J. Ind. Eng. Chem., Vol. 12, No.

6, (2006) 811-842
REVIEW

Rheology of Polymer/Layered Silicate Nanocomposites

Suprakas Sinha Ray†
Macromolecular Nanotechnology Research Group, Nanoscience Research Centre, CSIR Materials Science and
Manufacturing, PO Box 395, Pretoria 0001, Republic of South Africa
Received November 14, 2006

Abstract: Over the last few years, polymer/layered silicate (PLS) nanocomposites have been an area of intense
academic and industrial research. No matter the measure-journal articles, patents, and industry research and
development (R&D) funding-efforts in PLS-nanocomposite have been exponentially growing worldwide for
the last ten years. Aside from the understanding in fabrication, characterization, and improved mechanical and
other properties, the measurement of rheological properties of PLS-nanocomposites under molten state is
crucial to gain fundamental understanding of the processability of these materials. In the case of PLS-
nanocomposites, the measurements of rheological properties are also helpful to find out the strength of
polymer-layered silicate interactions and the structure-property relationship in nanocomposites. This is
because rheological behaviors are strongly influenced by their nanoscale structure and interfacial
characteristics. In this article, recent advances in melt-state rheological properties of PLS-nanocomposites are
highlighted. To begin this a very brief description of structure and dynamics of PLS-nanocomposites are also
described.

Keywords: polymer/layered silicate nanocomposite, structure, thermodynamics, melt rheology

Introduction [1], metal oxide nanoparticles [2,3], inorganic nanotubes

1)
The word composite is generally used to define any ma-
terial made of more than one component. Depending on
the matrix nature, composite materials can be broadly
divided into three categories such as polymeric, metallic,
and ceramic. In most of the commercially available com-
posite materials the structural unit is on the micrometer
‐6
(10 m) length scale and is used mostly to improve the
mechanical properties of matrix material. Now one can
change the dimension of the structural building block to
‐9
the nanometer (10 m) scale, the resulting composite ma-
terial is called a Nanocomposite. The nanometer is one
billionth of meter and ∼10,000 times finer than a human
hair. Figure 1 compares the morphology of classical- and
nano-filler filled composite.
Here we are interested on polymer nanocomposites that
means nanocomposite made with polymer and nano-
scale filler. Over the last few years, various types of
nano-fillers are in development such as layered silicates
†
To whom all correspondence should be addressed.
(e-mail: RSuprakas@csir.co.za)
[4], expandable graphite [5-7], layered titanate [8], cellu-
lose nanowhiskers [9], polyhedral oligomeric silses-
quioxanes (POSS) [10], carbon nanotubes [11-17], etc.
Polymer nanocomposites based on layered silicates have
attracted great interest in today’s materials research, as it
is possible to achieve impressive enhancements of prop-
erties when compared with virgin polymer [1,18-20].
These improvements can include high moduli [1,18], in-
creased strength and heat resistance [1,18], decreased gas
permeability [21-23] and flammability [24-27], and in-
creased degradability of biodegradable polymers [28-30].
On the other hand, there has been considerable interest in
theory and simulations addressing the preparation and
properties of these materials [31], and they are also con-
sidered to be unique model systems to study the structure
and dynamics of polymers in confined environments
[32].
The main reason for these improved properties in
nanocomposites is the interfacial interaction between the
matrix and layered silicate, as opposed to conventional
composites [1]. Layered silicates have layer thickness on
812 Suprakas Sinha Ray
Figure 1. Schematic comparison between microcomposite (classical filler filled) and “Nanocomposite. Reproduced with permission
from Elsevier Science Ltd., UK.
Figure 2. Schematic illustration of three different types of ther-
modynamically achievable polymer/layered silicate compo-
sites.
the order of 1 nm, and very high aspect ratios (e.g. 10∼
1,000). A few weight percent of layered silicate particles
that are properly dispersed throughout the matrix can
thus create a much larger surface area for polymer filler
interactions than do conventional composites. On the
basis of the strength of the polymer/layered silicate
interfacial interaction, three structurally different types of
composites are achievable (see Figure 2): (1) phase-
separated composite, when polymer matrix has no
interaction with layered silicate, (2) intercalated nanoco-
posites, where insertion of polymer chains into the
silicate structure occurs in a crystallographically regular
fashion, regardless of the polymer-to-layered silicate
ratio, and a repeat distance of few nanometers, and (3)
exfoliated nanocomposites, in which the individual
silicate layers are separated in the polymer matrix by
average distances that totally depend on the layered
silicate loading.
This article highlights recent advances in melt-state
rheological properties of PLS nanocomposites. To begin
this a brief description on structure and properties of
layered silicates, nanocomposites preparation techniques
and thermodynamics are described. Finally, attention is
drawn to how rheological behavior of PLS nanocom-
posites can be understood directly from their structure.
Structure and Properties of Layered Silicates
The commonly used layered silicates for the preparation
of PLS nanocomposites belong to the same general
family of 2 : 1 layered- or phyllosilicates [33]. Their
crystal structure consists of layers made up of two
tetrahedrally coordinated silicon atoms fused to an
edge-shared octahedral sheet of either aluminum or
magnesium hydroxide. The layer thickness is around 1
nm, and the lateral dimensions of these layers may vary
from 30 nm to several microns or larger, depending on
the particular layered silicate. Stacking of the layers leads
to a regular van der Waal’s gap between the layers called
the interlayer or gallery. Isomorphic substitution within
+3 +2 +2
the layers (for example, Al replaced by Mg or Fe , or
+2 +1
Mg replaced by Li ) generates negative charges that
are counterbalanced by alkali and alkaline earth cations
situated inside the galleries. This type of layered silicate
 Rheology of Polymer/Layered Silicate Nanocomposites
Figure 3. Structure of 2:1 phyllosilicates. Reproduced from ref.
[1] by permission of Elsevier Science Ltd., UK.
is characterized by a moderate surface charge known as
the cation exchange capacity (CEC), and generally
expressed as mequiv/100 gm. This charge is not locally
constant, but varies from layer to layer, and must be
considered as an average value over the whole crystal.
Layered silicates have two types of structure: tetrahed-
rally substituted and octahedrally substituted. In the case
of tetrahedrally substituted layered silicates, the negative
charge is located on the surface of silicate layers and,
hence, the polymer matrices can interact more readily
with these than with octahedrally substituted material.
Generally, layered silicate minerals are divided into
three major groups: (a) the kaolinite group, (b) the semc-
tite group and (c) the illite or the mica-clay group.
Among the three major groups, smectite types or more
precisely montmorillonite, saponite and hectorite are the
most commonly used layered silicates in the filed of pol-
ymer nanocomposite technology. Again, among mont-
morillonite, saponite, hectorite, montmorillonite (MMT)
is the most commonly used layered silicates for the fab-
rication of PLS nanocomposites, because it is highly
abundant and inexpensive. MMT is the name given to the
layered silicate found near montmorillonite in France,
where MMT was first identified by Knight in 1896. The
chemical formula of MMT is Mx(Al4‐xMgx)Si8O20(OH)4.
The CEC (generally 90∼110 meq/100 g) and particle
length of MMT (100∼150 nm) depends on the source.
The specific surface area of MMT is equal to 750∼800
m2/g and the modulus of each MMT sheet is around 170
GPa [34]. The interlayer thickness of hydrated MMT is
equal to 1.45 nm and the average density ρ= 2.385
g/mL. Drying MMT at 150 °C reduces the gallery height
to 0.28 nm which corresponds to a water monolayer and
hence the interlayer spacing decreases to 0.94 nm and the
average density increases to 3.138 g/mL [35]. The unit
structure of MMT is presented in Figure 3.
813
Two particular characteristics of layered silicates are
generally considered for PLS nanocomposites fabri-
cation. The first is the ability of the silicate particles to
disperse into individual layers inside the polymer matrix.
The second characteristic is the ability to fine-tune their
surface chemistry through ion exchange reactions with
organic and inorganic cations. These two characteristics
are, of course, interrelated, since the degree of dispersion
of layered silicate in a particular polymer matrix depends
on the interlayer cation. Pristine layered silicates usually
+ +
contain hydrated Na or K ions [1]. Obviously, in this
pristine state, layered silicates are only miscible with hy-
drophilic polymers such as poly(ethylene oxide) (PEO)
[36] or poly(vinyl alcohol) (PVA) [37]. To render lay-
ered silicates miscible with various polymer matrices,
one must convert the normally hydrophilic silicate sur-
face to an organophilic one, making the intercalation of
many polymers possible. Generally, this can be done by
ion-exchange reactions with cationic surfactants includ-
ing primary, secondary, tertiary, and quaternary alky-
lammonium or alkylphosphonium cations. Alkylam-
monium or alkylphosphonium cations in the organo-
silicates lower the surface energy of the inorganic host
and improve the wetting characteristics of the polymer
matrix, and result in a larger interlayer spacing.
Additionally, the alkylammonium or alkylphosphonium
cations can provide functional groups that can react with
the polymer matrix, or in some cases initiate the poly-
merization of monomers to improve the strength of the
interface between the inorganic and the polymer matrix
[1].
Preparative Methods
Intercalation of polymer chains inside layered silicate
galleries has proven to be a successful approach to fab-
ricate PLS-nanocomposites. Thermoplastic polymers
based PLS-nanocomposites may be prepared by one of
the three following routes: (i) in-situ intercalative poly-
merization of monomer, (ii) intercalation of polymer or
pre-polymer from solution, and (iii) melt-intercalation.
The second method may be processed using emulsion,
whereas when the good solvent is not available, re-
searchers have to choose either in-situ polymerization
method (i) or direct melt blending (iii).
The direct melt-intercalation process involves annealing
a mixture of the polymer and layered silicate (organically
modified or not) above the softening point of the poly-
mer, statically or under shear. While annealing, the poly-
mer chains diffuse from the bulk polymer melt into the
galleries between the silicate layers. A range of nano-
composites with structures from intercalated to exfoliate
can be obtained, depending on the degree of penetration
814 Suprakas Sinha Ray
of the polymer chains into the silicate galleries. This
process was found to be completely reversible in the pol-
ystyrene (PS) based nanocomposite because PS has al-
