Progress in Polymer Science 33 (2008) 1119–1198

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Progress in Polymer Science
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A review on polymer–layered silicate nanocomposites
S. Pavlidou
a
, C.D. Papaspyrides
b,∗
a
CLOTEFI, Clothing, Textile and Fibre Technological Development, 4 El. Venizelou Str., Kallithea, Athens 176 76, Greece
b
Laboratory of Polymer Technology, Department of Chemical Engineering, National Technical University of Athens, Zographou, Athens 157 80, Greece
a r t i c l e i n f o
Article history:
Received 25 June 2007
Received in revised form 11 July 2008
Accepted 25 July 2008
Available online 25 September 2008
Keywords:
Nanocomposites
Polymers
Layered silicates
Clays
a b s t r a c t
This review reports recent advances in the field of polymer–layered silicate nanocompos-
ites. These materials have attracted both academic and industrial attention because they
exhibit dramatic improvement in properties at very low filler contents. Herein, the struc-
ture, preparation and properties of polymer–layered silicate nanocomposites are discussed
in general, and detailed examples are also drawn from the scientific literature.
© 2008 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1120
2. Milestones in the research on polymer–layered silicate nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1121
3. Layered silicates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1122
3.1. Structure and characteristics of layered silicates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1122
3.2. Organic modification of layered silicates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1123
4. Nanocomposite structures and characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1126
4.1. Nanocomposite structures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1126
4.2. Nanocomposite structural characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1127
5. Preparation of nanocomposites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1129
5.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1129
5.1.1. Template synthesis (sol–gel technology) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1129
5.1.2. Intercalation of polymer or prepolymer from solution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1130
5.1.3. In situ intercalative polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1130
5.1.4. Melt intercalation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1130
5.2. Intercalation of polymer from solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1130
5.3. In situ intercalative polymerization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1131
5.3.1. In situ intercalative polymerization of thermoplastic polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1131
5.3.2. In situ intercalative polymerization of thermosetting polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1137
5.4. Polymer melt intercalation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1142
5.4.1. Introduction and advantages of the technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1142
5.4.2. Factors affecting polymer melt intercalation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1144

Corresponding author.
E-mail address: kp@softlab.ece.ntua.gr (C.D. Papaspyrides).
0079-6700/$ – see front matter © 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2008.07.008
1120 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
5.4.3. Compatibility issues in non-polar polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1151
5.4.4. Degradation problems encountered during melt intercalation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1154
6. Nanocomposite properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1156
6.1. Mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1156
6.1.1. The reinforcing mechanism of layered silicates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1156
6.1.2. Modulus and strength. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1157
6.1.3. Toughness and strain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1164
6.1.4. Comparison and synergistic effects of clays and conventional reinforcements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1168
6.2. Dynamic mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1169
6.3. Barrier properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1170
6.4. Thermal stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1173
6.5. Flame retardance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1178
6.5.1. Flame retardance of polymer–layered silicate nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1178
6.5.2. Synergism between nanocomposites and flame retardants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1183
6.6. Heat distortion temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1185
6.7. Rheological properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1185
6.8. Crystallinity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1186
6.9. Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1188
6.10. Photo-degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1189
6.11. Optical clarity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1190
7. Nanocomposites: advantages and applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1190
8. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1193
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1193
1. Introduction
Traditionally, polymeric materials have been filled with
synthetic or natural inorganic compounds in order to
improve their properties, or simply to reduce cost. Con-
ventional fillers are materials in the form of particles (e.g.
calciumcarbonate), fibers (e.g. glass fibers) or plate-shaped
particles (e.g. mica). However, although conventionally
filled or reinforced polymeric materials are widely used
in various fields, it is often reported that the addition of
these fillers imparts drawbacks to the resulting materi-
als, such as weight increase, brittleness and opacity [1–5].
Nanocomposites, on the other hand, are a new class of
composites, for which at least one dimension of the dis-
persed particles is in the nanometer range. Depending on
howmany dimensions are in the nanometer range, one can
distinguish isodimensional nanoparticles when the three
dimensions are on the order of nanometers, nanotubes or
whiskers whentwo dimensions are onthe nanometer scale
and the third is larger, thus forming an elongated structure,
and, finally, layered crystals or clays, present in the form of
sheets of one to a few nanometers thick and hundreds to
thousands nanometers inextent [1,4]. Among all the poten-
tial nanocomposite precursors, those based on clay and
layered silicates have been most widely investigated, prob-
ably because the starting clay materials are easily available
and because their intercalation chemistry has been studied
for a long time [6].
Polymer–layered silicate nanocomposites, which are
the subject of the present contribution, are prepared by
incorporatingfinelydispersedlayeredsilicatematerials ina
polymer matrix [2]. However, the nanolayers are not easily
dispersed in most polymers due to their preferred face-
to-face stacking in agglomerated tactoids. Dispersion of
the tactoids into discrete monolayers is further hindered
by the intrinsic incompatibility of hydrophilic layered sil-
icates and hydrophobic engineering plastics. Therefore,
layered silicates first need to be organically modified to
produce polymer–compatible clay (organoclay). In fact, it
has been well-demonstrated that the replacement of the
inorganic exchange cations in the cavities or “galleries” of
the native clay silicate structure by alkylammonium sur-
factants can compatibilize the surface chemistry of the clay
and a hydrophobic polymer matrix [7].
Thereafter, different approaches canbe applied to incor-
porate the ion-exchangedlayeredsilicates inpolymer hosts
by in situ polymerization, solution intercalation or sim-
ple melt mixing. In any case, nanoparticles are added
to the matrix or matrix precursors as 1–100␮m pow-
ders, containing associated nanoparticles. Engineering the
correct interfacial chemistry between nanoparticles and
the polymer host, as described previously, is critical but
not sufficient to transform the micron-scale composi-
tional heterogeneity of the initial powder into nanoscale
homogenization of nanoparticles within a polymeric
nanocomposite [8]. Therefore, appropriate conditions have
to be established during the nanocomposite preparation
stage.
The resulting polymer–layered silicates hybrids possess
unique properties – typically not shared by their more con-
ventional microscopic counterparts – which are attributed
to their nanometer size features and the extraordinarily
high surface area of the dispersed clay [1,4]. In fact, it is
well established that dramatic improvements in physical
properties, such as tensile strength and modulus, heat dis-
tortion temperature (HDT) and gas permeability, can be
achieved by adding just a small fraction of clay to a poly-
mer matrix, without impairing the optical homogeneity of
the material. Most notable are the unexpected properties
obtainedfromtheadditionof stiff filler toa polymer matrix,
e.g. the often reported retention (or even improvement) of
the impact strength. Since the weight fraction of the inor-
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1121
Nomenclature
AIBN N,N

-azobis(isobutyronitrile)
CEC cation exchange capacity
CX-clay X is the number of carbon atoms in clay
organic modifier
d spacing between diffractional lattice planes
D diffusivity
DETDA diethyl toluene diamine
DGEBA diglycidyl ether of bisphenol A
DM dioctadecyldimethyl ammonium chloride
DMA dynamic mechanical analysis
DSC differential scanning calorimetry
DTGA differential thermogravimetric analysis
E

storage modulus under bending mode
E

loss modulus under bending mode
EVA ethyl-vinyl-acetate copolymer
FTIR Fourier transform infrared spectroscopy
fwhm full-width-at-half-maximum
G

storage modulus under tensile mode
G

loss modulus under tensile mode
GPC gas-permeation chromatography
HDPE high density polyethylene
HDT heat distortion temperature
HRR heat release rate
MMT montmorillonite
NMR nuclear magnetic resonance
o-Clay organo-modified clay
OMLS organo-modified layered silicate, organosil-
icate, or organoclay
P permeability
PA polyamide
PAA poly(acrylic acid)
PBO polybenzoxale
PCL polycaprolactone
PCN polymer–clay nanocomposite
PDMS polydimethylsiloxane
PE polyethylene
PEI poly(ether imide)
PEO poly(ethylene oxide)
PET poly(ethylene terephthalate)
PHB poly(3-hydroxybutyrate)
PHRR peak heat release rate
PI polyimide
PA polylactide
PLS polymer–layered silicate nanocomposite
PMMA polymethyl methacrylate
PP polypropylene
PP-MA or PP-g-MA maleic anhydride-grafted
polypropylene
PS polystyrene
PSF polysulfone
PU polyurethane
PVA poly(vinyl acetate)
PVC poly(vinyl chloride)
PVE poly(vinyl ethylene)
PVOH poly(vinyl alcohol)
PVP poly(vinyl pyrrilidone)
S solubility
SBS poly(styrene-butadiene-styrene)
SEA specific extinction area
Tanı G

/G

T
c
crystallization temperature
TEM transmission electron microscopy
T
g
glass transition temperature
TGA thermogravimetric analysis
TGAP triglycidyl p-aminophenol
TGDDM tetrafunctional tetraglycidyldiaminodiphe-
nylmethane
TPO thermoplastic olefin
UP unsaturated polyester
WAXDor WAXS wide angle X-ray diffraction or scat-
tering
XRD X-ray diffraction
ganic additive is typically below10%, the materials are also
lighter than most conventional composites [2,9–12]. These
unique properties make the nanocomposites ideal mate-
rials for products ranging from high-barrier packaging for
food and electronics to strong, heat-resistant automotive
components [11]. Additionally, polymer–layered silicate
nanocomposites have been proposed as model systems to
examine polymer structure and dynamics inconfined envi-
ronments [12,13].
However, despite the recent progress in polymer
nanocomposite technology, there are many fundamental
questions that have not been answered. For example, how
do changes in polymer crystalline structure induced by
the clay affect overall composite properties? How does
one tailor organoclay chemistry to achieve high degrees
of exfoliation reproducibility for a given polymer system?
Howdo process parameters and fabrication affect compos-
ite properties? Further research is needed that addresses
such issues [14]. The objective of this work is to review
recent scientific and technological advances in the field of
polymer–layered silicate nanocomposite materials and to
develop a better understanding of how superior nanocom-
posites are formed.
2. Milestones in the research on polymer–layered
silicate nanocomposites
The incorporation of layered silicates into polymer
matrices has been known for over 50 years [15]. In fact,
one of the earliest systematic studies of the interaction
between a clay mineral and a macromolecule dates back
to 1949, when Bower [16] described the absorption of
DNA by montmorillonite. Even in the absence of X-ray
diffraction (XRD) evidence, this finding implied insertion
of the macromolecule in the lamellar structure of the sili-
cate. In 1950, Carter et al. [17] developed organoclays with
several organic onium bases to reinforce latex-based elas-
tomers and in 1958, Hauser and Kollman [18] were granted
a patent for “clay complexes with conjugated unsatu-
rated aliphatic compounds of four to five carbon atoms”.
Uskov [19], in 1960, found that the softening point of
poly(methyl methacrylate) derived by polymerization of
1122 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
methyl methacrylate was raised by montmorillonite modi-
fied with octadecylammonium, while in the following year
Blumstein[20] obtaineda polymer insertedinthe structure
of a montmorillonite by polymerizing a previously inserted
vinyl monomer. Two years later, Greenland [21] used a
poly(vinyl alcohol)/montmorillonite system to show that
a polymer could be directly inserted in a clay in an aqueous
solution. The same year, the incorporation of organoclay
into a thermoplastic polyolefin matrix was disclosed by
Nahin and Backlund [22] of Union Oil Co. They obtained
organoclay composites with strong solvent resistance and
high tensile strength by irradiation-induced cross linking.
However, they did not focus on the intercalation char-
acteristics of the organoclay or the potential properties
of the composites. In 1975, Tanihara and Nakagawa [23]
reached a similar result by intercalating polyacrylamide
and poly(ethylene oxide) froman aqueous solution. In 1976
Fujiwara and Sakamoto [24] of the Unichika Co. described
the first organoclay hybrid polyamide nanocomposite.
However, it was not until Toyota researchers began a
detailed examination of polymer–layered silicate compos-
ites that nanocomposites became more widely studied in
academic, government and industrial laboratories [25–28].
The Toyota research group disclosed improved methods for
producing nylon 6 clay nanocomposites using in situ poly-
merization similar to the Unichika process. They reported
that these polymer–clay nanocomposites exhibit superior
strength, modulus, heat distortion temperature, water and
gas barrier properties, with comparable impact strength as
neat nylon 6. They also reported on various other types of
polymer–clay hybridnanocomposites basedonepoxy resin
and polystyrene, acrylic polymer, rubber, and polyimides
formed using a similar approach.
On the other hand, work by Giannelis and co-workers
[29,30] revealed that intercalation of polymer chains into
the galleries of an organoclay can occur spontaneously on
heating a mixture of polymer and silicate clay powder
above the polymer glass transition or melt temperature.
Once sufficient polymer mobility is achieved, chains dif-
fuse into the host silicate clay galleries, thereby producing
an expanded polymer–silicate structure.
To summarize: although the intercalation chemistry of
polymers when mixed with appropriately modified lay-
ered silicates and synthetic layered silicates has long been
known, two major findings have stimulated the revival of
interest in polymer–layered silicate nanocomposite mate-
rials. First, the report from the Toyota research group
on a nylon 6/montmorillonite nanocomposite, in which
very small amounts of layered silicate loadings resulted
in pronounced improvements of thermal and mechanical
properties; and second, the observation by Giannelis and
his co-workers that it is possibletomelt-mixpolymers with
layered silicates, without the use of organic solvents.
Since then, the high promise for industrial applications
has motivated vigorous research, and today efforts are
being conducted globally, using almost all types of polymer
matrices. In fact, nanocomposites have been demonstrated
with many thermoplastic and thermosetting polymers of
different polarities including, among others, polystyrene,
polycaprolactone, polypropylene, poly(ethylene oxide),
epoxyresin, polysiloxaneandpolyurethane[7,14,15,31–33].
It must be noted, however, that so far most of these mate-
rials have been produced only on the laboratory scale; and
until a short time ago, research tended to center on proof
of exfoliation of the clay [32].
3. Layered silicates
3.1. Structure and characteristics of layered silicates
Layered silicates used in the synthesis of nanocompos-
ites arenatural or synthetic minerals, consistingof verythin
layers that are usually bound together with counter-ions.
Their basic building blocks are tetrahedral sheets in which
silicon is surrounded by four oxygen atoms, and octahe-
dral sheets in which a metal like aluminum is surrounded
by eight oxygen atoms. Therefore, in 1:1 layered structures
(e.g. in kaolinite) a tetrahedral sheet is fused with an octa-
hedral sheet, whereby the oxygen atoms are shared [34].
On the other hand, the crystal lattice of 2:1 layered sil-
icates (or 2:1 phyllosilicates), consists of two-dimensional
layers where a central octahedral sheet of alumina is fused
to two external silica tetrahedra by the tip, so that the
oxygen ions of the octahedral sheet also belong to the
tetrahedral sheets, as shown in Fig. 1. The layer thick-
ness is around 1nm and the lateral dimensions may vary
from 300Å to several microns, and even larger, depend-
ing on the particulate silicate, the source of the clay and
the method of preparation (e.g. clays prepared by milling
typically have lateral platelet dimensions of approximately
0.1–1.0␮m). Therefore, the aspect ratio of these layers
(ratio length/thickness) is particularly high, with values
greater than 1000 [1,35–37].
The basic 2:1 structure with silicon in the tetrahedral
sheets and aluminum in the octahedral sheet, without any
substitutionof atoms, is calledpyrophyllite. Sincethelayers
do not expand in water, pyrophyllite has only an external
surface area and essentially no internal one. When sili-
con in the tetrahedral sheet is substituted by aluminum,
the resulting structure is called mica. Due to this substi-
tution the mineral is characterized by a negative surface
charge, which is balanced by interlayer potassium cations.
However, because the size of the potassium ions matches
the hexagonal hole created by the Si/Al tetrahedral layer,
it is able to fit very tightly between the layers. Conse-
quently, the interlayers collapse and the layers are held
together by the electrostatic attraction between the nega-
tively charged tetrahedral layer and the potassium cations.
Therefore, micas do not swell in water and, like pyrophyl-
lite, have no internal surface area [38]. On the other hand, if
in the original pyrophyllite structure the trivalent Al-cation
in the octahedral layer is partially substituted by the diva-
lent Mg-cation, the structure of montmorillonite is formed,
which is the best-known member of a group of clay min-
erals, called “smectites” or “smectite clays”. In this case the
overall negative charge is balanced by sodium and calcium
ions, which exist hydrated in the interlayer [39]. A particu-
lar feature of the resulting structure is that, since these ions
do not fit in the tetrahedral layer, as in mica, and the layers
are held together by relatively weak forces, water and other
polar molecules can enter between the unit layers, causing
the lattice to expand [33].
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1123
Fig. 1. The structure of a 2:1 layered silicate [35]. Reproduced from Beyer by permission of Elsevier Science Ltd., UK.
Along with montmorillonite, hectorite and saponite
are the layered silicates that are most commonly used in
nanocomposite materials. Their chemical formula is given
in Table 1 [1].
The reason why these materials have received a great
deal of attention recently, as reinforcing materials for poly-
mers, is their potentially high aspect ratio and the unique
intercalation/exfoliation characteristics that will be dis-
cussed later [15].
In general, it is well established that structural perfec-
tion is more and more nearly reached as the reinforcing
elements become smaller and that the ultimate properties
of reinforcing composite elements may be expected if their
dimensions reach atomic or molecular levels. For exam-
ple, carbon nanotubes display the so far highest known
values of elastic modulus (ca. 1.7TPa!). Similarly, individ-
ual clay sheets, being only 1nm thick, display a perfect
crystalline structure. However, the smaller the reinforc-
ing elements are, the larger is their internal surface and
hence their tendency to agglomerate rather than to dis-
Table 1
Chemical structure of commonly used 2:1 phyllosilicates
a
[1].
2:1 Phyllosilicates General formula
Montmorillonite M
x
(Al
4−x
Mg
x
)Si
8
O
20
(OH)
4
Hectorite M
x
(Mg
6−x
Li
x
)Si
8
O
20
(OH)
4
Saponite M
x
Mg
6
(Si
8−x
Al
x
)O
20
(OH)
4
a
M: monovalent cation; x: degree of isomorphous substitution
(between 0.5 and 1.3).
perse homogeneously in a matrix [2]. In fact, the silicate
layers have the tendency to organize themselves to form
stacks with a regular van der Waals gap between them,
called an “interlayer” or “gallery” [1,35,36]. The interlayer
dimension is determined by the crystal structure of the sil-
icate (for dehydrated Na–montmorillonite this dimension
is approximately 1nm) [37].
Analysis of layered silicates has shown that there
are several levels of organization within the clay miner-
als. The smallest particles, primary particles, are on the
order of 10nm and are composed of stacks of parallel
lamellae. Micro-aggregates are formed by lateral joining
of several primary particles, and aggregates are com-
posed of several primary particles and micro-aggregates
[40].
3.2. Organic modification of layered silicates
Since, in their pristine state layered silicates are only
miscible with hydrophilic polymers, such as poly(ethylene
oxide) and poly(vinyl alcohol), in order to render them
miscible with other polymers, one must exchange the
alkali counter-ions with a cationic-organic surfactant, as
shown in Fig. 2. Alkylammonium ions are mostly used,
although other “onium” salts can be used, such as sul-
fonium and phosphonium [1,39,41]. This can be readily
achieved through ion-exchange reactions that render the
clay organophilic [42]. In order to obtain the exchange of
the onium ions with the cations in the galleries, water
1124 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 2. Schematic picture of an ion-exchange reaction. The inorganic, relatively small (sodium) ions are exchanged against more voluminous organic onium
cations. This ion-exchange reaction has two consequences: firstly, the gap between the single sheets is widened, enabling polymer chains to move in
between them and secondly, the surface properties of each single sheet are changed from being hydrophilic to hydrophobic [2]. Reproduced from Fischer
by permission of Elsevier Science Ltd., UK.
swelling of the silicate is needed. For this reason alkali
cations are preferred in the galleries because 2-valent and
higher valent cations prevent swelling by water. Indeed,
the hydrate formation of monovalent intergallery cations is
the driving force for water swelling. Natural clays may con-
tain divalent cations such as calcium and require exchange
procedures with sodium prior to further treatment with
onium salts [41]. The alkali cations, as they are not struc-
tural, can be easily replaced by other positively charged
atoms or molecules, and thus are called exchangeable
cations [43].
The organic cations lower the surface energy of the sili-
cate surface and improve wetting with the polymer matrix
[4,42]. Moreover, the long organic chains of such surfac-
tants, with positively charged ends, are tethered to the
surface of the negatively charged silicate layers, resulting
in an increase of the gallery height [44]. It then becomes
possible for organic species (i.e. polymers or prepolymers)
to diffuse between the layers and eventually separate them
[42,45]. Sometimes, the alkylammoniumcations may even
provide functional groups that can react with the poly-
mer or initiate polymerization of monomers [33]. The
microchemical environment in the galleries is, therefore,
appropriate to the intercalation of polymer molecules
[46]. Conclusively, the surface modification both increases
the basal spacing of clays and serves as a compatibilizer
betweenthe hydrophilic clay andthe hydrophobic polymer
[45].
The excess negative charge of layered silicates and their
capability to exchange ions can be quantified by a spe-
cific property known as the cation-exchange capacity (CEC)
and expressed in mequiv./g [1,39]. This property is highly
dependent on the nature of the isomorphous substitutions
in the tetrahedral and octahedral layers and therefore on
the nature of the soil where the clay was formed. This
explains, for example, whymontmorillonites fromdifferent
origins show differences in CEC, ranging from approxi-
mately 0.9–1.2mequiv./g [39,42]. The charge of the layer is
not locallyconstant, as it varies fromlayer tolayer, andmust
rather be considered as an average value over the whole
crystal. Proportionally, even if a small part of the charge
balancing cations is located on the external crystallite sur-
face, the majority of these exchangeable cations are located
inside the galleries [1].
Depending on the functionality, packing density, and
length of the organic modifiers, the organo-modified lay-
ered silicates (OMLSs, organosilicates or organoclays) may
be engineered to optimize their compatibility with a given
polymer [43,47]. It is worth noticing that, on the basis of
the CEC of the clay, the content of the surfactant is usually
about 35–45wt.% [48]. Actually, one way to measure the
clay CEC is by determining the amount of alkylammonium
salt retained by the organoclays. That is, dried clays that
have been subjected to organo-modification along with a
sample of the corresponding untreated clay are ignited at
1000

