Research Article

Received: 1 July 2010,

Revised: 15 October 2010,

Accepted: 17 October 2010,

Published online in Wiley Online Library: 6 December 2010

(wileyonlinelibrary.com) DOI: 10.1002/pat.1875

The use of functionalized nanoparticles

as non-specific compatibilizers for
polymer blends
W. Zhanga, M. Linb, A. Winesettc, O. Dhezc, A. LD. Kilcoynec, H. Adec,
M. Rubinsteind, K. V. P. M. Shafie, A. Ulmane, D. Gersappea, R. Tennef,
M. Rafailovicha *, J. Sokolova and H. L. Frischy
The ability to form blends of polymers offers the opportunity of creating a new class of materials with enhanced
properties. In addition to the polymer components, recent advances in nanoengineering have resulted in the
development of nanosized inorganic particles that can be used to improve the properties of the blend, such as the
flammability and the mechanical properties. While traditional methods using copolymer compatibilizers have been
used to strengthen polymer blends, here, we show that the inorganic nanosized filler additive can also serve as a
compatibilizer as it can localize to the interface between the polymers. We use experimental and theoretical studies to
show the fundamental mechanisms by which inorganic fillers with large aspect ratio and at least one-dimension in the
nanometer range, can act as non-specific compatibilizers for polymer blends. We examine a series of nanosized fillers,
ranging from nanotubes to nanoclays (with varying aspect ratios) in a model polystyrene (PS)/poly(methylmethacyralate) (PMMA) blend. Using a number of experimental techniques such as transmission electron microscopy (TEM),
scanning tunneling X-ray microscopy (STXM), and atomic force microscopy (AFM) we postulate that the mechanism of
compatibilization occurs as a result of the fillers forming in situ grafts with the immiscible polymers. We also use
theoretical studies to show that the aspect ratio and the bending energy of the fillers play a key role in the
compatibilization process. Our results indicate that the compatibilization is a general phenomenon, which should
occur with all large aspect ratio nanofiller additives to polymer blends. Copyright 2010 John Wiley & Sons, Ltd.
Keywords: polymer blends; nanocomposites; compatibilization; thermodynamics; nanoclay

INTRODUCTION
Organicinorganic nanocomposites are an emerging field of
intensive investigation.[15] Through nanoscale engineering one
can combine the flexibility of polymers with the high modulus
and flame resistance of the inorganic component to produce
a new class of lightweight materials.[6] Most of the effort thus far
has been focused on the use of organosilicate clays as the
inorganic component in melts of a single polymer component.[7]
Blending polymers is another, more traditional method, for
engineering a large variety of materials with carefully controlled
properties.[8] In this paper we explore the combination of both
techniques, which can overcome some of the fundamental
problems inherent in the two technologies when used separately.
We show that large aspect ratio inorganic fillers, with at least
one-dimension in the nanometer range, can form in situ grafts
by adsorbing large amounts of polymer. These in turn are
very effective at reducing interfacial tension and inducing
compatibilization in what would be otherwise highly immiscible
blends. We find that the bending energy of a large aspect filler
particle forces the formation of nanosized domains in the system.
Our results appear to be widely applicable to most polymer
blends.
Polymers are commonly blended in order to engineer specific
properties of materials. Fillers are added to improve mechanical
strength and resistance to thermal and chemical degradation.

Studies have also demonstrated how colloidal particles are

interfacially active agents.[9] Several groups have demonstrated
that when nanoscale fillers are added to phase-segregating

* Correspondence to: M. Rafailovich, Department Materials Science and Engineering, State University of New York, Stony Brook, NY 11794, USA.
E-mail: mrafailovich@notes.cc.sunysb.edu
a W. Zhang, D. Gersappe, M. Rafailovich, J. Sokolov
Department Materials Science and Engineering, State University of New York,
Stony Brook, NY 11794, USA
b M. Lin
National Institute of Standards and Technology, Gaithersburg, MD 20899,
USA
c A. Winesett, O. Dhez, A. L. Kilcoyne, H. Ade
Physics Department, North Carolina State University, Raleigh, NC 27695, USA
d M. Rubinstein
Chemistry Department, University of North Carolina, NC 27599, USA
e K. V. P. M. Shafi, A. Ulman
Department of Chemical Engineering, Polytechnic University, 6 Metrotech
Center, Brooklyn, NY 11201, USA
f R. Tenne
Weizmann Institute of Science, Rehovoth, Israel
y

Deceased.