most no interaction with the organically modified layered
silicate (OMLS) surface, but when polymer chains have
some favorable interaction with silicate surface, this
process found to be irreversible. However, for a large va-
riety of nanocomposites, this method requires often the
use of extrusion process in order to get a homogeneous
dispersion of intercalated silicate layers in the polymer
matrix.
Thermodynamics and Molecular Modelling of
PLS Nanocomposite Formation
The solution intercalation method is based on a solvent
system in which the polymer or pre-polymer is soluble
and the silicate layers are swellable. The layered silicate
is first swollen in a solvent, such as water, chloroform, or
toluene. When the polymer and layered silicate solutions
are mixed, the polymer chains intercalate and displace
the solvent within the interlayer of the silicate. Upon sol-
vent removal, the intercalated structure remains, resulting
in polymer/layered silicate nanocomposite.
For the overall process, in which polymer is exchanged
with the previously intercalated solvent in the gallery, a
negative variation in the Gibbs free energy is required.
The driving force for the polymer intercalation into lay-
ered silicate from solution is the entropy gained by de-
sorption of solvent molecules, which compensates for the
decreased entropy of the confined, intercalated chains.
Using this method, intercalation only occurs for certain
polymer/solvent pairs. This method is good for the inter-
calation of polymers with little or no polarity into layered
structures, and facilitates production of thin films with
polymer-oriented clay intercalated layers.
In recent years, the melt intercalation technique has be-
come the standard for the preparation of PLS-nano-
composites. During polymer intercalation from solution,
a relatively large number of solvent molecules have to be
desorbed from the host to accommodate the incoming
polymer chains. The desorbed solvent molecules gain
one translational degree of freedom, and the resulting en-
tropic gain compensates for the decrease in conforma-
tional entropy of the confined polymer chains. Therefore,
there are many advantages to direct melt intercalation
over solution intercalation. For example, direct melt in-
tercalation is highly specific for the polymer, leading to
new hybrids that were previously inaccessible.
So far, experimental results indicate that the outcome of
polymer chains intercalation into two dimensional sili-
cate galleries depends critically on layered silicate sur-
face functionalization and constituent interactions. Pre-
sent author observes that (a) an optimal interlayer struc-
ture on the OMLS, with respect to the number per unit
area and size of surfactant chains, is most favorable for
nanocomposite formation, and (b) polymer intercalation
depends on the existence of polar interactions between
the OMLS and the polymer matrix.
In order to understand the thermodynamic issue asso-
ciated with nanocomposite formation during melt-inter-
calation, Vaia and coworkers [38,39] applied a mean‐
field statistical lattice model, reporting that calculations
based on the mean field theory agree well with ex-
perimental results. Although there is entropy losses asso-
ciated with the confinement of a polymer melt during
nanocomposite formation, this process is allowed be-
cause there is an entropy gain associated with the layer
separation, resulting in a net entropy change near to zero.
Thus, from the theoretical model, the outcome of nano-
composite formation via polymer melt intercalation de-
pends primarily on energetic factors, which may be de-
termined from the surface energies of the polymer and
OMLS.
Based on the Vaia and coworkers [38,39] study and the
construction of product maps, general guidelines may be
established for selecting potentially compatible poly-
mer/OMLS systems. Initially, the interlayer structure of
the OMLS should be optimized in order to maximize the
configurational freedom of the functionalizing chains
upon layer separation, and to maximize potential inter-
action sites at the interlayer surface. For these systems,
the optimal structures exhibit a slightly more extensive
chain arrangement than with a pseudo-bilayer. Polymers
containing polar groups capable of associative inter-
actions, such as Lewis-acid/base interactions or hydrogen
bonding, lead to intercalation. The greater the polar-
izability or hydrophilicity of the polymer, the shorter the
functional groups in the OMLS should be in order to
minimize unfavorable interactions between the aliphatic
chains and the polymer.
One of the great advantages of the Vaia mean-field stat-
istical lattice model is the ability to determine analyti-
cally the effect of various aspects of the nanocomposite
formation. According to this model, the variation of the
free energy of mixing and subsequent dependence on en-
thalpic and entropic factor, suggest the formation of three
possible structures-phase separated, intercalated and
exfoliated. Although, Vaia model able to address some of
the fundamental and qualitative thermodynamic issues
associated with the nanocomposite formation, however,
some of the assumptions such as the separation of con-
figurational terms and intermolecular interaction and the
further separation of the entropic behavior of the con-
stituents, somewhat limit the usefulness of the model.
Not only that, this model is based on nanocomposites
where polymer chains are completely tethered with the
 Rheology of Polymer/Layered Silicate Nanocomposites
silicate surface, which is not the case for most of the pol-
ymer nanocomposites.
To overcome the limitation of Vaia model, Balazs and
coworkers [40] proposed a model based on a self-con-
sistent field (SCF) calculation, such as the Fleer and
Scheutjens theory [41]. In the Fleer and Scheutjens theo-
ry, the phase behavior of polymer systems is modeled by
combining Markov chain statistics with a mean field
approximation. These calculations involve a planar lat-
tice where lattice spacing represents the length of a stat-
istical segment within a polymer chain. Details regarding
this theory can be found in ref. [41]. Using this method
Balazs and coworkers tried to calculate the interactions
between two surfactant-coated surfaces and a polymer
melt. They considered two planar surfaces that lie paral-
lel to each other in the xy-plane and investigated the ef-
fect of increasing the separation between the surfaces in
the z-direction. The two surfaces are effectively im-
mersed within a polymer melt. As the separation between
the surfaces is increased, polymer from the surrounding
bath penetrates the gap between these walls. Each surface
is covered with monodispersed end-grafted chains, i.e.
surfactants. Now if χsurf represents the Flory-Huggins in-
teraction parameter between the polymers and the under-
lying solid substrate and χssurf represents the Flory‐
Huggins interaction between the surfactant and surface.
Therefore, χsurf -χssurf = 0. It should be noted here; in
their calculation Balazs and coworkers did not consider
electrostatic interaction.
Their calculations show that on increasing the attraction
between the polymers and the modified surfaces are
qualitatively similar to observation as made by Vaia and
coworkers [38,39]. However, Balazs and coworkers
found that the actual phase behavior and morphology of
the mixer can be affected by the kinetics of the polymers
penetrate the gap between the plates. At the beginning,
the polymer chains have to penetrate the space between
the silicate layers from an outer edge and then diffuse to-
ward the centre of the gallery. Now if we consider the
case where χsurf < 0 and thus, the polymer and surface
experience an attractive interaction. In this case as the
polymer diffuses through the energetically favorable gal-
lery, it maximizes contact with the two confining layers.
As a results, the polymer ‘glues’ the two surfaces togeth-
er as it moves through the interlayer. This ‘fused’ con-
dition could represent a kinetically trapped state and con-
sequently, increasing the attraction between the polymer
and layered silicate sheets would only lead to interca-
lated, rather than exfoliated structures. On the other hand,
in the case where χsurf > 0, the polymer can separate the
sheets, as the chain tries to retain its coil-like con-
formation and gain entropy. However, recent literatures
revealed that the melt mixing of organically modified
layered silicates and almost no attractive polymer ma-
815
trices always lead to the formation of phase separated
structure. The SCF calculations and phase diagrams lead
to the same conclusion.
To overcome this problem, Balazs and coworkers then
proposed the scheme of using a mixture of functionalized
and non-functionalized polymers for the melts [42].
While the stickers at the chain ends are highly attracted
to the surface, the remainder of polymer does not react
with the substrate. Thus, as the polymer chain penetrate
the sheets, the majority of the chain is not likely to glue
the surfaces together.
Balazs and coworkers [43,44] also proposed a simple
model that describes the nematic ordering in the poly-
mer-layered silicate systems. Because of the very high
degree of anisotropy (a typical layered silicate platelet is
∼1 nm in thickness and 100∼200 nm in diameter), lay-
ered silicate particles experience strong orientational or-
dering at low volume fractions and can form liquid crys-
talline phases such as nematic, smectic, or columnar, in
addition to traditional liquid and solid phases (see Figure
4). Starting from the Onsager free energy functional for
the nematic ordering of rigid rods, they developed a
modified expression to combine the disk orientational
and positional entropy, steric excluded-volume effects,
translational entropy of the polymer, and finally the
Flory-Huggins enthalpic interaction. The resulting iso-
thropic-nematic phase diagram correctly represents many
important features, such as the role of shape anisotropy
in depressing the ordering transition and the increase in
the size of the immiscibility region with increases in the
polymer chain length. Unlike most of the phenomeno-
logical theories of polymer-liquid crystal systems [45-
48], in the Onsager-type model the features of the phase
diagram are directly derived from the geometric charac-
teristics of the anisotropic component.
Balazs and coworkers first modified and expanded
Onsager theory by including nematic, smectic and
columnar crystalline phases. To do calculation, they also
adopted Somoza-Tarazona formalism of density functio-
nal theory (DFT) and then incorporated expressions that
describe the entropy of mixing between the different
components and the enthalphic interaction between the
platelets [34,49]. The resulting free energy function can
be minimized with respect to both the orientational and
positional single-particle distribution function of the
platelets, and thus, potentially, all phases and coexistence
regions can be determined. The resulting phase diagram
was shown to exhibit a strong dependence on the shape
anisotropy of the layered silicate particles, the polymer
chain length, and the strength of the interparticle
interaction. In particular, an increase in the shape
anisotropy for oblate ellipsoidal filler particles leads to
the broadening of the nematic phase at the expense of the
isotropic region. The increase in the polymer chain
816 Suprakas Sinha Ray