C. From the differences in the loss on ignition of the
sample andblank andthe molecular weight of the alkylam-
monium salt, the milliequivalents of the organic substance
retained by the clays are calculated and those values are
taken as their CEC. Alternatively, chemical analysis of the
clay can also be applied for CEC determination [42].
In general, the longer the surfactant chain length, and
the higher the charge density of the clay, the further apart
the clay layers will be forced. This is expected since both
of these parameters contribute to increasing the volume
occupied by the intragallery surfactant [7]. For example,
Wang et al. prepared organoclays with different alkylam-
monium chain lengths and also used an organophilic clay,
Cloisite 20A, which has two long alkyl chains. They found
that the interlayer spacing increases with the increase in
size of alkylamine chain length. The interlayer spacings of
C12M, C16M, C18M (with 12, 16 and 18 carbon atoms in
the alkylammonium chain) and 20A were 1.36, 1.79, 1.85
and 2.47nm, respectively [49].
However, the interlayer distance also depends on the
way the onium ion chains organize themselves in the
organoclay. In order to describe the structure of the
interlayer in organoclays, one has to knowthat, as the neg-
ative charge originates in the silicate layer, the cationic
head group of the alkylammoniummolecule preferentially
resides at thelayer surface, leavingtheorganic tail radiating
away from the surface [1,41].
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1125
Fig. 3. Alkyl chain aggregation in layered silicates: (a) lateral monolayer; (b) lateral bilayer; (c) paraffin-type monolayer and (d) paraffin-type bilayer [1].
Reproduced from Alexandre and Dubois by permission of Elsevier Science Ltd., UK.
Initially, the orientation of surfactant chains was
deduced from infrared and XRD measurements, according
to which the organic chains have been long thought to lie
either parallel tothe silicate layer, forming monoor bilayers
or, depending on the packing density and the chain length,
to radiate away from the surface, forming mono or even
a bimolecular tilted “paraffinic” arrangement, as shown in
Fig. 3 [1,7].
A more realistic description has been proposed by
Vaia et al., based on FTIR experiments. By monitoring
frequency shifts of the asymmetric CH
2
stretching and
bending vibrations, they showed that alkyl chains can vary
from liquid-like to solid-like, with the liquid-like struc-
ture dominating as the interlayer density or chain length
decreases, or as the temperature increases. When the avail-
able surface area per molecule is within a certain range,
the chains are not completely disordered but retain some
orientational order similar to that in the liquid crystalline
state (Fig. 4). As the chain length increases, the interlayer
structure appears to evolve in a stepwise fashion, from a
disorderedto more orderedmonolayer, then“jumping” to a
more disordered pseudo-bilayer. Inaddition, anNMRstudy
reportedbyWanget al. indicatedthecoexistenceof ordered
trans and disordered gauche conformations [50].
Fornes et al. conducted WAXS scans for different
organoclays and for pristine sodium montmorillonite, and
plotted basal spacing values obtained vs. the mass of
Fig. 5. WAXS results for organoclays: mass of organic per unit mass of
montmorillonite [51]. Reproduced from Fornes, Yoon, Hunter, Keskkula
and Paul by permission of Elsevier Science Ltd., UK.
organic component per unit mass of inorganic MMT for
each organoclay, as shown in Fig. 5. They further analyzed
the data by expressing the mass of organic material per unit
volume of gallery, or gallery density, as
¡
gallery
=
mass organic
gallery volume
=
1
d −d
0
mass organic]mass MMT
(area]side)]mass MMT
Fig. 4. Alkyl chain aggregation models: (a) short alkyl chains: isolated molecules, lateral monolayer; (b) intermediate chain lengths: in-plane disorder and
interdigitation to form quasi bilayers and (c) longer chain length: increased interlayer order, liquid crystalline-type environment [1]. Reproduced from
Alexandre and Dubois by permission of Elsevier Science Ltd., UK.
1126 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
where d−d
0
is the gallery height, as indicated by Fig. 5.
The slope of the linear relation between gallery height and
the second quantity in the above equation gives the den-
sity of the organic material in the gallery, ¡
gallery
. Forcing
the fit through an intercept d
0
=9.6Å, which is the basal
spacing of pristine sodium montmorillonite, produces a
calculated density of 1.07g/cm
3
. This range of densities
encompasses what might be expected for organic liquids
or solids. Therefore, the densities calculated in that work
agree with conclusions made by Vaia et al. about the con-
formation and structure of the organic interlayer of similar
organoclays, suggesting that organoclay galleries exhibit
molecular environments ranging from solid- to liquid-like
[51].
Summarizing this section, there are two particular
characteristics of layered silicates that are exploited in
polymer–layered silicate nanocomposites. The first is the
ability of the silicate particles to disperse into individual
layers. Since dispersing a layered silicate can be pictured
like opening a book, an aspect ratio as high as 1000 for
fully dispersed individual layers can be obtained (contrast
that to an aspect ratio of about 10 for undispersed or poorly
dispersed particles). 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 in a given matrix that, in turn, determines
aspect ratio, depends on the interlayer cation [4,40].
4. Nanocomposite structures and characterization
4.1. Nanocomposite structures
Any physical mixture of a polymer and silicate (or
inorganic material in general) does not necessarily form
a nanocomposite. The situation is analogous to polymer
blends. In most cases, separation into discrete phases
normally takes place. In immiscible systems, the poor
physical attraction between the organic and the inorganic
components leads to relatively poor mechanical proper-
ties. Furthermore, particle agglomeration tends to reduce
strength and produce weaker materials [4]. Thus, when the
polymer is unable tointercalate betweenthe silicate sheets,
a phase-separatedcomposite is obtained, whose properties
are in the same range as for traditional microcomposites
[1,35].
Beyond this traditional class of polymer-filler com-
posites, two types of nanocomposites can be obtained,
depending on the preparation method and the nature
of the components used, including polymer matrix, lay-
ered silicate and organic cation [1,35]. These two types of
polymer–layered silicate nanocomposites are depicted in
Fig. 6 [50].
Intercalated structures are formed when a single (or
sometimes more) extended polymer chain is intercalated
between the silicate layers. The result is a well ordered
multilayer structure of alternating polymeric and inorganic
layers, with a repeat distance between them. Intercalation
causes less than 20–30
´
˚
A separation between the platelets
[1,4,33,35,44,52].
On the other hand, exfoliated or delaminated structures
are obtained when the clay layers are well separated from
one another and individually dispersed in the continuous
polymer matrix [1,4,33,44]. In this case, the polymer sepa-
rates theclayplatelets by80–100
´
˚
Aor more[52]. That is, the
interlayer expansionis comparable tothe radius of gyration
of the polymer rather than that of an extended chain, as in
the case of intercalated hybrids [4].
The exfoliation or delamination configuration is of par-
ticular interest because it maximizes the polymer–clay
interactions making the entire surface of layers available
for the polymer. This should lead to the most significant
changes in mechanical and physical properties [35]. In fact,
it is generally accepted that exfoliated systems give bet-
ter mechanical properties than intercalated ones [5,33].
The complete dispersion of clay nanolayers in a polymer
optimizes the number of available reinforcing elements for
carrying an applied load and deflecting cracks. The cou-
pling between the tremendous surface area of the clay
and the polymer matrix facilitates stress transfer to the
reinforcement phase, allowing for mechanical property
improvements [35,53].
However, it is not easy to achieve complete exfolia-
tion of clays and, indeed with few exceptions, the majority
of the polymer nanocomposites reported in the literature
were found to have intercalated or mixed intercalated-
exfoliated nanostructures [33]. This is because the silicate
layers are highly anisotropic, with lateral dimensions rang-
ing from100 to 1000nm, andevenwhenseparatedby large
distances (i.e. when delaminated) cannot be placed com-
pletely randomly in the sea of polymer. Furthermore, the
majority of the polymer chains in the hybrids are teth-
ered to the surface of the silicate layers. Thus, it can be
expected that there are domains in these materials, even
above the melting temperature of the constituent poly-
mers, wherein some long-range order is preserved and the
silicate layers are orientedinsome preferreddirection. This
long-range order and domain structure is likely to become
better defined at the higher silicate contents, where the
geometrically imposed mean distance between the layers
becomes less than the lateral dimensions of the silicate
layers, thus forcing some preferential orientation between
the layers. However, there might be considerable polydis-
persity effects in terms of the orientation and the distance
between the silicate layers. Many such randomly oriented
grains make up the entire sample leading to the presence
of disordered material. Thus, in general the material pos-
sesses a layered structure, with grains wherein the silicate
layers are oriented in a preferred direction leading to the
presence of grain boundaries and concomitant defects [54].
At this point, it is worth mentioning six interrelated
structural characteristics, distinguishing polymer–silicate
nanocomposites from conventional filled systems. These
characteristics, which are attributed to the nanoscopic
dimensions and the extreme aspect ratios of layered sili-
cates, are [8]:

Low percolation threshold (ca. 0,1–2vol.%).

Particle–particle correlation (orientation and position)
arising at low volume fractions.
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1127
Fig. 6. Schematic illustration of two different types of thermodynamically achievable polymer/layered silicate nanocomposites [50]. Reproduced from Ray
and Bousima by permission of Elsevier Science Ltd., UK.

Large number of particles per particle volume (10
6
–10
8
particles/␮m
3
).

Extensive interfacial area per volume of particles
(10
3
–10
4
m
2
/ml).

Short distances between particles (10–50nm at
¢∼1–8vol.%).

Comparable size scales among the rigid nanoparticle
inclusions, distance betweenparticles, andthe relaxation
volume of polymer chains.
4.2. Nanocomposite structural characterization
Two complementary techniques are generally used to
characterize the structures of nanocomposites: XRD and
transmission electron microscopy (TEM) [1,35,55,56].
Due to its ease of use and availability, XRD is most
commonly used to probe the nanocomposite structure and
occasionally to study the kinetics of polymer melt inter-
calation [55]. This technique allows the determination of
the spaces between structural layers of the silicate utilizing
Bragg’s law: sin0 =nz/2d, where z corresponds to the wave
length of the X-ray radiation used in the diffraction exper-
iment, d the spacing between diffractional lattice planes
and 0 is the measured diffraction angle or glancing angle
[1,56]. By monitoring the position, shape and intensity of
the basal reflections fromthe distributed silicate layers, the
nanocomposite structure may be identified [55].
For immiscible polymer/OMLS mixtures, the structure
of the silicate is not affected, and thus, the characteristics
of the OMLS basal reflections do not change. On the other
hand, in comparison with the spacing of the organoclay
used, the intercalation of the polymer chains increases
the interlayer spacing, leading to a shift of the diffrac-
tion peak towards lower angle, according to Bragg’s law.
In such intercalated nanocomposites, the repetitive mul-
tilayer structure is well preserved, allowing the interlayer
spacing to be determined (Fig. 7). In contrast, the exten-
sive layer separation associated with exfoliated structures
disrupts thecoherent layer stackingandresults inafeature-
less diffraction pattern. Thus, for exfoliated structures no
morediffractionpeaks arevisibleintheXRDdiffractograms
either because of a much too large spacing between the
layers (i.e. exceeding 8nmin the case of ordered exfoliated
structure) or because the nanocomposite does not present
ordering [1,35,47].
The influence of polymer intercalation on the order of
the OMLS layers may be monitored by changes in the full-
width-at-half-maximum(fwhm) and intensity of the basal
reflections. An increase in the degree of coherent layer
stacking (i.e. a more ordered system) results in a relative
decrease in the fwhm of the basal reflections upon hybrid
formation. On the other hand, a decrease in the degree
of coherent layer stacking (i.e. a more disordered system)
results in peak broadening and intensity loss [47].
However, although XRD offers a conventional method
to determine the interlayer spacing of the silicate layers in
the original layeredsilicates andthe intercalatednanocom-
posites (within 1–4nm), little can be said about the
spatial distribution of the silicate layers or any structural
inhomogeneities in nanocomposites. Additionally, some
layered silicates initially do not exhibit well-defined basal
reflections. Thus, peak broadening and intensity decreases
are very difficult to study systematically. Therefore, con-
clusions concerning the mechanism of nanocomposite
Fig. 7. Typical XRD patterns from polymer/layered sili-
cates: (a) PE+organoclay→no formation of a nanocomposite,
(b) PS +organoclay→intercalated nanocomposite, (c) silox-
ane +organoclay→delaminated nanocomposite [35]. Reproduced
from Beyer by permission of Elsevier Science Ltd., UK.
1128 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
formation and structure based solely on XRD patterns are
only tentative. On the other hand, TEM allows a qualitative
understanding of the internal structure and can directly
provide information in real space, in a localized area, on
morphology and defect structures [57,58].
Since the silicate layers are composed of heavier ele-
ments (Al, Si and O) than the interlayer and surrounding
matrix (C, H and N), they appear darker in bright-field
images. Therefore, when nanocomposites are formed, the
intersections of the silicate sheets are seen as dark lines
which are the cross sections of the silicate layers, measur-
ing 1nm thick. However, special care must be exercised
to guarantee a representative cross-section of the sample
[56,57]. Fig. 8 shows the TEM micrographs obtained for an
intercalated and an exfoliated nanocomposite. As already
mentioned, besides these twowell definedstructures other
intermediate organizations can exist presenting both inter-
calation and exfoliation. In this case, a broadening of the
diffractionpeakis oftenobservedandone must relyonTEM
observation to define the overall structure [1].
Characterization of polymer/layered silicate nanocom-
posites by
13
C solid-state nuclear magnetic resonance (
13
C
NMR) has also been proposed. VanderHart et al. first used
this technique as a tool for gaining greater insight about
the morphology, surface chemistry, and to a very limited
extent, the dynamics of exfoliated polymer clay nanocom-
posites. They were especially interestedindeveloping NMR
methods to quantify the level of clay exfoliation, a very
important facet of nanocomposite characterization [59].
The main objective in solid-state NMR measurement is to
connect the measured longitudinal relaxations, T
1
s, of pro-
ton (and
13
C nuclei) with the quality of clay dispersion [55].
The surfaces of naturally occurring layeredsilicates such
as MMT are mainly made of tetrahedral silica, while the
central plane of the layers contains octahedrally coordi-
nated Al
3+
with frequent non-stoichiometric substitutions,
where an Al
3+
is replaced by Mg
2+
and, somewhat less fre-
quently, by Fe
3+
. The concentration of the later ion is very
important becauseFe
3+
is stronglyparamagnetic inthis dis-
torted octahedral environment. Typical concentrations of
Fe
3+
in naturally occurring clays produce nearest-neighbor
Fe–Fe distances of about 1.0–1.4nm, and at such distances,
the spin-exchange interaction between the unpaired elec-
trons ondifferent Fe atoms is expectedtoproduce magnetic
fluctuations in the vicinity of the Larmor frequencies for
protons or
13
C nuclei. The spectral density of these fluc-
tuations is important because the T
1
H
of protons (and
13
C nuclei) within about 1nm of the clay surface can
be directly shortened. For protons, if that mechanism is
efficient, relaxation will also propagate into the bulk of
the polymer by spin diffusion. Thus the paramagnetically
induced relaxation will influence the overall measured T
1
H
to an extent that will depend both on the Fe concentra-
tion in the clay layer and, more importantly, on the average
distances between clay layers. The latter dependence sug-
gests a potential relationshipbetweenmeasuredT
1
H
values
and the quality of the clay dispersion. If the clay particles
are stacked and poorly dispersed in the polymer matrix,
the average distances between polymer/clay interfaces are
greater, and the average paramagnetic contribution to T
1
H
is weaker. VanderHart et al. also employed the same argu-
ments in order to understand the stability of a particular
OMLS under different processing conditions [55,60,61].
Some authors also used Fourier transform infrared
spectroscopy (FTIR) to elucidate the structure of the
nanocomposites [62,63]. FTIRmaybe able toidentifydiffer-
ences between the bonding in a mixture and the bonding
in a related nanocomposite, but as these variations are
Fig. 8. TEM micrographs of poly(styrene)-based nanocomposites: (a) intercalated nanocomposite and (b) exfoliated nanocomposite [1]. Reproduced from
Alexandre and Dubois by permission of Elsevier Science Ltd., UK.
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1129
Fig. 9. DSC traces of pure PS, a physical mixture of PS/OLS, and PS-
intercalated OLS [41]. Reproduced from Zanetti, Lomakin and Camino by
permission of Wiley-VCH, Germany.
minute, evenwhenintercalationhas takenplace, at present
FTIR is an unreliable method of characterization in most
cases [56].
Finally, differential scanning calorimetry (DSC) provides
further information concerning intercalation. The many
interactions the intercalated chains of the polymer form
with the host species greatly reduce their rotational and
translational mobility. The situation is similar to that in
a reticulated polymer, where restrictions on its mobility
increase its glass transition temperature (T
g
). A similar
increase is anticipated to occur in a nanocomposite due
to elevation of the energy threshold needed for the tran-
sition. This effect is readily detected by DSC. Fig. 9 presents
DSC traces of polystyrene (PS), a PS/OMLS mixture and an
intercalated PS/OMLS nanocomposite. The PS and PS/OMLS
mixture curves clearly display the characteristic peak due
to glass transition of the polymer. The presence of this peak
in the mixture is evidence of the absence of interactions
between the organic and the inorganic phases. The tran-
sition is absent in the nanocomposite curve and in fact
occurs at temperatures higher thanthose showninFig. 9. In
addition to being an interesting analytical datum, the con-
siderable increase in T
g
is an important property of these
materials that enables themto be employed at higher tem-
peratures compared with the original polymer and thus
extends their fields of application [41]. To date, the afore-
mentioned subsidiary methods have only been used to
confirmthe evidence fromthe primary methods. However,
building a clearer picture of the changes that occur when
a nanocomposite forms is important, as it not only helps
to characterize the material, but in principle could indicate
novel methods of synthesis [56].
Concerning the evaluation of other nanocomposites
structural characteristics, it should be noted that the
amount of clay present in a sample may be estimated,
as for conventional composites, i.e. by placing pre-dried
nanocomposite pellets in a furnace at ca. 900

C for approx-
imately 45min. The resulting ash is then weighed and
corrected for loss of structural water [64].
However, unlike conventional fiber composites, the
determination of filler aspect ratio for layered silicate
nanocomposites is not straightforward. Good estimates
require a thorough analysis of TEM photomicrographs
at different magnifications. Fig. 10 depicts various com-
plications of calculating an aspect ratio from TEM
photomicrographs that arise from variations in both
length/diameter, and thickness. Clay platelets intrinsically
have a distribution of lateral dimensions. The recovery,
refinement, chemical treatment, and post-treatment of
these clays may contribute to the variation in filler geom-
etry. Furthermore, extrusion of these clays with polymer
and any additional melt processing steps that follow, e.g.
injection molding, will amplify the range of particle shapes
and sizes, particularly when the layered silicate is not
completely exfoliated, as illustrated in Fig. 10. Finally,
microtoming of the nanocomposite sample into thin sec-
tions for TEM analysis will also result in an apparent
distribution of observed particle sizes even if all disk-like
platelets were the same size [64].
It becomes obvious from this section that a major issue
when synthesizing polymer–layered silicate nanocompos-
ites is the characterization of the product. In fact, many of
the studies conducted so far in this field are solely dedi-
cated to structural characterization of the nanocomposites,
without reporting properties of the products.
5. Preparation of nanocomposites
5.1. Introduction
At present there are four principal methods for produc-
ing polymer–layered silicate nanocomposites: (1) in situ
template synthesis, (2) intercalationof polymer or prepoly-
mer from solution, (3) in situ intercalative polymerization
and (4) melt intercalation [1,14,35,44,52,65].
5.1.1. Template synthesis (sol–gel technology)
In this technique, the clay minerals are synthesized
within the polymer matrix, using an aqueous solution (or
gel) containingthe polymer andthe silicate buildingblocks.
As precursors for the clay silica sol, magnesium hydroxide
sol and lithium fluoride are used. During the process, the
polymer aids the nucleation and growth of the inorganic
host crystals and gets trapped within the layers as they
grow. Although theoretically this method has the poten-
tial of promoting the dispersion of the silicate layers in
a one-step process, without needing the presence of the
onium ion, it presents serious disadvantages. First of all,
the synthesis of clay minerals generally requires high tem-
peratures, which decompose the polymers. An exception is
the synthesis of hectorite-type clay minerals which can be
performed under relatively mild conditions. Another prob-
lem is the aggregation tendency of the growing silicate
layers. Therefore, this technique, although widely used for
the synthesis of double-layer hydroxide-based nanocom-
posites, is far less developed for layered silicates and will
not be considered in the following discussion. However,
it should be mentioned that several workers have suc-
1130 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 10. Examples of complications in the determination of the aspect ratio of layered silicate fillers within polymer nanocomposites [64]. Reproduced from
Fornes and Paul by permission of Elsevier Science Ltd., UK.
cessfully applied it for the preparation of nanocomposite
materials. For example, Carrado et al. and Carrado and
Xu synthesized hectorites from gels consisting of silica,
magnesium hydroxide, lithium fluoride and polymers like
poly(vinyl alcohol), polyaniline and polyacrylonitrile. Evi-
dently, some silicate layers aggregated, but most of them
remained uniformly distributed in the polymer matrix
[1,3,41]
5.1.2. Intercalation of polymer or prepolymer from
solution
Following this technique, the layered silicate is exfoli-
ated into single layers using a solvent in which the polymer
(or prepolymer in case of insoluble polymers, such as poly-
imide) is soluble. It is well knownthat suchlayeredsilicates,
owing to the weak forces that stack the layers together can
be easily dispersed in an adequate solvent. After the organ-
oclay has swollen in the solvent, the polymer is added to
the solution and intercalates between the clay layers. The
final step consists of removing the solvent, either by vapor-
ization, usually under vacuum, or by precipitation. Upon
solvent removal the sheets reassemble, sandwiching the
polymer to form a nanocomposite structure. Under this
process are also gathered the nanocomposites obtained
through emulsion polymerization where the layered sili-
cateis dispersedintheaqueous phase. Themajor advantage
of this method is that intercalated nanocomposites can be
synthesized that are based on polymers with low or even
no polarity. However, the solvent approach is difficult to
apply in industry owing to problems associated with the
use of large quantities of solvents [1,35].
5.1.3. In situ intercalative polymerization
Insitu-polymerizationwas the first methodusedtosyn-
thesize polymer–clay nanocomposites based on polyamide
6. In this technique, the modified layered silicate is swollen
by a liquid monomer or a monomer solution. The monomer
migrates into the galleries of the layered silicate, so that
the polymerization reaction can occur between the inter-
calated sheets. The reaction can be initiated either by heat
or radiation, by the diffusion of a suitable initiator or
by an organic initiator or catalyst fixed through cationic
exchange inside the interlayer before the swelling step by
the monomer. Polymerization produces long-chain poly-
mers within the clay galleries. Under conditions in which
intra- and extra-gallery polymerization rates are properly
balanced, the clay layers are delaminated and the resulting
material possesses a disordered structure [1,35,37].
5.1.4. Melt intercalation
This technique consists of blending the layered silicate
with the polymer matrix in the molten state. Under such
conditions – if the layer surfaces are sufficiently compati-
ble with the chosen polymer – the polymer can crawl into
the interlayer space and form either an intercalated or an
exfoliated nanocomposite [1,35,37].
Among the aforementioned methods, in situ poly-
merization and melt intercalation are considered as
commercially attractive approaches for preparing poly-
mer/clay nanocomposites. Melt intercalation, in particular,
is especially of practical interest, since it presents signifi-
cant advantages that will be discussedinthe corresponding
paragraph.
5.2. Intercalation of polymer from solution
Intercalation of a polymer froma solution is a two-stage
process in which the polymer replaces an appropriate, pre-
viously intercalated solvent, as shown in Fig. 11. Such a
replacement requires a negative variation in the Gibbs free
energy. It is thought that the diminished entropy due to the
confinement of the polymer is compensated by an increase
due to desorption of intercalated solvent molecules. In
other words, the entropy gained by desorption of solvent
molecules is the driving force for polymer intercalation
from solution [66–71].
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1131
Fig. 11. Schematic representation of PLS obtained by intercalation from solution.
Even though this technique has been mostly used with
water soluble polymers, such as PEO, PVE, PVP and PAA
[3,21,72–77], intercalation fromnon-aqueous solutions has
also been reported [78–81]. For example, HDPE-based
nanocomposites have been prepared by dissolving HDPE
in a mixture of xylene and benzonitrile with dispersed
OMLS. The nanocomposite was then recovered by precipi-
tation from THF [79]. PS/OMLS exfoliated nanocomposites
have also been prepared by the solution intercalation
technique, by mixing pure PS and organophilic clay with
adsorbed cetyl pyridium chloride [82]. Similarly, several
studies have focused on the preparation of PLA-layered
silicate nanocomposites using intercalation from solution.
The first attempts by Ogata [78], involved dissolving the
polymer in hot chloroform in the presence of organo-
modifiedMMT. However, TEMandWAXDanalyses revealed
that only microcomposites were formed and that an inter-
calated morphology was not achieved. In a later study,
Krikorian and Pochan [83] prepared PLA nanocomposites
using dichloromethane as the polymer solvent and as the
OMLS dispersion medium. The authors obtained interca-
lated or exfoliated nanocomposites, depending on the type
of OMLS used. That is, exfoliated nanocomposites were
formed when diols were present in the organic modifier of
the clay, due to the favorable enthalpic interaction between
these diols and the C O bonds in the PLA backbone.
Chang et al. [84] reported the preparation of PLA-based
nanocomposites with different kinds of OMLS via solution
intercalation using N,N