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W. ZHANG ET AL.
mixtures, both the dynamics as well as the morphology of the
blend can change.[1012] Under special conditions when the filler
is completely wetted by one of the blend components (i.e. there
is a strong preference for the filler to partition in one of the
phases) several authors have reported dynamic pinning effects
of the coarsening domains. Karim et al.[10] first demonstrated that
transient surface directed lateral concentration gradients were
formed around particle inclusions that were similar to those
observed at planar interfaces. Tanaka et al.[11] and later Ginzburg
et al.[12] also reported that strong interactions between the fillers
and one of the phases impedes the coarsening of the interfaces.
These are primarily dynamic events as the authors have
postulated that the role of the filler is to pin the location of
the interface thus inhibiting the growth of larger domains.
Studies using nanoclay particles also demonstrated that the
domain size in phase separated polymer blends could be
reduced without the restriction that the clay particles be strongly
attractive to one of the phase.[13] However, the authors were
unable to postulate the mechanism behind this reduction, and
applied this method to one particular system. Thus, while
all these studies have demonstrated the effect of adding
inorganic filler particles on the morphology of the blend, there
has been no understanding of the mechanism by which the
filler particles affects the morphology of the blend. Specifically,
while these studies can point out that the nanosize of the
filler particle allows the filler to migrate to the interface, they
cannot explain why certain types of fillers (high aspect filler
particles versus spherical) work better than others. Further,
these studies do not indicate whether the mechanism is
limited to particular systems or that it is a more general
phenomenon, which could have important applications in blend
compatibilization.
In earlier work we had shown that when polydisperse polymers
are mixed with clay particles[14] and sheared in a Braebender,
the domain sizes produced are much smaller than those for pure
polymer blends. We speculated that there may be a thermodynamic reason for these lower domain sizes, but because the
system was far from equilibrium we were not able to probe this
effect further. In that system, it was not possible to decouple the
shear and mixing forces from the thermodynamic effects. Here,
we present experimental and theoretical evidence that demonstrates, when small amounts of fillers are added, that the
predominant effect in causing miscisbility is thermodymanic in
nature. We show that the filler aspect ratio and bending energy
is the determining factor of the morphology in an immiscible
polymer blend. We focus on the more common case when the
fillers interact weakly with all the polymer components and
hence do not preferentially localize in either of the phases. For
our model system we chose to study the well-characterized
binary blends of the immiscible polymers, polystyrene (PS) and
poly(methylmethacrylate) (PMMA)[15,16] in thin film form. In all
the results presented we use 50:50 mixtures of PS and PMMA
unless otherwise mentioned. We chose to use the geometry of
thin films since these films lend themselves to a variety of
complementary characterization techniques that will allow us
to determine the mechanism that controls the morphology of
the nanofilled system. Further, in these thin films it is possible to
achieve thermal equilibrium and we can therefore distinguish
between a dynamically trapped state and a true equilibrium
morphology. We also note that our results are independent of
the thin film geometry (as we and others[13] see similar effects in
bulk systems) and also the material system chosen.