Figure 4. Possible mesophases of oblate uniaxial particles dispersed in a polymer: (a) isotropic, (b) nematic, (c) smectic A, (d) col-
umnar, and (e) crystal. The nematic director n in ordered phases is aligned along Z axis; the disks lie in the XY plane. Dashed lines
show smectic layers (c) and columns (d). Reprinted from ref. [44] with permission from American Chemical Society, USA.

length leads to the formation of the crystalline and/or
liquid crystalline mesophases and promotes segregation
between polymerrich regions and filler particles. Finally,
an increase in the strength of the interparticle potential
leads to the complete elimination of the nematic phase
and to the direct coexistence between isotropic and
crystal or columnar phases. The only limitation of this
model is that this model cannot determine the topology
of the phase diagram and the nature of the ordered phases
for intermediate and high volume fractions of colloidal
particles.
The huge interfacial area and the nanoscopic di-
mensions between nanoelements differentiate PLS-nano-
composites from conventional composites and filled
plastics. The dominance of interfacial regions resulting
from the nanoscopic phase dimensions implies that the
behavior of PLS nanocomposites cannot be understood
by simple scaling arguments that begin with the behavior
of conventional polymer composites. Since an interface
limits the number of conformations that polymer mole-
cules can adopt, the free energy of the polymer at the in-
terfacial region is fundamentally different from that of
polymer molecules far away from the interface i.e. bulk.
The influence of interface always depends on the funda-
mental length scale of the adjacent matrix. In the case of
polymer molecules, this is of the order of the radius of
gyration of a polymer chain, Rg and this is equal to 5∼10
nm. For this reason, in nanocomposites with a very few
 Rheology of Polymer/Layered Silicate Nanocomposites
volume percent of dispersed nanofillers in polymer ma-
trix, the entire matrix may be considered to be a nano-
scopically confined interfacial polymer. The restrictions
in chain conformations will alter molecular mobility, re-
laxation behavior, free volume, and thermal transition
such as the glass transition temperature.
Recent molecular dynamics simulation studies have
shown that the dynamics of the polymer chains undergo
radical changes at the interfacial region. For example,
both the chain mobility and the chain relaxation times
can be slowed by three orders of magnitude near phys-
isorbing surfaces. Not only that, extensive surface forces
apparatus experiments report how these novel dynamics
of nanoconfined polymers are manifested through vis-
cosity increases, two values orders of magnitude higher
than the bulk values solid-like responses to imposed
shear, and confinement induced ‘sluggish’ dynamics that
suggest the existence of a ‘pinned’, ‘immobilized’ layer
adjacent to the confining mica surface.
The kinetics of intercalation of polymer chains into the
silicate galleries to form layered nanocomposites has
been studied by Vaia and coworkers [50]. They have in-
vestigated the kinetics of the intercalation of PS above its
entanglement molecular weight into octadecylammonium
exchanged fluorohectorite. XRD reveals the average lay-
er spacing in the unintercalated silicate to be 2.13 nm.
During intercalation, this spacing increases to 3.13 nm.
Measurement of this layer spacing as a function of time
during intercalation yields a time-dependent fraction of
intercalated silicate that is directly comparable to the
time dependent number of beads in the slit, χ(t) and it is
well fit by the prediction of a continuum diffusion model.
In their model Vaia and coworkers considered the dif-
fusion of polymer chains into an empty cylinder with a
permeable wall and impermeable caps. The diffusion co-
efficient determined by fitting χ(t) to this model, effec-
tive diffusion coefficient, Deff, is large compared to the
equilibrium self-diffusion coefficient in bulk polystyrene
of the appropriate molecular weight. These results sug-
gested that the process of intercalation of polymer chains
into the two dimensional silicate galleries is limited by
the transport of the polymer chains into the primary par-
ticles of the silicate and not specifically by transport of
polymer chains inside the silicate galleries.
Now to understand the detail formation kinetics and
physical properties of PLS-nanocomposites we need a
clear molecular picture of the structure and dynamics of
confined polymers. Researchers generally used the surfa-
ces force apparatus [51-55] and computation studies [56-
67] to understand the behavior of confined fluids.
Confinement of a fluid on length scales comparable to
the molecular size has been demonstrated to dramatically
alter its structure and dynamical pictures [51-67]. For ex-
ample, confined fluids have been shown to solidify or
817
vertify at temperatures well above the bulk transition
temperature [65]. Because of the strong interactions be-
tween the confined molecules and the atoms or mole-
cules of the confining medium, the mobility of the mole-
cules in the confined environment is greatly reduced
compared to the bulk [51,68-71]. Molecules in films of
nanometer thickness organize in layers parallel to the
surface. However, the confining medium induces two di-
mensional orders in these layers [67]. On the other hand,
in certain circumstances, confinement phenomenon may
also have opposite effect of enhancing molecular mobi-
lities in a supercooled thin film, relative to the bulk.
Lee and coworkers [72] have presented an investigation
of the molecular mechanism of polymer melt inter-
calation using molecular dynamics simulations. They
tried to find out the motion of polymer chains from a
bulk melt into a confined volume. In their model they
represented macromolecules by bead-spring chains, leave
a reservoir of bulk melt to enter a slit of rectangular cross
section and fixed dimension. They adopted a coarse-
grained description of polymers, because such a picture
has been demonstrated to provide a useful description of
melt dynamics over longer time scales than would be ac-
cessible with an atomistic model [73,74]. They also con-
sidered a slit of fixed dimension to understand the trans-
port of a polymer melt from the bulk into a confined vol-
ume of fixed dimension. However, they did not consider
the presence of surfactant molecules in the slit and the
swelling of the slit during intercalation.
They found that the intercalation process can be approx-
imately characterized by an effective diffusion co-
efficient that is twice as large as the equilibrium self-con-
sistence in the bulk melt. Increasing the polymer-silicate
interactions is found to induce spontaneous intercalation,
but for a high-polymer silicate affinity, the amount of in-
tercalated material at a given time is reduced compared
to the case of a weaker polymer-silicate attraction. The
crossover from polymer-silicate miscibility to interca-
lated structures with increasing polymer-surface affinity
has already been mentioned by Vaia and coworkers [50].
However, their study suggested that an important role
may be played by the relaxations of polymer bridges that
connect the two silicate surfaces. The number of these
bridges, as well as their dynamical properties, will be
controlled by chain length [75].
Manias and coworkers [76] extended Vaia and cow-
orkers studies and presented a systematic study of the ki-
netics of polymers entering 2 nm wide galleries of mica-
type silicates as a function of polymer molecular weight
and polymer-surface interactions. They varied the poly-
mer-surface interactions in two ways: either through
changing the surface modification, i.e. by varying the or-
ganic coverage or through attaching strongly interacting
sites-sticky groups-along the polymer chain. The poly-
818 Suprakas Sinha Ray
mer-surface affinity is the one of the most crucial param-
eters during nanocomposite preparation, since it controls
the polymer-surface monomeric friction coefficient and
thus determines the motion of the polymer next to a solid
surface. The interaction between the polymer and silicate
surface can be controlled in two novel and well-con-
trolled ways: (i) keeping the polymer the same and mod-
ifying the silicate surface, via controlled surface covering
by surfactants of varying length at the same grafting den-
sity, and (ii) keeping the organically modified surface the
same and modifying the polymer friction coefficient, by
attaching along the polymer chain a controlled amount of
groups that interact strongly with the silicate surface.
They [76] used the PS as polymer and the same octade-
cylammonium modified fluorohectorite to study the in-
tercalation process. While Vaia and coworkers [50] made
all XRD measurements on similar hybrids during in-situ
annealing; Manias and coworkers [76] used ex-situ sam-
ple for XRD and other measurements. The ex-situ meth-
od has several advantages over the in-situ method: First,
one can able to anneal the sample under vacuum, thus re-
ducing any polymer chain degradation. Second, one can
heat and subsequently investigate the same side/surface
of the pellet sample by XRD, a procedure that provides a
much more accurate control of the annealing temperature
than in-situ case, where pellet is heated in one side and is
studied by XRD on the opposite side. They made several
comparative studies by using concurrent in-situ small-an-
gle neutron scattering (SANS) and intermediate-angle
neutron scattering (IANS) to monitor the changes in di-
mensions of the polymer, i.e. Rg, and also to follow the
changes in the single chain scattering function during
intercalation.
Results of concurrent SANS and IANS studies shown
that during intercalation the silicate gallery expansion di-
rectly reflects the motion inside the 2 nm slit pore of the
polymer chains. For the same polymer and the same an-
nealing temperature, they found the experimentally
measured effective diffusion coefficient depends strongly
on the surfactant used for the modification of fluorohec-
torite. For several different polymer molecular weights
and annealing temperatures they observed that Deff in-
creases markedly with longer surfactant lengths and
much more than is expected just from the enhancement
of polymer mobility resulting from the polymer dilution
by small hydrocarbon oligomers. Longer surfactants re-
sult in less silicate surface area exposed to the polymer,
thus effectively reduced the density attraction sites. On
the other hand, introducing controlled amount of groups
along the polymer chain that interact strongly with the
silicate surface, resulting in a strong decrease of Deff.
Therefore, increasing either the density or the strength of
these attractive sites leads to much slower intercalation
kinetics. However, an increase in site density or strength
must also increase the driving force for intercalation; evi-
dently such increases depress the friction coefficient ζ
much more strongly.
To understand the atomistic details of the structure of
the confined-intercalated-polystyrene chains inside the
two dimensional silicate gallery, Manias and coworkers
also carried out molecular dynamic simulation. Details
regarding simulation can be found in ref. [76]. They used
the rotational-isomeric-state (RIS) model to create initial
polymer conformations of PS oligomers. Conformations
that fit in the interlayer gallery were chosen, and the PS
chains were equilibrated by an off-lattice Monte Carlo
scheme that employed small random displacements of
the backbone atoms and orientational biased Monte
Carlo rotations of the phenyl rings; at the same time, the
surfactants were equilibrated by a configurational biased
scheme in coexistence with the polymer chains. After
equilibrium, MD simulations were used to obtain the
structure and density profiles of the intercalated poly-
mer/surfactant films. The numbers of polymer chains and
alkylammonium surfactants were chosen so as to match
the densities found in the experimental studies. The re-
sults suggested that the confined film adopts a layered
structure normal to the solid surfaces, with the polar phe-
nyls dominating the organic materials adsorbed on the
walls, and the aliphatic groups predominantly in the cen-
1 29
ter of the pore. H‐ Si cross-polarized nuclear magnetic
resonance (NMR) measurements revealed a coexistence
of ultra-fast and solid-like slow segmental dynamics
throughout a wide temperature range, below and above
Tg, for both the styrene phenyl and the backbone groups.
The mobile moieties concentrate at the center of the slit
pore, especially for the higher temperatures. This leads to
a strong density inhomogeneity in the direction normal to
the surface. Fast dynamics occur in the lower density re-
gions, whereas slower dynamics occur in high-segment‐
density regions close to the surface. This heterogeneous
mobility combined with an observed persistence of mo-
bility below the bulk glass transition temperature has im-
plications to nanocomposite properties.
Rheology
Let us begin with‐what is rheology? Rheology is the
study of the flow of matter. The name derives from the
greek word “rheo” which means “to flow”. A solid will
usually respond to a stress force by deforming and
storing energy elastically. A liquid, however, will flow
and dissipate energy continuously in viscous losses. A
Newtonian liquid has a linear relationship between the
shear rate and stress. Complex fluids are interesting
because they exhibit both an elastic and viscous
responses and exhibit a non‐linear relationship between
 Rheology of Polymer/Layered Silicate Nanocomposites
Figure 5. Schematic diagram describing the end‐tethered
nanocomposites. The layered silicates are highly anisotropic
with a thickness of 1nm and lateral dimensions (length and
width) ranging from ∼100 nm to a few microns. The polymer
chains are tethered to the surface via ionic interactions between
the silicate layer and the polymer-end. Reproduced from ref
[78] by permission of American Chemical Society.
the shear rate and strain.
One of the properties often dealt within rheology is
viscosity which measures how thick a fluid is. Some
materials are intermediate between solids and fluids and
the viscosity is not enough to characterize them. A solid
material can be described by its elasticity or resilience:
when it is deformed it will store the energy and fight
back. Imagine a spring that regains its original shape
after being deformed. The other extreme is a fluid which
stores no energy while deformed and just flows. A
viscoelastic material is intermediate and stores some
energy and flows a little when deformed. Consider a
system where a micron-sized probe particle is doped
inside a rheologically complex fluid such as polymer
network and Brownian fluctuations are recorded. Now
question is how to predict the mechanical properties of
the medium from the observed Brownian motion of the
particle. If the fluid is Newtonian and the probe molecule
is spherical, one can easily determine the viscosity of the
medium from the measured diffusion coefficient by
using the standard Stokes-Einstein (SE) relation. How-
ever, a polymer network is generally viscoelastic, with a
complex shear modulus having both elastic i.e. solid-like
and viscos i.e. liquid-like components of similar magni-
tudes over a large range of frequencies. Now question is-
is it possible to extend the SE relation to determine shear
complex modulus for such a system? An affirmative
answer would allow one to measure the local rheological
819
properties not only in inhomogeneous materials but also
at high frequencies that are inaccessible using mechani-
cal rheometer. This subject is known as ‘microrheology’
[77].
Now consider a similar system where nanoscopic-sized
particles are dispersed in polymer network, enjoying rap-
id development in recent years, known as ‘nanorheol-
ogy’. Here we are going to discuss about the melt-rheo-
logical behavior of polymer materials where nanometer-
size highly anisotropic particles are dispersed, known as
polymer nanocomposites. In this section author survey
some of the current development in the melt-state rheo-
logical behavior of polymer nanocomposites based on
layered silicates.
The measurement of rheological behavior of any poly-
meric material under molten state is crucial to gain fun-
damental understanding of its processability. In the case
of PLS-nanocomposites, the melt-rheological properties
are also helpful to find out the degree of polymer-filler
interactions and the structure-property relationship in
nanocomposites. This is because rheological material
functions are strongly influenced by the structure and the
interfacial properties.
Linear Dynamic Rheological Properties
Small deformation amplitude oscillatory shear measure-
ments of polymeric materials are generally performed by
applying a time dependent strain
γ(t) = γ0 sin(ωt) (1)
and measuring the resultant shear stress
σ(t) = γ0 [G'sin(ωt) + G"cos(ωt) ] (2)
where G' and G" are the storage and loss moduli, re-
spectively and ω is the frequency.
Krishnamoorti and coworkers [78] first described the
flow behavior of delaminated nanocomposites based on
poly(ε-caprolactone) (PCL) and nylon 6 (N6). Both
nanocomposites were prepared by in-situ polymerization
method in the presence of organically modified MMT,
which engendered direct grafting of macromolecular
chains on the MMT surface-a hairy layered silicate
platelets structure (see Figure 5). The authors coded these
nanocomposites as ‘end-tethered polymer layered silicate
nanocomposites’. Figure 6 represents the rheological
master curves based on linear viscoelastic measurements
for a series of end-tethered PCL-MMT nanocomposites.
The flow behavior of PCL nanocomposites differed
significantly from that of the corresponding neat
matrices, whereas the thermorheological properties of the
nanocomposites were entirely determined by the
behavior of the matrices. The slopes of log G'(ω) and
820 Suprakas Sinha Ray

Figure 6. Storage modulus (G') for PCL‐based silicate nan-

ocomposites. Silicate loadings are indicated in the figure.
Master-curves were obtained by application of time-temper-
ature superposition and shifted to T0 = 55 oC. Reproduced from
ref. [78] by permission of American Chemical Society.