-dimethylacetamide (DMA).
In the case of polymeric materials that are infusible and
insoluble even in organic solvents, the only possible route
toproducenanocomposites withthis methodis tousepoly-
meric precursors that can be intercalated in the layered
silicate and then thermally or chemically converted to the
desired polymer [1,85].
Summarizing the above: although a number of
nanocomposites have been produced by intercalation from
solution(representativeexamples arepresentedinTable2),
it is important to note that, in using this method, intercala-
tion only occurs for certain polymer/clay/solvent systems,
meaning that for a given polymer one has to find the right
clay, organic modifier and solvents [1,50]. Moreover, from
the industrial point of view, this method may involve the
copious use of organic solvents, which is usually environ-
mentally unfriendly and economically prohibitive [50].
5.3. In situ intercalative polymerization
5.3.1. In situ intercalative polymerization of
thermoplastic polymers
The Toyota research group first reported the ability
of ␣,␻-amino acid (COOH–(CH
2
)
n−1
–NH
2
+
, with n=2, 3,
4, 5, 6, 8, 11, 12, 18) modified Na
+
-MMT to be swollen
by ␧-caprolactam monomer at 100

C and subsequently
initiate ring opening polymerization to obtain PA6/MMT
nanocomposites [25]. The number of carbon atoms in the
␣,␻-amino acid was found to have a strong effect on the
swelling behavior as reported in Fig. 12, indicating that
the extent of intercalation of ␧-caprolactam monomer is
high when the number of carbon atoms in the ␻-amino
acid is large [93]. Moreover, it was found from a com-
parison of different types of inorganic silicates that clays
having higher CEC lead to more efficient exfoliation of
the silicate platelets [51]. Fig. 13 represents the concep-
tual view of the swelling behavior of ␣,␻-amino acid
modified Na
+
-MMT by ␧-caprolactam[93]. In a typical syn-
thesis, 12-aminolauric acid-modified MMT (12-MMT) was
Table 2
PLS nanocomposites prepared by intercalation from solution.
Nanocomposite Solvent(s) Ref.
PVOH/Na
+
-MMT Water [86]
PVA/Na
+
-MMT Water [87]
TPU/OMLS Toluene/DMAc [88]
PEO/Na
+
-MMT or
Na
+
-hectorite
Acetonitrile [89]
PEO/MMT Chloroform [90]
PLA/OMLS Dichloromethane [83]
PLA/OMLS DMAc [84]
HDPE/protonated
dodecylamine modified
MMT
Xylene/benzonitrile
(80/20wt.%)
[91]
PSF/OMLS DMAC [92]
PI/dodecylammonium
modified MMT
DMAC [85]
1132 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 12. XRDpatterns of ␻-amino acid[NH
2
(CH
2
)
n−1
COOH] modifiedNa
+
-
MMT [93]. Reproduced from Usuki, Kawasumi, Kojima, Okada, Kurauchi
and Kamigaito by permission of Materials Research Society, USA.
mixed with ␧-caprolactam and the mixture was heated at
250–270

Cfor 48hto polymerize ␧-caprolactam, using 12-
MMT as a catalyst (when the relative amount of 12-MMT
in the mixture was less than 8wt.%, 6-aminocaproic acid
was added as a polymerization accelerator and the heating
profile was slightly modified). Depending on the amount
of 12-MMT introduced, either exfoliated (for less then
15wt.%) or intercalatedstructures (from15to70wt.%) were
obtained, as evidenced by XRDand TEM. Comparison of the
titrated amounts of COOH and NH
2
end groups present in
the synthesized nanocomposites with given values, such as
the CEC of the montmorillonite used (119mequiv./100g),
have led to the conclusion that the COOH end groups
present along the 12-MMT surface are responsible for the
polymerization initiation [25].
Further work demonstrated that intercalative poly-
merization of ␧-caprolactam could be realized without
Fig. 13. Swelling behavior of ␻-amino acid modified MMT by ␧-
caprolactam [93]. Reproduced from Usuki, Kawasumi, Kojima, Okada,
Kurauchi and Kamigaito by permission of Materials Research Society, USA.
Table 3
Peak intensity (I
m
) and interlayer spacing (d) of nylon-6-based nanocom-
posites prepared in presence of different acid derivatives by the one-pot
technique [95].
Acid I
m
(cps) d (Å)
Phosphoric acid 0 0
Hydrochloric acid 200 21.7
Isophtalic acid 255 20.2
Benzenesulfonic acid 280 19.3
Acetic acid 555 20.3
Trichloroacetic acid 585 21.3
No acid 1840 18.6
modifying the MMT surface. Indeed, this monomer was
able to directly intercalate the Na
+
-MMT in water in the
presence of hydrochloric acid, as proved by the increase in
interlayer spacing from 10 to 15.1Å. At high temperature
(200

C), in the presence of excess ␧-caprolactam, the clay
somodifiedcanbe swollenagain, allowingthe ringopening
polymerization to proceed at 260

C when 6-aminocaproic
acid is added as an accelerator. The resulting composite
does not present a diffraction peak in XRD, and TEMobser-
vation agrees with a molecular dispersion of the silicate
sheets [94].
In attempts to carry out the whole synthesis in one pot,
the system proved to be sensitive to the nature of the acid
used to promote the intercalation of ␧-caprolactam. Table 3
gives results obtained for different acids in relation to the
intensity (I
m
) of the XRD intercalation peak that might be
present in the nanocomposites obtained (Fig. 14). These
results showthat, for unclear reasons, only phosphoric acid
allows for the preparation of a truly exfoliated nanocom-
posite, the other acids tending to promote the formation
of partially exfoliated-partially intercalatedstructures. One
can also point out that an intercalated structure is obtained
even if no acid is added [95].
Another polyamide, nylon 12, has also been reported to
form nanocomposites via in situ intercalative polymeriza-
tion. Reichert et al. [96] used 12-aminolauric acid (ALA) as
both the layered silicate modifier and the monomer. They
first studied by XRD the dependence of the clay swelling
process on ALA concentration in HCl, and found that it
can be separated in two regimes: a cation-exchange of
inorganic cations by protonated ALA at lowALA concentra-
Fig. 14. XRD intensity curve of injection molded nylon-6 nanocomposite
as obtained by the one-pot intercalation polymerization process in the
presence of acetic acid [95]. Reproduced from Kojima, Usuki, Kawasumi,
Okada, Kurauchi and Kamigaito by permission of John Wiley & Sons, Inc.
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1133
Fig. 15. Interlayer distance of fluoro-modified talc (ME 100) in function
of an increasing amount of aminolauric acid used as the organic mod-
ifier [96]. Reproduced from Reichert, Kressler, Thomann, Mulhaupt and
Stoppelmann by permission of Wiley-VCH, Germany.
tion and a further diffusion of zwitterionic 12-aminolauric
acid into the interlayer space, when the ALA concentration
exceeds the amount of HCl in the medium(Figs. 15 and 16).
The swelling was found to be independent of the swelling
temperature, the layered silicate concentration and the
type of acid used to protonate ALA (HCl, H
2
SO
4
, H
3
PO
4
).
ALA was then polymerized at high temperature (280

C)
and under elevated pressure (ca. 20bar) with both types
of swollen clay. XRD and TEM, coupled with energy disper-
sive X-ray (EDX), as well as atomic force microscopy (AFM),
confirmed that the resulting structures were partially exfo-
liated and otherwise intercalated nanocomposites.
However, although in situ polymerization was success-
fully applied for the preparation of PA6 and PA12/clay
nanocomposites, few publications focused on the prepa-
ration of polyamide from diamine and diacid. In one of
these studies, Wu et al. [97] investigated the preparation
of PA1012 nanocomposite by polycondensation polymer-
ization. A dispersion of organoclay in absolute alcohol
was added to 1,10 diaminodecane in absolute alcohol.
Then, this mixture was added to an absolute alcohol
solution of 1,10-decanedicarboxylic acid under vigorous
stirring, resulting in the immediate precipitation of a
diaminodecane–decanedicarboxylic acid salt. The salt was
recrystallized from a mixture of alcohol and water and
was obtained as a white powder. It was then added with
a slight excess of diaminodecane to a U-shaped glass tube
which was purged with nitrogen before the reaction. The
tube was immersed in an oil bath and the temperature was
quickly raised to 200

C to start the reaction. After main-
taining the autoclave for 2h at 200

C, the temperature was
increased to 215

C and held for 1.5h under these condi-
tions. The glass tube was flushedwithnitrogeneachtime to
remove the water producedinpolycondensation. Inthe last
step a vacuum (<0.1atm) was applied to remove the water
and residual monomer, the temperature was increased to
225

C, and the reaction was continued for another 2h.
The glass tube was then cooled to room temperature and
the resulting PA1012/organoclay hybrid was obtained as a
white solid. The absence of peaks in the XRD pattern indi-
cated the exfoliation of the clay platelets in the PA1012
matrix.
The in situ polymerization technique has also been
applied for the preparation of nanocomposites based on
thermoplastic polymers other than polyamides, including
polymethyl methacrylate (PMMA) [98,99], polystyrene (PS)
[100], polybenzoxale (PBO) [101], polyolefins (PP and PE)
[102–105], and polyethylene terephthalate (PET) [106].
For example, in a study discussing the synthesis of PET
nanocomposites using in situ polymerization, the organo-
modified montmorillonite is reported to react with PET
comonomers (ethylene glycol and terephthalic acid deriva-
tives) to form an intercalated nanocomposite [106].
However, according to Lee et al. [107] endeavors to
prepare PET nanocomposites using direct condensation
polymerization of diol and diacid result in formation of
oligomers with significantly low molecular weight, due
to ineffective control of stoichiometry; and thus, a large
increase in intragallery distance is hard to obtain. On
the other hand, attempts to prepare PET nanocomposites
through melt intercalation have resulted in limited inter-
calation of guest molecules, presumably due to the high
viscosity of PET polymer. Therefore, the authors proposed
and successfully applied the ring-opening polymerization
of ethylene terephthalate cyclic oligomers (ETCs) with
organically modified MMT, as an alternative approach to
the preparation of PET-based nanocomposites. Because of
low molecular weight and cyclic molecular architecture,
cyclic oligomers of PET have much lower solution and melt
viscosities than the corresponding polymer; so it may be
expected that, when clay intercalation is intended by mix-
Fig. 16. Schematic representation of the swelling behavior of the fluoro-modified talc ME 100 in presence of aminolauric acid [96]. Reproduced from
Reichert, Kressler, Thomann, Mulhaupt and Stoppelmann by permission of Wiley-VCH, Germany.
1134 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 17. Schematic representation of nanocomposite formation by ring-
opening reaction of cyclic oligomers in between silicate layers [107].
ReproducedfromLee, Ma, RheeandKimJ bypermissionof Elsevier Science
Ltd., UK.
ing with cyclic oligomer instead of linear polymer, easier
diffusion and a higher degree of intercalation or exfoliation
would be obtained. In addition, problems such as precise
control of stoichiometry and high vacuum requirements,
strictly required in preparation of PET by conventional con-
densation polymerization of difunctional monomers, can
be effectively avoided through ring opening reaction of
cyclic oligomers (Fig. 17).
HDPE nanocomposites have been synthesized by the
so-called polymerization-filling technique (PFT), which
involves anchoring in a first step a Ziegler-Natta type or any
other coordination catalyst onto a filler surface and then
in situ polymerizing ethylene directly from the surface-
treatedfillers. Inorder toapplythis techniquetonanofillers,
layered silicates in aqueous colloidal suspension were
made less hydrophilic through elimination of water by
freeze drying. The fluffy materials obtained could then be
nicely dispersed in non-polar solvents such as heptane
or toluene. The clay dispersion was then surface-treated
with MAO, and after solvent removal by evaporation, a
high temperature treatment at 150

C was applied to mod-
ify the layered silicate. After removal of unreacted MAO,
the silicate layers were contacted with a metallocene
pre-catalyst, i.e. (tert-butylamido)dimethyl(tetramethyl-
Z5-cyclopentadienyl) silane titanium dimethyl, for 1h to
form the active catalyst species. The polymerization was
carried out by adding ethylene to the medium. It has
to be pointed out that no ion exchange reaction was
required. Rather, this strategy relied on the immobiliza-
tion of the active species through electrostatic interactions
with surface anchored MAO. Some typical in situ interca-
lation experiments are gathered in Table 4. When ethylene
polymerization was carried out in the absence of molec-
ular hydrogen (thus without any transfer agent), layered
silicate/UHMWPEwas produced, whichis anextremelyvis-
cous material, very difficult to melt (Table 4, entries 1 and
2). Addition of hydrogen to the polymerization medium
allows molecular weight to be reduced with substantial
improvement of melt processability (Table 4, entry 3).
Examinationof the TEMpictures reveals partial exfoliation,
even at high filler content (ca. 30wt.% montmorillonite)
[108–110].
Similarly, Bergman et al. [103] used a palladium-based
complex and synthetic fluorohectorite as the polymeriza-
tion catalyst and inorganic component respectively for the
synthesis of polyethylene nanocomposites. They first inter-
calated palladium catalyst into the galleries of modified
fluorohectorite (C14N-2) and exposed the dry powder to
ethylene gas. Over a 2h period, they observed monomer
consumption and a dramatic increase in the size of the
silicate-catalyst composite, while after 12h a large mass of
colorless, rubbery polymer formed. Analysis of the toluene-
extracted polyethylene by GPC revealed a high molecular
weight. Moreover, the complete absence of diffraction
peaks in the XRD patterns strongly suggests the formation
of an exfoliated nanocomposite.
Jin et al. [105] also applied the in situ exfoliation
method during ethylene polymerization by fixing a Ti-
based Ziegler-Natta catalyst at the inner surface of MMT.
They used organic salts with hydroxyl groups for the mod-
Table 4
Synthesis and composition of PE-based nanocomposite produced by in situ intercalative polymerization of ethylene (P(C
2
H
4
) =10bar) in non-organo-
modified layered silicates
a
[1].
Filler MAO (10
−3
mol) Catalyst (10
−6
mol) P(H
2
)
b
(bar) Filler loading
c
(wt.%) HDPE M
n
(g/mol)
h 33.00 15.6 0 4.2 –
d
m 27.20 12.5 0 3.3 –
d
h 23.75 16.2 0.3 3.4 77.000
a
h: hectorite and m: montmorillonite.
b
Hydrogen partial pressure at start.
c
Measured by thermogravimetric analysis (TGA).
d
Insoluble UHMWPE that cannot be eluted by SEC.
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1135
Fig. 18. Mechanistic representation of the fixing of TiCl
4
between the sil-
icate layers of MMT–OH [105]. Reproduced from Jin, Park, Im, Kwak and
Kwak by permission of Wiley-VCH, Germany.
ification of MMT (MMT–OH) since hydroxyl groups in
intercalation agents offer facile reactive sites for anchoring
catalysts betweensilicate layers. Fig. 18represents the TiCl
4
fixation mechanism between silicate layers of MMT–OH.
The polymerization of ethylene was conducted by inject-
ing ethylene into the catalyst slurry (30–50

C, 4bars).
After predetermined reaction times, polymerization was
quenched with a dilute HCl solution in methanol. The poly-
mer was precipitated in methanol, separated by filtration
anddriedinvacuum. Thepowder was thenusedas themas-
ter batch and mixed with HDPE by melt extrusion. WAXD
analysis again revealed exfoliation of MMT layers in both
the powdery reaction product and the HDPE matrix.
In a study by Shin et al. [111] montmorillonite was
intercalated with triisobutylaluminumand ␻-undecyleny-
alcohol. The intercalation process allows the transition
metal catalyst and the activator methylaluminoxane to
enter the clay galleries and polymerize ethylene, while for-
mation of polyethylene inside the galleries leads to the
exfoliation of layered silicates. The authors noted that two
types of polymerization are possible: (a) the homopoly-
merization of ethylene, and (b) the copolymerization of
ethylene and the vinyl ends of alcohol modifier con-
nected to the surface during intercalation, which produces
polyethylene chains, chemically connected to the silicate
surface.
Heinemann et al. [112] carried out ethylene poly-
merizations in the presence of layered silicates, such as
organo-modified bentonite and unmodified hectorite and
fluoromica, using 1-octene as comonomer. Different cat-
alysts were used, affording HDPE and ethylene–octene
copolymers (zirconium-based catalyst) and branched
polyethylene (nickel and palladium-based catalysts). It
appeared that the modified bentonites had a dramatic
negative effect on the polymerization activity of the
zirconium-basedcatalyst due toits highsensitivitytowards
any kind of polar functionality, while Ni-and Pd-based
catalysts were much less affected by the nature of the
clay. However, nanocomposites formed only in the case of
organo-modified clays, while in situ polymerization with
unmodified silicates gave microcomposite structures.
PP/clay nanocomposites have also been prepared by in
situ intercalative polymerization. Tudor et al. [104] treated
a synthetic hectorite with methylaluminoxane (MAO) to
remove the acidic protons and to prepare the interlayer
spacing to receive the transition metal catalyst. Details of
the preparationroute are showninFig. 19. Using a synthetic
fluorinated mica-type layered silicate deprived of protons
inthe galleries, the catalyst was intercalateddirectly within
the silicate layers, without the need of MAOtreatment. Sun
and Garces [102] also reported the preparation of PPCN by
in situ polymerization with metallocene/clay catalysts.
Following the in situ intercalative polymerization tech-
nique, Doh and Cho [113] compared the ability of several
tetraalkylammonium cations incorporated into Na
+
-MMT
to promote the intercalation of PS through the free radical
polymerization of styrene, initiated by AIBNat 50

C. Three
tetraalkylammonium cations were tested, all based on the
following formula: (CH
3
)
2
N·(hydrogenated tallow alkyl)R,
where hydrogenated tallowalkyl corresponds to a mixture
of mainly octadecyl chains together with small amounts
of lower linear homologs and R may be either another
hydrogenated tallowalkyl (Ta), 2-ethyl hexyl (Eh) or benzyl
(Bz) group. The so-modified o-MMTs were coded as Ta-
MMT, Eh-MMT and Bz-MMT, respectively. Layer spacings
obtained for the three MMTs and corresponding compos-
ites are presented in Table 5 and reveal that the best
intercalation occurs for Bz-MMT. This is probably due to
a better affinity between styrene and benzyl groups spread
all along the layered MMT surfaces. It is worth mentioning
that even though the interlayer spacing for Ta-MMT does
not change much, the authors assumed that intercalation
occurs in this case also; however this is not evident from
the d-spacings because such hydrogenated tallow alkyl
chains should be long enough (mainly C18 chains) to easily
accommodate the PS. Eventhoughthis technique allows for
extensive intercalation of PS chains through the choice of
Fig. 19. Schematic illustration of the modification and ion exchange of laponite with [Zr(n–C
5
H
5
)
2
Me(thf)]BPh
4
and propene polymerization [104]. Repro-
duced from Tudor, Willington, O’Hare and Royan by permission of The Royal Society of Chemistry, UK.
1136 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 5
Interlayer spacings of organo-modified montmorillonites (X-MMT) and
as-obtained PS-based nanocomposites and the clay dispersibility within
the polymerization medium [113].
X
a
-MMT Interlayer spacing (Å) Dispersibility
b
In X-MMT In PS/X-MMT
Sodium MMT 11.8 14.2 −
BZ-MMT 19.1 34.0 ++
Eh-MMT 20.4 28.5 +
Ta-MMT 32.7 32.9 +
a
Organo-modifiers: (CH
3
)
2
N
+
(hydrogenated tallowalkyl)R with R=Bz
(benzyl), Eh (2-ethylhexyl), or Ta (hydrogenated tallow alkyl).
b
It was judged by the appearance of the montmorillonite dispersion
in styrene monomer (++) fully dispersible, (+) partly dispersible and (−)
non-dispersible.
an appropriate alkylammonium cation, neither exfoliation
nor control over the molecular weight of PS produced has
been observed.
Akelah and Moet [100] modified MMT with vinylben-
zyltrimethyl ammonium cation, and they dispersed and
swelled the modified clay in various solvent and co-solvent
mixtures, such as acetonitrile or acetonitrile/toluene under
N
2
. Styrene polymerizations were carried out in presence
of AIBN at 80

C for 5h. In this way, intercalated PS/MMT
nanocomposites were produced, with the extent of inter-
calation depending upon the nature of the solvent used.
However, although PS is well intercalated, one drawback
of this procedure is that the macromolecule produced is
not a pure PS, but rather a copolymer between styrene and
surfactant.
A similar approach has been applied by Weimer et al.
[114], who modifiedNa
+
-MMT by anchoring anammonium
cation bearing a nitroxide moiety known for its ability to
mediate the free radical polymerization of styrene in bulk.
The absence of WAXD peaks together with TEM observa-
tions of silicate layers randomly dispersed within the PS
matrix attest to the complete exfoliation of the layered sil-
icate.
In another study, Yei et al. [115] prepared PS/clay
nanocomposites through emulsion polymerization, by sus-
pending the clay in styrene monomer. The clay was treated
witheither cetyl-pyridiniumchloride(CPC) or theinclusion
complex of CPC in ␣-cyclodextrin (CPC/␣-CD). This was the
first study reporting cyclodextrins (CDs) as surfactants for
intercalation in clay. CDs comprise a series of ␣-1,4-linked
cyclic oligosaccharides with shapes resembling hollow
truncated cones. The cavities of CDs are hydrophobic; thus
CDs have the ability to include hydrophobic molecules
within their cavities. For the preparation of an inclusion
complex, CPC was mixed with a saturated solution of ␣-CD
in water and the complex was obtained as a white crys-
talline precipitate. The modified clays were also obtained
as white precipitate after adding a solution of the surfac-
tant (CPC or CPC/␣-CD inclusion complex) in a Na
+
-MMT
suspension. Emulsion polymerization was performed as
follows: a surfactant solution (CPC or CPC/␣-CD inclusion
complex) was addedtoanaqueous suspensionof clay. After
stirring for 4h, KOH and SDS were added to the solution
and the temperature was raised to 50

C. Styrene monomer
and K
2
S
2
O
8
were added slowly and polymerization was
performed at 50

C for 8h. After cooling, 2.5% aqueous alu-
minum sulfate was added to the polymerized emulsion,
followed by dilute HCl with stirring. Finally, acetone was
addedtobreakthe emulsion. XRDpatterns indicate that the
CPC surfactant is intercalated successfully into the galleries
of the clay, increasing their spacing from 1.43 to 2.27nm.
Furthermore, the d-spacing caused by the inclusion com-
plex is 5.12nm, i.e. substantially higher than that caused by
CPC alone. This was explained by the authors considering
that the linear, aliphatic chain within the CPC/␣-CD cannot
bend within the galleries of the clay. On the other hand, no
peak was detected in the XRD patterns for polymer/clay
nanocomposites prepared from the CPC and CPC/␣-CD
treated clays which implies that they all possess exfoliated
structures.
In another study, exfoliated PLA/clay nanocomposites
were prepared by in situ coordination-insertion polymer-
ization method [116]. The authors used two different kinds
of OMLS (C30B and C25A) for the preparation of nanocom-
posites. In a typical synthetic procedure, the clay was
thoroughly dried and placed in the polymerization vial.
l,l-Lactide solution in dried THF was then transferred to
the vial under nitrogen and the solvent was eliminated
under reduced pressure. Polymerizations were conducted
in bulk at 120

C for 48h, after 1h of clay swelling in the
monomer melt. When C30B was used, the polymeriza-
tion was co-initiated by AlEt3, while Sn(Oct)
2
was used to
catalyze the polymerization of l,l-lactide in the presence
of C25A. The clay C30B led to fully exfoliated structure,
whereas C25A-based nanocomposites exhibited an inter-
calated morphology.
Messersmith and Giannelis [117] reported the first
preparation of PCL nanocomposites, in 1993, by in situ
intercalative polymerization, using Cr
3+
exchanged fluo-
rohectorite (FH). In a typical synthesis, a mixture of Cr
3+
FH and CL was heated at 100

