Materials Science and Engineering A 393 (2005) 1–11

Review

Experimental trends in polymer nanocomposites—a review

Jeffrey Jordana , Karl I. Jacobb , Rina Tannenbaumc ,
Mohammed A. Sharafb , Iwona Jasiukd,∗
a School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0405, USA
b School of Polymer, Textile and Fiber Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0295, USA
c School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0245, USA
d Department of Mechanical and Industrial Engineering, Concordia University, Montreal, Que. H3G IM8, Canada

Received 17 November 2003; received in revised form 24 September 2004; accepted 27 September 2004

Abstract

A review of the recent work on polymer matrix nanocomposites is presented. This review is not intended to be comprehensive, but provides
an overview of the processing techniques and trends in the mechanical behavior and morphology of nanocomposites. A number of composite
systems with amorphous and/or crystalline polymer matrices and different nano-sized filler materials are discussed.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Nanocomposites; Polymer matrix composites; Mechanical properties

Contents

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Experimental procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Experimental results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.2. Viscoelastic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3. Crystallinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.4. Density/volume change . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

1. Introduction nature. However, polymers have lower modulus and strength

as compared to metals and ceramics. One way to improve
Polymer systems are widely used due to their unique at- their mechanical properties is to reinforce polymers with in-
tributes: ease of production, light weight, and often ductile clusions (fibers, whiskers, platelets, or particles). The embed-
ding of inclusions in a host matrix to make composites, which
gives material properties not achieved by either phase alone,
∗ Corresponding author. Tel.: +1 514 848 2424x3143; has been a common practice for many years. Using this ap-
fax: +1 514 848 3175. proach, polymer properties can be improved while maintain-
E-mail address: ijasiuk@me.concordia.ca (I. Jasiuk). ing their light weight and ductile nature [1–6]. Improvements

0921-5093/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2004.09.044
2 J. Jordan et al. / Materials Science and Engineering A 393 (2005) 1–11
in properties can often be found even at relatively low filler
content [4,7,8].
Traditionally, composites were reinforced with micron-
sized inclusions. Recently, processing techniques have been
developed to allow the size of inclusions to go down to
nanoscale. For this work, the nano-sized inclusions are de-
fined as those that have at least one dimension in the range
1–100 nm. Experiments have shown that nanoscale reinforce-
ment brings new phenomena, which contribute to material
properties. In this review, the interest is in how mechanical
properties of polymer matrix composites are altered by intro-
ducing nano-sized versus micron-sized reinforcement, and
what additional factors contribute to the material response of
nanocomposites.
Current micromechanics theories rely on the idea that the
effective properties of composite materials, such as Young’s
modulus, are functions of properties of constituents, volume
fraction of components, shape and arrangement of inclusions,
and matrix-inclusion interface. These theories, therefore, pre-
dict that the properties of composite materials are indepen-
dent of the size of inclusions. In general, this is correct for
systems with micron size reinforcement, but, as mentioned
above may not be true for nanocomposite systems.
With the recent developments in the nanoscience and nan-
otechnology fields, the correlation of material properties with
filler size has become a point of great interest. As a result,
much of the work is still ongoing and there is yet to be a
definite conclusion on the effect of nano-sized inclusions on
polymer systems. In the following sections, a review is pre-
sented on the processing, experimental results, and possible
interpretations of those results for polymer matrix nanocom-
posites.
2. Experimental procedures
Making good samples of polymer matrix nanocompos-
ites is a challenging area that draws considerable effort. Re-
searchers have tried a variety of processing techniques [9–16]
to make polymer matrix nanocomposites. These include melt
mixing, in situ polymerization, and other approaches. Creat-
ing one universal technique for making polymer nanocom-
posites is difficult due to the physical and chemical differ-
ences between each system and various types of equipment
available to researchers. Each polymer system requires a spe-
cial set of processing conditions to be formed, based on the
processing efficiency and desired product properties. The dif-
ferent processing techniques in general do not yield equiva-
lent results [17].
Vollenberg and Heikens [9] were able to produce good
nanocomposite samples by thoroughly mixing filler particles
with polymer matrix. The polymer matrices used in these
experiments were polystyrene (PS), styrene–acrylonitrile
copolymer (SAN), polycarbonate (PC) and polypropylene
(PP). The inclusions were alumina beads 35 nm and 400 nm
in size and glass beads 4, 30, or 100 ␮m in diameter. The
volume fraction of particles ranged from 0 to 25%. Sample
preparation consisted of dissolving polymers in a polar sol-
vent and mixing in the beads for several hours. The mixture
was then poured over a large surface to allow the solvent to
evaporate and it was subsequently dried under a vacuum at
100 ◦ C. This mixture involved 30% volume fraction of parti-
cles. Pure polymer was then added to samples to achieve the
desired particle volume fractions.
Chan et al. [11] made nanocomposites with polypropylene
(PP) matrix and calcium carbonate (CaCO3 ) through melt
mixing of the components. First the components were dried
in an oven at 120 ◦ C and then cooled to a room temperature.