G"(ω) versus log aTω are much smaller than 2 and 1,

respectively. Values of 2 and 1 are expected for non-
crosslinked polymer melts, but large deviations occur,
especially in the presence of a very large amount of
layered silicate loading, which may be due to the
formation of a network structure in the molten state.
However, nanocomposites based on the in-situ poly-
merization technique exhibit a fairly broad molar mass
distribution in the polymer matrix, which hides the
relevant structural information and impedes the inter-
pretation of the results. The similar behavior was also
observed in the case of end-tethered N6-MMT nan-
ocomposites.
Ren and Krishnamoorti [79] then showed significant
modification of flow behavior of nanocomposites when
polymer chains are not tethered on the silicate surface.
The nanocmposites of polystyrene-1, 4-polyisoprene (7
mol% 3, 4 and 93 mol% 1, 4) diblock copolymer (PSPI
18) were prepared with (0.7, 2.1, 3.5, 6.7, and 9.5 wt%)
dimethyl dioctadecyl ammonium modified MMT by
solution mixing in toluene. The homogeneous solution
was dried extensively at room temperature and
o
subsequently annealed at 100 C in a vacuum oven for ∼
12 h to remove any remaining solvent and to facilitate
complete polymer intercalation between the silicate
layers. The XRD patterns of PSPI18/2C18-MMT and
PS/2C18-MMT clearly indicates the formation of
intercalated structures, whereas the composite prepared
with 1, 4-polyisoprene (PI) showed no change in gallery
height. The intercalation of 2C18-MMT by PS and not
by PI is consistent with the results of previous
experimental work and theories of Vaia and coworkers
[37,38] and of Balazs and coworkers [39,40]. The
Figure 7. Time-temperature superposed linear storage modulus
(a, top) and loss modulus (b, bottom) for the series of
2C18M-based PSPI18 intercalated hybrids. As expected, the
moduli increase with increasing silicate loading at all
frequencies. At high frequencies, the qualitative behavior of the
storage and loss moduli are essentially unaffected. However, at
low frequencies the frequency dependence of the moduli grad-
ually changes from liquidlike to solidlike for nanocomposites
with 6.7 and 9.5 wt% silicate. Reproduced from ref. [79] by
permission of American Chemical Society.
intercalation of PS into the silicate layers may be due to
the slight Lewis base character imparted by the phenyl
ring in PS, leading to the favorable interactions with the
2C18-MMT layers.
All rheological measurements were conducted in the
temperature range of 80∼105 °C. The time-temperature
master curves for neat PSPI and various nanocomposites
are presented in Figure 7. It is clear from the figures that
viscoelastic behavior of PSPI significantly modified after
nanocomposite formation. At high frequency region
(where frequency > 10 rad.s), viscoelastic properties of
PSPI were unaffected by the presence of silicate particle,
while at the low frequency region (region where fre-
quency < 10 rad.s), both G' and G" for the nano-
composites exhibited a significant diminished frequency
 Rheology of Polymer/Layered Silicate Nanocomposites
dependence and this behavior was more prominent with
higher loading of silicate layers, similar behavior as ob-
served in the case of end-tethered nanocomposite.
Similar behavior has also been noted for carbon black
[80], calcium carbonate [81], and talc [82] filled
polymers. However, in those cases the particle volume
fractions were substantially higher, 5∼10 wt% for which
strong frequency independent behavior is seen for PLS‐
nanocomposites.
Time-temperature superposition required simultaneous
horizontal and vertical shifting of the shear moduli: bT G'
and bT G" versus aTω, where aT is the horizontal shift
factor, bT is the vertical shift factor and ω is the
frequency. While aT for all nanocomposites followed the
same WLF (Williama-Landel-Ferry) [83] dependence but
bT did not. The authors attributed this could be the block
architecture of the polymer examined, and the relative
proximity of the order-disorder temperature to the tem-
perature of the experimental measurements or may be
due to formation of different types of structural ori-
entation in the presence of organocaly.
To understand the viscoelastic behavior observed at low
frequencies region in the dynamic measurements for the
nanocomposites, they conducted stress relaxation mea-
surements. The stress relaxation data of these nano-
composites in the terminal region showed a solid-like
behavior. Like G', the effect was particularly pronounced
at ≥ 6.7 wt% silicate loading. The authors attributed this
behavior is due to the presence of stacks of intercalated
silicate layers and those are randomly oriented in the pol-
ymer matrix, forming three dimension network structure.
These stacked intercalated silicate layers have only trans-
lational motion. A large-amplitude oscillatory shear is
able to orient these structures and reduce the solid like
behavior. Another explanation may be the formation of
PI micro-domains. Results of XRD revealed that only
PS block diffused into the interlayer galleries, leaving the
PI block out of the silicate galleries. These PI blocks can
form phase-separated micro-domain structures, which ac-
tually hinder the orientation of stack intercalated silicate
layers under small-amplitude shear.
Another explanation is the physical jamming of the dis-
persed stack intercalated silicate layers owing to their
highly anisotropic nature. Transmission electron micro-
scopy image revealed the formation of intercalated struc-
ture for the PSPI-based nanocomposites. On the basis of
this mesoscopic structure and at low silicate loadings, au-
thors suggested that, beyond a critical volume fraction,
the tactoids and the individual layers are incapable of
freely rotating and when subjected to shear are prevented
from relaxing completely. This incomplete relaxation
due to the physical jamming or percolation of the nano-
scopic fillers leads to the presence of the pseudo-solid-
like behavior observed in both the intercalated and ex-
821
foliated hybrids.
To verify above percolation theory, Krishnamoorti and
coworkers estimated the percolation threshold for these
hybrids on the basis of stack size of the intercalated sili-
cate layers. They assumed a hypothetical hydrodynamic
sphere surrounding each tactoid and the percolation of
these hydrodynamic spheres to signify the onset of in-
complete relaxation and the presence of pseudo-solid-
like behavior in the intercalated nanocomposites. To find
out the relation between the number of silicate layers per
tactoid, nper and the layered silicate weight fraction at
percolation, wsil, per, as
       
    
             

(3)
where Rh is the radius of the hydrodynamic volume (in
this case equivalent to the radius of the disk-like layered
silicates), øper is the percolation volume fraction, hsil is
the thickness of the silicate layers (generally 1 nm), ρorg
and ρsil are the densities of the organic component and
layered silicate respectively. By considering the uniform
disks diameter (2Rh) of 0.5 µm and the wsil, per to be
0.067, they calculated the average tactoid size to be
around 30 layers. This calculated value was well matched
with the value calculated from XRD pattern and TEM
measurement. Furthermore, this tactoid size implies that
the effective anisotropy associated with the filler is 5∼
10. It is this anisotropy, along with the random relative
arrangement of the tactoids that leads to the observation
of the percolation phenomenon at extremely low loading
of the silicate.
Krishnamoorti and coworkers also used above equation
to estimate the percolation threshold for the exfoliated
nanocomposites by assuming the same geometrical pa-
rameters as considered previously. They suggested that
in the case of exfoliated nanocomposites, there exist con-
siderable local orientational order which has enormous
consequences for the physical and mechanical properties
of the hybrids. This orientational ordering along with the
end-tethering of the polymer chains on the layered sili-
cate surface in fact responsible for the non-terminal inter-
mediate frequency response in the PCL and N6-based
nanocomposites.
Over the last few years, the linear dynamic and steady
rheological properties of several nanocomposites have
been examined for a wide range of polymer matrices
including N6 with various matrix molecular weights
[84], polyamides [85-91], polystyrene [92-96], poly-
propylene [97-102], polyethylene [103], ethylene vinyl
copolymers [104-106], polycarbonate [107-109], poly
(ethylene oxide) [110-112], poly(ε-caprolactone) [113,
114], poly(ethylene terephthalate) [115], polylactide
822 Suprakas Sinha Ray

Figure 8. Complex viscosity versus frequency from a dynamic parallel plate rheometer (solid points) and steady shear viscosity ver-
sus shear rate from a capillary rheometer (open points) at 240 °C for (a) pure HMW and its (HE)2M1R1 organoclay nanocomposite,
(b) pure MMW and its (HE)2M1R1 organoclay nanocomposite. The nanocomposites contain ∼3.0 wt% MMT. Reproduced from ref.
[84] by permission of Elsevier Science Ltd., UK.