C for 48h. Upon cooling to
room temperature the reaction mixture solidified. Inter-
calation of the CL monomer was revealed by XRD, which
showed an increase in the silicate d-spacing from 1.28 to
1.46nm. The d
001
spacingobservedprior topolymerization
was found to be consistent with the orientation of the CL
ring perpendicular to the silicate layers. XRDanalysis of the
nanocomposites after polymerizationindicates a reduction
in the silicate d-spacing from 1.46 to 1.37nm, as presented
in Fig. 20. The decrease in the d-spacing is consistent with
the dimensional change accompanying polymerization of
CL monomer.
The same researchers also modified a Na
+
-MMT by
the protonated aminolauric acid and dispersed this mod-
ified clay in liquid ␧-caprolactone before polymerizing it
at high temperature. The PCL nanocomposites were pre-
pared by mixing up to 30wt.% of the modified clay with
␧-caprolactone at roomtemperature for two h, followed by
the ring opening polymerization at 170

C for 48h. Inter-
estingly enough, XRD patterns of the modified clay after
contact with ␧-caprolactone at room temperature do not
show any significant increase in the layer spacing (13.6Å).
The authors assumed that the monomer intercalates in the
gaps betweenthe aminolauric acidchains so that no gallery
expansion could be seen, in contrast to what is usually
observed in in situ intercalative polymerization, where the
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1137
Fig. 20. Powder XRDof the composite before (solidline) andafter (dashed
line) polymerization. Insets are schematic illustrations (not drawn to
scale) corresponding to the intercalated monomer (left) and intercalated
polymer (right) [117]. Reproduced from Messersmith and Giannelis by
permission of the American Chemical Society, USA.
monomer insertion within the silicate gallery induces an
increase in the interlayer spacing. Another possibility may
bethat intercalationof themonomer occurs onlyduringthe
heating stepof the solution. After polymerization, XRDpat-
terns of the obtained composites did not showa diffraction
peak, indicating that exfoliation occurred [118].
Pantoustier et al. [119,120] compared PCL nanocompos-
ites prepared by intercalative polymerization using both
pristine MMT and␻-aminododecanoic acidmodifiedMMT.
The polymerization of CL with pristine and modified MMT
gives PCL with a molar mass of 4800 and 7800g/mol,
respectively, and a narrow distribution. For comparison,
the authors also conducted the same experiment with-
out MMT, but found no CL polymerization. These results
demonstrate the ability of MMT to catalyze and control
CL polymerization, at least in terms of a molecular weight
distribution that remains remarkably narrow. Even though
the polymerization mechanism of ␧-caprolactone in the
presence of clay generally remains unclear and differ-
ent assumptions have been made [121–123], the authors
assumed that CL is activated through interaction with the
acidic site on the clay surface.
On the other hand, Gorrasi et al. [6] suggested that
the low molecular weight of PCL synthesized by in situ
polymerization in the presence of layered silicate may
be responsible for the high brittleness of the resulting
nanocomposites. Therefore, they proposed the prepara-
tion of blends of high molecular weight PCL with different
amounts of o-MMT/PCL nanocomposite preparedvia insitu
polymerization and containing a high amount (30wt.%)
of clay. More specifically, they added a suspension of an
intercalated PCL nanocomposite (prepared by intercalative
polymerization of ␧-CL and having a basal spacing of 24Å)
in chloroform to a chloroform solution of PCL and after
stirring for 15h, they obtained the final composite by pre-
cipitation into hexane. The XRD patterns of this product
showed a peak corresponding to a basal spacing of 18Å,
suggesting that the PCL is indeed intercalated within the
silicate layers of the clay in the blend that, however, under-
went partial restructuring during the blend formation.
At this point, it is worth mentioning that, even though
in situ intercalative polymerization has proved success-
ful in the preparation of various polymer–layered silicate
nanocomposites, important drawbacks of this technique
have also been pointed out: (1) it is a time-consuming
preparation route (the polymerization reaction may take
more than 24h); (2) exfoliation is not always thermody-
namicallystable; andthe platelets mayre-aggregate during
subsequent processing steps; and (3) the process is avail-
able only to the resin manufacturer who is able to dedicate
a production line for this purpose [124].
5.3.2. In situ intercalative polymerization of
thermosetting polymers
Despite the aforementioned disadvantages of in situ
intercalative polymerization, this is the only viable tech-
nique for the preparation of thermoset-based nanocom-
posites, since such nanocomposites obviously cannot be
synthesized by melt intercalation, which is the other com-
mercially important preparation method [42,125–127].
In this case, the exfoliation ability of the organoclays is
determinedbytheir nature, includingthe catalytic effect on
the curing reaction, the miscibility with the curing agent,
etc. Since there is a curing competition between intra-
gallery and extragallery resin, as long as the intragallery
polymerization occurs at a rate comparable to the extra-
gallery polymerization, the curing heat produced is enough
toovercometheattractiveforces betweenthesilicatelayers
and an exfoliated nanocomposite structure can be formed.
In contrast, if the extragallery polymerization is more rapid
than the intragallery diffusion and polymerization or if
intragallery polymerization is retarded, the extragallery
resin will gel before the intragallery resin produces enough
curing heat to drive the clay to exfoliate; consequently,
exfoliation will not be reached. It can be inferred, therefore,
that factors promoting the curing reaction of intragallery
resin will facilitate the exfoliation of the clay. Such factors
include the catalytic effect of organoclayonthe curingreac-
tion, the goodpenetrating ability of curing agent to clay, the
long alkyl-chain of the organo-cation, meaning a greater
amount of intragallery resin preload and a completed orga-
nization of the clay, and meaning weaker attractive forces
between the silicate layers [33,128].
In fact, a number of research groups have studied the
effect of various parameters on the exfoliation of clays
in epoxy resins. Pioneering studies by Pinnavaia and co-
workers [129] on MMT/epoxy systems established the
initial conceptual methodology. Interfacial modifiers, such
as primary ammonium alkyls are intercalated between
the MMT layers, not only to compatibilize the inorganic
aluminosilicate and organic resin, but also to accelerate
the crosslinking reaction between the layers through acid
catalysis. That is, as the curing agent is mixed into the
clay/epoxy mixture, it is thought that the modifiers intro-
duced into the galleries of the clay sheets would promote
the reaction between the epoxy in the gallery with the cur-
1138 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 6
d-Spacing of tixogel and OPTC18 at 5 phr in epoxy/amine systems at the beginning and at the end of polymerization.
Epoxy system+5 phr Tixogel Epoxy system+5 phr OPTC18
DGEBA/MCDEA DGEBA/D2000 DGEBA/MCDEA DGEBA/D2000
d-Spacing when reaction starts (Å) 33.2 33.7 33.0 54.5
d-Spacing at the end of the reaction (Å) 33.9 35.0 70 110
ing agent. This would make the intragallery curing reaction
faster than the extragallery reaction, thus facilitating the
expansion of the clay sheets and helping to achieve exfoli-
ation [130].
For the diglycidyl ether of bisphenol A (DGEBA),
crosslinked with m-phenylene diamine (MPDA) and con-
taining 5% modified MMT, Lan et al. [131] found that the
clays with primary and secondary oniumions formed exfo-
liated nanocomposites, whereas those with tertiary and
quaternary onium ions retained an intercalated structure.
It was arguedthat acidic alkyl ammoniumions tendtofavor
exfoliation by catalyzing homopolymerization of DGEBA
molecules inside the clay galleries. It was also found that
the length of alkyl chains of modified MMT may determine
whether an intercalated and partially exfoliated or a totally
exfoliated nanocomposite will be obtained. The same kind
of study was also conducted by Zilg et al. [132] who cured
DGEBAwith hexahydrophthalic acid anhydride in the pres-
ence of different types of clays, again modified with a wide
variety of surfactants.
Another parameter of the clay that greatly affects
the outcome of nanocomposite processing is the cation
exchange capacity (CEC), which determines the amount of
surfactant ions present between the clay layers and there-
fore controls the space available for diffusion of epoxy
molecules during mixing with the organoclay. It has been
established that the highest CEC provides the minimum
space. Inthis context, theswellingphaseis of critical impor-
tance to the final nanocomposite structure. An MMT with a
low CEC is exfoliated already during swelling in the epoxy
resin prior to curing. A possible mechanismexplaining this
phenomenon is homopolymerization of the epoxy resin
during the swelling phase, causing diffusion of new epoxy
molecules into the clay galleries. The large amount of space
available between the layers favors the diffusion. On the
other hand, the duration of swelling of the clay with high
CEC is shown to be critical for the synthesis of an exfoliated
nanocomposite [42].
Other researchers investigated the effect of the polymer
resin. For example, Becker et al. [133] prepared nanocom-
posites of three different epoxy resins: diglycidyl ether of
bisphenol A (DGEBA), triglycidyl p-aminophenol (TGAP)
andtetrafunctional tetraglycidyldiaminodiphenylmethane
(TGDDM), using a mixture of two diethyltoluene diamine
(DETDA) isomers as the hardener and a commercially avail-
able octadecyl ammonium ion modified MMT as the clay.
All epoxy resin systems intercalated the organically mod-
ified layered silicate and increased the d-spacing from 23
up to 80Å. Similarly, Hackman and Hollaway [134] noted
that the epoxy resin component of the nanocomposite has
little effect on the exfoliation of the clay layers; although
it is the basic unit, the curing agent controls the rate of
cure. Lower viscosity resins lead to faster pre-intercalation,
but they do not seem to offer any significant long-term
advantage.
Interestingly, much research has focused on the effect
of curing agent on the intercalation/exfoliation of clays in
epoxy resins. Messersmith and Giannelis [135] analyzed
the effect of different curing agents on the formation of
nanocomposites based on DGEBA and a montmorillonite
modified by bis(2-hydroxyethyl)methyl hydrogenated tal-
lowalkyl ammoniumcation. Theyfoundthat whenprimary
and secondary amines, such as methylene dianiline, were
used, only intercalated epoxy–clay structures could be
obtained. This was attributed to either the bridging of
the silicate layers by the bifunctional amine molecules,
which prevents further expansion of the layers from tak-
ing place, or to the strong polarity of the N–H groups
in the primary and secondary amines that causes a re-
aggregation of dispersed silicate layers. When other curing
agents, suchas nadic methyl anhydride(NMA), borontriflu-
oride monomethylamine (BTFA) or benzyldimethylamine
(BDMA) were added, delamination during heating of the
reaction mixture occurred. Addition of the curing agent
induced first an increase of the interlayer spacing from 36
to 39Å, indicating some partial intercalation. With further
heating, disappearance of the interlayer spacing reflection
indicated that delamination had occurred. Study of the
curing reactions tended to prove that the particular alky-
lammoniumused(that bears twohydroxyl functions) could
play an active role, especially when BDMA or NMA were
addedas thecuringagents. For example, BDMAcancatalyze
the reaction between the hydroxyl groups of the alkylam-
moniumand the oxirane of the monomer, producing a new
hydroxyl that subsequently reacts with free DGEBA via a
similar base-catalyzed oxirane ring opening to build up the
epoxy network.
Recently, Le Pluart et al. [136] investigated the influ-
ence of curing agent and clay organophilic treatment on
the reactivity and cure behavior of epoxy networks and
on the morphology of the final composites. They used two
different curing agents: an aliphatic diamine with a poly-
oxypropylene backbone (D2000) and 4,4

-methylenebis[3-
chloro-2,6-diethylaniline] (MCDEA) as well as two mont-
morillonites modified with different alkyl ammoniumions
having the same chain length. The first MMT is Tixo-
gel MP250, a benzyl dimethyl tallow alkyl ammonium
MMT, while the second is OPTC18, an octadecylammo-
nium ion modified MMT. The authors noticed that gel
time was decreased in the presence of Tixogel for both
the DGEBA/D2000 and the DGEBA/MCDEA systems. How-
ever, for unclear reasons the authors could not determine
a gel time in the presence of OPTC18. Concerning the influ-
ence of network formation on organoclay dispersion, the
d-spacings of the clays at the beginning and the end of
polymerization are presented in Table 6. In the case of
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1139
Tixogen, both reactive mixtures have swelled the organ-
oclay already at the beginning of the reaction, since the
d-spacing increased from 20.2 up to 34Å. During the poly-
merizations the d-spacing remains the same, whatever the
curing agent used, demonstrating that the polymerization
of the epoxy/amine systems does not modify the dispersion
of Tixogen. The observations are very different inthe case of
OPTC18. Again the initial state of dispersion is good, but the
d-spacing further increases during isothermal reaction of
bothreactive mixtures. This demonstrates the possibility of
improving the quality of dispersion at the nanometer scale
during the polymerization of the network. The authors
noted that such improvement is not only due to the kind of
organoclay used nor to the epoxy systemchosen, but rather
is linked with interactions and chemical affinities between
the organoclay and the network precursors, as well as with
reaction and diffusion kinetics of the reactive systems.
In another study, Chin et al. [33] confirmed the for-
mation of exfoliated nanocomposites when DGEBA was
auto-polymerized with MMTs. Exfoliated nanocomposites
were also observed with DGEBA cured with MPDA of
less than equimolar concentration. However, as the curing
agent concentration increased, the extragallery crosslink-
ing dominated, resulting in intercalated nanocomposites.
Among the various parameters, the effect of processing
has also been investigated. Jiankun et al. [128] interca-
lated an organically modified MMT by epoxy resin by both
direct or solutionmixing. XRDpatterns indicatedthat inter-
calation was realized irrespective of the mixing method
applied. It was also concluded that prolonging the stirring
time above a certain level or using solution intercalation
would not further improve the intercalation. An important
finding was that the intercalated hybrids were quite stable
for storage. In order to prepare nanocomposites, a curing
agent was addedinto the hybridandmixedthoroughly. The
results indicated that if the organoclays can be exfoliated
at all, the exfoliation will be finished before the gel point of
the epoxy.
Koerner et al. [137] studied the impact of shear dur-
ing epoxy nanocomposite processing and demonstrated
that with proper mechanical processing conditions, uni-
formdispersion and a high degree of exfoliation is possible
in systems that typically only show intercalated mor-
phologies after traditional cure cycles. Conceptually, this
is achieved by maximizing epoxy viscosity by halting cure
before gelation and by compounding at sub-ambient tem-
peratures near the resin’s glass transition. High shear
forces, due to the high viscosity of the system, facilitate
homogenization of the layered silicate nanocomposite.
The so-called “high pressure mixing” (HPM) method,
involving clay processing in solvent (acetone) under high
pressure and also against solid obstacles, has been applied
by Liu et al. [130] for the preparation of epoxy nanocom-
posites. Using this method, nanoclays can be dispersed in
acetone and an epoxy solution to forma stable suspension,
in which the basal spacing of the nanoclay is increased.
Using TGDDM as the matrix, 4,4

-diaminodiphenyl sulfone
(DDS) as the hardener and an octadecyl amine modi-
fied MMT, nanocomposites of up to 7.5wt.% clay loading
were successfully synthesized with the HPM method. TEM
images showthat the agglomerates of nanoclays were bro-
ken down to form small particles consisting of several clay
platelets.
Similarly, the “slurry compounding” approach has
been developed for epoxy/clay nanocomposite preparation
using sodium MMT [138]. The most significant feature of
this technique is that very little (<5wt.%) organic modi-
fier is required to facilitate the exfoliation and dispersion
of the clay, reducing the cost of the nanocomposites. To
further reduce the cost of polymer/clay nanocomposites
Wang et al. prepared epoxy/crude clay nanocomposites
using the “slurry-compounding” technique. Aclay–acetone
slurry was mixed with required quantities of epoxy resin at
50

C. Acetone was then evaporated and a stoichiometric
quantity of the curing agent was added. The mixture was
degassed and dried, leading to the formation of ordered
exfoliated nanocomposites.
As for epoxy-based nanocomposites, the synthesis of
unsaturated polyester (UP)/layered silicate nanocompos-
ites involves two steps: first the mixing process, wherein
the UP linear chains are mixed with the curing agent
and layered silicate and second the curing process, during
which the crosslinking reaction takes place by decompos-
ing the initiators [139].
The synthesis of nanocomposites based on montmo-
rillonite and UP has been reported by different research
groups. In a typical example, Bharadwaj et al. [140]
described the preparation of crosslinked polyester/clay
nanocomposites by dispersing organically modified
MMT in pre-promoted polyester resin and subsequently
crosslinking the system using methyl ethyl ketone per-
oxide (MEKP) catalyst at several clay concentrations. The
formation of exfoliated nanocomposites was confirmed by
XRD and TEM.
In another study, montmorillonite was treated with
methacrylate-silane coupling agent in order to rend the
filler hydrophilic andreactive. Then, UPwas polymerizedby
thefreeradical polymerizationwiththemodifiedmontmo-
rillonite dispersed in it. The authors claimed the formation
of exfoliated structure, based on XRD and TEM findings
[127].
Furthermore, Suh et al. [139] reported on the formation
mechanism of UP nanocomposites. They used two differ-
ent kinds of MMT: a dodecyl ammonium bromide MMT
and Cloisite 20A, containing dimethyl dehydrogenated tal-
low ammonium as an organic modifier, and used two
different ways of mixing in order to prepare UP-based
nanocomposites, i.e. simultaneous mixing or sequential
mixing, where in the first step, pre-intercalates of the UP
andMMTnanocomposites (i.e. themixtures of UPandmod-
ified MMT) are prepared; and then the styrene monomer,
acting as the curing agent, is added with varying mixing
times from 15 to 180min. Finally, all mixtures were cured
at 80

C for 3h and post-cured at 120

C for 4h. The struc-
tures of UP/MMT nanocomposites were investigated by
XRD and TEM, whereas in order to investigate the forma-
tion mechanism of UP/MMT nanocomposites, the authors
used DMTA, solution rheometry and melt rheometry. The
results led the authors to suggest the following mecha-
nism of UP/silicate nanocomposite formation: The styrene
monomer moves more easily than uncured UP chains. This
may generate higher styrene monomer concentration in
1140 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 7
Polyurethane characteristics.
PU reference PU nanocomposite Polyol
Name Calculated M
n
Functionality
a
Wt.% EO
b
end
I NC-I Acclaim 2220 2000 2 15
II NC-II Acclaim 4220 4000 2 15
III NC-III Daltocel F435 4000 2.5 17
IV NC-IV Arcol 1374 6000 2.3 15
a
Approximated.
b
EO=ethylene oxide.
the MMT gallery than in any other part in a simultaneous
mixing system. If polymerization occurs in these condi-
tions, thetotal crosslinkingdensityof thesampledecreases,
because of the low concentration of styrene in uncured
UP linear chains. In the sequential mixing method, the
styrene monomer diffuses into the gallery of MMT interca-
lated with UP as time goes on. Therefore, it is thought that
crosslinking density and T
g
of UP/silicate nanocomposite
increase to some extent. Hence, the styrene monomers are
more easily dispersed inside and outside the silicate lay-
ers as mixing time increases. Therefore, the crosslinking
reaction takes place homogeneously inside and outside the
silicate layers, and crosslinking density reaches the degree
of crosslinking density of the cured pure UP.
Anumber of researchers have synthesizedpolyurethane
(PU)-based nanocomposites by the in situ polymeriza-
tion method. The first examples of elastomeric PU/clay
nanocomposites with improved properties compared to
the pristine polymer were reported by Wang and Pinnavaia
[141]. Conventional PU microcomposites are usually for-
mulated by premixing the inorganic component with the
polyol and then curing the mixture with the diisocyanate.
The approach of Wang and Pinnavaia to formpolyurethane
nanocomposites, therefore, focused on the solvation of the
organoclay by polyols. Interestingly, they found that mont-
morillonites exchangedwithlongchainoniumions (carbon
number >12) are easily solvated by several polyols that are
commonly used in polyurethane chemistry.
More recently, Yao et al. [142] reported the preparation
of a novel kind of PU/MMT nanocomposite using a mixture
of modified 4,4

-diphenyl methylate diisocyanate (MMDI),
modified polyether polyol (MPP) and Na
+
-MMT. In a typical
synthetic route, a known amount of Na
+
-MMT was blended
witha knownamount of MMDI andcuredat 78

Cfor 168h.
As measured through XRD, the gallery spacing of the lay-
ered clay is 1.1nm and increases to 1.6nm for the PU/clay
(21.5%) nanocomposites, indicating that the PUchains were
intercalated between the layers of the clay.
On the other hand, Mulhaupt and co-workers [143]
prepared PU nanocomposites from modified reactive
fluoromica clay. The dried organophilic mica was dis-
persed by means of a high shear mixer in trihydroxy-
terminated oligo-propylene-oxide. Stable and transparent
polyol dispersions were obtained and then cured with
diisocyanatophenylmethane and accelerated with 0.6wt.%
N,N-dimethyl-benzyl-amine.
Berta et al. [144] synthesized elastomer polyurethane
nanocomposites showing several degrees of dispersion,
using polyols with different molecular weight and func-
tionality (see Table 7) as well as methylenediphenylene
diisocyanate (MDI). For the preparation of nanocompos-
ites, the desired weights of polyol and organoclay were
mixed and then butanediol (chain extender), catalyst and
MDI were added in appropriate amounts. The system was
cured at 120

C for 3h and 80

C for 24h. The synthesis
of the PU/clay nanocomposites is schematically illustrated
in Fig. 21. Table 8 summarizes the d-spacings determined
by SAXS for the PU/clay nanocomposites. It is clear that
all the PU/clay materials are nanocomposites, as the 18Å
d-spacing, associated with the base organoclay has dis-
appeared. No peaks associated with clay gallery spacings
were observed for NC-II and NC-IV, indicating that in these
nanocomposites there is no longer sufficient ordering of
the clay platelets to produce a scattering peak. The authors
Fig. 21. Preparation of PU/clay nanocomposites [144]. Reproduced from Berta, Lindsay, Pans and Camino by permission of Elsevier Science Ltd., UK.
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1141
Table 8
d-Spacings for organoclay and PU/clay nanocomposites.
Material Clay d-spacing
Cloisite 30B (organoclay) 18
NC-I 65
NC-II None
NC-III 102
NC-IV none
postulated that this is due to the higher equivalent M
w
(M
n
/functionality) of the polyols in these nanocomposites.
According to the authors, this is of particular importance,
since it means that the dimensions of the polyol molecule
control the gallery spacing in the initial step of dispersing
the clay in polyol.
Finally, Gao et al. [145] prepared PU nanocompos-
ites, as well as their foams by in situ polymerization
and batch foaming with different modified MMTs. MMT
was modified by dibutyldimethoxytin (DBDMT) and, thus,
organophilic montmorillonite with a catalytic function,
denoted as MMT–Tin, was obtained. For the synthesis
of PU nanocomposites and foams, the authors used a
polymeric aromatic isocyanate based on diphenylmethane
4,4

-diisocyanate (MDI) and two trifunctional polyester
polyols. For PU nanocomposites, clay was first mixed with
one monomer and then the second monomer was added.
Catalyst was always added with polyol. After polymeriza-
tion under ambient conditions, the hybrid was post-cured
at 100

C for 4h. For reactive foaming of PU, a surfac-
tant as well as pentane (blowing agent) were also used.
The mixture of all ingredients was mixed and foaming
occurred in a closed plastic container with fixed volume
at ambient temperature, followed by curing at 100

C. By
XRD analysis it was found that the basal spacing of the
organoclay increased compared to MMT (d
001
=1.16nm),
because the gallery of MMT was expanded by molecular
chains of the modifier. However, the d-spacing decreased
from 1.77 to 1.43nm when MMT–OH was further mod-
ified by DBDMT—an effect attributed to conjugation of
hydroxyl groups from different layers. The authors stud-
ied the effect of the clay–monomer mixing sequence
on clay dispersion and found that the two-step process
offered better clay dispersion than the one-step approach,
wherein all ingredients were mixed simultaneously. Espe-
cially, premixing the functional clays with isocyanate
provides better clay dispersion, which was attributed to
the reaction between the isocyanate monomers and the
hydroxyl groups on alkyl chains of MMT–OH, causing an
increase of gallery spacing of clay. In the XRD spectra no
diffraction peak was observed for PU nanocomposite with
MMT–Tin. In fact, TEM analysis revealed that nanocom-
posites containing both MMT–OH and MMT–Tin exhibited
good clay dispersion, however MMT–Tin showed better
exfoliation and more uniform dispersion, probably due
to the intragallery catalysis of organotin. Turning to the
reactive foaming of PU nanocomposites, Fig. 22 shows
SEM images of the freeze fractured surface of PU foams.
It is clearly observed that the neat PU foam has fewer
cells and a larger cell size than PU nanocomposite foams
with 5wt.% organoclay, whereas there is little difference
Fig. 22. SEMmicrographs of PUfoams at cross-sections parallel to foamrising direction[145]. Reproduced fromGao, Lee, Widya and Macosko by permission
of Elsevier Science Ltd., UK.
1142 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 9
PLS nanocomposites prepared by in situ polymerization.
Nanocomposite Monomer Polymerization conditions Ref.
PA6/12-aminolauric acid modified
MMT
␧-Caprolactam Ring opening, 250–270