The polypropylene was mixed first with an anti-oxidant. The
CaCO3 nanoparticles, which were 44 nm in diameter, were
then added slowly and mixing continued for a fixed time after
all particles were added. This technique produced good, rea-
sonably well-dispersed samples at lower filler volume frac-
tions, 4.8% and 9.2%, but aggregation was found at a higher
volume fraction, 13.2%. Other researchers have also used a
form of melt-mixing to produce nanocomposites [17].
Polyurethane–silica nanocomposites have been made by
Pétrovic et al. [10] by first mixing the silica with polyol. The
mixture was then cured with diisocyanate at 100 ◦ C for 16 h
in presence of 0.1% catalyst Cocure 55 (from CasChem) and
subsequently poured into a mold. The particles were spherical
with an average diameter of 12 nm and had narrow size dis-
tribution (10–20 nm). Good samples were produced at 10%,
20%, 30%, and 40% filler weight fraction, but the 50% filler
weight fraction sample did not cure completely.
It is believed that one of the main issues in preparing good
polymer matrix nanocomposite samples is the good disper-
sion of the nanoparticles in a polymer matrix. Rong et al. [12]
grafted monomers made of styrene to surround the particles
to produce better dispersion. They used isotactic polypropy-
lene as the matrix and SiO2 as inclusions which were ap-
proximately 7 nm in size. The particles were heated first to
remove any water absorbed on the surface. Then, they were
mixed with one of the monomers and solvent. This mixture
was then irradiated and the solvent was removed. Samples
were then made by adding polypropylene, tumble mixing,
compounding and extruding. This technique produced sam-
ples without aggregation and, in addition, greatly increased
the particle–polymer matrix interfacial interaction.
In situ polymerization is another technique that has been
used to make polymer matrix nanocomposites [13–15,18,19].
It is a method in which particles are dispersed first in
monomer and then the mixture is polymerized. In Yang et
al. [13], nanocomposites with polyamide-6 matrix and silica
inclusions were prepared by first drying the particles to re-
move any water absorbed on the surface. Then, the particles
were mixed with ␧-caproamide and concurrently a suitable
polymerization initiator was added. The mixture was then
polymerized at a high temperature under nitrogen [13]. This
technique produced well-dispersed samples when the inclu-
sions were around 50 nm in size, but aggregation occurred for
smaller particles around 12 nm in size [15]. This was most
 J. Jordan et al. / Materials Science and Engineering A 393 (2005) 1–11
likely due to the increased surface energy for the smaller par-
ticles, which, in the absence of a stabilizer, favored further
particle segregation.
Ash et al. [20,21] and Siegel et al. [6] used yet another
technique and produced nanocomposites with polymethyl-
methacrylate (PMMA) matrix and alumina inclusions, which
were well dispersed throughout the matrix. The particles
were added to methylmethacrylate (MMA) monomer and
dispersed through sonication in the low-viscosity solution.
An initiator and a chain transfer agent were added later. The
mixture was then polymerized under nitrogen, broken into
smaller pieces, and dried in a vacuum. Tensile specimens
were made through compression molding and cooled to room
temperature under pressure.
Li et al. [16] used a unique approach to prepare high-
density polyethylene (HDPE)–polypropylene nanocompos-
ites. Seventy-five percent weight HDPE and 25% polypropy-
lene were melt-mixed and extruded into tapes. These tapes
were then cut into shorter pieces and melt-processed by
either extrusion or compression molding. This produced a
nanocomposite with HDPE as the matrix and polypropylene
fibrils ranging from 30 to 150 nm in diameter.
For clay nanocomposites, the specific choice of processing
steps depends on the final morphology required in the com-
posite, i.e., exfoliated or intercalated form. In the intercalated
form, matrix polymer molecules are introduced between the
ordered layers of clay resulting in an increase in the inter-
layer spacing, but still maintaining the order. On the other
hand, in an exfoliated form, clay layers are separated and are
distributed within the matrix. Intercalated nanocomposites
are generally formed by melt blending or by in situ poly-
merization. Exfoliation ability depends on the nature of clay,
blending process, and the agents used for curing. The final
structure of clay composite has a wide range of variations,
depending on the degree of intercalation and exfoliation. A
number of experimental techniques were used to character-
ize intercalated or exfoliated nanocomposites, such as X-ray
diffraction, transmission electron microscopy (TEM), DSC,
and thermogravimetric analysis (TGA).
Thus, in general, there is no single procedure that is fol-
lowed for making polymer matrix nanocomposites. A com-
bination of melt mixing, extrusion, and compression molding
seems to be the method of choice for many researchers. As
seen from the above mentioned summary the most important
factor to consider in deciding between different processing
techniques is the requirement of good particle dispersion in
the polymer matrix. This dispersion will play a major role in
the results reviewed below.
3. Experimental results
While there has been much experimental work done in
the area of polymer matrix nanocomposites, there is yet to
be a consensus on how nano-sized inclusions affect material
properties. This is partly due to the novelty of the area, and
3
the challenges in processing of nanocomposites, lack of sys-
tematic experimental results, and scarcity of theoretical stud-
ies. Moreover, some material properties have been studied
more in-depth than other, leaving gaps in the knowledge on
nanocomposite behavior. The following sections will outline
some of the experimental results that are available to-date and
identify the trends that can be obtained from these results. The
focus of this summary will be on particles and matrix mor-
phology (degree of crystallinity, particle size and arrange-
ment) and the mechanical behavior of the nanocomposite
materials (elastic modulus, strength, yield stress, strain-to-
failure, fracture toughness, and viscoelastic properties).