EXPERIMENTAL
Materials
The organoclay, Cloisite 6A, was provided by Southern Clay
Products, Inc., which is a natural montmorillonite modified with
N,N-dimethyl dihydrogenated tallow quaternary ammonium
chloride. Tallow is the mixture of octadecyl, hexadecyl, and
tetradecyl. Octadecyl is the major component (>60%). The
polymers were obtained from SigmaAldrich. We used monodisperse PS (Mw/Mn < 1.1, Mw 109 K) and mondisperse polymethylmethacrylate (Mw/Mn < 1.2, Mw 219 K). The other nanofillers used, Tungsten disulfide multi-layered onion shaped
particles[17] and Tungsten disulfide nanotubes[18] made by
ultrasonic functionalization treatment described elsewhere.[19]
Sample preparation
Silicon wafers, 14 ml thick, were first cleaned using Pirahan Etch
followed by etching in dilute (5%) HF acid and rinsing in DI water.
Solutions were made in toluene (spectroscopic grade, Aldrich
Chemical) using monodisperse PS (Mw/Mn < 1.1, Mw 109 K)
and mondipersed polymethylmethacrylate (Mw/Mn < 1.2,
Mw 219 K) in a ratio of 1:1 by mass. In the case of films with
nanoparticles, Cloisite 20A (Southern Clay) Di-tallow coated clay
nanoparticles were first added into the solution and sonicated for
10 min to increase dispersion. The polymers were then added and
sonicated further for another 5 min. The solutions were spun cast
onto the freshly cleaned Si wafers at a frequency of 2500 rpm.
All samples were annealed in an oil free vacuum oven
(Hotpoint) in a vacuum of 10
3 Torr at T 1708C for up to 3 days.
Characterization
Scanning probe microscopy (SPM)
After the samples were removed they were analyzed using
scanning force microscopy in the contact mode where both
topography and lateral force were recorded using a DI-3000
(Veeco Instruments).
Scanning transmission X-ray microscopy (STXM) and Transmission
electron microscopy (TEM)
The STXM samples were taken from the cross sections of TEM,
which are thin enough for the X-ray beam to go through. The
images were taken at specific photon energies that correspond
to strong absorption of one of the components. The dark phases
represent high absorption, and light areas represent lower
absorption. The measurements were performed with the BL5.3.2
STXM at the Advanced Light Source at Lawrence Berkeley
National Laboratory. The spatial resolution in these experiments
is around 40 nm. TEM studies were performed using a JEOL
JEM1200ex TEM at 60 kV.

RESULTS
In our experiments three types of alkane functionalized fillers
(Fig. 1, insets) were studied; (a) Tungsten disulfide multi-layered
onion shaped particles[17](b) Tungsten disulfide nanotubes[18]
made by ultrasonic functionalization treatment[19] and (c)
Montomorilonite clays. These three types of fillers were chosen
so that we could span a range of aspect ratio and bending

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THE USE OF FUNCTIONALIZED NANOPARTICLES AS NON-SPECIFIC COMPATIBILIZERS FOR POLYMER BLENDS

Figure 1. Topography (top) and PS composition map (bottom), as determined by SPM and STXM, of PS/PMMA films spun cast on HF etched Si and
annealed for 96 hr at 1708C. The fillers added to each film, at a volume fractions of 5%, are shown in the top inset, while the PS composition in the as cast
films is shown in the bottom inset. (a) WS2 nano onion, (b) WS2 nanotube and, (c) Cloisite 6A clay. SPM images are 20 mm  20 mm. This figure is available
in color online at wileyonlinelibrary.com/journal/pat.

energies. 100200 nm thick films of the two polymers, with and

without fillers, were spun cast onto Si wafers and annealed for up
to 96 hr, at T 1708C, well above the glass transition temperature,
Tg, of both polymers. The results are presented in Fig. 1, where
we show the effect of filler aspect ratio on the surface
morphology and the lateral composition across the samples.
The addition of spherical particles, onions, does not affect the
phase segregated morphology, while addition of nanotubes
decreases the polymer domain size. STXM[20] shows that the
domain boundaries become jagged. When clay platelets are
added, the domain structure decreases even further. We also
show a sample morphology for a bulk mixed nanofilled polymer
blend with clay indicating that even in bulk systems the domain
size is still highly reduced.
In order to determine the domain size of clay-filled polymer
blends more accurately, we performed small angle neutron
scattering with an incident beam normal to the surface of a stack
of five Si wafer samples where 100 nm films of deuterated
PS/PMMA blends with 5% added clay had been spun cast
(Fig. 2a). The data was analyzed using the standard scattering
function for clay particles.[21] Each of the samples had also been
annealed for 96 hr at 1708C in a vacuum of 10
6 Torr prior to
stacking. Fig. 2b is a Guiner plot of the intensity versus the square
of the incident wave vector, q. From the slope of we obtain a
mean radius for the dPS domains of 70.4(0.5) nm, which is
significantly smaller than the domain size previous reported in
PS/PMMA blend films of similar thicknesses after annealing.[20]
This result is further confirmed in Fig. 3, where we show TEM
images of microtomed sections from samples spun cast and
annealed on polyamide substrates. In the absence of clay, a
fully segregated bilayer structure is formed (Fig. 3a). When 5%
by volume of clay is added, isolated domains of PMMA are formed
in a continuous PS matrix (Fig. 3b). From the figure, we can also
see that the clay platelets are highly exfoliated and localized
in the interfacial regions where they bend in order to follow
the contours of the interfaces between the two polymers. Note
that the mean radius of the domains is approximately 60 nm,
in agreement with the SANS data for similar samples. With the