C, 48h [25]
PA12/Somasif ME 100 ␻-Amino dodecanoic acid (ADA) 280

C, 20bar, 9.5h (after an initial swelling stage) [44]
PCL/aminolauric acid modified MMT ␧-Caprolactone Ring opening, 170

C, 48h [117]
PCL/Cr
3+
exchanged fluorohectorite ␧-Caprolactone 100

C, 48h [118]
PE/MMT with fixed Ti-based
Ziegler-Natta catalyst
Ethylene 30–50

C, 4bars [105]
PMMA/OMLS MMA Free radical, 80

C, 5h [98,99]
PS/OMLS Styrene Free radical, 100

C, 16h [98,99]
PS/vinylbenzyl-trimethyl-ammonium-
MMT
Styrene Free radical, 80

C, 5h, AIBN [100]
PET/o-MMT Ethylene glycol, terephthalic acid derivatives [106]
Epoxy/o-MMT DGEBA Crosslinking, diamine curing agent [125]
Epoxy/octadecylammonium modified
MMT
DGEBA, TGAP, TGDDM DETDA curing agent [126]
UP/MMT treated with a
mathacrylate-silane coupling agent
Unsaturated polyester Free radical crosslinking [127]
between MMT–Tin/PU and MMT–OH/PU nanocomposite
foams in terms of cell size and density. The appearance
of a shoulder at very low angle in the XRD patterns of
nanocomposite foams implies that clay orientation and
dispersion is somewhat affected by the foaming process.
However, as the authors noted, the detailed mechanism of
hownanoparticles influence cell morphologyneeds further
investigation.
A list of representative thermoset and thermoplastic –
based nanocomposites prepared through in situ polymer-
ization is given in Table 9.
5.4. Polymer melt intercalation
5.4.1. Introduction and advantages of the technique
For most technologically important polymers, both
in situ polymerization and intercalation from solution
are limited because neither a suitable monomer nor
a compatible polymer–silicate solvent system is always
available. Moreover, they are not always compatible with
current polymer processing techniques. These disadvan-
tages drive the researchers to the direct melt intercalation
method, which is the most versatile and environmentally
benign among all the methods of preparing polymer–clay
nanocomposites (PCNs) [4,146].
As already mentioned, nanocomposite synthesis via
polymer melt intercalation involves annealing, usually
under shear, of a mixture of polymer and layered silicate
above the softening point of the polymer. During anneal-
ing, polymer chains diffuse fromthe bulkpolymer melt into
the galleries between the silicate layers, as shown in Fig. 23
[13,15,47].
The advantages of formingnanocomposites bymelt pro-
cessing are quite appealing, rendering this technique a
promising new approach that would greatly expand the
commercial opportunities for nanocomposites technology
[14,15,46,47]. If technically possible, melt compounding
would be significantly more economical and simpler than
insitupolymerization. It minimizes capital costs because of
its compatibility with existing processes. That is, melt pro-
cessing allows nanocomposites to be formulated directly
using ordinary compounding devices such as extruders
or mixers, without the necessary involvement of resin
production. Therefore, it shifts nanocomposite production
downstream, giving end-use manufacturers many degrees
of freedom with regard to final product specifications (e.g.
selection of polymer grade, choice of organoclay, level of
reinforcement, etc.). At the same time, melt processing
is environmentally sound since no solvents are required
[14,15]; and it enhances the specificity for the intercalation
of polymer, by eliminating the competing host-solvent and
polymer–solvent interactions [29].
Thus, the majority of thermoplastic polymers, includ-
ing PA [14,36,51,147], PET [148] (and recycled PET [149]),
EVA [81,150], thermoplastic polyurethane [88], polyolefins
[111,151], PLA[152–154], PCL [155,156], etc., have beenused
to study nanocomposite formation by melt intercalation.
Before discussing in detail the factors affecting clay
delamination during melt blending as well as the degrada-
tion issues involved in this technique, it is worth describing
Fig. 23. The ‘melt intercalation’ process [35]. Reproduced from Beyer by permission of Elsevier Science Ltd., UK.
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1143
a slightly modified approach aiming to facilitate exfolia-
tion and consisting of melt processing the polymer with a
pre-intercalated clay or slurry.
Following such an approach, Liu and Wu [146] prepared
a co-intercalated clay, by absorbing epoxide compound
between the silicate layers. They expected strong inter-
action between PA66 and this new kind of modified clay,
since Ishida had successfully prepared PA6, PA12 and other
polymer nanocomposites usingsimilarlymodifiedclay. The
preparationof the newkindof co-intercalatedorganophilic
clay used was as follows. Na
+
-MMT was dispersed in hot
water using a homogenizer. Then, hexadecyltrimethylam-
monium bromide, dissolved in hot water, was poured
into the Na
+
-MMT–water solution with vigorous stirring
for 30min to yield a white precipitate, which was col-
lected and washed with hot water. After thorough drying
in a vacuum oven, the precipitate was ground into a
product termed PrEMMT. PrEMMT and epoxy resin GY
240 were mixed in a Haake Reocorder 40 mixer for 1h;
thus the co-intercalated clay, termed EMMT was obtained.
Subsequently, a twin-screw extruder was used for the
preparation of nanocomposites. In XRD patterns, Na-MMT
showed a characteristic diffraction peak corresponding to
the (001) plane at 1.24nm. PrE-MMT showed a 1.96nm
basal spacing in the XRD pattern, while the basal spac-
ing of E-MMT was 3.77nm. The obviously larger layer
distance of E-MMT demonstrates the advantage of co-
intercalated organophilic clay. As the authors pointed out,
the alkylammonium ion exchange enables conversion of
the hydrophilic interior clay surface to hydrophobic and
increases the layer distance as well. This is the condition
of PrEMMT. In this organophilic environment, epoxy resin
then diffuses into the clay galleries to further increase the
layer distance. In addition, the co-intercalated clay also
brings the active functional group into the PA66 system.
Therefore, a better dispersion effect can be expected for
EMMT. Infact, usingtheaforementionedprocedure, Liuand
Wu obtained well exfoliated nanocomposites when clay
loading was less than 7wt.%.
Alsointhe case of polyolefins, the use of a swelling agent
(a monomer or polymer known to intercalate/exfoliate
smectite clay) next to the surfactant placed at the clay
surfaces after an ion-exchange reaction has allowed the
preparation of nanocomposites. Present in small amounts,
the swelling agent serves to swell the clay layers, allow-
ing the organic matrix to be virtually any polymer [2].
As an example, Wolf et al. [157] modified a commercially
available organo-ammonium-exchanged montmorillonite,
using an organic swelling agent (with boiling point
between 100 and 200

C, such as ethylene glycol, naph-
tha or heptane) in order to increase the interlayer spacing.
The swollen organo-modified clay was then compounded
with PP in a twin-screw extruder at 250

C. The swelling
agent was volatilized during extrusion, leading to the for-
mation of nanocomposites. Similarly, Liu and Wu [158]
reported the preparation of PP nanocomposites via melt-
compounding, using a type of co-intercalated organophilic
clay. One of the co-intercalation monomers is unsaturated,
so it could tether on the PP backbone through a grafting
reaction. The co-intercalated organophilic clay (EM-MMT)
was prepared as follows. Hexadecylammonium modified
MMT (C16-MMT) was mixed with epoxypropyl methacry-
late in a Haake mixer for 1h. Before mixing with clay,
the initiator for the grafting reaction, dibenzoyl peroxide
(BPO) and a donor agent were dissolved in epoxypropyl
methacrylate. The nanocomposites were prepared using
a twin-screw extruder with a screw speed of 180rpm
operating at 200

C. WAXD patterns and TEM observations
establishedthat the larger interlayer spacing andthe strong
interaction caused by grafting can improve the dispersion
effect of silicate layers in the PP matrix.
In another study, Zheng et al. [159] used an oligomer-
ically modified clay, prepared by ion-exchange with
the oligomer prepared from maleic anhydride (MA),
styrene (ST) and vinylbenzyltrimethylammonium chlo-
ride (VBTACl) terpolymer, herein called MAST, to prepare
PS/clay nanocomposites by melt blending. The synthetic
route for the formation of the terpolymer MAST is depicted
in Fig. 24. Thereafter, a portion of MAST oligomer, dis-
solved in acetone was added drop-wise to a dispersion
of clay in distilled water and acetone. A precipitate
(MAST hectorite clay) formed immediately. Nanocom-
posites were subsequently prepared by melt blending
in a Brabender Plasticorder at 60rpm and 190

C for
15min. XRD measurements indicated a mixed interca-
lated/delaminated structure for the MAST modified clay,
whereas no peaks were observed for the PS/MAST. By com-
bining XRD and TEM analyses the authors concluded that
the hybrids formed were characterized by a mixed immis-
cible/intercalated/delaminated structure.
Recently, Hasegawa et al. [160] reported a novel
compounding process for the preparation of PA6/MMT
Fig. 24. The synthetic route for the formation of the terpolymer MAST [159]. Reproduced from Zheng, Jiang and Wilkie by permission of Elsevier Science
Ltd., UK.
1144 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
nanocomposites, using a Na
+
-MMT water slurry as analter-
native for organically modified MMT. In this process, the
Na
+
-MMT slurry was blended with PA6 using an extruder,
followed by removal of the water. WAXD patterns and TEM
observations clearly indicate the exfoliation of MMT layers
in the PA6 matrix but the final properties of PA6/Na
+
-MMT
nanocomposites were nearly equal tothose of conventional
PA6/MMT nanocomposites prepared by dry compounding
with MMT. Fig. 25 shows schematically dispersion of the
Na
+
-MMT silicate layers of the clay slurry into the PA6
matrix during compounding by an extruder. According to
this study, the exfoliation of silicate layers into the PA6
matrix occurs as follows: (a) the clay slurry is first pumped
into the melting matrix under vigorous shear; (b and c) the
clay slurry reduces to finer drops during blending and, at
the same time, the water of the slurry drops begins to evap-
orateincontact withthePA6melt; (d) theevaporatedwater
is removed under vacuum, and silicate layers are dispersed
into the PA6 melt as monolayer or as a few layers. The
dispersion of silicate layers in this process is quite differ-
ent from that of conventional compounding process using
organophilic clay, where polymer chains first intercalate
into the stacked silicate galleries and then exfoliate into
the matrix. In this process, the exfoliated silicate layers are
directly fixed in the polymer matrix without aggregation of
the silicate layers.
5.4.2. Factors affecting polymer melt intercalation
Predicting whether or not a polymer–silicate nanocom-
posite will form through melt compounding is not
straightforward, as a wide variety of factors influence the
outcome. These include energy changes, arising from the
confinement of the polymer within the silicate, the expan-
sion of the spaces between the layers of the silicate, and
those associated with intermolecular interaction among
silicate surface, tethered chain and polymer. With a view
to improving predictability, attempts have been made to
model the behavior of hybrids that formas a result of direct
melt intercalation with organically modified clays and to
assess the parameters required to favor intercalation [56].
Some of the questions that need to be addressed are, for
example, why do certain polymer–silicate systems favor
intercalated hybrids, others delamination, and yet others
are immiscible, leading to microcomposites? How does
packing density and chain length of the alkylammonium
chains in the organosilicate layer, charge of the silicate or
specific groups on the polymer (or the alkyl chains) affect
hybrid formation and miscibility? How does temperature
or shear affect processing? And finally, how does the type
of bonding at the polymer/silicate interface (i.e. hydro-
gen, dipole–dipole, van der Waals or covalent in which the
alkylammoniumchains become part of the polymer chain)
affect the properties of the hybrid [4].
Fig. 25. Schematic figures depicting dispersion of the Na
+
-MMT slurry into nylon-6 during compounding [160]. Reproduced from Hasegawa, Okamoto,
Kato, Usuki and Sato by permission of Elsevier Science Ltd., UK.
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1145
5.4.2.1. Thermodynamic aspects. To address some of these
questions Giannelis et al. focused on the thermodynam-
ics governing nanocomposite formation. To that end,
theydevelopedamean-field, lattice-basedthermodynamic
model. Assuming the configurations and interactions of
the various constituents are independent, the free energy
change of hybrid formation can be separated into inde-
pendent enthalpic and entropic terms. The entropic term
is the sum of the configurational changes associated with
the polymer and the silicate (including the alkylammo-
nium chains in organosilicates). Configurational changes
of the silicate are determined using a modified Flory-
Huggins lattice model in which the occupation of the
lattice is weighted to simulate the preferred orienta-
tions of the alkylammonium cations in the presence
of two impenetrable surfaces (silicate layers). The con-
finement of the intercalated polymer chains is similarly
approximated using a self-consistent field treatment of
a random-flight polymer with excluded volume between
two surfaces. For the enthalpic term a modified mean-
field, site-fraction approach, where the number of contacts
per lattice site is replaced by an interaction area per lat-
tice site, is used. This modified approach allows one to
express the interaction parameter as energy per area and
may be approximated by interfacial or surface energies
[1,4].
In general, the conclusions of the mean-field model
developed, whichare widelyacceptedbyother researchers,
may be summarized as follows. Since the spacing (or
“gallery”) betweenthe sheets is onthe order of 1nm, which
is smaller than the radius of gyration of typical polymers,
there is obviously a large entropic barrier that inhibits the
polymer from penetrating this gap and intermixing with
the clay [9,11,147]. In this case, of course, unlike the solu-
tion intercalation method, the decreased entropy due to
the confinement of the polymer is not compensated by
an increase due to desorption of solvent molecules. How-
ever, this entropy loss, associated with the confinement
of a polymer melt is not prohibitive to nanocompos-
ites formation, because an entropy gain, associated with
layer separation and greater conformational energy of the
aliphatic chains of the alkylammonium cations, balances
the entropy loss of polymeric intercalation, resulting in
a net entropy change near zero. Thus, from the theoreti-
cal model, the outcome of hybrid formation via polymer
melt intercalation depends on energetic factors which may
be determined from the surface energies of the polymer
and OMLS. Thus, whether a mixture of polymer and OMLS
produces an exfoliated or intercalated nanocomposite or a
conventional microcomposite depends critically upon the
characteristics of the polymer and the OMLS, including the
nature of the polymer as well as the type, packing den-
Fig. 26. (a) Molecular structure and nomenclature of amine salts used to organically modify sodium montmorillonite by ion exchange. The symbols M:
methyl, T: tallow(predominantlycomposedof chains with18carbons (∼65%)), HT: hydrogenatedtallow, HE: 2-hydroxy-ethyl, R: rapeseed(consistinglargely
of chains with 22 carbons (∼45%)), C*: coco (product made fromcoconut oil, consisting predominantly of chains with 12 carbons (∼48%)), and H: hydrogen
designate the substituents on the nitrogen. (b) Organoclays used to evaluate the effect of structural variations of the amine cations on nanocomposite
morphology and properties [51]. Reproduced from Fornes, Yoon, Hunter, Keskkula and Paul by permission of Elsevier Science Ltd., UK.
1146 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 10
Interlayer spacing of various modified montmorillonites and the resulting composites obtained with EVA (10.76mol% vinyl acetate).
Code Cation Interlayer spacing
In modified clay In EVA composite
Mont-Na Na
+
12.2 12.6
Mont-2CN2C
18
(CH
3
)
2
N
+
(C
18
H
37
)
2
31.9 40.3
Mont-NC
11
COOH H
3
N
+
C
11
H
22
COOH 16.3 16.7
Mont-3CNC
21
COOH (CH
3
)
3
N
+
C
21
H
42
COOH 20.1 20.1
sity and size of the organic modifiers on the silicate surface
[1,2,4,41,47,147,161].
It is worth mentioning that even when the surfactant
chains are miscible with the polymer matrix, a complete
layer separation depends on the establishment of very
favorable polymer–surface interactions to overcome the
penalty of polymer confinement. If this is not the case,
good dispersion of the particles may be achieved by the
help of strong shear forces during the preparation and
processing of the nanocomposite materials; the system,
however, remains thermodynamicallyunstable. This canbe
observed, e.g. in the case of PP or PE nanocomposite mate-
rials prepared by melt mixing of the polymers with surface
modified clay using high shear forces. If such a mixture is
heated (e.g. during processing) to temperatures above the
melting temperature, a (partial) re-agglomeration of the
particles takes place [2] immediately.
5.4.2.2. The effect of layered silicates and their organic mod-
ification. In order to achieve clay exfoliation, the interlayer
structure of the OMLS should be optimized to maximize
the configurational freedom of the functionalizing chains
upon layer separation and to maximize potential interac-
tionsites at the interlayer surface [47]. Therefore, as already
mentioned in Section 3.2, the organic modification of the
clay is a very important factor affecting the resulting struc-
tures. Inthis respect, the type of surfactant, the chainlength
and the packing density may play an important role.
In a detailed study, Fornes et al. [51] used various amine
compounds to exchange the sodium ion of native mont-
morillonite clay. The selection of amines shown in Fig. 26a
permitted the authors to make six structural comparisons,
as presented in Fig. 26b. Among different variables, three
surfactant structural issues were found to significantly
affect nylon 6 nanocomposite morphology and properties:
decreasing the number of long alkyl tails from two tallows
to one, use of methyl rather than hydroxy-ethyl groups, and
use of an equivalent amount of surfactant with the mont-
morillonite, as opposed to adding an excess, led to greater
extents of silicate platelet exfoliation. However, the authors
emphasized that these effects may be specific to nylon 6
matrices.
In fact, Hotta and Paul [162] prepared PE/clay nanocom-
posites by melt compounding various combinations of
LLDPE-g-MA, LLDPE and two organoclays in a co-rotating
twinscrewextruder witha barrel temperature set at 200

C
and a screw speed of 280rpm. Nanocomposites based on
the organoclay having two alkyl chains are superior to the
nanocomposites based on the organoclay having one alkyl
chain, in terms of clay dispersion. This was attributed to
the relatively better affinity of LLDPE for the alkyl chains
than for the silicate surface. Therefore, it is reasonable that,
in this case, increasing the number of alkyl chains should
leadtobetter dispersionof theorganoclay. As deducedfrom
these findings, the conditions favoring exfoliation may be
quite different depending on the specific system investi-
gated.
The effect of clay organo-modification on the mor-
phology of EVA-based nanocomposites has also been
investigated. In a relevant study EVA was melt mixed
with two clays: Cloisite Na
+
and Cloisite 30B (modified
with methyl-tallow-bis-2-hydroxyethyl ammonium ions).
Mixing was performed in a Brabender Laboratory Mixer
at 160

C. Even though, quite surprisingly, XRD measure-
ments revealed a decrease in clay interlayer spacing after
blending with EVA, for both montmorillonites, the authors
claimed that nanocomposites were formed in the case of
Cloisite 30B, on the basis of TEM observations. However,
microstructures were obtained in the case of Cloisite Na
+
[163].
Zhang et al. [164] also synthesized EVA/clay nanocom-
posites through a melt blending method, using differ-
ent EVAs and octadecyltrimethyl ammonium, dioctade-
cyldimethyl ammonium, and tricetadecymethyl ammo-
nium ion exchange MMTs. Again, EVA chains intercalated
into the organo-modified MMT sheets, but in the case of
sodium montmorillonite (Na
+
-MMT) there was no such
intercalation.
Moreover, differences in the intercalation behavior have
also been observed between clays modified with differ-
ent surfactants. For example, two different EVAs containing
12 and 19% vinyl acetate, abbreviated as EVA-12 and EVA-
19, respectively, were processed into their nanocomposites
with synthetic clay fluorohectorite (FH) organo-modified
by octadecyl ammonium ion (ODA) and aminododecanoic
acid. These materials were melt-blended at 120

C in
a twin screw microcompounder to obtain nanocompos-
ites. Octadecyl ammonium ion intercalated FH (FH-ODA)
formed a delaminated nanostructure, whereas ammonium
dodecanoic acid intercalated FH formed a microcompos-
ite. This means that the octadecyl ammonium ion is more
compatiblethanammoniumdodecanoic acidwheninterca-
lated inFHduring the synthesis of EVA/FHnanocomposites
[165].
In another study by Alexandre et al. [166], several
exchanging cations bearing either simple alkyl chains
or aliphatic chains terminated by a carboxylic group
were studied for modifying montmorillonites as described
in Table 10. Nanocomposites were only formed when
EVA copolymers were melt mixed with unfunctional-
ized organo-montmorillonites, such as montmorillonite
exchanged with dimethyldioctadecyl ammonium (Mont-
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1147
Table 11
Characteristics of the various studied clays.
Filler Clay type Interlayer cations Ammonium content
a
(wt.%) Interlayer distance
b
(Å)
Cloisite Na Montmorillonite Na
+
0 12.1
Cloisite 20A Montmorillonite (CH
3
)
2
N
+
(hydrogenated tallow)
2
29.2 22.1
Cloisite 25A Montmorillonite (CH
3
)
2
N
+
(hydrogenated tallow)(2-ethylhexyl) 26.9 20.7
Cloisite 30B Montmorillonite (CH
3
)
2
N
+
(tallow)(CH
2
CH
2
OH)
2
20.3 18.5
Nanofil 757 Montmorillonite Na
+
0 12.2
Nanofil 15 Montmorillonite (CH
3
)
2
N
+
(hydrogenated tallow)
2
28.9 ∼29 (broad)
Somasif ME100 Fluoromica Na
+
0 12.2
Somasif MAE Fluoromica (CH
3
)
2
N
+
(hydrogenated tallow)
2
40.8 31.1
Tallow: linear alkyl chains (C18 (65%), C16 (30%), C14 (5%) with ∼40% mono-unsaturated chains.
a
Determined by thermogravimetric analysis under helium atmosphere.
b
Determined by X-ray diffraction on as-received clays.
2CNC18), whereas with the same EVA matrix, the use of
ammonium cations functionalized with carboxylic groups
did not lead to the formation of an intercalated structure,
indicating that functionalization of the clay interlayer is
detrimental to the intercalation process.
In order to determine the effect of the nature of the
clay and clay organic modifier on nanocomposite mor-
phology and properties, Peeterbroeck et al. [167] used EVA
copolymer containing 27wt.% VA and various commercial
organoclays, presented in Table 11. EVA and clay (5wt.%)
were compounded in a two-roll mill for 12min at 140