[116-118], poly(butylene succinate) [119-121], poly
[(butylene succinate)-co-adipate] [122,123], synthetic
biodegradable aliphatic polyester (BAP) [124,125],
liquid crystal polymer [126,127], PLS-nanocomposites
based on immiscible and miscible polymers blend [128,
129], etc.
Choi and coworers described the melt-state rheological
behavior of a series of PEO/organoclay nanocomposites
[111,112]. To understand both the effect of degree of dis-
persion of silicate layers and the interaction between the
organoclay surface and polymer matrix, they used three
types of surfactants modified montmorillonite. First, they
selected two different organoclays, which have different
modifier concentration but the same alkylamonium salt.
Second, they differentiated the types of alkylamonium
salts having the same organic modifier. All nanocompo-
sites were prepared via solvent casting method using
chloroform as a co-solvent. XRD patterns and TEM ob-
servations revealed the formation of intercalated
nanocomposites. Rheological properties measurements
under molten state revealed that an increase in shear vis-
cosity and storage and loss moduli of nanocomposites
with clay content. Like other properties, they also fond
that rheological properties of nanocomposites directly re-
lated to the degree of dispersion of silicate layers in the
polymer matrix and also the level of interfacial inter-
actions between the layered silicate surface and polymer
chains. They concluded that linear rheological properties
are strongly correlated with the mesoscopic structure and
it was postulated that the molecular weight and inter-
action strength would affect the mesoscopic structure and
the rheological properties of these nanocomposites.
Fornes and coworkers [84] have conducted dynamic
and steady shear capillary experiments over a large range
of frequencies and shear rates of pure N6 with different
molecular weights, and their nanocomposites with
OMLS. Figure 8 shows bilogarithmic plots of the
complex viscosity, |η*| vs. ω at 240 oC for pure N6 and
(HE)2M1R1 nanocomposites based on (a) high molecular
weight (HMW), (b) medium molecular weight (MMW),
 Rheology of Polymer/Layered Silicate Nanocomposites
Figure 9. Influence of frequency on shear storage modulus for
pure LMW, and for LMW, MMW and HMW based nano-
composites. Reproduced from ref. [84] by permission of
Elsevier Science Ltd., UK.
and (c) low molecular weight (LMW), obtained using the
parallel plate oscillating rheometer. Figure 8 also shows
a bilogarithmic plot of the steady-state shear viscosity η
versus shear rate  , obtained using a capillary rheometer.
Inspection of these figures reveals a significant differ-
ence between the nanocomposites, particularly at low
frequencies. The HMW-based nanocomposites show
very strong non-Newtonian behavior, and this is more
pronounced at low frequencies. On the other hand, the
magnitude of the non-Newtonian behavior gradually de-
creases with decreasing molecular weight of the matrix,
and with LMW it behaves like pure polymer. This trend
is more clearly observed in the plot of G' vs. ω, due to
the extreme sensitivity of G' towards dispersed morphol-
ogy in the molten state (see Figure 9). The difference in
the terminal zone behavior may be due to different ex-
tents of exfoliation of the clay particles in the three types
of matrices.
At the other extreme, the steady shear capillary rheol-
ogy shows a trend with respect to the matrix molecular
weight. The HMW and MMW-based nanocomposites
exhibit lower viscosities compared to that of their corre-
sponding matrices, whereas the viscosities of LMW-
based nanocomposites are higher than the pure matrix.
This behavior is also due the higher degree of exfoliation
in the case of HMW and MMW-based nanocomposites
compared to the LMW-based nanocomposite.
Finally they considered the differences in the melt vis-
cosity among the three systems. Over the range of fre-
quencies and shear rates tested, the melt viscosity of the
823
three systems follows the order HMW > MMW > LMW,
and hence the resulting shear stresses exerted by the pure
polymers also follow the same order. Therefore, during
melt mixing the level of stress exerted on the OMLS by
the LMW polyamide is significantly lower than those de-
veloped in the presence of HMW or MMW polyamides.
As a result, the break-up of layered silicate particles is
much easier in the case of HMW polyamides, and lay-
ered silicate particle dispersion is ultimately improved.
The role of polymer molecular weight is believed to stem
from an increase in the melt viscosity, facilitating the
degradation of the taller stacks into shorter ones. The fi-
nal step in exfoliation involves peeling away the platelets
of the stacks one by one, and this takes time and requires
the strong matrix-OMLS interaction to cause sponta-
neous wetting.
Aubry and coworkers were studied the dynamaic and
steady flow properties of a polyamide-12 (PA12) melt
layered silicate nanocomposites as a function of the sili-
cate volume fraction, ø [88]. They found above a vol-
ume fraction threshold øp is equal to 1.5 %, and below a
critical strain γc, the storage (G') and loss moduli (G")
were shown to exhibit a low-frequency plateau and the
flow curve was shown to exhibit a stress, τy. The study
of G', γc, and τy as a function of ø showed the energy
needed for removing connectivity on a mesoscale did not
depend on the silicate loading. These original properties
were attributed to the existence, in the quiescent state, of
mesoscopic domains composed of correlated silicate
layers. Moreover, the steady shear response of all sam-
ples at solid volume fractions above øp showed the ex-
istence of a critical shear rate is equal to 1/s, separating a
behavior governed by the networked domains from a be-
havior dominated by the polymer matrix.
Gelfer and coworkers have investigated the particular
relationship among the molecular structure of polymer
chains, morphology, and rheology of nanocomposites
prepared by melt-blending of Cloisite organoclays and
ethylene-co-vinyl acetate (EVA) and ethylene-co-methyl
acrylate (EMA) random copolymers [104,106]. TEM ob-
servation confirmed the mixed intercalated-exfoliated
morphology in these nanocomposite systems. The melt-
state rheological properties were very similar in EVA-
and EMA-based nanocomposites. These materials ex-
hibited a pseudo-solid like rheological behavior, which
became more pronounced upon heating, especially at
temperature above 180∼200 °C. Authors attributed this
behavior is due to the physical gelation due to the for-
mation of 3D tactoid network in the polymer matrix.
They found that this gelation behavior is directly related
to the overall content of organoclay and the extent of
miscibility between the organoclay and polymer matrix.
The SAXS data indicated that the silicate gallery
spacing (d001), intercalated by EVA and EMA chains,
824 Suprakas Sinha Ray
Figure 10. G' vs. reduced frequency for PS100 matrix (black
line), CPS (A), and C-PEA (W). Silicate loading: 5 wt%.
Reproduced from ref. [89] by permission of Wiley-VCH,
Germany.
decreases with increasing temperature. At temperature
above 200 °C, the desorption of surfactant in organoclay
decreases the compability between the clay surface and
the polymer matrix, which finally exhibited a LCST
(lower critical solution temperature) type behavior
between organoclays and polymer, enhancing the state of
gelation. This behavior manifested itself by a reverse
temperature dependence of viscoelastic properties and
strong deviation of rheological behavior from the time‐
temperature superposition principle.
Hoffmann and coworkers [89] recently conducted rheo-
logical measurements of nanocomposites of polystyrene
(PS100) with synthetic mica (ME100) modified with
amine-terminated polystyrene (AT-PS8) and 2-phenyl-
ethylamine (PEA) respectively, in order to verify the
presence of a particle network formation via inter-par-
ticle interaction and self-assembly. Figure 10 represents
G'(ω) vs. aTω for PS100 and its corresponding nano-
composites prepared with AT-PS8 modified ME100 (C-
PS) and PEA modified ME100 (C-PEA). The rheological
responses of PS100 and C-PEA are the same, whereas
the rheological response of C-PS is completely different.
At the lowest frequencies, which correspond to the
marked region III, G'(ω) strongly increases, and the
slope approaches to zero. Such behavior is an indication
of network formation involving the assembly of in-
dividual plates composed of silicate layers. In the regime
of intermediate frequencies (region II, see Figure 10) the
G'(ω) value is lower in comparison to that of PS100.
This might be due to dilution of the amine-terminated PS
being below the entanglement molecular weight. On the
other hand, in high frequency region (region I, Figure 10)
the rheological behavior is the same for all systems.
Sinha Ray and coworkers [116-118] have conducted the
Figure 11. Reduced frequency dependence of storage modulus,
G' and loss modulus, G" of PLA and various PLACNs.
Reprinted from ref. [118] by permission of Wiley-VCH,
Germany.
dynamic oscillatory shear measurements of PLA nano-
composites with intercalated structure. Melt rheological
measurements were conducted on Rheometric Dynamic
Analyzer (RDAII) instrument using 25 mm diameter
parallel plates with a sample thickness of ca. 1.5 mm and
in the temperature range of 175∼205 °C. To avoid
nonlinear response, the strain amplitude was fixed to 5 %
to obtain reasonable signal intensities even at elevated
temperature or low w. For each nanacomposite investiga-
ted, the limits of linear viscoelasticity were determined
by performing strain sweeps at a series of fixed
frequencies. The master curves were generated using the
principle of time-temperature superposition and shifted
to a reference temperature (Tref) of 175 °C, which was
chosen as the most representative of a typical processing
temperature of PLA.
The master curves for G' and G" of pure PLA and
various nanocomposites with different weight percenta-
ges of C18 MMT loading are presented in Figure 11. At
high frequencies (aT.ω > 10), the viscoelastic behavior
of all nanocomposites was the same. On the other hand,
at low frequencies (aTω < 10), both moduli exhibited
weak frequency dependence with increasing C18MMT
content, with a gradual change of behavior from liquid-
like [G' ∝ω2 and G" ∝ω] to solid-like ( G' ≥ G") with
 Rheology of Polymer/Layered Silicate Nanocomposites
Figure 12. Flow activation energy as a function of C18-
MMTcontent. Reprinted from ref. [118] by permission of
Wiley-VCH, Germany.
increasing C18MMT content.
The slope of G' and G" in the terminal region of the
master curves of PLA matrix was 1.85 and 1
respectively. On the other hand, the slopes of G' and G"
were considerably lower for all PLACNs compared to
those of pure PLA. In fact, for PLACNs with high
C18MMT content, G' becomes nearly independent at low
aTω and exceeds G", characteristic of materials exhibit-
ing a pseudo-solid-like behavior.
Figure 12 represents the C18MMT content dependent
(wt%) flow activation energy (Ea) of pure PLA and vari-
ous nanocomposites obtained from an Arrhenius fit of
master curves [118]. There was a significant increase of
Ea for PLA/C18 MMT3 compared to that of pure PLA
followed by a much slower increase with C18MMT
content. This behavior may be due to the dispersion of
intercalated and stacked C18MMT silicate layers in the
PLA matrix.
The dynamic complex viscosity (｜η*｜) master curves
for the pure PLA and nanocomposites, based on linear
dynamic oscillatory shear measurements, are presented in
‐1
Figure 13 [118]. At low aTω region ( < 10 rad.s ), pure
PLA exhibited almost Newtonian behavior while all
nanocomposites showed very strong shear-thinning
tendency. On the other hand, Mw and PDI of pure PLA
and various nanocomposites were almost the same, thus
the high viscosity of PLACNs were explained by the
flow restrictions of polymer chains in the molten state
due to the presence of MMT particles.
Figure 14 represents the master curves for G' and G" of
neat PBS and various PBSCNs prepared with two
different types of OMLS [120]. At all frequencies, both
G' and G" of nanocomposites increased monotonically
with increasing OMLS loading with the exception of
PBS/C18MMT1 and PBS/qC16SAP1 for which viscoe-
825
Figure 13. Reduced frequency dependence of complex vis-
cosity (｜η*｜) of PLA and various PLACNs. Reprinted from
ref. [118] by permission of Wiley-VCH, Germany.
lastic behavior was almost identical to that obtained for
neat PBS. At high frequencies (aTω< 5), both moduli
exhibited weak frequency dependence with increasing
clay content, which means that there are gradual changes
of behavior from liquid-like to solid-like with increasing
clay content.
Lepoittevin and coworkers [113] reported the melt rheo-
logical properties of PCL-based nanocomposites pre-
pared by melt intercalation method. G' and G" of unfilled
+
PCL and PCL filled with 3 wt% of MMA-Na , MMT‐
Alk or MMT-(OH)2 were measured at 80 ºC in the fre-
‐2
quency range from 16 to 10 Hz. The rheological behav-
ior of the PCL filled with 3 wt% of MMT-Alk and
MMT-(OH)2 was significantly different compared to un-
filled PCL and PCL/MMT-Na composites. The fre-
quency dependence of G' and G" was, however, per-
turbed by organically modified MMT. The effect was
dramatic in the slope of G' which drops from 2 to 0.14
and 0.24 for MMT-(OH)2 and MMT‐Alk, respectively.
The dependence of G' and G" on frequency with the
filler content is presented in Figure 15 for the MMT-
(OH)2 clay. When the clay content exceeded 1 wt%, not
only the classical power laws for the frequency depend-
ence of G' and G" were deeply modified, particularly in
the case of G' but the moduli increased dramatically at
low frequency. This is a characteristic of pseudo-solid-
like behavior due to the formation of a network percolat-
ing clay lamellae. The same behavior was also observed
in the case of PLA or PBS-based nanocomposites [118,
120,121].
Sinha Ray and his coworker recently described the
melt-state rheological properties of poly[(butylene
succinate)-co-adipate] (PBSA) nanocomposites [122].
®
Cloisite 30B (C30B) organoclay was used for the
preparation of nanocomposites. Nanocomposites were
826 Suprakas Sinha Ray

Figure 14. (a) Reduced frequency dependence of the storage modulus,G'(ω), and the loss modulus, G"(ω), of PBS and various
PBSCNs prepared with C18-mmt clay. Tref ) 120 °C. (b) Reduced frequency dependence of the storage modulus, G'(ω), and the
loss modulus, G"(ω), of PBS and various PBSCNs prepared with qC16‐sap. Tref ) 120 °C. Reproduced from ref. [120] with permis-
sion of American Chemical Society, USA.
o
prepared at 135 C in a batch mixer. Nanocomposites
(PBSACNs) prepared with three different amount of
C30B of 3, 6, and 9 wt% were correspondingly
abbreviated as PBSACN3, PBSACN6, and PBSACN9.
The structure of the nanocomposites was studied using
XRD and TEM that revealed a coexistence of exfoliated
and intercalated silicate layers dispersed in the PBSA
matrix, regardless of the silicate loading.
The angular ω dependence of storage, G'(ω) and loss
modulus, G"(ω) of neat PBSA and PBSACNs with three
different wt% of C30B loading are presented in Figure
16, parts a and b, respectively. At all frequencies, both
G'(ω) and G"(ω) for PBSACN6 and PBSACN9 in-
crease with increasing C30B content with the exception
of PBSACN3 for which the viscoelastic response is al-
most identical to that observed for neat PBSA. At high-
ω region, the viscoelastic behavior of all PBSACNs is
quite the same, with only a small systematic increase in
G'(ω) with the C30B loading, indicating that the ob-
served chain relaxation modes are almost unaffected by
the presence of the layered silicate particles (Figure 16a
and b). However, at the low-ω region, both dynamic
moduli exhibit weak frequency dependence with C30B
loading. For the 9 wt% of C30B loading, G'(ω) exceeds
G"(ω) and becomes nearly independent of ω.
To verify the interesting viscoelastic behavior observed
at low frequency region in the dynamic oscillatory shear
measurements for the nanocomposites with high wt%
C30B loading, the linear stress relaxation measurements
were conducted. Results of linear relaxation behaviors of
neat PBSA and PBSACNs are presented in Figure 17.
For any fixed time after imposition of strain, the relaxa-
tion modulus, G(t) increases with increasing C30B load-
ing, similar to that observed in the dynamic oscillatory
shear measurements.
Similar to the behavior observed at high frequencies in
dynamic mode (Figure 16a and b), the stress relaxation
modulus of all PBSACNs is quite of the same magnitude
as that of the neat PBSA at short times, with only a slight
increase with C30B content (Figure 17). However, at
long time periods, the pure PBSA and PBSACN3 relaxes
like a viscoelastic liquid, while the PBSACNs with 6 and
9 wt% of C30B loading behave like a pseudo-solid-like
material.
Therefore, on the basis of both the dynamic oscillatory
shear (Figure 16a and b) and linear stress relaxation
measurements (see Figure 17), it is clear that C30B lay-
ered silicate has a profound effect on the long relaxation
time of the nanocomposites. For PBSACNs with C30B
loading in excess of 3 wt% , the liquid-like behavior ob-
served in the case of pure PBSA gradually changes to
pseudo-solid-like behavior.
A reasonable explanation for this low frequency
viscoelastic behavior of PBSACNs is that the moderate
interactions of the PBSA backbone with C30B surface
lead to the high degree of confinement of polymer chains
inside the silicate layers. As a result anisotropic silicate
layers are fully dispersed in the PBSA matrix, as
 Rheology of Polymer/Layered Silicate Nanocomposites
Figure 15. Storage modulus (G0) and loss modulus (G00) for
unfilled PCL and PCL modified by 3 wt% of MMT-Na,
MMT-Alk, MMT-(OH)2 at 80 C [160]. Reproduced from ref.
[113] by permission of Elsevier Ltd., UK.
observed in XRD patterns and TEM images [122].
Because of their highly anisotropic nature, the dispersed
layered silicate particles would exhibit local correlations
that finally cause the formation of micro-domains or
mesoscopic structure [116,124,125]. Like in liquid
crystalline and ordered block copolymer systems [130-
133] the presence of these micro-domains or mesoscopic
structure causes only a slight increase of the low-ω
elastic modulus that varies in low power-law fashion.
This is the case for low C30B concentration (∼3 %).
However, beyond this concentration, exfoliated and or
disordered intercalated silicate layers form a network-
type structure rendering the system highly elastic as
revealed by the low frequency plateau. Such a plateau is
similar to the one observed in rubber-toughened
polymers [134,135] where rubber particles form a
827
Figure 16. Frequency dependence of (a) dynamic storage, G'
(ω) and (b) loss, G"(ω) moduli of neat PBSA and various
PBSACNs. Reprinted from ref. [122] by permission of Wiley‐
VCH, Germany.
percolating network that imparts the blend with solid-like
behavior. Such a behavior can also be seen on the
dynamic complex viscosity, η*(ω), shown in Figure
18. Little effect of C30B addition is observed at high
frequencies, where the relaxation mechanism is mainly
dominated by that of the PBSA matrix, whereas at low
frequencies, the relaxation is that of particle-particle
interactions inside the percolating network of the silicate
layers.
In a recent literature Huang and Han reported the melt-
state rheological behavior of PLS nanocomposites based
on thermotropic liquid-crystalline polymers (TLCP)
[126]. In their study they used two different types of
TLCPs such as TLCP having pendent pyridyl group
(PyHQ12) and TLCP having pendent phenylsulphonyl
group (PSHQ12). They also used two different types of
828 Suprakas Sinha Ray