3.1. Mechanical properties
Vollenberg and Heikens [9] performed a wide range of
tests on composites with matrices made of polystyrene (PS),
styrene–acrylonitrile copolymer (SAN), polycarbonate (PC)
and polypropylene (PP) with micro- as well as nano-sized
glass or alumina inclusions. The PS and PP were observed to
have a very poor interaction with the particles due to their non-
polar character while the interfacial interaction was much
more noticeable for the SAN and PC. For composites with
PS, PC and PP matrix and glass or alumina particles the mod-
ulus increased with decreasing size of particles. In order to
investigate the effect of interface adhesion separate experi-
ments were done on SAN and PC matrix composites in which
particles were pretreated with siloxane DF 1040 (General
Electric Plastics) to decrease the filler–matrix adhesion. No
size effect on elastic modulus was found for composites with
SAN and PC matrix with either excellent adhesion or very
poor adhesion due to treated particles. However, these exper-
iments were done for three different particle sizes which were
in micron range only, not nanosize range. For all systems the
elastic modulus increased with increasing volume fraction of
the inclusions. It is necessary to point out that in these ex-
periments, while there were several different sizes within the
micron range, only one particle size can be considered in the
nanosize regime by the definition provided earlier.
Similar conclusions were obtained by Chan et al. [11] for
composites with polypropylene (PP) matrix and calcium car-
bonate (CaCO3 ) nanoparticles. In their system the CaCO3 in-
clusions had an average size of 44 nm and a strong interaction
with the polymer matrix. The addition of CaCO3 nanoparti-
cles to a PP matrix produced an increase in the elastic mod-
ulus compared to the pure matrix as shown in Fig. 1. The
increase in modulus coincided with an increase in nanopar-
ticle volume fraction. The reverse effect was found for the
yield stress and the tensile strength of the composites; both
of these quantities were highest for the pure polypropylene
and decreased as the volume fraction of CaCO3 increased.
The strain-to-failure did not change much between the vari-
ous systems.
Clay-reinforced nanocomposites have received consid-
erable attention in recent years (more than 100 articles
have been published in the literature on clay composites
4 J. Jordan et al. / Materials Science and Engineering A 393 (2005) 1–11
Fig. 1. Polypropylene with CaCO3 (from [11]).
in the past three years). A number of polymers, such as
PC, PAN, PP, etc. were used as the matrix. Shelley et al.
[22] examined a polyamide-6 system with clay platelets. The
platelets constituted 2% and 5% weight fraction and were
1 nm × 10 nm × 10 nm in size [23]. Good interaction was
found between the matrix and inclusions. With this setup, the
elastic modulus was found to improve for both the 2% and 5%
samples. For the smaller weight fraction (2%), the increase
in effective elastic modulus was 40% over the modulus of
the pure polymer system. The larger weight fraction (5%)
improved the effective modulus by a factor of two as com-
pared to that of pure polymer. These results were for tensile
specimens cut in both longitudinal and transverse directions.
In addition, the yield stress also improved for both weight
fractions, with the greatest improvement found for the higher
concentration of inclusions. The other quantity studied was
the strain-to-failure. The 2% system was found to give higher
strain-to-failure than the pure system in the longitudinal di-
rection but close to that in the pure system in the transverse
direction. The higher filler content resulted in a decline in
strain-to-failure from the pure system in both directions [22].
Properties of nanocomposites are highly related to theirs
microstructure [24]. For epoxy–silicate clay nanocomposites,
Luo and Daniel [24] found that the ideal case for maximiz-
ing stiffness and thermal properties is through full exfolia-
tion and dispersion, which is not achieved usually, but often
one obtains partial exfoliation and intercalation. Similar re-
sults were presented by Mark and co-workers [25] for clay
reinforced natural and epoxidized rubber. For sodium mont-
morillonite silicate clay the degree of its dispersion deter-
mined its reinforcing effect in rubber. Zhang et al. [26] further
demonstrated the similar behavior for clay–polypropylene
nanocomposites. They also showed that the reinforcing ef-
fects demonstrated by storage modulus, thermal stability,
etc., are directly related to the dispersion of clay particles
in the matrix. Park et al. [27] fabricated clay nanocomposites
where organophilic clay particles were embedded in a syn-
diotactic polystyrene with melt intercalation. They found that
stepwise mixing method (where styrene polymer is blended
with the clay first to enable intercalation followed by blend-
ing with polystyrene matrix) resulted in a higher degree of
intercalation (than a simultaneous mixing method) and that
the higher degree of intercalation in the structure resulted
in higher tensile strength and other mechanical properties.
In another work [28] on polystyrene–clay nanocomposites,
prepared by free-radical polymerization, the authors found
that exfoliated nanocomposites had better thermal stabil-
ity and better mechanical properties than pure polystyrene.