Figure 2. (a) Experimental set up for the SANS data. 100 nm films of dPS/
PMMA conatining 5% clay were spun cast onto Si wafers and 5 such
samples were stacked normal to the incident beam direction. The
scattering intensity data was collected in a two-dimensional detector,
as shown. (b) Guinier plot (circles), and linear fit, of the scattering intensity
plotted as a function of the square of the incident wave vector, q. This
figure is available in color online at wileyonlinelibrary.com/journal/pat.

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W. ZHANG ET AL.

Figure 3. TEM micrographs (left) and corresponding microcalorimetry measurements of the glass transition from PS/PMMA films with and without
fillers (right). The TEM samples were spun cast on polyamide substrates and microtomed after annealing for 24 hr at 1708C. RuO4 staining indicates that
dark and light areas are PS and PMMA, respectively. The same films were spun cast onto 1 m thick Ni foils and heated with a pulsed source (inset, a and Ref.
[14]
) to measure the resistivity as a function of temperature. The peaks are obtained by taking the derivative of the resulting curve and indicate the Tg of
the components. (a) In the absence of clay the film segregated into a bilayer, with two distinct values of Tg. (b) Film containing 5% Cloisite 6A clay, where
domains of PMMA are seen among a continuous PS matrix. The clay platelets appear as dark lines. Note a third Tg peak is apparent. Inset: Illustration of the
three types of graft that can form in situ. (c) Film containing 10% Cloisite 6A where no distinct domains are seen and the clay appears oriented. Note that
the third Tg peak is now dominant. Inset: Cartoon of clay induced miscibility. This figure is available in color online at wileyonlinelibrary.com/journal/pat.

addition of more clay (10% by volume), no distinct domains are

visible, indicating that the phases may have mixed (Fig. 3c).
In order to further quantify the degree of compatibilization,
200 nm thick films were spun cast onto thin Ni foils and heated
with a pulsed current source in a vacuum of 10
6 Torr. This
apparatus, as described by Yu et al.,[22] has been shown to be an
effective method of determining the Tg of polymer films. The
differential change in resistance, which senses the discontinuity
in the heat capacity of the polymer at Tg, is also shown in Fig. 3 as
a function of temperature for films without clay and those
containing 5 and 10% by volume. In the absence of clay two
distinct values of Tg are observed at T 375 K and T 399 K,
which correspond to the bulk values of PS and PMMA. With
the addition of clay, a third peak, intermediate to that of the pure
polymers, becomes visible at a concentration of 5% by volume
(Fig. 3b). As the amount of clay is increased to 10%, the amplitude
of the third peak increased at the expense of the other two
(Fig. 3c). We note that while the peak in Fig. 3b is not clearly
evident due to the noise in the measurement, its presence can be
clearly seen in Fig. 3c and occurs at the same point. In bulk
samples of PMMA/cloisite 6A composites, earlier studies have
clearly shown an increase in Tg as the concentration of clay is
increased so this intermediate peak (which represents a decrease
in Tg) would seem to indicate that this represents a Tg for the
mixed blend. Indeed, if we compute the ideal mixing Tg for a
50:50 blend system, we get Tg (ideal) 386.6 and the
experimentally observed Tg is 3838. These results indicate that
we are observing the formation of a mixed phase of the two
polymers with increasing clay concentrations.
In order to determine whether this observation is a result of the
clay compatibilizing PS and PMMA or whether we are simply