Table 1. Characteristics of Organically Modified Layered Silicates (OMLS) used in this Research
Modifier Concentration a
Organoclay Type Code Chemical Structure of Organic Modifier δ of Organic Modifierb, c
(meq/ 100 g)

CH 3

Cloisite 15 A C15 A 125 H3C N+ HT 16.94

HT

Cloisite 93 A C93 A 90 H3C N+ HT 17.96

HT

CH 2CH 2OH

Cloisite 30 B C30 B 90 H3C N+ HT 21.08

CH 2CH 2OH
a
HT is hydrogenated tallow (∼65 % C18; ∼30 % C16; ∼5 % C14)
b
δ is the solubility parameter calculated by group contribution method of Fedors
c
δ value of neat PBSA is 23.8

Authors presented dramatic differences in linear dy-

Figure 17. Stress relaxation behavior of Neat PBSA and vari-
ous PBSACNs. Reprinted from ref. [122] by permission of
Wiley-VCH, Germany.
OMLS such as C30B and C20A for the preparation of
nanocomposites. Nanocomposites were prepared by
solution blending method using pyridine as a co-solvent.
XRD patterns and TEM revealed the high degree of
dispersion of silicate layers in PyHQ12/C30B nanocom-
posites, whereas silicate layers formed aggregates in
PyHQ12/C20A and PSHQ12/C30B nanocomposites.
namic viscoelastic properties between PyHQ12/C30B
and PSHQ12/C30B nanocomposites. They attributed that
the presence of strong interaction between PyHQ12 poly-
mer chains with C30B surface through hydrogen bond is
main responsible factor for significant improvement in
rheological properties in case of PyHQ12/C30B nano-
composite. Authors also observed a considerable amount
of loss in the degree in liquid crystallinity of PyHQ12
matrix in PyHQ12/C30B nanocomposite, although it has
intercalated structure. This is due to the strong interaction
between polymer backbone and clay surface, which fi-
nally lead to the highly restricted movement of the poly-
mer chains in nanocomposite. The same type of con-
clusion has been made by this group of researchers in
case of PC/C30B nanocomposite, but they did not con-
sider the degradation of matrix or C30B at the processing
temperature (260 oC) [109].
To find out the direct relation between the structure and
melt-state rheological properties in case of nanocompo-
sites, Sinha Ray and coworkers prepared a series of PLS
nanocomposites based on PBSA [123]. Three different
types of commercially available organically modified
montmorillonite (OMMT) were used for the preparation
of nanocomposites. By varying the hydrophobicity, and
consequently the favorable interactions of the surfactant
with the polymer matrix, a spectrum of structures
including phase-separated, intercalated, disordered inter-
 Rheology of Polymer/Layered Silicate Nanocomposites
Figure 18. Frequency dependence of dynamic complex vis-
cosity (η*) of neat PBSA and various PBSACNs. Reprinted
from ref. [122] by permission of Wiley-VCH, Germany.
calated, and intercalated-exfoliated were obtained (Fig-
ure 19). The chemical structure of the specific surfactant
and the cation exchange capacity of each of the OMMT
used in this research are presented in Table 1.
The small amplitude oscillatory shear storage modulus,
G'(ω), of the neat PBSA and the three nanocomposites
Figure 19. TEM bright field images of (a) PBSA/6CNa hybrid, (b) PBSA/6C15A nanocomposite, (c) PBSA/6C93A nanocomposite,
and (d) PBSA/6C30B nanocomposite. Reproduced from ref. [123] by permission of Elsevier Science Ltd., UK.
829
is presented in Figure 20. As expected, G'(ω) of the
nanocomposites increases with increasing the degree of
dispersion of the silicate layers in the PBSA matrix over
all frequency range. At high frequencies, only a slight in-
crease in modulus with respect to that of the pure PBSA
is observed. G'(ω) of the matrix and the nanocomposites
decreases linearly with lowering of frequency. However,
at very low frequencies a significant increase in G'(ω) is
observed in the case of PBSA/C30B nanocomposite, in-
dicating that C30B silicate layers have strong effect on
the chain relaxation of PBSA. Upon increase in the fa-
vorable specific interactions between the surfactant and
PBSA matrix, G'(ω) becomes a weak function of fre-
quency and exhibits a pseudo-plateau in the terminal
zone of the pure PBSA. This gradual change of behavior
from liquid-like to solid-like is mainly attributed to the
extent of dispersion and distribution of the clay lamellae
that form three dimensional percolating networks [116].
This of course depends on the extent of enthalpic
interactions between the PBSA backbone and the surface
of OMMTs, which finally leads to the confinement of
polymer chains inside the silicate galleries. Because of
their highly anisotropic nature, the fully dispersed silicate
layers would exhibit local correlations, which finally lead
to the formation of three dimensional mesoscopic
structures [123] and the tendency of formation of this
mesoscopic structure gradually decreases with decreasing
830 Suprakas Sinha Ray
Figure 20. Frequency dependence of dynamic storage modulus,
(G'(ω)), of neat PBSA and various nanocomposites. Repro-
duced from ref. [123] by permission of Elsevier Science Ltd.,
UK.
the degree of dispersion of intercalated silicate layers in
the polymer matrix. Among the three OMMTs used for
the preparation of PBSA nanocomposites, C30B has the
higher degree of interactions with PBSA matrix and as a
result intercalated silicate layers are relatively well
dispersed in the PBSA matrix (see Figure 19). Conse-
quently, silicate layers are highly correlated in the
PBSA/C30B nanocomposite. With decreasing the degree
of dispersion of intercalated layers in the PBSA matrix,
the tendency of formation of this type of correlated
structure is also decreased and thus the increment in
modulus systematically decreases from PBSA/C30B
nanocomposite to PBSA/C15A nanocomposite. The
solidlike behavior can also be evidenced by the sharp
increase in viscosity in the low frequency region for
nanocomposites, where the pure PBSA shows rather a
Newtonian behavior (see Figure 21).
Parts a and b of Figure 22 show the time dependent
evolution of the storage and loss moduli for PPCH8 (PP
= 91 wt%, MMT = 9 wt%) and PPCH9 (PP = 82 wt%,
MA = 9 wt% and MMT = 9 wt%) samples, subjected to
small strain oscillatory shear tests every 10 min during
their total annealing time of 3 h at 200 oC [97]. At high
frequencies the elastic moduli of PPCH8 and PPCH9 are
comparable at similar annealing times, and both decrease
with annealing due to possible degradation of the PP-
matrix. At low frequencies the elastic modulus of PPCH
9 is qualitatively different than that of PPCH 8. The
low-frequency elastic modulus of as-extruded PPCH9 is
always higher than that of PPCH8, indicating that most
of the micro-structural development in PPCH9 has
already occurred during the extrusion process, while only
subtle micro-structural changes occurred during annealing.
Figure 21. Frequency dependence of dynamic complex vis-
cosity (η*) of neat PBSA and various nanocomposites.
Reproduced from ref. [123] by permission of Elsevier Science
Ltd., UK.
Furthermore, the elastic modulus of PPCH8 at low fre-
quency decreases with annealing time, but that of PPCH9
remains more or less unchanged. Thus at high frequency,
the response of the PPCH9 hybrid is dominated by the
matrix, while at lower frequencies its solid-like response
is strongly influenced by the presence of clay. On the
other hand, the low frequency response of PPCH8 is not
dominated by the presence of clay, which highlights the
important role played by PP-MA in the formation of the
hybrids.
The above results show that the solid-like rheological
behavior of nanocomposites at lower frequencies is com-
pletely independent on the fine structure of the nano-
composites i.e., whether it is end-tethered or stacked in-
tercalated, but it is depends primarily upon the amount of
clay loading in the nanocomposites. Galgali and cow-
orkers [97] have also shown that the typical rheological
response in nanocomposites arises from frictional inter-
actions between the silicate layers and not due to the im-
mobilization of confined polymer chains between the sil-
icate layers. They have also shown a dramatic decrease
in the creep compliance for the PPCH prepared with MA
modified PP and 6 wt% MMT. In contrast, for PPCH
prepared with MA modified PP and 9 wt% of MMT,
they show a dramatic three-order of magnitude drop in
the zero shear viscosity beyond the apparent yield stress,
suggesting that the solid‐like behavior in the quiescent
state is a result of the percolated structure of the layered-
silicate.
In order to characterize the viscoelastic properties of the
so-called network formation, Aubry and coworkers [88]
measured G' as a function of the layered silicates volume
fraction, ø. Parts a and b of Figure 23 respectively
 Rheology of Polymer/Layered Silicate Nanocomposites
Figure 22. Zero shear viscosity as a function of annealing time
for several PPCH samples in the presence (denoted by filled
symbols) and absence (denoted by open symbols) of PP-MA.
(b) Zero-shear viscosity as a function of clay content for sam-
ples with and without compatibilizer. Reproduced from ref.
[97] by permission of American Chemical Society.
represents G' and G" of PA12‐based nanocomposites.
The ø dependence of G' is presented in Figure 24, which
is rather well fitted by a quadratic equation:
G' ∝ø (4)
According to them the appearance of nonlinearities in the
viscoelastic response of nanocomposites at a strain γc
(see Figure 25) is due to partial rupture of connectivity
within the system and it is found that γc is inversely re-
lated to the volume fraction of layered silicate added
(ø), i.e.
γc ∝ø‐1 (5)
The amount of elastic energy stored in the nano-
composite at γc is the energy needed (termed as yield
energy, Ey) to break some crucial connections between
silicate entities and allowing the system to yield, but not
to disturb, as shown by the relatively smooth decrease of
both viscoelastic moduli above γc (see Figure 25).
831
Figure 23. (a) Storage modulus G' as a function of frequency at
(●) 0 %, (O) 0.5 %, (■) 1 %, (□) 1.5 %, (∆) 2.5 %, (▲) 5
%, and (▼) 10 %. (b) Loss modulus G" as a function of fre-
quency at (●) 0 %, (O) 0.5 %, (■) 1 %, (□) 1.5 %, (∆) 2.5
%, (▲) 5 %, and (▼) 10 %. Reproduced from ref. [88] by per-
mission of The Society of Rheological, USA.
This yield energy, Ey can be defined as follows:


   
    ′

(6)
where τis the shear stress.
Combining the equations (5) and (6), the yield energy,
Ey is found to be independent of the layered silicate vol-
ume fraction, ø:
  ∝ø0 (7)
Now it will be very interesting if we compa0re this
yield energy data with the “cohesive” energy (Ec) data
for aqueous clay suspensions. Ramsay in 1986 [130,131]
and Sohm and Tadors in 1989 [132] respectively
determined the ø dependence of Ec for laponite
1.8
dispersion (Ec ∝ø ) and for MMT suspensions (Ec ∝
3.1
ø ) in the gel structure. However, the concept of
cohesive energy, although defined by the same equation
as (6), still differs from the concept of yield energy
832 Suprakas Sinha Ray

Figure 24. Plateau storage modulus G' as a function of nano-

filler volume fraction. The solid line corresponds to Eq. (4).
The square of the correlation coefficient r2 is 0.95. Reproduced
from ref. [88] by permission of The Society of Rheological,
USA.