With clay–polyurethane nanocomposites, Tortora et al. [29]
showed that exfoliation occurred for low montmorillonite
content but when the clay content was increased more interca-
lation was observed associated with higher elastic modulus
and yield strength. However, breaking stress and breaking
strain decreased with increasing clay content.
Masenelli-Varlot et. al [30] studied the effects of
polyamide-6 with intercalated and exfoliated montmoril-
lonite. The intercalated samples ranged from 1.7 to 2.7% clay
while the exfoliated samples ranged from 2.4 to 4.2%. Under
low-deformation tests, Young’s modulus increased linearly
with filler content with no major difference between interca-
lated and exfoliated. Under compression tests, the exfoliated
samples had one direction that was higher than the rest while
the intercalated samples did not. The intercalated samples are
likely weaker due to the weaker mechanical coupling. The
ultimate stress and strain-to-failure were lower for all filler
concentrations than pure polyamide-6. With the same level of
dispersion and filler content, the exfoliated samples exhibited
greater stress at failure than the intercalated samples while
the intercalated samples had a greater strain-to-failure [30].
Few micromechanical models were developed which are
in agreement with the behavior of some nanocomposites
[31–35]. A recent theoretical study [34] shows that when the
structure changes from intercalated to an exfoliated struc-
ture, the morphological change is accompanied by a mod-
erate change in modulus rather than an abrupt change. This
theoretical prediction was supported by experimental results
in [36]. There is a general agreement in the literature that
exfoliated systems have better mechanical properties, par-
ticularly higher modulus, than intercalated nanocomposites
[37]. Also, studies on nylon 6–clay nanocomposites showed
that morphology or physical properties are not significantly
reduced from reactions or polymer molecular degradation
during the processing stage [38].
Polyamide-6 nanocomposites with silica inclusions have
been examined (e.g. [15]). In contrast to the polyamide–clay
system described in [22], the nanoparticles were 17, 30, or
80 nm in diameter. The elastic modulus was slightly higher
for the nanocomposites than for the pure system, but there was
little difference between composites with different nanopar-
ticle sizes. This can be seen in Fig. 2 where S refers to the
smallest particle size and L to the largest particle size. As in
the polyamide–clay system, the yield stress increased with
increasing filler content and also increased slightly with the
decreased size of the particles. The strain-to-failure followed
the opposite pattern as it decreased greatly for an increase
in volume fraction and decrease in particle size. In addition,
there existed a sharp decrease in the stress immediately be-
fore failure in all systems [15]. A separate study involving
 J. Jordan et al. / Materials Science and Engineering A 393 (2005) 1–11
Fig. 2. Polyamide-6 with small (S) and large (L) inclusions (from [15]).
these same materials examined the influence of a silane pre-
treatment, which improved the matrix–filler interface. For the
treated system, there was an improvement in strength as well
as toughness, which was in contrast with the untreated system
in which strength improved as toughness decreased [19].
Another study centered on polyurethane–silica compos-
ites [10]. Silica nanoparticles have relatively strong interac-
tion with polyurethane matrix. Polyurethane–silica compos-
ites were formed with inclusions of 12 nm and 1.4 ␮m at
10–50% weight fraction of inclusions. The tensile strength
varied little between the micron and nano-sized particles, up
to a filler composition of 20% weight fraction. Above 20%,
the tensile strength was higher for the nanocomposite as com-
pared to pure polyurethane polymer. In the nanocomposite,
the strain-to-failure increased by 500% over the pure system
while for composites with larger inclusions the increase was
only by 100% [10].
A unique set of experiments was performed by Rong et
al. [12] with SiO2 nanoparticles in a polypropylene matrix
with and without the addition of grafting polymers (either PS
or PMMA), which have the ability to improve dispersion of
nanoparticles and interfacial interactions between the parti-
cles and the matrix. The elastic modulus increased with in-
creasing volume fraction in both systems but was much higher
in the untreated composite systems (without grafting poly-
mers). The modulus for the composites treated with grafting
polymer only improved minimally as a function of volume
fraction of SiO2 particles. The opposite effect was found for
the tensile strength where the treated composites showed in-
creased strength while the strength changed very little in the
untreated composites as a function of volume fraction of par-
ticles. Interestingly, the results for strength were insensitive
to change in volume fraction of particles. The strain-to-failure
was lower in the untreated systems than the pure polypropy-
lene samples. In the treated system the strain-to-failure in-
creased for volume fraction of particles up to 2% and then
started decreasing. This change in behavior at approximately
2% volume fraction was attributed to the change in disper-
5
Fig. 3. Stress strain curve for PMMA and alumina (from [20]).
sion of particles, namely the change from the uniform disper-
sion to clustering resulting in microcomposite agglomeration
[12]. In another study on palladium–PMMA nanocomposites
showed that addition of Pd in PMMA increased the oxidative
thermal stability of the system. Improvement in thermal sta-
bility was linearly related to the volume fraction of palladium
inclusions [35], although the elastic modulus decreased as a
function of the Pd content.
Very interesting results were obtained by Ash et al.