pinning the domains by the clay particles, in Fig. 4 we show a time

series of the blend morphology up to 96 hr of annealing at 1658C.
If we compare the clay/blend system to the binary blend (in the
absence of clay), we can clearly see that, upon annealing, in the
presence of the clay, the domain size first decreases and then
appears to reach a steady state where we see no further change.
We note that we cannot quantify this decrease as a function of
time since the domain sizes become very quickly smaller than the
experimental resolution. As a result we only have a few snapshots,
but nonetheless we observe a clear trend. In the absence of
the clay, on the other hand, there is an obvious coarsening of the
domains. If the effect of clay on blend was pinning of the
domains, we should be observing a reduced rate of coarsening
of domains, i.e. we should never observe a decrease in domain
size. Indeed the only mechanism that can account for a decrease
in the domain size is if the clay is compatibilizing the blend and
forcing it to form smaller domains. Furthermore, Hu et al.[23]
measured the tracer diffusion coefficient of PS and PMMA as
a function of clay concentration. They found that for the cloiste/
polymer system diffusion was reduced by a factor of 4 in PMMA
and less than 20% in PS. Consequently, polymer diffusion over
several microns was possible during the time scale of the present
experiments. Hence, we believe that the observed effects are
an equilibrium phenomena rather than pinning of the as cast
mixed phase.

DISCUSSION
In order to explain this effect we postulate the following
mechanism. We know that the process of spin casting polymer

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THE USE OF FUNCTIONALIZED NANOPARTICLES AS NON-SPECIFIC COMPATIBILIZERS FOR POLYMER BLENDS

Figure 4. Time series of the evolution of the morphology of a PS/PMMA blend with and without cloisite. (a) Time series in the absence of clay showing
the growth of domains in the normal phase separation process. (b) In the presence of clay note how the domain size decreases from the initial state and
then continues to decrease until no further change is observed.

clay solutions naturally produces films with highly exfoliated and

oriented clay platelets. Further, when the films are annealed
above 1508C, one can assume that the polymer chains adjacent
to the clay interfaces are strongly adsorbed, forming in situ
grafts, whose composition reflects the one in the as cast films.
We note that the grafting onto the clay surfaces was assumed
to occur during annealing and represent the equilibrium
configuration of the blends. Only homopolymers were used
and grafts refer to constructs formed during the annealing
phase where competitive adsorption occurred onto the clay
surfaces. Three types of grafts can form, as illustrated in inset of
Fig. 3b; types A and B are platelets where all surfaces are covered
by an excess of one of the homopolymers, and type C where the
platelet surfaces are covered with a mixture of the two polymers.
We note that since the polymers are immiscible and if lateral
motion is possible, preliminary calculations show that adsorption
can occur in patches. This does not affect the conclusions drawn
here. Platelets of type A or type B will be localized in their
respective phases (Fig. 3b). On the other hand, the energy of type
C platelets is minimized when they are localized at domain
interfaces. Since these platelets have a high aspect ratio, they can
deliver a large amount of grafts to the interface, without entropic
constraints or competition from micelle formation. Note that
clay platelets can deform and follow the interface between the
two polymers, covering the surface of domains, while nanotubes
and spherical fillers cannot and this could explain why the clay
particles are more effective compatibilizers than the nanotubes
or the spherical fillers. Indeed, one could argue that the
effectiveness of the filler will be strongly related to the degree
of curvature. Thus while we anticipate that both spherical and
nanotube fillers will migrate to the interface, they will not be able
to reduce the interfacial tension as effectively as the clay particles.
The relative fractions of these three grafts will depend on the
annealing sequence. For example, if the platelets are first mixed
with either one of the homopolymers and annealed prior to the

addition of the second homopolymer, an excess of type A or B will

occur. Since types A and B are not interfacially active, prior
annealing is expected to reduce the effectiveness of clay in
compatibilization. This can be seen in Fig. 5 where we compare
the effectiveness of compatibilization in bilayer samples where
7% clay was first mixed in the PMMA phase, covered with a PS
films and annealed at 1708C for 72 hr. From the figure we can see
that the effectiveness is clearly reduced when the PMMA/clay
sublayer is preannealed for 24 hr before application of the PS
layer.
It is interesting to note that compatibilization occurs without
forming the usual microemulsion structure observed when block
copolymers are used.[24] This is probably due to larger rigidity
of the clay, which increases the interfacial bending energy,
relative to polymer surfactants. The equilibrium morphology can
then be estimated by balancing the reduction in interfacial
energy with the increase in bending energy when type C platelets
are placed at the interface. The free energy F for a polymer blend/
clay system, of constant volume V, can be expressed in terms of
r, the radius of the domains in the system by calculating the
energy penalty associated with the presence of interfaces;
F gn
ml 2 g 0 ml2 mFbending