C.
The results of XRD analysis are reported in Table 12. Evi-
dently, while all the tested organo-modified clays result in
both intercalated and exfoliated structures, the nanocom-
posites basedonCloisite 30Bdisplay the highest exfoliation
and clay stacking destruction, characterized by the absence
of a characteristic XRD peak. This better filler dispersion
might arise from interactions between the acetate func-
tions of EVA and the hydroxyl-bearing ammonium cations
that modify Cloisite 30B. It is also worth noticing that,
whatever the clay nature, dispersion of unmodified clays
(Cloisite Na, Nanofil 757 or Somasif ME100) in EVA is char-
acterized by the formation of microcomposites, since no
significant increase in the basal spacings recorded for these
materials can be observed. When comparing Cloisite 20A,
Nanofil 15 and Somasif MAE, characterized by clays of var-
ious origins but modified by the same ammonium cation,
one can remark that the final interlayer spacings are very
close, independent of the interlayer spacing of the clays
used or the amount of modifier.
Concerning the conformation of surfactant chains, it is
generally accepted that at low interlayer packing densi-
ties of the organic modifier, the chains adopt a disordered
monolayer arrangement. As the packing density increases,
the chains adopt more extended conformations (and thus
larger initial galleryheights), ultimatelyresultingina solid-
like paraffinic arrangement of the chains [47].
According to Vaia and Giannelis, the optimal structure
appears toexhibit achainarrangement slightlygreater than
a pseudo-bilayer. That is, there is an optimum interlayer
structure favoring hybrid formation that is intermedi-
ate between a disordered monolayer and a solid-like
paraffinic arrangement of aliphatic chains. The difference
between primary and quaternary ammonium head groups
did not appear to be a predominant factor, at least for the
polystyrene intercalation, which they examined [47].
Ginzburg et al. calculated phase diagrams and showed
that as the length of the grafted chains and/or their density
is increased, the miscibility betweenthe clay sheets andthe
polymer is improved and the resulting mixture can exhibit
exfoliated structure for a range of clay volume fractions.
According to their work, for short surfactant molecules, the
polymer is unable to penetrate the gallery between the clay
surfaces, andthe equilibriummorphology becomes immis-
cible (two-phase) for most values of the Flory-Huggins
parameter and the clay volume fraction. Only in the limit of
large negative , (strong attraction between grafted chains
andpolymer melt) cansucha composite become exfoliated
[9].
Next to these studies, Balazs and co-workers proposed a
theoretical model that uses numerical self-consistent field
calculations to study the effect on morphological behav-
ior of varying the surfactant–matrix enthalpic interaction,
surfactant coverage, and surfactant length. The model
indicated that longer surfactants (clay organic modifiers)
promote intercalation of matrix molecules in the modi-
fied clay galleries by providing a reduction in the entropic
penalty to the intercalating polymer. However, very high
degrees of surfactant coverage on the silicate surface make
intercalation and exfoliation unfavorable [168].
Table 12
Interlayer spacing variation as obtained from diffraction peaks measured by XRD on clays and the resulting melt-blended EVA composites.
Filler Filler interlayer distance (Å) Composite interlayer distance(Å) Interlayer distance variation (Å)
Cloisite Na 12.1 12.2 0.1
Cloisite 20A 22.4 38.7 16.3
Cloisite 25A 20.7 36.8 16.1
Cloisite 30B 18.5 – –
Nanofil 757 12.2 12.2 0
Nanofil 15 Ca 29 (broad) 40.2 Ca 11
Somasif ME100 12.2 12.3 0.1
Somasif MAE 31.1 40.4 9.3
1148 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 27. Illustration, for a bimodal surfactant brush, of one possible outcome on longer surfactant conformation of the densely packed brush of a shorter
surfactant [169]. Reproduced from Kurian, Dasgupta, Beyer and Galvin by permission of John Wiley & Sons Inc.
This last conclusion is consistent with that from the
experimental work of Kurian et al. These authors ini-
tially prepared organically modified clays by exchanging
most cation exchange positions in Na
+
-MMT with custom-
madequaternaryammoniumionterminatedPSsurfactants
of five different molecular weights. They showed that
high levels of modification resulted in dense polymer
brushes on the clay surfaces, preventing intercalation of
PS homopolymer molecules. Phase-separated morpholo-
gies were observed in all cases, regardless of surfactant
molecular weight. This was explained within the frame-
work of well-established theories of dewetting from dense
polymer brushes [169].
Thus, in a later study the authors described a new
scheme termedmixedcoverage, whereinthe silicate is mod-
ified with a mixture of PS-based surfactants of different
lengths, to create a silicate surface grafted with a bimodal
brush. Texturing of the silicate surface was expected to
allow intercalation of matrix molecules in the galleries
by providing a favorable entropic gain to the intercalat-
ing polymer through interaction with the longer grafted
molecules, and reduced enthalpic interaction with the clay
surface. However, XRD data indicated that the samples
remained in a phase-separated morphology, with no indi-
cation of intercalation or exfoliation of the layered silicate
in the PS matrix. To explain this result, the authors sug-
gested that, despite the bimodal nature of the brushes in
this experiment, it is still possible that the brush is still
effectively dense (only 17% of the exchangeable cations
were replaced by the longer surfactant and the remaining
83% by the short surfactant), making the long surfactant
fraction ineffective in fostering wetting and intercalation.
Fig. 27 shows a schematic of this scenario. In Fig. 27a, a
long surfactant is illustrated at low coverage over a surface
that is repulsive to the polymer matrix (PS homopolymer).
In this case, the surfactant will stretch away from the sur-
face until the energy required to stretch is no longer less
than that of the repulsive enthalpic interactions. This is the
scenario for typical surfactant-modified clay at very low
coverage. In the bimodal brush, the shorter surfactant at
full coverage (83%) effectively replaces the silicate surface.
As illustrated in Fig. 27b, the surface now can be thought
of as being comprised of the dense brush. When a small
fraction of those surfactants are replaced with longer sur-
factants, the situation may become something like that
illustrated in Fig. 27c. The length of the longer surfactant
is still important, but the conformation of the longer sur-
factant must also be considered. If the mixed surfactants
used to create the textured surface do not differ much in
their lengths, one has effectively a short surfactant at high
coverage. As the molecular weight difference between the
two surfactants increases, the surfactant present in lesser
amount becomes effectively longer, but still it is possible
that it does not actually assist in the wetting and intercala-
tion processes, because there is nowno enthalpic repulsion
causing the surfactant to stretch away fromthe silicate sur-
face. This would result in the scenario illustrated in Fig. 27c,
where the longer surfactant nowremains close to the brush
of chemically similar molecules and does not aid interca-
lation by interacting with matrix polymer molecules [169].
This work clearly demonstrates that when tailoring the sil-
icate characteristics that favor intercalation or exfoliation,
one has to simultaneously consider different factors, e.g.
the surfactant chain length and packing density.
Summarizing the above, the simple organic modi-
fication of the clay through ion-exchange reactions is
not always enough to achieve nanocomposite formation.
This is because an ideal compatibilization agent between
two intrinsically incompatible components should have
(combined in one molecule) parts which mix thermody-
namically stable and easily with both components [2]. In
fact, Balazs et al. likened the situation found in nanocom-
posites to the behavior of fiber-reinforced composites. The
clay substrate represents the surface of a fiber and the “sur-
factants” represent a coating, which is applied to enhance
the adhesion between the fiber and polymer matrix [11].
Unfortunately, surfactants fulfill only partly this require-
ment. That is, the ionic part interacts certainlyina favorable
way with the charged surface of the sheet-like clay par-
ticles; however, the long alkyl tail displays only a limited
compatibility with the polymer chains. Second, as stated
above, polymer–surface interactions are also important for
a complete andstable dispersion. Therefore, better compat-
ibilization should be expected from “macro-surfactants”
like block or graft copolymers combining blocks which can
interact with the solid particle surface and with the matrix
polymer – thus meeting most of the requirements listed
above (Fig. 28) [2]. For example, the clay compatible block
could be PEO. The PEOblock acts as a complexing group for
thesodiumions locatedbetweenthesheets of theinorganic
clay. Therefore, an ion-exchange reaction may not even be
necessary. Alternatively, the block copolymer may also be
used as a “co-surfactant” with the surfactant on the sur-
face of organo-clays, thus fine-tuning the thermodynamic
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1149
Fig. 28. Schematic picture of the action of block copolymer for an exfolia-
tion of clay sheets within a polymeric matrix [2]. Reproduced fromFischer
by permission of Elsevier Science Ltd., UK.
characteristics of the clay surface with respect to the poly-
mer matrix material. Toyota, for example, developed such
a process for the incorporation of MMT sheets into PP. In
this procedure, a first ion-exchange step with double tailed
ammonium cations is followed by a further incorporation
of end-group modified (grafted) oligomeric polypropylene
between the organically modified sheets and a subse-
quent mixing with the matrix polymer. This process
relies on the compatibilizing action of the functionalized
oligomers [2].
Finally, it is important to note that, apart from the clay
chemistry, the amount of clay incorporated in the poly-
mer matrix also plays a determining role. In fact, it is
often reported that while low clay loadings favor exfoli-
ation, higher amounts of clay (usually above 10wt.%) allow
only intercalation of polymer chains in the layered sili-
cate galleries to occur. Further dispersion of clay platelets
is hindered, most probably due to percolation phenomena
[2,170].
5.4.2.3. The effect of the polymer matrix. Polymer matrix
parameters mayalsodetermine the outcome of melt blend-
ing a polymer and a layered silicate.
Inthis context, the effect of the matrix molecular weight
has been considered. Early work by Vaia and Giannelis
showed that, for statically annealed PS samples, the final
hybrid structure is independent of the molecular weight of
the polymer. Only the time needed for intercalation to pro-
ceed was different, going from 6h for M
w
of 30,000 to 24h
for 90,000 and 48h for 400,000 at 160

C. Clearly, high M
w
PS decreases the kinetics of intercalation by decreasing the
diffusivity of the polymer in the interlayer. However, the
authors noted that additional experimental work examin-
ing the intercalationbehavior of a broader range of polymer
molecular weights coupled with dynamic blending of con-
stituents to enhance equilibriummixing would be required
to further explore this issue [47].
In another study, Fornes et al. [14] prepared nanocom-
posites based on three different molecular weight grades
of nylon 6 (low, medium and high) using a co-rotating
twin screw extruder. WAXD and TEM results collectively
reveal a mixed structure for the LMW based nanocom-
posites, having regions of intercalated and exfoliated clay
platelets. Qualitative TEM observations were supported by
a quantitative analysis of high magnification TEM images.
The average number of platelets per stacks was shown
to decrease with increasing molecular weight, thereby
revealing larger extents of clay platelet exfoliation for
the nanocomposites in the order HMW>MMW>LMW
composites. As a result, tensile tests revealed superior
performance for the higher molecular weight nylon 6
composites, particularly those based on HMW, as will be
discussed in Section 6.1.2.
However, probably the most critical condition for the
formation of intercalated and especially exfoliated hybrids
via polymer melt intercalation, is the presence of polar
type interactions (i.e. other than Van der Waals forces).
Therefore, polar polymers containing groups capable of
associative type interactions, such as Lewis acid-base inter-
actions or hydrogen bonding, favor the intercalation of
macromolecular chains into the silicate galleries [47,49],
while in the case of apolar polymer matrices, clay delam-
ination typically requires the use of compatibilizers, as
discussed in the following paragraph.
A good example demonstrating the importance of polar
interactions is the formation of EVA-based nanocompos-
ites via melt intercalation. It is well established that the
presence of polar groups (ester groups of the vinyl acetate
moieties) all along the chains improves the ability of these
polymers to intercalate in organo-modified montmoril-
lonites [1]. Therefore, several studies have focused on the
effect of the vinyl acetate content on the dispersion of
clay nanoplatelets. In general, it has been observed that
the higher the vinyl acetate content the larger is the basal
spacingincreaseof theclay, inducingtheformationof inter-
calated to exfoliated nanostructures.
In a representative study, Chaudhary et al. [171]
prepared EVA-based nanocomposites via melt intercala-
tion using an intermeshing counter-rotating twin screw
extruder. They used EVA copolymers with 9, 18 and 28% VA
(vinyl acetate) and two organo-modified clays: Cloisite 15A
(C15A), which is more suitable for the less polar EVA9 due
to long aliphatic chains in C15A, and Cloisite 30B (C30B),
suitable for the more polar polymers, like EVA18 or EVA28.
They prepared composites with filler level varying from2.5
to 7.5wt.%, and subsequently characterized the structures
obtainedby WAXDandTEM. The results indicatedthat only
intercalation occurred in the case of the less polar EVA9,
while the clay was exfoliated in the more polar EVA18 and
EVA28. Therefore, the authors concludedthat anincrease in
the content of polar VAgroups inEVA18andEVA28as com-
pared to EVA9, which lowered the thermodynamic energy
barrier for clay–polymer interaction, possiblyalloweda rel-
atively higher number of polymer chains to migrate and
stabilize within the clay platelet and form partially exfoli-
ated and/or disordered intercalated states.
It is worthmentioning that despite the presence of polar
groups in EVAs, polymer compatibilizers have been used in
the preparation of EVA-based nanocomposites. For exam-
ple, Li andHa [172] selecteda maleic anhydride graftedEVA
containing 18mol% VA to process its nanocomposites with
organo-modified Cloisite through melt blending at 175

C
andfoundthat the dispersionof Cloisite inthe maleic anhy-
1150 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
dride grafted EVA was much better than in the simple EVA
matrix.
5.4.2.4. The effect of melt intercalation processing conditions.
Melt processing conditions play a key role in achieving
high levels of exfoliation. Indeed, nanocomposites have
been formed using a variety of shear devices (e.g. extrud-
ers, mixers, ultrasonicators, etc.), among which twin screw
extruders have proven to be most effective for the exfolia-
tion and dispersion of silicate layers [14].
The screws in twin screw extruders intermesh so that
the relative motion of the flight of one screw inside the
channel of the other acts as a paddle that pushes the mate-
rial from screw to screw and from flight to flight. Two
different patterns for intermeshing twin-screw extruders
are possible. In the co-rotating pattern the screws rotate
in the same direction and the material is passed from one
screw to another and follows a path over and under the
screws. This gives high contact with the extruder barrel,
which improves the efficiency of heating. The path also
ensures that most of the resin will be subjected to the same
amount of shear as it passes between the screws and the
barrel. The self-wiping nature of the co-rotating screws is
much more complete than in the counter-rotating system,
thus in the co-rotating case there is less likelihood that
material will become stagnant. In the counter-rotating pat-
tern, on the other hand, the screws rotate counter to each
other and the material is brought to the junction of the two
screws, building up in what is called the material bank on
the top of the junction. This buildup of material is con-
veyed along the length of the screw by the screw flights.
As the material passes between the screws, high shear is
created, but shear elsewhere is very low. Since only a small
amount of material passes between the screws, total shear
is lower than in single-screw extruders and in co-rotating
twin-screw extruders. Therefore, co-rotating systems are
more effective than either counter-rotating or single-screw
extruders [173]. On the other hand, although it is often
stated that twin screw extruders favor intercalation when
compared to single screwsystems, this may not be the case
for counter-rotating extrusion systems, for the aforemen-
tioned reason.
Focusing on the effect of the extrusion system on the
degree of intercalation, Cho and Paul [15] prepared nylon
6/o-MMTnanocomposites usingeither anintermeshingco-
rotating twin screw extruder or a single screw extruder.
They found that for the composite prepared by single
screwextrusion, full exfoliation is not achieved, which was
attributed to insufficient amount of shear and short resi-
dence time. On the other hand, by mixing in the twin screw
extruder, the organoclay is uniformly dispersed into nylon
6 and the individual layers are aligned along the flow axis.
However, other researchers have reported on nanocom-
posite preparation using single-screwextruders. For exam-
ple, McNally et al. [36] successfully prepared PA12/clay
nanocomposites using conventional single-screw melt
blending.
Moreover, it is important to notice that, even for a given
extruder, processing conditions may determine the out-
come. More specifically, increasing the mean residence
time in the extruder generally improves the delamination
and dispersion. However, there appears to be an optimum
extent of back mixing and an optimum shear intensity;
excessive shear intensity or backmixing apparently causes
poorer delamination and dispersion [52]. Often, special
screw designs, including provisions for additional mixing,
or static mixers at the end of the screware used to enhance
mixing and thus the silicate dispersion [173].
Li et al. [174] developed an ultrasonic extrusion technol-
ogy, which organically combines extruder and ultrasound
power. The authors claimed that the introduction of ultra-
sonic irradiation in extrusion processing of polymer can
improve the processibility of polymer materials, and also
reduce the size and size distribution of dispersed parti-
cles in polymer blends. They used the ultrasonic oscillation
extrusion system developed to prepare polymer/MMT
nanocomposites. The system, consisting of an extruder and
a cylinder die connected to a generator of ultrasonic oscil-
lations in the direction parallel to the flow of the polymer
melt, was found to improve the exfoliation of the clay,
though only for specific matrices.
It should be noted at this point that, apart of the vari-
ous extrusion systems, internal mixers (i.e. batch mixing
devices where mixing occurs in a closed chamber) may
also be successfully used for the preparation of exfoliated
nanocomposites, as demonstrated, for example, in the case
of PEI matrix [46,52]. However, these devices appear to be
much less popular in nanocomposite preparation.
Another factor affecting the resulting structures in the
case of crystalline polymer matrices, is the crystalliza-
tion temperature. For example, Okamoto and co-workers
[175,176] observed through X-ray analyses that the inter-
gallery spacing of PP-MA based nanocomposites increases
with the crystallization temperature T
c
for any amount of
clay content in the nanocomposites. The microstructure
of the nanocomposites, observed directly by TEM, showed
that the clay particles are well dispersed at low T
c
and
that segregation of silicate layers occurs at high T
c
. This
implies that, by controlling intercalation through crystal-
lization at a suitable temperature, one can control the fine
structure, the morphology—andthus the properties of crys-
talline polymer/clay nanocomposites.
Conclusively, a number of factors affect the outcome of
melt intercalation. In this context, Dennis et al. [52] pre-
sented a simplified scheme to underline the conditions
under which clay exfoliation into a polymer occurs dur-
ing melt blending. The proposed scheme (Fig. 29a) is based
on the relationship between the compatibility of the chem-
istry of the clay treatment and the matrix and the process
conditions used to make a nanocomposite. It distinguishes
three cases. The first case is chemistry-dependent. When
the clay chemical treatment and the resin are compati-
ble, almost any set of processing conditions can be used to
form an exfoliated nanocomposite. In case 2, clay chemi-
cal treatment and polymer are marginally compatible. In
this situation, the process conditions can be optimized
to give an exfoliated nanocomposite. That is, the organ-
oclay chemical treatment and the matrix are compatible
enough that processing conditions can be tailored to opti-
mize delamination and dispersion. Finally, in case 3, there
is no apparent compatibility of the clay chemical treatment
andthe polymer. Processing conditions canbe optimizedto
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1151
Fig. 29. Proposed mechanism of how the organoclay particles disperse
into polymers during melt processing. Part (a) shows three cases involving
the interplay between chemistry and process conditions in the mixing
device. Part (b) illustrates schematically how platelets peel apart under
the action of shear [52]. Reproduced from Dennis, Hunter, Chang, Kim,
White, Cho and Paul DR by permission of Elsevier Science Ltd., UK.
give intercalants or tactoids that are minimized in size, but
even partial exfoliation does not occur.
These authors also presented possible clay delamina-
tion paths (Fig. 29b) to demonstrate that increasing shear
intensity is not enough to achieve exfoliation. In pathway
1, stacks of platelets are decreased in height by sliding
platelets apart from each other, a pathway that requires
shear intensity. Pathway 2 shows polymer chains entering
the clay galleries pushing the ends of platelets apart. This
pathway does not require high shear intensity, but involves
diffusionof polymer into the clay galleries (drivenby either
physical or chemical affinity of the polymer for the organ-
oclay surface) and is, thus, facilitated by residence time in
the mixing device. As more polymer enters and goes fur-
ther in between clay platelets, especially near the edge of
the claygalleries, the platelets appear topeel fromthe edge,
since they are able to bend [14,52].
5.4.3. Compatibility issues in non-polar polymers
In contrast to polar polymers, like polyamides, that
can effectively exfoliate organically modified clays using
conventional melt processing techniques, for non-polar
polymers, such as the most widely used polyolefins, PE or
PP, synthesis of well exfoliated nanocomposites appears to
be more difficult, because these polymers are so hydropho-
bic andlacksuitable interactions withthe claysurface, even
after it has been organically modified [49,162,177–179].
However, the development of polyolefin/clay nanocompos-
ites is a field of rapidly growing industrial relevance due to
their promise of improved performance in packaging and
engineering applications [111]. Therefore, ways to resolve
the difference in polarity between polyolefins and clays,
in order to prepare nanocomposites by conventional melt
compounding, have been proposed.
More specifically, initial attempts to create non-polar
polymer/clay nanocomposites by simple melt mixing were
based on the introduction of a modified oligomer to medi-
ate the polarity between the clay surface and the polymer
[2,49,177]. The most promising strategy at the present time
is to adda small amount of a maleic anhydride graftedpoly-
olefinthat is miscible withthe base polyolefin. It is believed
that the polar character of the anhydride has an affinity
for the clay materials, such that the maleated polyolefin
can serve as a “compatibilizer” between the matrix and the
filler [162,180,181].
In fact, Zhai et al. [179] showed that two kinds of
hybrids are formed by melt mixing: an o-MMT with PE
and with PE-g-MA, respectively. For the PE/o-MMT sys-
tem the intercalate effect is limited and the dispersion of
clay is unsatisfactory. However, for the PE-g-MA/o-MMT
nanocomposites, MMT was exfoliated in the matrix, as tes-
tified by both XRD and TEM.
Wang et al. [49] prepared several types of nanocompos-
ites withdifferent compositions of the organicallymodified
clay and maleated polyethylene by melt compounding at
140

C using a Brabender mixer operating at 60rpm for
20min. They found that the alkylammonium chain length
may change the degree of interaction between clay and
polyethylene and that the original basal reflection peak of
the clay disappeared completely above a certain grafting
level of MA, about 0.1wt.%.
Quite interestingly, Zhang andWilkie [182] obtainedPE-
organoclay nanocomposites by adding maleic anhydride
directlyas a compatibilizer duringthe melt blending. As the
authors suggested, the maleic anhydride probably reacted
with PE during the high temperature blending in air, lead-
inguptotheformationof a graft copolymer inwhichmaleic
anhydride units are attached to the PE chains.
In another study, Tang et al. [183] described the prepa-
ration of PP-based nanocomposites through a successful
combination of clay modification and intercalation in one
step. The authors mixed pristine MMT with the surfac-
tant (C16) and PP with or without PP-MA using a high
speed mixer. The mixed powder was then processed in a
twin screw extruder and nanocomposites were obtained.
The results of this study showed that the structure of PP-
clay nanocomposites is sensitive to the compatibilizer and
the surfactant, since their increasing concentrations will
reduce the free energy of the system, which is favorable
for thermodynamic stability. The dispersion mechanism
proposed is the following. At first, some surfactant chains
diffuse into the interlayer under physical absorption and
shear, rendering the clay organophilic. However, some sur-
factant remains in the polymer matrix, which may enhance
the compatibility when the matrix is intercalated into the
interlayer. In fact, the authors suggested that there is some
1152 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 13
Structures of the polar polymers used as composite matrices.
Polymer Structure
LDPE
EMA (y =0.215)
EVA −18, −28 (x =0.18, 0.28)
EMAAA (y =0.18, z =0.06)
PE-g-MAH (y ≈0.02)
interactionbetweenthe polymer matrixandthe surfactant,
just as in the interaction between the surfactant and the
silicates. On the other hand, some PP-MA may be interca-
lated into the interlayer of MMT, after the surfactant makes
the clay sufficiently organophilic. At the same time, PP-MA
may act as a high molecular weight surfactant. The inter-
layer spacing of the clay increases and, if the miscibility of
PP-MA with PP is good enough to allow dispersion at the
molecular level, the exfoliation of intercalated MMT should
take place.
In addition to maleic anhydride and maleic anhydride
grafted PE, EVA has also been used as a compatibilizer to
prepare PE-based nanocomposites. For example, Zanetti
and Costa [177] prepared several types of composites with
different PE/EVA ratios and 5wt.% organoclay by melt
compounding at 150

C using a Brabender internal mixer
with a screw speed of 60rpm for 10min. The polymer
EVA contained 19wt.% VA. No interaction was obtained by
compounding the PE with the clay in absence of a com-
patibilizer. However, 1wt.% EVA was enough to intercalate
all the organoclay. Further increasing the amount of EVA
above 10wt.% caused a decrease in the degree of coherent
layer stacking (i.e. a more disordered system).
Zhao et al. [184] investigated chlorosilane-modified
montmorillonites and their results showed that inter-
calated PE nanocomposites were obtained by melt
intercalation using common alkylammonium intercalated
clay, which was pretreated with chlorosilane. In a later
work, the authors used directly a reactive intercalating
agent (N-␥-trimethoxyl-silanepropyl) octadecyldimethy-
lammonium chloride (abbreviated JSAc) to modify the
montmorillonite clay, so that the chemical reaction with
hydroxyl groups at the edge of the clay layers and the inter-
layer ion exchange were carried out in one step. PE/clay
nanocomposites were then directly prepared by melt inter-
calating PE and the above mentioned clay in a twin screw
extruder at 180