[20] who performed a series of tests on PMMA–alumina
nanocomposites. The alumina nanoparticles were around
40 nm and had very little interfacial interaction with the poly-
mer matrix. As filler content increased, there was a sharp ini-
tial drop in Young’s modulus followed by a steady increase.
Even at the highest filler content, however, the effective elas-
tic modulus was lower than the pure system. In addition, the
yield stress and tensile strength of the pure matrix was higher
than for the composite as shown in Fig. 3. These results for the
strength are very different from the other systems that have
been examined. In addition, the strain-to-failure increased by
around 800% over that for the pure system.
Elastic properties were found to increase for a nanocom-
posite system made 75 wt% of high-density polyethelyne
(HDPE) matrix and 25 wt% polypropylene (PP) [16]. During
processing the compound was fibrillated and PP nanofibers
were created. The fibers were cylindrical in shape, 30–150 nm
in diameter. The elastic modulus, yield stress, and tensile
strength were greater for the nanocomposite system than for
samples of pure HDPE [16]. However, the strain-to-failure
was lower for nanocomposite systems.
From the above discussion, it is possible to extract a few
trends for the behavior of polymer matrix nanocomposites
based on the nature of the polymer matrix, particularly crys-
talline or amorphous nature of the polymer, and the inter-
action between the filler and matrix. The elastic modulus
tends to increase with the volume fraction of inclusions in
every case. In some systems, there is a critical volume frac-
tion at which aggregation occurs and the modulus goes down
[1–4,8]. In general, there is also an increase in modulus as
the size of the particle decreases. Interaction between ma-
trix and filler may play an important role in the effects of
the nanoparticles [1–3] on composite properties. For polymer
systems capable of having a higher degree of crystallinity, the
increase in modulus with decreasing particle size is found to
6 J. Jordan et al. / Materials Science and Engineering A 393 (2005) 1–11
be greater in systems with poor interaction between filler and
matrix as opposed to those with good interaction. However,
the overall trend of the modulus of polymer nanocomposites
is not found to be greatly dependent upon the nature of the
matrix nor the interaction between filler and matrix.
An examination of the yield stress gives a different trend
than that of the elastic modulus. For composites with good in-
teraction between filler and matrix, the yield stress tends to in-
crease with increasing volume fraction and decreasing parti-
cle size, similarly to the increase in modulus under same con-
ditions. The pattern changes when there is poor interaction
between the matrix and particles. The addition of nanopar-
ticles with poor interaction with the matrix causes the yield
stress to decrease, compared to the neat matrix, regardless
of the filler concentration or size. The ultimate stress fol-
lows a similar pattern as that observed for the yield stress.
It generally increases in polymer systems (both crystalline
and amorphous) with good filler–matrix interaction and it
increases in general as particle size decreases. There is no
uniform trend with respect to the volume fraction of particles
for the ultimate stress. A poor filler–matrix interaction leads
to a decrease in the ultimate and yield stress as compared to
the pure matrix system.
The change in strain-to-failure behavior for nanocompos-
ites, like the yield and ultimate stress, is different depending
on the system. In this case, however, the change is with re-
spect to the nature of the polymer matrix as opposed to the
filler–matrix interaction. In general, the addition of nanopar-
ticles to a mostly crystalline or semi-crystalline polymer, re-
gardless of the filler–matrix interaction, reduces the maxi-
mum strain. The opposite trend is found in amorphous poly-
mers with the increase in strain-to-failure coinciding with a
decrease in particle size.
3.2. Viscoelastic properties
Viscoelastic properties were found to improve with the ad-
dition of particles in a polyamide-6 matrix with clay platelet
inclusions. More specifically, the storage modulus was found
to be higher for the composite systems than for the pure
polyamide-6 system. The increase in modulus coincided with
the increase in filler content [22,30]. However, experimental
results also showed that the onset of the decrease in mod-
ulus occurred at lower temperatures as the filler content in-
creased [22]. The storage modulus was also found to increase
with increasing volume fraction for polyamide-6 nanocom-
posite with silica nanoparticles rather than clay platelets
[15]. A similar increase in storage modulus was found for
poly(vinylidene fluoride)–clay nanocomposites [39].
Viscoelastic properties were also found to improve in other
systems, including polyurethane–silica composites. The stor-
age modulus increased for such composites with both micron
and nano-sized particles. This modulus also increased as the
weight fraction of the particles was increased to 50%. It is
also noteworthy to mention that in the rubbery state of the sys-
tem, the modulus is highest for the nanocomposite when the
weight fraction of the filler is as large as 40 or 50%. However,
if the weight fraction is below this level, the microcomposite
has the higher modulus [10].
In general, viscoelastic properties tend to be higher in
nanocomposites than in pure polymer systems. When there is
good filler–matrix interaction, the storage modulus generally
increases with increasing volume fraction. The modulus also
seems to increase as the particle size decreases. However,
there is little experimental work in this area for composites
with poor filler–matrix interactions. Overall, the storage mod-
ulus tends to increase with the presence of nanoparticles in a
composite system.