discussed here.
Indeed the term cohesive energy is appropriate for sys-
tems which extensively disrupt at a critical strain γc due
to rupture of all elastic links, as observed in clay gels
[130], whereas the term yield energy is more appropriate
for systems which yield above γc due to the rupture of
some crucial elastic links, as generally observed in the
case of layered silicate-based nanocomposites as dis-
cussed here. The difference in scalling behavior of the
elastic energy stored at γc means that the structure of the
percolated network in layered silicate nanocomposites
differs significantly from that of the gel in concentrated
aqueous swelling layered silicate suspensions. Recently,
Okamoto and coworkers completely disagree with these
interpretations. In the former structure, adding clay par-
ticles seems to have no significant effect on the average
connectivity of the network as Ey ∝ø0, whereas increas-
ing the layered silicate loading in the latter increases the
number of network links as Ec depends strongly on ø.
The peculiar feature of the scaling behavior of the Ey of
the percolated network guggests that the entities respon-
sible for the yield properties of the nanocomposites are
not individual layered silicate particles, rather, silicate
domains, whose characteristic size independent of lay-
ered silicate loading, as mentioned by Solomon and cow-
orkers [98] to interpret results from flow reversal
experiments. However, Mederic et al. proposed that the
existence of a unique characteristic fc ∼ 0.2 Hz, making
a change in the power-law frequency dependency of G'
for all nanocomposites samples, is another macroscopic
time signature of these domains.
Not only that, it should be noted here that for a given
Figure 25. (a) Storage modulus G' as a function of strain γ at
(●) 0 %, (O) 0.5 %, (■) 1 %, (□) 1.5 %, (∆) 2.5 %, (▲) 5
%, and (▼) 10 %. (b) Loss modulus G"(ω) as a function of
strain γ at (●) 0 %, (O) 0.5 %, (■) 1 %, (□) 1.5 %, (∆) 2.5
%, (▲) 5 %, and (▼) 10 %. Reproduced from ref. [88] by per-
mission of The Society of Rheological, USA.
sample at a given frequency, G' and G" have the same or-
der of magnitude showing that dissipative phenomena
are as important as elastic phenomena in the behavior of
nanocomposites. This point is all the more important to
be emphasized since G" results are scarcely presented
and discussed in the leature dealing with the rheology of
layered silicate nanocomposites.
The ø dependence of the low-frequency plateau value
of G", presented in Figure 26, shows that
G' ∝ø 2.4 (8)
This observation tends to show that, contrary to elastic
contributions, viscous contribution depend on the layered
silicate loading in a more significant way. It is also
confirmed by the ø dependence of the frequency marking
 Rheology of Polymer/Layered Silicate Nanocomposites
Figure 26. Plateau storage modulus G" as a function of nano-
filler volume fraction. The solid line corresponds to Eq. (8).
The square of the correlation coefficient r2 is 0.95. Reproduced
from ref. [88] by permission of The Society of Rheological,
USA.
Figure 27. The steady-shear rheological behavior for a series of
intercalated nanocomposites of poly(dimethyl 0.95-diphenyl
0.05 siloxane) with layered silicate (dimethyl ditallow mont-
morillonite) at 25 °C. The silicate loading is varied and are not-
ed in the legend. Reproduced from ref. [130] with permission
of Springer‐Verlag Berlin Heidelberg.
the change in the power-law dependency of the loss
modulus. The solid content dependence of the dissipative
properties could be assigned to the multiscale origin of
the viscous dissipation. However, viscous dissipation
comes from many contributions such as from viscous
dissipation due to relative motions of domains on a
mesoscopic length scale but also from relative motions of
exfoliated dispersed layered silicate particles on nano- or
micro-scopic length scales.
Steady Shear Rheology
In 1996, Krishnamoorti and coworkers [77] first
described the steady shear rheological behavior of nano-
833
Figure 28. The steady-shear rheological behavior for a series of
delaminated nanocomposites of polydimethylsiloxane with di-
methyl ditallow montmorillonite at 25 °C. The steady-shear
viscosity shows an increase with respect to that of the pure-pol-
ymer at low shear rates but still obeys Newtonian type behav-
ior, even at the highest silicate loadings examined. Reproduced
from ref. [130] with permission of Springer-Verlag Berlin
Heidelberg.
composites based on poly(dimethyldiphenyl siloxane)
(PDS) and dimethyl ditallow ammonium modified
montmorillonite (2M2T-MMT). Figure 27 represents the
steady-shear rheological behavior of a series of
intercalated poly(dimethyldiphenyl siloxane) [it is a
copolymer of poly(dimethyl siloxane) and poly (diphenyl
siloxane)]/2M2T‐MMT nanocomposites with varying
silicate contents at 28 °C. The viscosity of nano-
composites was increased considerably and for a fixed
shear rate, increases monotonically with silicate loadings.
In the low-shear rate region ( < 2 s‐1) neat polymer
showed Newtonian behavior, whereas intercalated
nanocomposites showed shear thinning behavior and this
shear thinning behavior was more prominent with higher
silicate loading. At high shear rate both neat polymer and
nanocomposites displayed strong shear thinning be-
havior. This observation indicates highly anisotropic
intercalated layered silicate particles alter the relaxation
dynamics of the polymer, leading to the non-Newtonian
viscosity behavior of nanocomposites at all shear rates.
More interesting behavior was observed in the case of
poly(dimethyl siloxane)/2M2T-MMT nanocomposites,
where layered silicates are fully delaminated in the
polymer matrix, the steady-shear viscosity behavior of
nanocomposites systematically increased with silicate
loading but still obeys the Newtonian behavior in the
lower shearrate region. Figure 28 represents the steady-
shear rheological behavior of a series of intercalated
poly(dimethyl siloxane)/2M2T‐MMT nanocomposites
with varying silicate contents at 28 °C This indicates
delaminated silicate layers have no effect on the
relaxation dynamics of poly(dimethyl siloxane). There-
fore, the rheological behavior of these nanocomposite
834 Suprakas Sinha Ray
Figure 29. shear rates dependent viscosity of pure PLA and
various PLACNs measured at 175 oC.
systems is similar to the rheological behavior of
conventional filler filled systems.
Figure 29 represents the shear rates dependent viscosity
of pure PLA and various PLACNs measured at 175 oC.
While the pure PLA exhibits almost Newtonian behavior
at all shear rates, PLACNs exhibited a non-Newtonian
behavior. All PLACNs showed a very strong shear-thin-
ning behavior at all measured shear rates and this behav-
ior is analogous to the results obtained in the case of os-
cillatory shear measurements (see Figure 13). Additio-
nally, at very high shear rates, the steady shear vis-
cosities of PLACNs were comparable to that of pure
PLA. These observations suggest that the silicate layers
are strongly oriented towards the flow direction at high
shear rates.
Like PLA-based nanocomposite systems, all PBSCNs
show very strong shear thinning behavior at all shear
rates whereas neat PBS exhibits Newtonian behavior. At
very high shear rates the viscosities of the nano-
composites are comparable to that of pure PBS.
The shear viscosity as a function of shear rate for
BAP/OMMT and BAP is presented in Figure 30
[124,125]. Like previous systems, the viscosity of the
BAP/OMMT nanocomposites were also decreased with
increasing shear rate, however, at very low shear rates,
the shear viscosity data exhibited a Newtonian plateau
even for high OMMT content. With increasing shear
rate, the nanocomposites exhibit higher degrees of shear-
thinning behavior compared to the pure polymer. A
similar behavior was also observed by Krishnamoorti
and coworkers [78] in the case of delaminated PCL-
based nanocomposites with several silicate loadings.
These observations suggest that the silicate layers are
strongly oriented towards the flow direction at high shear
rates, and that the shear thinning behavior observed at
high shear rates is dominated by that of pure polymer.
Figure 30. Shear viscosity vs. shear rate of BAP/OMMT nano-
composites for various OMMT loadings at 140 ºC. Reproduced
from ref. [124] with permission of American Chemical Society,
USA.
Like dynamic viscoelastic properties, steady shear vis-
cosity of nanocomposites also systematically increased
with increasing favorable interaction between the PBSA
matrix and organic modifier. For comparison purposes,
the small amplitude oscillatory shear viscosity is also re-
ported on the Figure 31. As can be expected, the steady
shear viscosity and the dynamic viscosity overlap very
well for the pure PBSA for ω =  (Cox-Merz rule
holds). However, for the nanocomposites, such a rule
fails. The steady shear viscosity becomes lower than the
dynamic shear viscosity. At high shear rate, the nano-
composites loose their solid‐like behavior and a rather
classical. Newtonian behavior is observed for the three
nanocomposites. This might be due to the destruction of
the percolating network and the alignment of the silicate
layers in the direction of flow. The polymeric chains en-
trapped between these thin channels of silicate layers are
highly oriented and flow easily due to the loss of the den-
sity of their entanglements with the neighbouring chains.
This loss of local entropy decreases the local frictions
and thus facilitates the chain movements in the direction
of flow. Such behavior is similar to that of layered poly-
mer blends or reinforced polymers that show a dramatic
decrease in their viscosity when submitted to a strong
shear flow [38-40].
The increase in shear viscosity of the PLS-nano-
composites was recently analyzed using a mean- field
theory [111]. The viscosity at high shear rates showed
more decreased values from the zero-shear viscosities
with increasing clay loading, and the values were
identical to those of virgin polymer. Although the exact
mechanism which causes the shear-thinning behavior
still is not clear, however, it can be deduced that the
orientation of the silicate layers under shear is the main
 Rheology of Polymer/Layered Silicate Nanocomposites
Figure 31. Steady shear viscosity of neat PBSA and various
nanocomposites as a function of shear rate. Reproduced from
ref. [123] with permission of Elsevier Science Ltd.
cause. With increasing shear rate, the intercalated poly-
mer chain conformations change as the coils align
parallel to the flow [133]. Nevertheless, because of this
shear-thinning property, the nanocomposites can be
processed in the melt state using the conventional
equipment available in a manufacturing line.
PLS nanocomposites [1] always exhibit significant de-
viations from the empirical Cox-Merz relation [134],
while all neat polymers obey the empirical relation,
which stipulated that, for  = ω, the viscoelastic data
obeys the relationship
η( ) = ｜η*(ω)｜ (9)
Typically, the quiescent state linear dynamic oscillatory
η*(ω) exceeds the steady shear η( ), with the
discrepancy being largest at low shear rates.
Furthermore, a comparison of the steady shear η( ) with
the aligned state ηal*(ω) clearly demonstrates that η( )
≥ηal*(ω), with the values at high shear rates being
comparable. These results suggest that even at low shear
rates, the application of steady shear results in at least
some alignment of the silicate layers. The first normal
stress difference (N12=σ11 - σ22), a measure of the
elasticity, for the disordered PS-PI based nanocomposites
when compared at the same shear stress (σ12), is
independent of silicate loading and identical to that of the
unfilled polymer [135]. Those measurements were
typically restricted to high shear rates (to obtain reliable
values of N12), where the silicate layers are believed to be
oriented and only relatively small changes are observed
in the viscosity data. It has been suggested that the near
independence of the recoverable strain (=N12/σ12) on the
silicate loading and the near equivalence to that of
835
Figure 32. Steady shear viscosityηas a function of shear rate 
at (●) 0 %, (O) 0.25 %, (■) 0.5 %, (□) 0.75 %, and (∆) 1
%. Reproduced from ref. [88] by permission of The Society of
Rheological, USA.
the unfilled polymer melt, is a result of the ability of the
two-dimensional silicate layers to be preferentially
oriented by shear flow [135].
Solomon and coworkers [89] have performed flow re-
versal experiments to examine changes in structure due
to flow in PP based nanocomposites. The transient flow-
reversal stress response exhibits a stress overshoot,
whose magnitude increases with increased quiescent
waiting time between flow reversals. While a scaling of
the stress overshoot by 1/c (c being the concentration)
leads to the development of a mastercurve with respect to
time, the start-up transient stress exhibits a simple strain
scaling. These results are interpreted in the context of the
silicate layers being non-Brownian and the stress re-
sponse being dictated by hydrodynamics alone.
Figure 32 represents the steady shear apparent viscosity
η, for PA12-based nanocomposite samples at low load-
ings, from 0 wt% up to 1 wt%. On the basis these data,
Aubry and coworkers tried to determine an intrinsic vis-
cosity [η] and an interaction constant k, by fitting the
curve to the second‐order Einstein‐type equation:
2
η0 = 1+[η]ø + k([η]ø) (10)
The least-squares fit leads to [η] ∼100 and k ∼0.5,
which confirms the same results obtained by Utracki and
coworkers [136] for the similar organoclay based nano-
composite systems.
In 2003 Jeon and coworkers [110,111] proposed an
alternative method to calculate the [η] by fitting the
relative viscosity versus volume fraction plot using a
modified Krieger’s empirical equation, replacing the
effective maximum packing volume fraction by the
836 Suprakas Sinha Ray
Figure 33. (a) Relative Newtonian viscosity as a function of
nanofiller volume fraction, ø. The solid line corresponds to
Eq. (10), with [η] = 100 and k = 0.5. The square of the corre-
lation coefficient r2 in 0.83. (b) Relative Newtonian viscosity as
a function of normalized nanofiller volume fraction. The line
corresponds to Eq. (11), with øvp = 1 % and [η] = 65. The
2
square correlation coefficient r = 0.85. Reproduced from ref.
[88] by permission of The Society of Rheological, USA.
viscosity percolation threshold øvp as
−[η ]φvp
⎡ of PPCN4, measured with a constant  of 0.001 s at 150
φ ⎤
η 0r = ⎢1 − ⎥
⎣⎢ φ vp ⎦⎥ (11)
On the basis of Figure 32, they considered øvp is equal
to 1 wt% is the viscosity percolation threshold corre-
sponds to the critical volume fraction at which the vis-
cosity tends to diverge, showing no Newtonian plateau at
low shear rates. Figure 33b shows that the relative vis-
cosity versus volume fraction plot can be well fitted by
Eq. (11); [η] obtained from the beast least-squares fit is
∼ 65. This result is in good agreement with the result
obtained from equation 5, given the uncertainty in the de-
termination of the critical volume fraction øvp. By
knowing the value of [η] and the aspect ratio p (ratio of
diameter and thickness) of the disk-like layered silicate
particles can be inferred:
1.47
[η] = 2.5 + 0.025 (1 + p ) (12)
Again by considering the value of [η] in between 65 to
100, p is shown ti lie between 200 and 260. This result is
about one-half of the average aspect ratio of individual
MMT particles [135]. This indicates exfoliation of lay-
ered silicates particles is not perfectly achieved, even at
very low layered silicate content.
The volume fraction of freely rotating disks with radius
2
r and thickness e (aspect ratio, p = 2r/e) isπr e/4 = 3/2p
3
(3πr ) times the volume fraction of equivalent of hard
spheres. Assuming a hard sphere random close packing
∼64 %, they calculated the maximum packing volume
fraction of disk-like particles (ømcalc) with an aspect ratio
200 and 260 respectively and this value is about 0.48 %
and 0.38 % respectively. Further, assuming a critical vol-
ume fraction of spherical particles at percolation to be ∼
30 %, the freely rotating disk-like layered silicate par-
ticles are expected to be percolated at ømcalc ∼0.23 %
and 0.18 % respectively. All of these calculations are ap-
proximate, insofar as they do not take into account the
presence of large aggregates. Present author believe that
the real close packing volume fraction and percolation
threshold most likely occur at higher volume fractions,
possibly explaining the relatively “high” value of øvp.
Elongation Flow Rheology
Okamoto and coworkers [137] first conducted elonga-
tion tests of polypropylene based nanocomposite
(PPCN4) in the molten state at constant Hencky strain
‧
rate, ε 0 using elongation flow rheometer. Figure 34
shows double-logarithmic plots of the transient elonga-
‧
tion viscosity ηE(ε 0 ; t) versus time t, observed for
PPCN4 (4 wt% of MMT) at 150 oC with different ε ‧
0 val-
‐1
ues ranging from 0.001 to 1.0 s . The solid line on the
‧ 
curve ε 0 represents 3η0(  ; t), the 3-fold shear viscosity
‐1
o ‧
C. At short times, ηE(ε0 ; t) gradually increases with
‧
time, but is independent of ε 0 ; this is generally called the
‧
linear region of the ηE (ε0 ; t) curve. After a certain
time tηE, generally called the up-rising time (marked
with the upward arrows), there is a rapid upward devia-
‧
tion of ηE (ε 0 ; t) from the curves of the linear region.
On the other hand, the shear viscosity curve shows two
distinctive features: first, the extended Trouton rule is not
valid in this case and second, the shear viscosity of
PPCN4 increases continuously with time within the ex-
perimental time span. This time-dependent thickening
 Rheology of Polymer/Layered Silicate Nanocomposites 837