C and 200rpm, whereas only microcom-
posites were formed when using common intercalating
agent.
It is also worth mentioning the work of Preston et al.
[178], who prepared nanocomposites using the following
matrices: two EVAs with different vinyl acetate contents,
poly(ethylene-co-methyl acrylate) (EMA), poly(ethylene-
co-methyl acrylate-co-acrylic acid) (EMAAA), and a blend
of LDPE with maleated ethylene copolymer (PE-g-MA).
Structures for each of these materials are given in Table 13.
The organoclay they used was organically modified ben-
tonite clay. Composites were prepared by melt mixing in
a twin screw extruder operating at 380rpm with a screw
configured for intensive mixing. Through XRD measure-
ments, the authors concludedthat no interactionwas likely
between the LDPE and the silicate, whereas intercalation of
the organoclay occurred in the presence of the four polar
polymers.
As in the case of PE, it is difficult to get exfoliated
and homogenous dispersion of the silicate layer at the
nanometer level in polypropylene, due to its low polar-
ity. Consequently, PP also is usually modified with polar
oligomers prior to introduction of modified clay, in order
to achieve nanometric dispersion of the clay [161].
One typical example is the PP/clay nanocomposite
system described by Toyota. The Toyota research group
prepared PP/clay nanocomposites by direct melt com-
poundingof PPwithorgano-modifiedMMT, inthepresence
of a maleic anhydride grafted PP (PP-g-MA). They added
three times as much PP-g-MA as the clay by weight to
prepare well mixed PP/clay nanocomposites, and pointed
out that the miscibility between maleated oligomer and
matrix polymer played a key role in composite properties
[2,49,177,185]. Infact, it has beensuggestedthat the relative
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1153
Fig. 30. Schematic illustration of OMLS dispersion process in PP-g-MA matrix [187]. Reproduced fromHasegawa, Okamoto, Kawasumi, Kato, Tsukigase and
Usuki by permission of Wiley-VCH, Germany.
content in maleic anhydride cannot exceed a given value,
in order to retain some miscibility between PP-MA and PP
chains. When too many carboxyl groups were spread along
the polyolefin chains, no further increase in the interlayer
spacing was obtained in PP/PP-g-MA/clay blends, leading
rather to the dispersion of PP-g-MA intercalated clay in the
PP matrix [1].
Similarly, Hasegawa et al. [186] reportedthe preparation
of exfoliated PP-based nanocomposite by melt blending
PP-g-MA and organically modified MMT at 200

C, using
a twin screw extruder. Fig. 30 shows a schematic repre-
sentation of the clay dispersion process in PP-MA-based
nanocomposites. Accordingtotheauthors, thedrivingforce
of exfoliation originates fromthe strong hydrogen bonding
between the MA groups and the polar clay surface.
Kato et al. [188] prepared PP-based nanocomposites
by the melt intercalation of PP chains modified by either
maleic anhydride (PP-g-MA) or hydroxyl groups (PP-OH)
in o-MMT. For both matrices, intercalated nanocomposites
were recovered after melt blending at 200

C for 15min.
However, a PP-g-MA matrix with a lower maleic anhydride
content didnot intercalate under the same conditions, indi-
cating that a minimal functionalization of PP chains has to
be reached for intercalation to proceed. The authors also
noticed that intercalation increased with the polymer-to-
clay ratio, i.e. when the PP-g-MA fraction was increased.
Using the same method, Okamoto et al. [189] prepared
PP/MMT nanocomposites. The authors mixed PP-g-MA
(0.2wt.% MA) and different amounts (2, 4 and 7.5wt.%)
of C18-MMT in a twin screw extruder at 200

C and
obtained nearly exfoliated structures when 2 wt.% clay
was added. However, addition of 4 and 7.5wt.% clay led to
disorderedintercalatednanocomposites andorderedinter-
calated structures, respectively.
Lopez et al. [161] used two different polar coupling
agents, diethyl maleate grafted PP (PP-g-DEM) and com-
mercial maleic anhydride grafted PP (PP-g-MA) to prepare
PP-basednanocomposites. DEMwas chosenas the compat-
ibilizing agent, because of its high thermal stability, high
boiling point, and good compatibilization with polyolefins,
compared to other compatibilizing agents. Furthermore,
the low homopolymerization behavior of DEM allows
better control of the functionalization reaction. Maleic
anhydride was used as reference, since it has been widely
used as compatibilizer for this kind of system. The PP/clay
hybrids were prepared by melt compounding with two
different clays, commercial modified montmorillonite and
sodium bentonite modified with octadecylammonium
ions. The results showed that althoughthe commercial clay
outperforms the octadecylammonium treated bentonite,
differences in mechanical properties when using different
clays are smaller if DEM is used instead of MAH. This is
a consequence of the very low degree of compatibiliza-
tion between the polymer matrix and the clay. In fact, this
study proves that clay dispersion and interfacial adhesion
aregreatlyaffectedbythekindof matrixmodification. DEM
has a lower polarity compared to MAH, providing a less
effective interaction with the polar components of the clay.
Theauthors therefore, concludedthat clayandmatrixmod-
ification are synergistic factors which need to be properly
modulated in order to obtain the desired final properties in
this kind of non-polar polymer-based nanocomposite.
Finally, as in the case of PE and PP matrices, compat-
ibilization is a critical issue also for other polymers, such
as PS. Therefore, Wang and Wilkie [190] prepared PS/clay
nanocomposites by in situ reactive blending with both
the organically modified clays and the pristine inorganic
clay in the presence of maleic anhydride, and found that
maleic anhydride increases the possibility of nanocompos-
ite formation. Also, Hasegawa et al. [191] producedpartially
exfoliated PS/clay nanocomposites by compounding in a
twin-screw extruder organically modified MMT with an
blend of PS and ≥50% of another compatibilizer, namely
poly(styrene-co-methyl vinyl oxazoline).
1154 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 14
Molecular weight of host polymers.
SPU HPU
M
n
PDI M
n
PDI
As-received PU 216.000 1.8 85.000 2.0
Solvent cast 121.000 1.7 82.000 2.1
Melt compounded 66.000 2.0 59.000 1.9
5.4.4. Degradation problems encountered during melt
intercalation
Despite the aforementioned advantages of polymer
melt intercalation, this technique may involve polymer
degradation problems since, when preparing clay/polymer
nanocomposites using melt blending, a certain temper-
ature is needed in the processing. Also, apart from the
polymer matrix degradation, if the processing tempera-
ture to make the PLS is beyond the thermal stability of
the organic treatment on the OMLS, some decomposition
will take place. The onset temperature of decomposition
of the organic modifier is, therefore, important in the pro-
cess to make a polymer/clay nanocomposite, since polymer
processing is normally done above 150

C. Moreover, in
addition to common detrimental aspects of degradation,
the resulting products may play a major but yet to be deter-
mined role in the formation of exfoliated nanostructures
[43].
Therefore, the degradation issues encountered during
melt intercalation have been addressed in several studies.
For example, Finnigan et al. [88] prepared TPU nanocom-
posites by both twin screw extrusion and solvent casting,
in order to compare the outcomes of these methods. The
authors employed two TPUs: a soft elastomer (SPU) and a
hard elastomer (HPU) consisting of the same soft and hard
segments, but in different relative amounts. As demon-
strated by WAXD analysis, both processing routes led to
delaminated structures, which illustrates that if there is a
good driving force for intercalation between the polymer
and organosilicate, the need for an optimized processing
route is diminished. Although melt compounding offered
slightly better silicate dispersion than solvent casting,
the authors suggested that solvent casting must be the
preferred processing route for these materials, owing to
elimination of PU and surfactant degradation. In fact, as
shown in Table 14, it was found that the number average
molecular weight (M
n
) of PUsignificantly decreases during
melt compounding and, to a smaller extent, during solvent
casting (due toanultrasonic probe that was applied). Inthis
particular case, the authors identified as additional causes
of thermal degradation the small size of the extruder (and
thus thelargesurfacetovolumeratio) as well as theabsence
of additives to reduce degradation.
Xie et al. [43] focused on the effect of organic modi-
fiers on the thermal decomposition of OMLSs and found
that, while different long alkyl substituents have no effect
or very little effect, the thermal degradation of organi-
cally modifiedmontmorillonite is quite different compared
to that of pure montmorillonite. The DTGA thermal curve
shown in Fig. 31 for the OMLS was considered in four
parts: (a) the free water region below 200

C; (b) the
region where organic substances evolve in the tempera-
Fig. 31. Comparison of DTGA curves of various OMLS [43]. Reproduced
from Xie, Gao, Liu, Pan, Vaia, Hunter and Singh by permission of Elsevier
Science Ltd., UK.
ture range 200–500

C; (c) the structural water region in
the temperature range 500–800

C; (d) a region between
800 and 1000

C where organic carbon reacts in some yet
unknown way. In OMLS sample the free water disappears
by 40

C. There is no interlayer water inOMLS as the quater-
nary ammonium salt has been exchanged for the hydrated
sodiumcation. The most distinguishing difference between
the sodium montmorillonite and the organically modified
montmorillonite is in the temperature range 200–500

C,
as the organic constituent in the organo-clay starts to
decompose somewhat above 200

C. Another distinguish-
ing difference between sodium montmorillonite and the
organically modified montmorillonite is in the tempera-
ture range from 800 to 1000

C. Sodium montmorillonite
is very stable when the temperature is higher than 800

C,
however, the OMLS continues to lose weight and a larger
amount of CO
2
is released at temperatures over 800

C.
Davis et al. [192] found that during melt blending
MMT/PA6 nanocomposites in a twin-screw extruder at
240

C, a particular quaternary alkyl ammonium treat-
ment of the montmorillonite clay degraded it to an extent
correlated with extruder residence time. To address this
issue, they conducted an investigation on the processing
degradation of PA6/MMT nanocomposites and clay organic
modifier. The results ledthemto the following conclusions:
1. PA6 nanocomposites significantly degraded during pro-
cessing at 300

C. Within experimental uncertainty,
drying at 120

Crather than80

Cprior to processing had
little effect on the degree of degradation. Virgin PA6 did
not degrade under identical processing conditions.
2. Thermal decompositionof PA6nanocompositemayhave
resulted from hydrolytic peptide scission. The catalytic
activity of MMT was not investigated in this particu-
lar study; however, on the basis of previous research, it
appeared that MMT could be involved in PA6 thermal
degradation.
3. Heating at 120

Cfor 4hthoroughly driedvirginPA6; but
drying at 80

C resulted in no water loss. The amount of
volatile water in PA6 nanocomposites was greater than
was observed in virgin PA-6. Longer drying times and
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1155
Fig. 32. Synthesis of the thermally stable organoclay [193]. Reproduced from Chang, Kim, Joo and Im by permission of Elsevier Science Ltd., UK.
higher temperatures resulted in drier PA6 nanocompos-
ites.
4. MMT and water are responsible for the degradation of
PA6 nanocomposites.
5. When PA6 was processed at 300

C some water was
present, however, little degradation was observed. This
means that: (a) water itself may not be sufficient tocause
degradation, (b) water escapes from PA-6 faster than
from the nanocomposite, (c) clay and water are a spe-
cial catalyst combination and/or (d) clay is a source of
high-temperature reactive water or hydroxyls.
In addition to the aforementioned studies, which focus
mainly on the degradation mechanism, others are explor-
ing ways to overcome or limit degradation during polymer
melt intercalation. In general, when a material is subjected
to extrusion, degradation is detected as discoloration and
lowered physical or mechanical properties. A strong odor
may alsoindicate degradation. If the degradationis general,
that is, the entire extrudate is affected, as shown by discol-
oration throughout, although darker streaks may also be
present, the most likely cause is that the heat is too high for
the speed of extrusion. The obvious solutions are to reduce
the heat or to increase the extrusion speed. Some combina-
tionof thesetwovariables arelikelyfeasiblesincethespeed
of the extruder affects mechanical heating of the mate-
rial [173]. However, this needs to be done carefully since,
as mentioned above, processing conditions may affect the
morphology of the resulting material.
On the other hand, a number of researchers have
developed and applied clays exhibiting high thermal
stability. In this context, Chang et al. [193] developed a
thermally stable montmorillonite through an ion exchange
reaction between Na
+
-MMT and dodecyl triphenyl phos-
phonium chloride (C
12
PPh-Cl

) (Fig. 32). Gilman et al.
[194] described the preparation of PA6-based nanocom-
posites of MMT modified with trialkylimidazolium
cations to obtain high stability OMLS at high processing
temperatures.
A surprising result reported in another study was that
poly(3-hydroxybutyrate) (PHB) nanocomposites prepared
via melt intercalation showed severe degradation as testi-
fied by GPC, when an organically modified MMT was used,
whereas no degradation was found with nanocomposites
based on organically modified fluoromica. Even though
there is no explanation on how organically modified flu-
oromica acted to protect the system, the authors suggest
that the presence of Al Lewis acid sites, which catalyze the
Table 15
PLS nanocomposites prepared by melt intercalation.
Nanocomposite Mixing device and conditions Ref.
PA6/[(HE)
2
M
1
R
1
] modified MMT Co-rotating twin screw extruder, 240

C, 280rpm [14]
PA6/Na
+
-MMT water slurry Extrusion and drying [160]
PS/alkylammonium modified MMT Statically heating at 165

C, vacuum, 25h [29]
PEI/hexadecylamine modified MMT Internal mixer, 370

C, 30min [46]
PEO/Li
+
or Na
+
-MMT Statically annealing, 80

C, 6h [196]
PLA/C18-MMT Twin screw extruder, 190

C [153]
PP/stearylammonium modified clay Twin screw extruder, PP-MA compatibilizer [197]
PP-MA/C18-MMT Twin screw extruder, 200

C [186]
PP/o-MMT modified using an organic swelling agent (T
b
=100–200

C) Twin screw extruder, 250

C [166]
EVA/dimethyl-dioctadecyl ammonium modified MMT 130

C [166]
PET/1,2-dimethyl-3-N-alkyl imidazolium salt modified MMT Co-rotating mini twin screw extruder, 285

C [148]
1156 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 16
Predicted reinforcing factors per number of platelets per stack.
No. of platelets per stack Reinforcing factor (RF) Halpin–Tsai equation Mori–Tanaka theory
d
001
=0.96nm d
001
=1.8nm d
001
=0.96nm d
001
=1.8nm
1 49.2 49.2 34.8 34.8
2 39.7 27.5 23.8 16.6
3 33.5 21.1 18.3 11.7
4 29.0 17.5 14.9 9.3
5 25.6 15.1 12.7 7.8
10 16.3 9.3 7.5 4.6
hydrolysis of ester linkages at high temperature, may be
one reason [195].
Finally, it is worth noting at this point that, despite the
aforementioneddegradationproblems encounteredduring
melt intercalation, very fewauthors have usedstabilization
systems in the preparation of polymeric nanocomposites.
In Table 15 several PLS nanocomposites prepared via
melt intercalation are presented as typical examples.
6. Nanocomposite properties
6.1. Mechanical properties
6.1.1. The reinforcing mechanism of layered silicates
The first mechanism that has been put forward to
explain the reinforcing action of layered silicates is one also
validfor conventional reinforcements, suchas fibers, which
is schematically depicted in Fig. 33. That is, rigid fillers
are naturally resistant to straining due to their high mod-
uli. Therefore, when a relatively softer matrix is reinforced
with such fillers, the polymer, particularly that adjacent to
thefiller particles, becomes highlyrestrainedmechanically.
This enables a significant portion of an applied load to be
carried by the filler, assuming, of course, that the bonding
between the two phases is adequate [64]. From this mech-
anism it becomes obvious that the larger the surface of the
filler in contact with the polymer, the greater the reinforc-
ing effect will be. This could partly explain why layered
silicates, having an extremely high specific surface area
(on the order of 800m
2
/g) impart dramatic improvements
of modulus even when present in very small amounts
in a polymer. In fact, the low silicate loading required
in nanocomposites to effect significant property improve-
Fig. 33. Reinforcement mechanism in composite materials.
ments, is probably their most distinguishing characteristic.
In most conventionally filled polymer systems, the mod-
ulus increases linearly with the filler volume fraction,
whereas for nanocomposites much lower filler concentra-
tions increase the modulus sharply and to a much larger
extent [55].
However, some authors have argued that the dramatic
improvement of modulus for such extremely low clay con-
centrations (i.e. 2–5wt.%) cannot be attributed simply to
the introduction of the higher modulus inorganic filler lay-
ers. A proposed theoretical approach assumes a layer of
affected polymer on the filler surface, with a much higher
modulus than the bulk equivalent polymer. This affected
polymer can be thought of as a region of the polymer
matrix that is physisorbed on the silicate surface, and is
thus stiffened through its affinity for and adhesion to the
filler surface. Obviously, for such high aspect ratio fillers as
the layered silicate layers, the surface area exposed to the
polymer is huge and, therefore, the significant increases in
the modulus with very lowfiller content are not surprising.
Furthermore, beyond the percolation limit, the additional
silicate layers are incorporated in polymer regions that
are already affected by other silicate layers, and thus it is
expected that the enhancement of modulus will become
much less dramatic [198].
In order to prove the effect of degree of exfoliation
on nanocomposite mechanical properties, Fornes and Paul
[64] used an analytical approach to elucidate how incom-
plete exfoliation influences nanocomposite stiffness. They
expressed the modulus of a simple clay stack in the direc-
tion parallel to its platelets, by using the rule of mixtures:
£
stack
= ¢
MMT
£
MMT