Morphological details, such as exfoliation, intercalation,
or cross-linked matrix versus uncross-linked matrix, have a
significant effect on the viscoelastic properties of nanocom-
posites. In epoxy–clay nanocomposite system forces from
cross-linked epoxy molecules cause intercalated clay gal-
leries to exfoliate, associated with a gradual increase in
viscosity and a relatively fast increase in storage modulus
[40]. In maleated polypropylene–layered silicate nanocom-
posites, exfoliated nanocomposite systems were reported to
have higher shear and complex viscosities, while in a shear
flow exhibiting the largest drop in complex viscosity due to
alignment of clay layers [41]. Dynamic storage moduli also
show a similar behavior [41]. Experiments with clay–nylon-
12 nanocomposite systems have shown that melt processing
under low shear improves intercalation, while larger shear
enhances exfoliation associated with a decrease in melt vis-
cosity [42].
3.3. Crystallinity
The degree of crystallinity of a polypropylene system
was found to change very little with the addition of CaCO3
nanoparticles. On the other hand, the peak crystallization
temperature was increased by around 10 ◦ C with the addition
of the CaCO3 inclusions. This increase was found to be nearly
the same for all filler volume fractions. Moreover, the size of
the crystalline domain spherulites was found to change dra-
matically in different systems. Scanning electron microscopy
(SEM) showed that the spherulites in the pure system had an
average size of around 40 ␮m, but no spherulites could be
seen when CaCO3 nanoparticles were added to the system
[11]. It is possible that the spherulites were too small and
they were not detected by SEM.
The addition of nano-sized montmorillonite clay platelets
to a polyamide-6 matrix was found to have no effect on the de-
gree of crystallinity of the polymer with weight fraction up to
5%. However, the nanoparticles did have an effect on the size
of the crystallites. The size of crystallites in the nanocom-
posites was nearly an order of magnitude smaller than the
size of spherulites in the pure matrix system [22]. Results
for a polyamide-6 matrix composite with silica nanoparticles
showed that neither the size nor the filler content had any
effect on the crystallinity of the system [15].
 J. Jordan et al. / Materials Science and Engineering A 393 (2005) 1–11
Fig. 4. Young’s modulus and glass transition temperature vs. filler weight fraction (from [20,21]).
In a separate experiment with clay–polyamide nanocom-
posites, the glass transition temperature of the system in-
creased with increasing clay nanoparticle content. This in-
crease was attributed to either the effect of the clay layers
retarding the polyamide molecule main-chain motion or a
slightly higher molecular weight of the polymer due to the
reactive organoclay used [43]. Another study, however, found
a 10 ◦ C drop in the glass transition temperature for all clay
filler contents. This drop was attributed to the presence of
surfactants [30].
Ash et al. [21] studied the glass transition temperature of
PMMA–alumina nanocomposites. They found that for filler
weight fractions less than 0.5%, the glass transition tempera-
ture did not change, but for filler weight fraction above 0.5%
the glass transition temperature dropped by more than 20 ◦ C
and stabilized at a new temperature at weight fractions above
1% as shown in Fig. 4b. This drop occurred at the same weight
fraction as the drop in the elastic modulus, as shown in Fig. 4a,
and as mentioned in previous discussion about this system.
A different result was found for the glass transition tem-
perature of a polyurethane matrix with silica inclusions. In
this nanocomposite system, the glass transition temperature
was found to increase as filler concentration increased. Dif-
ferent techniques produced differing results but the consen-
sus was that the glass transition temperature increased by
around 10 ◦ C for the nanocomposite above the neat resin as
the weight fraction of the filler was increased to 50%. The
transition temperature also increased with the use of micron-
sized inclusions, but the increase was not as great as that for
the nanocomposite [10].
The pattern that the crystallinity was little affected
by the addition of particles was also observed in a
polypropylene–SiO2 composite that was treated with graft-
ing polymers. The particles were found to have a small nu-
cleation effect on the polypropylene matrix, but, overall, the
crystallinity was not greatly influenced by the addition of the
nanoparticles [12].
Park et al. [37] found that for (syndiotactic)
polystyrene–organoclay nanocomposites, dispersed clay
layers act as nucleating agent competing with crystal growth
in polymers. Thus, exfoliated clay nanocomposites have
lower degree of crystallinity with faster crystallization rate.
However, the crystallinity of crystalline and semi-crystalline
7
polymers is not affected very much by the addition of
nanoparticles. There may be some changes in particular
nanocomposite systems, but overall no major differences
in crystallinity of nanocomposites versus neat polymers
were observed in any of the systems examined. On the other
hand, the glass transition temperature was influenced by
the addition of particles. When there is good filler–particle
interaction, the glass transition temperature tends to increase
with a decrease in the size of particles for amorphous poly-
mers. For crystalline polymers, the transition temperature
decreases with an increase in particle concentration. For an
amorphous system with poor filler–polymer interfacial in-
teraction, the glass transition temperature decreased overall.
Thus, while the degree of crystallinity is not significantly
affected by the presence of particles, the glass transition
temperature is very dependent upon this factor.