Figure 34. Time dependence of elongation viscosity for

PP/clay (4) (PPCN4) melt at 150 ºC. The upward arrows in-
dicate up-rising time for different strain rate. The solid line
shows three times the shear viscosity, taken at a low shear rate
‐1
of 0.001 s on a cone plate. Reproduced from from ref. [137]
with permission of American Chemical Society, USA.
behavior, as mentioned before, is called rheopexy. These
Figure 36. Double‐logarithmic plots of the transient elongation
‧
viscosity ηE(ε 0 ; t) versus time t, observed for PLACN5 at 170
o
C with different ε&0 values ranging from 0.01 to 1.0 s‐1.
differences in the time-dependent responses reflect
differences in the shear flow-induced versus elongation-
induced internal structure formation in the case of

Figure 35. TEM micrographs showing PPCN4 elongated at 150 ºC with (a) ε0 = 1.0 s‐1 up to ε0 = 1.3 s‐1 (λ = 3.7) and (b) ε0 =
‐1 ‐1
0.001 s up to ε0 = 0.5 s (λ = 1.7); respectively. Upper pictures are in the x-y plane, and lower are in x-z plane along the stretch-
ing direction. Reproduced from from ref. [138] by permission of American Chemical Society, USA.
838 Suprakas Sinha Ray
Figure 37. Hencky strain rate dependence of the up-rising
‧ o
Hencky strain (εηE) = ε0 × tηE taken for PLACN3 at 170 C.
PPCN4 in the molten state. The same experiments
conducted with a PP-MA matrix without clay did not
exhibit any strain-induced hardening or rheopexy
behavior in the molten state.
Figure 35 represents typical TEM photographs of the
center portions of the recovered samples after elongation.
The x- and y-axes of the elongated specimen correspond
to directions parallel and perpendicular to the stretching
direction, respectively. A converging flow is applied to
the thickness direction (y- and z-axis) with stretching if
the assumption of an affine deformation without volume
change is valid. Interestingly, for the specimen elongated
with a high strain rate, there is perpendicular alignment
of the silicate layers (edges) along the stretching
direction (x-axis) in the x-y plane. For the x-z plane, the
silicate layers (edges) disperse into the PP-MA matrix
along the z-axis direction rather than randomly, but these
faces cannot be seen in this plane. On the basis of experi-
mental results and two-directional TEM observations, the
authors concluded that the formation of a “house-of-
cards” like structure was observed under slow elongatio-
nal flow. Details regarding the data collection and
explanations are presented in reference [137].
Sinha Ray and coworkers [118] conducted elongation
tests of PLACN5 (PLA nanocomposites prepared with 5
wt% of C18MMT) in the molten state at constant
‧
Hencky strain rate, ε 0 using elongation flow rheometry
[138]. On each run of the elongation test, samples of 60
3
× 7 × 1 mm size were annealed at a predetermined tem-
perature for 3 min before starting the run in the rhe-
ometer, and uniaxial elongation experiments were con-
‧ ‐1
ducted at various ε 0 ranging from 0.01 to 1 s . Figure 36
shows double-logarithmic plots of the transient elonga-
‧
tion viscosity ηE(ε 0 ; t) versus time t, observed for
o ‧
PLACN5 at 170 C with different ε 0 values ranging
‐1
from 0.01 to 1.0 s . Figure shows a strong strain-induced
hardening behavior for PLACN5. In the early stage, ηE
‧
gradually increases with t but almost independent of ε 0.
This is generally calling the linear region of the viscosity
curve. After a certain time, tηE which is the up-rising
time (marked with the upward arrows in figure), was
‧
strongly dependent on ε 0 , and a rapid upward deviation
of ηE from the curves of the linear region was observed.
On the other hand, Sinha Ray and coworkers [118] tried
to measure the elongational viscosity of pure PLA but
they failed to do that accurately. Low viscosity of pure
PLA may be the main reason. However, they confirmed
that neither strain‐induced hardening in elongation nor
rheopexy in shear flow took place in the case of pure
PLA having the same molecular weights and poly-
dispersity with that of PLACN3 [118].
Like polypropylene/OMLS systems, the extended Trou-
ton rule, 3η0 ( ; t) ≅ ηE (ε ‧
0 ; t), does not hold for
PLACN5 melt, as opposed to the melt of pure polymers
[138]. These results indicate that in the case of PLACN5,
the flow induced internal structural changes also
occurred in elongation flow, but the changes were quite
different from shear flow. The strong rheopexy observed
in shear measurements for PLACN5 at very slow shear
rate reflected a fact that the shear-induced structural
change involved a process with an extremely long
relaxation time.
As to the elongation‐induced structure development,
Figure 37 represents the Hencky strain rate dependence
of the up‐rising Hencky strain (εηE) =ε ‧
0 × tηE taken for
o
PLACN3 at 170 C. The εηE values increased systemati-
‧ ‧
cally with the ε 0 . The lower the value of ε0 , the smaller
is the value of εηE. This tendency probably corresponds
to the rheopexy of PLACN5 under slow shear flow.
Conclusions
Rheological properties of several polymer nano-
composites with layered silicates have been discussed
herein. On a global scale, the linear viscoelastic behavior
of the polymer chains in the nanocomposites, as detected
by conventional rheometry, is dramatically altered after
nanocomposites formation. Linear rheological material
functions showed that the nanocomposites are charac-
terized by a solid-like behavior as revealed by the pres-
ence of a low-frequency plateau on storage modulus. The
magnitude of such plateau or pseudo-plateau is found to
strongly depend on the level of interactions between the
polymer matrix and the surfactant of the modified lay-
ered silicate. Such specific interactions favour the state of
dispersion-distribution of the layered silicate lamellae
within the polymeric matrix that lead to the formation of
a long range or short range percolating network.
However, such a network does not seem very stable
 Rheology of Polymer/Layered Silicate Nanocomposites
vis-a-vis of steady shear flow. In fact steady shear flow
destroys such connectivity and imparts the material with
a rather Newtonian behavior in the high-shear rate
region. For the moment it is not clear whether or not such
percolating network can be maintained when the nano-
composites are reprocessed in machines such as ex-
truders and injection moldings, where the flow has a
complex pattern combining shear, elongational, hyper-
bolic and eventually chaotic flows. However, some of
these systems show close analogies to other intrinsically
anisotropic materials such as block copolymers and
smectic liquid crystalline polymers and provide model
systems to understand the dynamics of polymer brushes.
Under uniaxial elongational flow, the nanocomposites
generally exhibit very high viscosity and a tendency to
strong strain‐induced hardening, which author believes
originate from the perpendicular alignment of the silicate
layers towards the stretching direction.
Although a significant amount of work has already been
reported on rheological properties of PLA-nanocom-
posites, much research still remains in order to under-
stand the complex structure-property relationships in var-
ious PLA-nanocomposites.
Abbreviations
BPA, biodegradable aliphatic polyester; CEC, cation
exchange capacity; Deff, effective diffusion coefficient;
EMA, ethylene-co-methyl acrylate; EVA, ethylene-co-
vinyl acetate; HMW, high molecular weight; IANS, in-
termediate-angle neutron scattering; LCST, lower critical
solution temperature; LMW, low molecular weight; MD,
molecular dynamics; MMT, montmorillonite; 2M2T-
MMT, dimethyl ditallow ammonium modified montmor-
illonite; MMW, medium molecular weight; N6, nylon 6;
NMR, nuclear magnetic resonance; OMLS, organically
modified layered silicate; PA12, polyamide 12; PBS,
poly(butylene succinate); PBSA, poly[(butylene succi-
nate)-co-adipate]; PCL, poly(ε-caprolacton); PEO, poly
(ethylene oxide); PDS, poly(dimethyl siloxane); PLA,
polylactide; PLS, polymer layered silicate; PP, poly-
propylene; PPCH, polypropylene hybride; PS, poly-
styrene; QA+, quaternary ammonium cation; Rg, radius of
gyration; RIS, rotational-isomeric-state; SE, Stokes-
Einstein; SFM, synthetic fluorine mica; TEM, trans-
mission electron microscopy, XRD, x-ray diffraction,
POSS, polyhedral oligomeric silsesquioxanes; PVA, poly
(vinyl alcohol); SCF; self-consistent field; SANS, small-
angle neutron scattering.
839
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