gen- quency are obtained. Then the glass temperature is calculated by averaging predictions of 20 RVEs. shown in Fig. Therefore. in the remainder of this paper. it can be expected that different specific distributions of particles will lead to different predictions of glass transition temperature of the composites. the complex modulii of the composites for homogenous dispersions are constructed (Examples are are retrieved and the corresponding tan  as a function of fre.

The error bars cl = 10%). The error bars in x and y represent the standard deviations of the volume fractions of interphase and the predicted Tg . it is unsur- prising that increased inhomogeneity weakens the influence on Tg .8% and f = 5. 20. 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. Instead. the model shown in Figure 4 (c.8%. FULL PAPER WWW. As agglomeration of nanoparticles leads to loss of interphase volume as the interphase in agglomerate overlap.4%.  = 2. Columns that the interphase regions are percolated and form a connec- from left to right in each category are the Tg for random disper.8%. where Figure 4(b) is an example FIGURE 5 The predicted Tg for two unit cells with different of cl = 10% and Figure 4(c) is of cl = 15%. the interphase domains remain discrete in indicate the standard deviations of the predicted Tg . (a) random. 10. However.ORG FIGURE 4 Three models showing the interphase morphology for different clustering degree with f = 3. it can be seen that the predicted Tg of composite is not strictly proportional to the interphase vol- ume. 740–748 . f = 3. 49. (c) cl = 15%. cl = 8. and 30%. while. examining the relationship between the mean value of Tg and the average volume fraction of interphase of the RVEs [see Fig.POLYMERPHYSICS. Interphase-1 is represented in dark blue and Interphase-2 is in light blue. and (d) cl = 30%. FIGURE 6 Relationship between mean value of predicted Tg and averaging interphase volume for samples with (a) f = 3.  = 3 and (b) f = 5.b) (random and sion. It can be seen nanoparticle concentrations. It is clear that the inter- phase forms a connective network in (a) and (b) while interphase regions are discrete in (c) and (d). respectively.4%. 15. To explain this phenomenon. we examine the microstructures of the RVEs shown in Figure 4. 25. tive network inside of matrix in Figure 4 (a. (b) cl = 10%. 744 JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS 2011. The numbers above symbols indicate the clustering degree of each data point. 6(a)].d) (cl = 15% and cl = 30%).

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. percolation effect. the Delaunay triangulation is applied to The material properties of interphase used in this work measure the interparticle distance in nanocomposites. considered here. 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 = 5.2. the interphase percolation effect is diminished in the second example [Fig. the agglomeration of nanopar. 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.COM JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS 2011. due to small size of the unit cell.4. with the percolated paths saturated. FIGURE 7 Microstructures for different volume fraction of ber of clusters in the unit cell is larger for the higher volume nanoparticles (f = 3. 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. In such higher loadings of nanofiller.ORG FULL PAPER A percolated interphase network has significant effect on the viscoelastic properties of polymer composite. In the case shown here. However. self-attraction of nanoparticles real nanocomposites with 3D morphology. we can observe ticles will have even more pronounced effect.39 Thus. 156. media is much lower than that of the disc shape in 2D media These results can qualitatively explain the experimental obser.4. 34. Thus.  and high volume fraction of nanoparticles. There. the effect is not as pronounced as in Figure 6(a) both because of small interphase/nanofiller ratio. 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. 49. 740–748 745 . 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. which can be achieved only if Interphase-1 satu. in the prepercolation regime [Figure 4(c. the maximum increase of Tg relative to pristine polymer tions with the length of the unit cell. although the RVEs have the same agglomeration degrees in both examples.4% is plotted in mobility of polymer chain and thus increase Tg by tens of Figure 9. respectively. In the postpercolation regime. 6). A similar phenomenon is also observed in the unit cells with higher f [Fig. the effect of changes in agglomeration have a modest impact on the predicted Tg (lower slope at lower volume fractions of interphase in Fig.33. In contrast. 38 In such systems. 35 At will form a connective network at lower thresholds.POLYMERPHYSICS.4% in the fraction case because the clusters are randomly dispersed right one) with cluster degrees cl = 10% and cl = 15%. 8). 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. 6). was replicated and copied along x and y axis in both direc- fore. and 153 ◦ C for gon (Fig. It is clear in the matrix.8% in the left figure and f = 5. As shown above. 7). the microstructure Interphase-1. Only those ligaments is 9. persion. 5. 6(b)]. 41 Here. the num. 6(b)] with higher nanoparticle volume fraction. the destruction leads to more prevalent nanoparticle clustering36. the interphase regions is not a monotonic function of nanofiller loading. interphase regions than the situations considered here. 6).4 ◦ C. 9.8% and f = 5.4% (right column). Moreover. particularly on the loss modulus and Tg . fore. which diminishes the interphase interphase regions (Two examples are shown in Fig. 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. There. with at least one end inside the unit cell were taken into rated the matrix.MATERIALSVIEWS. 6. Interphase-2. that the interphase/nanoparticle ratio is smaller and the parti- formly distributed. in typical composites with randomly vations in some nanocomposites that the enhancement of Tg oriented nanotubes or nanofibers. The smaller interphase/nanofiller ratio causes the interphase to play a smaller role compared with the first example with a larger . To diminish the edge effect. In the percolation regime where percolating paths are being formed [Fig. The interparticle distance data are quite scattered degrees. the clustering can have a compounding effect due to loss of Interparticle distance is often used to quantify the particle dis- interphase percolation. WWW. and pure PC.4. leading to a decrease of predicted Tg WWW. 4(b)]. 40. The particles and interphase are more uni.d)].

8%. (1) d FIGURE 9 Relationship between interparticle distance and pre- dicted Tg for samples with (a) f = 3. We hypothesize that. thus. To validate this approximation. simulations based on a continu- ous gradient model are made for different particle clustering degrees (random. The error bars in x and y indicate the standard deviations. 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 + . It is to be remarked that the form in eq 1 has been altered to account for the attractive attraction between particles and polymers. in nanocomposites.  = 2. This behavior agrees well with the exper- imental observation by Bansal et al. 10. and 30%). 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. 49. Because of the computa- posite. The microstructure has been double layer interphase model are equivalent to the shifting replicated both along x and y direction to diminish the edge function aT (d) in the continuous gradient model. FULL PAPER WWW.POLYMERPHYSICS.e. we derived the shift factor func- tion aT [Fig. only one configuration is considered.79 were used here). where the relaxation time of the interphase decays as a func- tion of the distance from the particle/polymer interface.. A and  are both material parameters (A = 0. of integral over the interphase area. On the basis of this relation between Tg and distance.ORG of nanocomposites. 740–748 . Also the values of A and  were chosen FIGURE 8 An example of measuring interparticle distance for the to make sure that the two shift factors (i.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.  = 3 and (b) f = 5. Comparing the predicted 746 JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS 2011. 20. the Tg changes in the same way as that in thin films. f = 3. The circles in black denote the particles within the com.6%.05 and  = 0. This gradient model is implemented in ABAQUS using the user subroutine UTRS by manually defining the shift factor for each element in models. in the sense effect.4%. 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. 2 and 1) in the model with cl = 10%. Only the edges in solid blue are taken into account for the tional demands of this calculation.. where d is the distance of the element to its nearest particle. for each clustering degree average of interparticle distance. 10(a)].

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