3.4. Density/volume change
It is natural for the density of a composite to be higher than
the density for a pure polymer system. The inclusions typi-
cally have much higher density than the polymer leading to
a higher density for the composite. This was found to be true
in a polyurethane matrix with micron and nano-sized silica
inclusions. The density increased, as expected, as the filler
content increased. However, the density of the composites
with the micron-sized inclusions was higher than the density
for the nano-sized inclusions [10].
The volume change of a composite undergoing tensile
elongation was examined by Reynaud et al. [15] using a
polyamide-6 composite with silica inclusions of various sizes
within the nanometer range. Reynaud et al. [15] reported a
volume increase for the pure polyamide-6 but larger increases
for the composite systems. The volume change was highest
for composites containing the smallest particles, which pro-
vides support for their debonding model that will be discussed
later in this article.
Investigations examining the change in the density or vol-
ume of polymer nanocomposites are limited. Nevertheless,
the trend is that nano-sized inclusions affect the volume of
a composite more than micron-sized inclusions do. The vol-
ume for the composite is higher for a nanocomposite than
a microcomposite with the same filler weight and the same
8 J. Jordan et al. / Materials Science and Engineering A 393 (2005) 1–11
polymer weight. It is important to point out that these results
are only for composites with relatively good filler–polymer
interaction.
4. Discussion
From the experimental results presented above, we ob-
serve that different composite systems can lead to very dif-
ferent results. One important observation is that composites
with nano-sized inclusions generally have different proper-
ties than composites with larger scale inclusions. The specific
reasons why the polymer matrix composites with nano-sized
reinforcement have different properties than composites with
micron-sized reinforcement are not fully understood, but sev-
eral theories have been introduced to explain some of the
changes in material morphology and behavior that are seen
at the nano-scale. It is important to point out, however, that
most of these theories were developed to explain particular
results and, therefore, are not necessarily applicable to a large
number of polymer nanocomposites.
Chan et al. [11] proposed that properties such as elas-
tic modulus, tensile strength, and yield strength decrease
in nanocomposites with polypropylene matrix due to the
change in nucleation caused by the nanoparticles (Fig. 5). The
nanoparticles produce a much larger number of nucleating
sites but, in turn, greatly reduce the size of these spherulites.
In their experimental work, no spherulites were found in the
nanocomposites by SEM indicating that either none were
present or they were reduced to such a small size that SEM
could not detect them. It was further proposed that there was
another mechanism which was causing these same properties
to increase. The increase occurred when there was a strong
interaction between the polymer and filler. This interaction
had larger impact in nanocomposites due to the large inter-
facial area between the filler particles and the matrix. Other
investigators have suggested that this interaction leads to a
layer of polymer that is directly adsorbed and bound to the
particles [9,10,20,21]. Experimental work that has been per-
formed on a polystyrene–cobalt nanocomposite with cobalt
nanoparticles with an average size of 21 nm has shown that
the polymer layer was about 24 nm, and varied non-linearly
with molecular weight [44].
Fig. 5. (a) Pure polypropylene and (b) polypropylene with 9.2% volume filler (from [11]).
An increase in yield and tensile strength and modulus in
nanocomposite systems as compared to microcomposites can
be partially explained on the basis of the interaction between
the filler and the matrix. It has been found that a greater adhe-
sion between the matrix and inclusion causes less debonding
when a stress is applied and, consequently the elastic modu-
lus and strength are improved [45]. Vollenberg and Heikens
[9] explained that if there is a strong interaction between the
polymer and the particle, the polymer layer in the immediate
proximity of the particle will have a higher density. For most
systems, density is proportional to elastic modulus, so the
region directly surrounding the inclusions will be a region of
high modulus. The polymer right outside this high modulus
region will have a lower density due to the polymer chains
that are moved towards the particle. For large particles, the
size of the low density region will be relatively large, and the
contribution of the high modulus filler will be diminished.
For nanoparticles, the number of particles for a given volume
fraction is much larger, thus the particles will be much closer
to one another. If the particles are densely packed, then the
boundary layer of polymer at the interface will comprise a
large percentage of the matrix and can create a system where
there is no space for a low modulus region to form. This re-
sults in the elastic moduli of composites with smaller particle
size (nano) being greater than the moduli of composites with
larger inclusions [9,10].
The small interparticle distance in nanocomposites was
used as another parameter to explain the changes in the elas-
tic modulus and strength of these materials when compared
with the composites with micron-sized particles. The same
parameter also plays a role in the glass transition tempera-
ture changes observed in nanocomposites versus composites
with micron-sized reinforcement. Ash et al. [21] found that
for their system the glass transition temperature was constant
until around 0.5% weight fraction of particles, then had a
sharp drop, and then it remained constant for weight frac-
tions above 1%. When there is little or no interfacial inter-
action between the filler and matrix and the interparticle dis-
tance is small enough, the polymer between two particles
acts as a thin film. For a thin film, the glass transition tem-
perature decreases as film thickness decreases. The distance
between particles in a composite with the filler weight frac-
tion below 0.5% is relatively large, and hence, in this case the
 J. Jordan et al. / Materials Science and Engineering A 393 (2005) 1–11
Fig. 6. Debonding around 50 and 12 nm particles (from [15]).