(1)

Here, g is the energy per unit area of the interface between

the two polymers, g 0 the interfacial energy when clay platelets are
at the interface, n the total number of clay platelets (of type C)
in the system, m the number of clay platelets present at the
interface between the two polymers and l2 is the surface area
of the platelets. The first term represents the energy penalty
of putting type C platelets in either of the phases, the second
term represents the interfacial energy of the platelet covered
domains, and the last term represents the bending energy of the
platelets due to interfacial curvature. If we assume that platelets
fully cover all the domains and that the blend has equal amounts

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W. ZHANG ET AL.

Figure 5. STXM maps of the PS concentration and corresponding SPM topography (insets) for bilayer films of PS and PMMA with 7% Cloisite 6A clay
annealed at 1708C for 72 hr. (a) The PMMA/clay layer was pre-annealed for 24 hr at 1708C before being covered with the PS layer. (b) The PMMA/clay layer
was spun cast onto Si and the PS layer was floated immediately above it. STXM images are 15 mm  15 mm. This figure is available in color online at
wileyonlinelibrary.com/journal/pat.

of each phase, we can derive an expression for m:

m

V
2rl 2

(2)

where V is the total volume of the blend. The bending energy

per platelet can be obtained from[25]
Fbending 

Ehz4
l2

(3)

where E is the Youngs modulus, l2 the area of a typical platelet

of thickness h, and z  l2/r is the displacement of the platelet for
small deformations. Substituting Eqns.(2) and (3) in Eqn. (1) and
minimizing the free energy with respect to r we obtain r al,
where

a

Eh
g
g 0

1=4
:

(4)

In this expression, r is the radius of the domain that can form

before it is destabilized by the bending penalty. Note that in the
limit of no platelets, g g 0 and r 1; that is, we recover the
limit of a planar interface (the thermodynamically stable state).
If we substitute g 2 mN/m,[21] E  1 GPa for exfoliated clays,[26]
h 10 A and assume that g 0  g, we can roughly estimate that
a  5 and the minimum domain radius should be approximately
equal to five times the average linear dimension of the platelets. If
we estimate this value to be approximately 100 nm, as seen in the
TEM images in Fig. 3, then the value of r is somewhat larger with
that obtained from SAN scattering measurements from samples
with comparable clay volume fractions (500 nm versus 70 nm
from the SANS). Note, however, that we are using a theoretical
estimate for E[22] and though a is relatively insensitive to the value
of E, its actual value will range from around 2.5 to 8 if the estimate
for E is off by an order of magnitude up or down, respectively.

CONCLUSION
Therefore, while a direct comparison of the theory and
experiment might seem unsatisfactory, the main message of

the theory is that the domain sizes in this system appear to be

limited to a small multiple of the linear dimension of the clay
platelets. When the clay concentration increases further, no new
interfaces can be created to accommodate the increased
concentration of type C platelets. Hence, as can be seen in
Fig. 3c, domain formation is suppressed and the PS/PMMA chains
can become mixed at the molecular level (inset of Fig. 3c). The
proposed mechanism relies only on in situ grafting of the
components to the filler surfaces and is relatively insensitive to
the system parameters (Eqn. (4)). Hence, it can be a general
phenomenon that should occur in all systems with large aspect
ratio fillers such as nanotubes or exfoliated clay platelets.

Acknowledgements
This manuscript is dedicated to the memory of Prof. Harry L.
Frisch, with whom we had the pleasure and honor to collaborate
and who initiated the theoretical work presented here. He had
the following sign on his office door; Polaroid Harry-theories
developed while you wait. This work was supported by the
NSF-MRSEC program. STXM data acquired with the Stony Brook
STXM at the National Synchrotron Light Source and the 5.3.2
Polymer STXM at the Advanced Light Source. One of us (M. R.)
acknowledges support of NASA University Research, Engineering
and Technology Institute on Biologically Inspired Materials Award
NCC-0102037.

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THE USE OF FUNCTIONALIZED NANOPARTICLES AS NON-SPECIFIC COMPATIBILIZERS FOR POLYMER BLENDS

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