polymer between each particle is not considered to belong to
the thin film regime. As the filler concentration increases,
the interparticle distance and the resulting thickness of the
film, decrease. This theory, however, does not explain why
the glass transition temperature levels off rather than contin-
ues to drop as a function of increasing weight fraction of the
filler. A drop-off in Young’s modulus was found for the same
filler weight fraction as the drop in glass transition tempera-
ture. It was proposed that as the glass transition temperature
decreased, the relative testing temperature increased. Also,
the elastic modulus of the matrix, PMMA, decreases as tem-
Table 1
Summary of polymer nanocomposite trends
Crystalline
Elastic modulus Increase w/volume fraction
Increase or no change with decrease of size
Increase w/volume fraction
Increase w/decrease size
Greater increase than for good interaction
Yield stress/strain Increase w/volume fraction
Increase w/decrease size
Decrease with addition of particles
Ultimate stress/strain Increase w/decrease size
No unified result for change inVf
Lower than pure for small volume fractions
Density/volume Increased volume as size decreases
N/A
Strain-to-failure Decrease with addition of particles
Decrease with addition of particles
Tg Decrease with addition of particles
N/A
Crystallinity No major effect
No major effect
Viscoelastic Increase w/volume fraction
Increase w/decrease size
N/A
9
perature increases, so the drop in glass transition temperature
is correlated with the drop in modulus [20,21].
Reynaud et al. [15] found that during tensile testing, the
volume of polymer nanocomposites increased, with the great-
est increase occurring in systems with the smallest particles.
To explain this, the debonding process of the polymer next
to the inclusions was examined, as shown in Fig. 6. It was
proposed that the smallest particles tend to aggregate and
debonding occurs around each individual particle. As a re-
sult, the large clusters of small particles act as larger soft
particles. On the other hand, the larger filler particles do not
aggregate and each particle undergoes a single debonding
process.
Due to the different results obtained and the different na-
ture of the various polymer nanocomposite systems, there
is no observed universal trend that can be modeled and ex-
plained. There are, however, observations that show the be-
havior of nanocomposites different from composites with
larger scale inclusions. The particle size and the polymer
and particle morphology tend to play a very important role.
In addition, the nature of dispersion and aggregation of par-
ticles can affect the properties of composites significantly.
Filler–matrix interaction is another factor that influences the
properties. The strength of the interaction plays a role in the
thickness and density of the interphase, which consists of a
layer of high density polymer around the particle. The ef-
fects of the interface on the behavior of a composite depend
upon the interparticle distance. For constant filler content,
with reduction in particle size, number of filler particles in-
Amorphous
Increase w/volume fraction Good interaction
Increase w/decrease size
Increase w/volume fraction Poor interaction
Increase w/decrease size
N/A Good Interaction
Decrease with addition of particles Poor interaction
Nano>micro after 20%weight Good interaction
Decrease with addition of particles Poor interaction
Increased volume as size decreases Good interaction
N/A Poor interaction
Increase with addition of particles Good interaction
Increase w/decrease size
Increase with addition of particles Poor interaction
Increase w/decrease size Good interaction
Level until 0.5%, drops off level from 1–10% Poor interaction
N/A Good interaction
N/A Poor interaction
Increase w/volume fraction nano less regular Good interaction
Decrease with addition of particles—drop at 1% with rise following Poor interaction
10 J. Jordan et al. / Materials Science and Engineering A 393 (2005) 1–11
creases, bringing the particles closer to one another. Thus, the
interface layers from adjacent particles overlap, altering the
bulk properties significantly. These issues play a major role
in the effect of nano-sized inclusions in a polymer matrix.
For nanoparticles, any configuration changes in the matrix
will have a significant effect when the characteristic radius of
polymer chains is of the same order as the inclusions [45,46].
There are other areas addressed in literature. For exam-
ple, López et al. [47] examined the processing and thermal
and mechanical properties of magnetic nanocomposites. In
another work the mechanical properties of clay nanocompos-
ites were analyzed as a function of filler loading and orien-
tation [30]. Zhang et al. [48] provided a look at matrix–filler
interfacial properties. Effect of matrix on the polymer matrix
composites were examined by Friedlander et al. [49].
5. Conclusions
Currently, a significant amount of work is being published
on polymer nanocomposites. In an attempt to further under-
stand the synthesis, processing, and properties analysis of
polymer nanocomposites, a selection of representative and
recent literature was chosen to highlight some of the issues re-
lated to the preparation and mechanical behavior of compos-
ites with nano-sized reinforcement in comparison with com-
posites with larger micron-sized inclusions. As was discussed
above, some trends are observed but no universal patterns for
the behavior of polymer nanocomposites can be deduced in
general. These observed trends are summarized in Table 1. In
general, the material properties of polymer nanocomposites
are superior to the pure polymer matrix or composites with
larger sized inclusions. The effects of the nanoparticles are
dependent on many variables but especially upon the relative
crystalline or amorphous nature of the polymer matrix as well
as the interaction between the filler and matrix.
Acknowledgments
I.J. acknowledges the support by the National Science
Foundation (Grant CMS-0085137) and the Air Force Office
of Scientific Research (Dr. Thomas Hahn, monitor).
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