gallery
£
gallery
where ¢
MMT
is the volume fraction of silicate layers in the
stack, E
MMT
is the modulus of MMT, ¢
gallery
is the volume
fraction of gallery space and E
gallery
is the modulus of the
material in the gallery, which is expected to be much less
than E
MMT
. The volume fraction occupied by gallery space,
¢
gallery
can be expressed in terms of X-ray d-spacings, as
¢
gallery
=
(n −1)(d
001
−t
platelet
)
d
001
(n −1) +t
platelet
where n is the number of platelets per stack, d
001
is the
repeat spacing between silicate particles, and t
platelet
is the
thickness of a silicate platelet. Obviously, when the number
of platelets in a stack is equal to one, the system repre-
sents an individual exfoliated platelet. Table 16 shows how
the number of platelets in a stack affects the reinforce-
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1157
Fig. 34. The effect of the number of platelets per stack on the (a) modulus and (b) aspect ratio for the simplified arrangement of platelets [64]. Reproduced
from Fornes and Paul by permission of Elsevier Science Ltd., UK.
ment factor (RF in an unexchanged, non-expandable clay
(d
001
=0.96nm) as well as in an intercalated or organically
modified clay (d
001
=1.8nm). Increasing n in both stacking
scenarios leads to lower reinforcement efficiencies, espe-
ciallyfor theintercalatedclay. Interestingly, thelargest drop
in reinforcement is experienced when going from one to
two platelets per stack. Overall, the trends in Table 16 show
the high sensitivity of nanocomposite stiffness to the level
of exfoliation. Fornes et al. concludedthat stacks of platelets
reduce stiffness of nanocomposites through lower effective
filler moduli and reduced aspect ratio, the effects shown
separately in Fig. 34.
6.1.2. Modulus and strength
In general, the addition of an organically modified lay-
ered silicate in a polymer matrix results in significant
improvements of Young’s modulus, as can be seen in
Table 17 for a number of different materials. For exam-
ple, Gorrasi et al. [156] reported an increase from 216
to 390MPa for a PCL nanocomposite containing 10wt.%
ammonium-treated montmorillonite, while in another
study [201], Young’s modulus was increased from 120 to
445MPa with addition of 8wt.% ammonium treated clay
in PCL. Similarly, in the case of nylon 6 nanocomposites
obtained through the intercalative ring opening polymer-
ization of ␧-caprolactam, a large increase in the Young’s
modulus at rather low filler content has been reported,
whatever the method of preparation: polymerization
within organo-modified montmorillonite, polymerization
withinprotonated␧-caprolactamswollenmontmorillonite
or polymerization within natural montmorillonite in the
presence of ␧-caprolactam and an acid catalyst [45].
However, exceptions to this general trend have
been reported. As shown in Fig. 35, in crosslinked
polyester/OMLS nanocomposites, the modulus decreases
with increasing clay content; in fact, the drop for the
2.5wt.% nanocomposite was greater than expected. To
explain this phenomenon, it was proposed that the inter-
calation and exfoliation of the clay in the polyester resin
serve to effectively decrease the number of crosslinks from
a topological perspective. The origin of the greater drop in
properties of the 2.5wt.% nanocomposites may be traced
to the morphology; i.e. it was observed that the sam-
ple showed exfoliation on a global scale compared to the
nanocomposite containing 10wt.% clay, indicating that the
crosslinking density is inversely proportional to the degree
of exfoliation [140].
Apart from the modulus, the addition of OMLS in a
polymer matrix usually also increases the tensile strength
compared to that of the neat polymer material. For exam-
ple, Shelley et al. [32] reported a 175% improvement in
yield stress accompanied by a 200% increase in tensile
modulus for a nylon 6 nanocomposite containing 5wt.%
clay. However, it should be emphasized that the effect of
nanocomposite formationontensile strengthis not as clear
as in the case of the modulus since reductions of tensile
strength upon nanocomposite formation have also been
reported. Such examples are included in Table 18, which
lists the tensile strengths of a number of nanocomposite
materials and compares them with the corresponding val-
ues for the neat polymers.
Most polymer–clay nanocomposite studies report ten-
sile properties, such as modulus, as a function of clay
content [31], as in Fig. 36. This plot of Young’s modulus of
nylon 6 nanocomposite vs. filler weight content, shows a
Fig. 35. Tensile modulus vs. clay concentration for crosslinked polyester
nanocomposites [140]. Reproduced fromBharadawaj, Mehrabi, Hamilton,
Trujillo, Murga, Fan, Chavira and Thompson by permission of Elsevier Sci-
ence Ltd., UK.
1158 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 17
Young modulus of various PLS nanocomposites.
Nanocomposite Clay content (wt.%) Young modulus (GPa) Ref.
PA6/MMT (in situ
polymerization)
0 1.11 [199]
4.7 1.87
5.3 2.04
PA6(LMW)/MMT (melt
intercalation)
0 2.82 [14]
3.2 3.65
6.4 4.92
PA6(MMW)/MMT
(melt intercalation)
0 2.71 [14]
3.1 3.66
7.1 5.61
PA6(HMW)/MMT (melt
intercalation)
0 2.75 [14]
3.2 3.92
7.2 5.70
PP(7.2%
PP-g-MA)/OMLS
0 0.714 [186]
7.2 0.838
PP(21.6%
PP-g-MA)/OMLS
0 0.760 [186]
7.2 1.010
EVA/Cloisite Na 0 0.0122 [167]
3 0.0135
EVA/Cloisite 20A 0 0.0122 [167]
3 0.0249
EVA/Cloisite 25A 0 0.0122 [167]
3 0.0220
EVA/Cloisite 30B 0 0.0122 [167]
3 0.0228
EVA/Nanofil 757 0 0.0122 [167]
3 0.0116
EVA/Nanofil 15 0 0.0122 [167]
3 0.0240
EVA/Somasif ME100 0 0.0122 [167]
3 0.0124
EVA/Somasif MAE 0 0.0122 [167]
3 0.021
Soft PU/30B (solution
intercalation)
0 0.0075 [88]
3 0.0138
7 0.024
Soft PU/30B (melt
intercalation)
0 0.0072 [88]
3 0.0114
7 0.0193
Hard PU/30B (solution
intercalation)
0 0.050 [88]
3 0.086
7 0.134
Hard PU/30B (melt
intercalation)
0 0.061 [88]
3 0.081
7 0.119
HDPE/o-MMT 0 1.020 [200]
0.9 1.060
1.8 1.250
2.8 1.380
4.0 1.360
constant large rate of increase of modulus up to ca. 10wt.%
of nanoclay, whereas above this threshold the aforemen-
tioned levelling-off of Young’s modulus is observed. This
change corresponds to the passage from totally exfoliated
structure (below 10wt.%) to partially exfoliated—partially
intercalatedstructure (for 10wt.%clay andabove), as deter-
mined by XRD and TEM [1,55].
In another study, Liu and Wu [146] studied the mechan-
ical performance of PA66 nanocomposites prepared via
melt intercalation, using epoxy co-intercalated clay. The
tensile strength increases rapidly from 78MPa for PA66
up to 98MPa for PA66CN5, but the increasing amplitude
decreases when the clay content is above 5wt.%. A simi-
lar phenomenon is observed in the dependence of tensile
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1159
Table 18
Tensile strength of various PLS nanocomposites.
Nanocomposite Clay content (wt.%) Tensile strength (MPa) Ref.
PA6/MMT (in situ
polymerization)
0 68.6 [199]
4.7 97.2
5.3 97.3
PA6(LMW)/MMT (melt
intercalation)
0 69.2 [14]
3.2 78.9
6.4 83.6
PA6(MMW)/MMT
(melt intercalation)
0 70.2 [14]
3.1 86.6
7.1 95.2
PA6(HMW)/MMT (melt
intercalation)
0 69.7 [14]
3.2 84.9
7.2 97.6
PMMA/OMLS 0 53.9 [1]
12.6 62.0
PS/OMLS 0 28.7 [1]
17.2 23.4
24.6 16.6
EVA 0 28.4 [167]
EVA/Cloisite Na 3 25.9
EVA/Cloisite 20A 3 25.8
EVA/Cloisite 25A 3 26.2
EVA/Cloisite 30B 3 30.7
EVA/Nanofil 757 3 27.6
EVA/Nanofil 15 3 26.7
EVA/Somasif ME100 3 24.5
EVA/Somasif MAE 3 25.1
Soft PU/30B (solution
intercalation)
0 45 [88]
3 31
7 21
Hard PU/30B (solution
intercalation)
0 58 [88]
3 44
7 34
PU/MMT 0 5.9 [142]
5 6.2
10 6.5
21.5 8.3
PE/JS 0 22 [184]
5 25
10 27
15 28
PE/DM 0 22 [184]
5 21
10 23
15 24
HDPE/o-MMT 0 27 [200]
0.9 26
1.8 26
2.8 26
4.0 25
modulus of PA66CN on clay content. The smaller increase
inamplitude observed witha clay loading above 5wt.%was
again attributed to the inevitable aggregation of the layers
at high clay content.
Another example (Fig. 37) shows both the tensile
modulus and the yield strength of neat PA12 and the
nanocomposites, which increased steadily with increas-
ing organoclay loading. Compared to the virgin polymer,
the tensile modulus of PA12/clay systems was improved
by about 40% upon adding only 5wt.% of clay, while lim-
ited improvement of the tensile strength was observed
by incorporating clay in the matrix. Again, it was sug-
gested that there is an optimum clay concentration for
nanocomposite tensile strength improvement. With fur-
ther increase in clay loading a moderate decrease of tensile
strength was observed, suggesting that the relative amount
of intercalation/exfoliation of the clay morphology gradu-
ally increases withincreasing clay content, since the tensile
strength is usually sensitive to the degree of dispersion
[147].
1160 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 36. Effect of clay content on tensile modulus, measured at
room temperature, of organo-modified montmorillonite/nylon-6-based
nanocompositeobtainedbymelt intercalation[170]. ReproducedfromLiu,
Qi and Zhu by permission of John Wiley & Sons, Inc.
Similarly, other factors that influence the degree of exfo-
liation, apart from the clay content, also have an impact on
nanocomposite modulus and strength.
This explains the variations observed in moduli of PA6
nanocomposites prepared by intercalative ring opening
polymerization of ␧-caprolactam, with different kinds of
acids to catalyze the polymerization (Table 19). The WAXD
peak intensity I
m
, which is inversely related to the amount
of exfoliated layers in the nanocomposite, also depends on
the nature of the acid used to catalyze the polymerization
process. For an increase in I
m
, a parallel decrease in Young’s
modulus is observed, indicating that exfoliated layers are
the main factor responsible for the improvement in stiff-
ness, while intercalated particles, having a smaller aspect
ratio, play a rather minor role [1,55].
Cho and Paul [15] studied the effect of mixing device
and processing parameters on the mechanical properties
Fig. 37. Tensile modulus and yield strength of PA12/clay nanocomposites
as a function of clay concentration [147]. Reproduced from Phang, Liu,
Mohamed, Pramoda, Chen, Shen, Chow, He, Lu and Hu by permission of
John Wiley & Sons Ltd. on behalf of the SCI.
Table 19
XRD peak intensity (I
m
) and Young’s modulus of various nylon-6-based
nanocomposites obtained by a one-step in situ intercalative polymer-
ization of ␧-caprolactam with Na–montmorillonite in the presence of
different acids.
Acid I
m
(cps) Young’s modulus (GPa)
Phosphoric acid 0 2.25
Hydrochloric acid 200 2.05
Isophtalic acid 255 1.74
Benzenesulfonic acid 280 1.74
Acetic acid 555 1.63
Trichloroacetic acid 585 1.67
of polyamide nanocomposites. In the case of composites
formed by single-screw extrusion, the exfoliation of the
clay platelets is not extensive. Even after a second pass
through this extruder, undispersed tactoids are still easily
observedwithnakedeye. However, the tensile strengthand
modulus were slightly improved by the second pass. Onthe
other hand, nylon 6 nanocomposites with good properties
can be obtained over a broad range of processing condi-
tions in the twin screw extruder. The final nanocomposite
properties are almost independent of the barrel tempera-
ture over the range of typical nylon 6 processing, but they
are slightly improved by increasing the screw speed or by
a second pass through the extruder. Therefore, processing
conditions need to be optimized to allow greater exfolia-
tion of the clay platelets and, thus, greater improvement in
mechanical properties.
The effect of PA6 molecular weight and MMT content
on nanocomposite tensile modulus is shown in Fig. 38.
The addition of organoclay leads to a substantial improve-
ment in stiffness for the composites based on each of the
three PA6 samples examined, i.e. LMW, MMW and HMW
(low, medium and high molecular weight, respectively).
Interestingly, the stiffness increases with increasing matrix
molecular weight at any given concentration, even though
the moduli of the neat PA6s are all quite similar. Similar
trends with respect to the level of organoclay content and
molecular weight are evident in the yield strength results
(Fig. 39). Yield strength increases with MMT content; how-
Fig. 38. Effect of MMT content on tensile modulus for LMW, MMW,
and HMW based nanocomposites [14]. Reproduced from Fornes, Yoon,
Keskkula and Paul by permission of Elsevier Science Ltd., UK.
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1161
Table 20
Influence of maleic anhydride-modified polypropylene content on the stiffness of PP matrices and PP/clay nanocomposites
a
.
Sample Filler content (wt.%) PP-MA content (wt.%) Young’s modulus (MPa)
PP 0 0 780
PP/PP-MA 7 0 7.2 714
PP/PP-MA 22 0 21.6 760
PPCC 6.9 0 830
PPCH 1/1 7.2 7.2 838
PPCH 1/2 7.2 14.4 964
PPCH 1/3 7.2 21.6 1010
a
PP=polypropylene; PP-MA x: polypropylene modified by maleic anhydride (x =wt.% of PP-MA in the blend); PPCC=polypropylene-based microcom-
posite, PPCH y/z =polypropylene based nanocomposite (y/z =weight ratio between y parts of filler and z parts of PP-MA).
Fig. 39. Effect of MMT content on yield strength for LMW, MMW,
and HMW based nanocomposites [14]. Reproduced from Fornes, Yoon,
Keskkula and Paul by permission of Elsevier Science Ltd., UK.
ever, while the HMW and MMW-based nanocomposites
show a steady increase in strength with clay content,
the LMW-based nanocomposites show a less pronounced
effect. These differences with respect to molecular weight
are attributed to the better exfoliation achieved for the
higher molecular weight matrices [14].
Other factors that may play a crucial role in improve-
ment of nanocomposite mechanical properties include the
organic modification of the clay and the addition of com-
patibilizers to the polymer matrix. As a representative
example, Young’s modulus values of PP/PP-MA nanocom-
posites are listed in Table 20 and compared with the
corresponding microcomposite as well as simple PP-MA/PP
polymer blends. It is readily observed that increasing the
amount of PP-MA increases the modulus, while compari-
son of PP with the simple PP-MA/PP blends rules out any
possible effect of matrix modification due to the presence
of increasing amounts of PP-MA [1].
In another study, Hotta and Paul [162] performed ten-
sile tests on various PE and PE-MA nanocomposites based
on organoclays with one or two alkyl tails. The increase
in modulus with addition of MMT is much stronger for the
organoclaywithtwoalkyl tails thanfor theonewithasingle
tail, as would be expected on the basis of the much better
dispersion of clay platelets for the surfactant with two alkyl
tails. Similar trends were observed also for nanocomposite
yield strength. Interestingly, the authors noted that there
is no advantage in adding PE-MA for building modulus or
strength at low MMT content (≤2.5wt.%), in spite of the
morphological differences seen. On the contrary, there is a
clear advantage in adding PE-MA at higher MMT contents.
Eventhoughthe benefit for modulus is not as great as might
be expected, in the absence of PE-MA, the yield strength
actually decreases on addition of MMT beyond 2.5wt.%.
Table 21 lists the strength and modulus values for
PE-based nanocomposites, in which the initial montmo-
rillonite was modified by two intercalating agents: the
commonly used dioctadecyldimethyl ammonium chloride
(DM) and the reactive N-␥-trimethoxysilanepropyl octade-
cyldimethyl ammonium chloride (JS). Both strength and
modulus are higher in the case of the reactive intercalat-
ing agent, owing to the better dispersion of the organoclay
[184].
The effect of clay organic modification on nanocom-
posite mechanical properties is also demonstrated in
Fig. 40, which presents the ultimate strength of PU-
nanocomposites with different contents of two organically
treated montmorillonites: MO-MMT, treated with a ther-
mally stable, aromatic amine modifier containing active
groups, and C
16
-MMT, treated with a quaternary alkyl
ammonium salt. As can be seen the ultimate strength
increased dramatically with clay content and reached a
maximum at 5wt.% MMT, where the ultimate strength of
Table 21
Mechanical properties of PE and PE/clay composites.
Sample Tensile strength (MPa) Flexural strength (MPa) Flexural modulus (MPa) Izod impact strength (J/m)
PE 22 26 710 20
PE/JS5 25 28 780 16
PE/JS10 27 33 1050 16
PE/JS15 28 38 1330 12
PE/DM5 21 26 750 22
PE/DM10 23 31 980 16
PE/DM15 24 30 1030 14
1162 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 22
Tensile test results of Polypox H205 nanocomposites processed with low shear.
Specimen Average ultimate tensile stress (N/mm
2
) Average tensile modulus (N/mm
2
) Relative ultimate stress Relative tensile modulus
0% I30E 59.0 ± 0.6 2565 ± 11 1.000 1.000
5% I30E 54.3 ± 9.2 2796 ± 31 0.920 1.090
10% I30E 53.6 ± 6.5 3075 ± 56 0.909 1.199
Fig. 40. Effect of organic-MMT loading on the tensile strength of (a)
PU/MO-MMT and (b) PU/C16-MMT [202]. Reproduced from Xiong, Liu,
Yang and Wang by permission of Elsevier Science Ltd., UK.
the nanocomposites increased by about 450% for C
16
-MMT
and 600% for MO-MMT, compared with that of pure PU,
indicating that the improved mechanical strength depends
on the characteristics of the modifier [202].
The extent of improvement of nanocomposite mechan-
ical properties will also depend directly upon the average
length of the dispersed clay particles, since this determines
their aspect ratio and, hence, their surface area [55,203].
At this point we note that several authors have also
pointedout factors that haveanadverseeffect onnanocom-
posite modulus and/or strength and need to be taken into
consideration when preparing nanocomposite materials.
Quite interestingly, Gopakumar et al. [151] found that
the exfoliation of 5 and 10wt.% clay in PE-MA increased
Young’s modulus by 30 and 53%, respectively, whereas the
tensile stress at yield showed only a marginal increase, up
to a maximumof 15% for the 10wt.% clay composition. The
authors noted that the greatly enhanced interfacial area
derived fromexfoliation of the clay improves the mechani-
cal reinforcement potential of the filler. However, giventhat
the mechanical properties of a filled systemdepend on two
principal factors, i.e. crystallinity of the polymer matrix and
the extent of filler reinforcement, the degree of crystallinity
must also be considered.
In another study dealing with the effect of matrix
variations on mechanical properties of nanocomposites,
Chaudhary et al. [171] studied the tensile properties of
nanocomposites based on EVAs with various VA contents
and two alternative organoclays. Since in EVAwith increas-
ing VA content the crystallinity of the polymer decreases
(and will lower the stiffness), while the polarity increases
(and will increase the intercalation), the authors suggested
that in their system, the stiffness and toughness responses
would reflect an interplay of two factors: (a) an increase in
the “rigid” amorphous phase due to polymer–clay interca-
lation and (b) an increase in the “mobile” amorphous phase
due to the increasing VA content. Experimental results
showed that the influence of increasing clay concentration
onthe tensile behavior of EVAmatrices was significant only
with a lowor moderately polar EVA matrix (9 and 18% VA).
Thus, a linear proportionality was found between clay con-
centration and tensile modulus for EVA-9 and EVA-18, a
relation not observed with EVA-28. In fact, it is very dif-
ficult to compare the extent of the improvement of the
mechanical properties of different EVA/clay nanocompos-
ites reported so far, because EVAs of different vinyl acetate
contents have been processed into the nanocomposites
with different clays and different modifying agents by dif-
ferent methods [81].
In the case of high T
g
thermosets, it has been suggested
that neither intercalated nor exfoliated nanosilicates lead
to an improvement of the tensile stress at break, but rather
make the materials more brittle. This effect appears to be
generallymorepronouncedfor intercalatedstructures than
for exfoliated ones [1].
The results of tensile tests conducted by Hackman and
Hollaway [134] on epoxy nanocomposites conventionally
prepared under low-shear (stirring for 5h at 90

C) are
highlighted in Table 22. The tensile modulus increased
by 9.0 and 19.9% with 5 and 10wt.% clay loading respec-
tively. However, the ultimate tensile stress decreased with
increasing clay content, although the variation was large.
The authors attributed this phenomenon to the fact that
large clay particles act as impurities and increase stress
concentrations. Flexural tests were also conducted and the
results are outlined in Table 23. As can be seen, the flexural
modulus and ultimate flexural stress increased by 19.6 and
Table 23
Flexural test results of Polypox H205 nanocomposites processed with low shear.
Specimen Average flexural modulus (N/mm
2
) Average ultimate flexural stress (N/mm
2
) Relative flexural modulus Relative flexural stress
0% I30E 2755 ± 83 95.0 ± 1.8 1.000 1.000
5% I30E 2966 ± 90 97.3 ± 2.0 1.076 1.034
7.5% I30E 3101 ± 85 102.2 ± 3.2 1.126 1.055
10% I30E 3294 ± 76 102.4 ± 3.1 1.196 1.077
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1163
Table 24
Summary of tensile properties of thermoplastic PU-based nanocomposites.
30B content (wt.%) Solvent cast Melt compounded
Young’s modulus (MPa) Tensile strength (MPa) Fail strain (%) Young’s modulus (MPa) Tensile strength (MPa) Fail strain (%)
SPU
0 7.5 45 1136 7.2 21 1445
3 13.8 31 1109 11.4 22 1163
7 24 21 1030 19.3 7 568
HPU
0 50 58 898 61 44 776
3 86 44 808 81 20 283
7 134 34 704 119 15 100
7.7%, respectively, for specimens containing 10wt.% clay.
For nanocomposites processedunder highshear, thetensile
modulus and ultimate tensile stress increased by 18.7 and
9.3%, respectively, when 5wt.% clay loading was applied.
In this case, the improvement in ultimate tensile strength
was attributedtothe smaller particles not generating stress
concentrations leading to premature failure.
A summary of the tensile properties of soft (SPU)
and hard (HPU) polyurethane elastomers and of the cor-
responding nanocomposites, prepared by either solvent
casting or melt compounding, is provided in Table 24. As
can be seen, upon silicate addition large improvements in
stiffness were observed, which however were accompa-
nied by a decrease in tensile strength and elongation [88].
Similar trends have been reported by Tortora et al. [204].
Both exfoliated and intercalated PU/o-MMT nanocompos-
ites showed an improvement in the elastic modulus upon
increasing the clay content, but a decrease in the stress and
strain at break.
In general, it has been argued that in the presence of
polar or ionic interactions betweenthe polymer andthe sil-
icatelayers, thestress at breakis usuallyincreased, whereas
when there is lack of interfacial adhesion, no or very slight
tensile strength enhancement is recorded [1]. Pegoretti et
al. [149] found that the yield strength was not reduced
by the addition of clay to recycled PET and considered
this to be a sign of good interfacial adhesion; however, in
the same study, a slight decrease of stress at break and a
dramatic reduction of strain were reported. On the other
hand, in PS intercalated nanocomposites the ultimate ten-
sile stress was found to decrease compared to that of the
PS matrix and dropped further at higher filler content.
This lack of strength was attributed to the fact that only
weak interactions exist at the PS/clay interface, contrary to
other compositions inwhichpolar interactions mayprevail,
strengthening the matrix interface [205].
It should be noted that several authors have reported
inability to measure nanocomposite yield stress, because
the materials often become brittle and fail before reach-
ing the yield point. Such remarks were made by Gorrasi
et al. [6], who conducted tensile tests on PCL nanocom-
posite, containing 30wt.% clay, and also on blends of this
nanocomposite with HMW PCL. For the blend containing
15wt.% clay only the elastic modulus could be evaluated
since the sample did not reach the yield point, while lower
clay concentrations in the blend led to better mechanical
properties in terms of flexibility and drawability. For the
initial nanocomposite, however, it was not even possible to
draw the sample because of its brittleness.
An interesting study was performed by Chang et al.
[193] who prepared PET-based nanocomposites through
in situ intercalative polymerization, and subsequently pro-
Table 25
Tensile properties of PET hybrid fibers.
Organoclay (wt.%) DR
a
Ultimate strength (MPa) Modulus (GPa) E.B.
b
0 (Pure PET) 1 46 2.21 3
3 47 2.24 3
10 51 2.28 3
16 51 2.39 2
1 1 58 2.88 3
3 56 2.80 3
10 50 2.63 3
16 48 2.47 3
2 1 68 3.31 3
3 55 2.63 3
10 54 2.51 3
16 51 2.29 3
3 1 71 4.10 3
3 68 3.40 3
10 62 3.12 2
16 55 3.08 3
a
Draw ratio.
b
Elongation percent at break.
1164 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 26
Bending modulus of various PLS nanocomposites.
Nanocomposite Clay content (wt.%) Bending modulus (GPa) Ref.
PLA/OMLS 0 4.8 [208]
4 5.5
5 5.6
7 5.8
PE/JS 0 0.71 [184]
5 0.78
10 1.050
15 1.330
PE/DM 0 0.71 [184]
5 0.75
10 0.98
15 1.030
duced nano-hybrid fibers by extrusion through the die of
a capillary rheometer. The hot extrudates were stretched
through the die of a capillary rheometer at 270

C and
immediately drawn to various draw ratios (DR). As is evi-
dent from Table 25, the tensile properties of the fibers
formed increased with increasing amount of organoclay
at DR=1. When the organoclay was increased from 0 to
3wt.% in hybrids at DR=1, the strength linearly improved
from 46 to 71MPa, and the modulus from 2.21 to 4.10GPa.
On the other hand, it is quite interesting to note the effect
of DR on the tensile strength and modulus of PET and PET
nanocomposite fibers. As shown in Table 25, for pure PET,
the strength and modulus increased from46 to 51MPa and
2.21 to 2.39GPa, respectively, as the DR was increased from
1 to 16. However, the ultimate strength and modulus of the
hybrid fibers decreased markedly with increasing DR. An
increase in the mechanical tensile strength with increasing
DR is very common for engineering plastics and is usually
observedinflexible coil-like polymers. However, nanocom-
positefibers didnot followthis trend. Changet al. suggested
that higher stretching of the fiber leads to debonding and
creation of voids in the hybrid, which reduce the tensile
mechanical properties. This study clearly illustrates that
nanocomposite materials may have a different response
to mechanical loads than the corresponding neat polymer
matrices.
Finally, even though nanocomposite researchers are
generally interested in the tensile properties of the final
materials, there are a few reports concerning the flexural
properties of PLS nanocomposites [206,207]. Some results
obtained by bending tests on nanocomposite materials are
presented in Tables 26 and 27.
6.1.3. Toughness and strain
The brittle behavior often exhibited by nanocompos-
ites probably originates from the formation of microvoids
due to debonding of clay platelets from the polymer
matrix upon failure. This has been testified through care-
ful inspection of fracture surfaces and is also correlated to
observations byinsitudeformationexperiments usingTEM
[147,181]. In fact, the observation of nanocomposite frac-
ture surfaces is quite interesting. Fig. 41(a) shows a typical
fracture morphology in virgin nylon 12 and a ductile frac-
ture as evidenced by plastic deformation. Fig. 41(b) and (c)
show fracture surfaces of the nanocomposites containing
1 and 5wt.% clay, respectively. No distinct clay agglomer-
ates are observed by scanning electron microscopy (SEM)
even at high magnification, as shown in Fig. 41(d). For
1wt.%clayaddition(Fig. 41(b)), thefracturesurfacebecame
smoother compared with that of neat PA12; an even
more brittle feature for clay concentration of 5wt.% was
observed in Fig. 41(c). Careful inspection of the fracture
surface at higher magnification of nanocomposite with
5wt.% clay (Fig. 41(d)) verifies the formation of microvoids
due to the debonding of clay platelets from the matrix.
Usually, microvoids are formed around the large inhomo-
geneities, which become evident especially at high clay
loadings. These microvoids will coalesce with formation of
larger cracks causing embrittlement, ultimately resulting
in reduced toughness [147].
Table 27
Bending strength of various PLS nanocomposites.
Nanocomposite Clay content (wt.%) Bending strength (MPa) Ref.
PLA/OMLS 0 86 [208]
4 134
5 122
7 105
PE/JS 0 26 [184]
5 28
10 33
15 38
PE/DM 0 26 [184]
5 26
10 31
15 30
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1165
Fig. 41. SEMimages showing fracture surfaces after impact tests: (a) neat PA12; (b) and (c) PA12 nanocomposites containing 1 and 5wt.% clay, respectively;
(d) high magnification of (c) [147]. Reproduced from Phang, Liu, Mohamed, Pramoda, Chen, Shen, Chow, He, Lu and Hu by permission of John Wiley & Sons
Ltd. on behalf of the SCI.
In the case of nylon 12 nanocomposites, Fig. 42 shows
that the Izod impact strength monotonically decreases as
the clay concentration increases. The toughness (repre-
senting the energy absorption during the fracture process)
decreases by about 25% with 5wt.% of clay. Similar obser-
Fig. 42. Izod impact strength of PA12/clay nanocomposites as a func-
tion of clay concentration [147]. Reproduced from Phang, Liu, Mohamed,
Pramoda, Chen, Shen, Chow, He, Lu and Hu by permission of John Wiley &
Sons Ltd. on behalf of the SCI.
vations of reduction in impact strength are also reported
in nylon 6/clay nanocomposites and PE-based nanocom-
posites, indicating that the incorporation of clay into
semicrystalline thermoplastics usually results intoughness
reduction, i.e. the aforementioned embrittlement effect
from clay addition [147].
On the other hand, some studies report little or no
change of toughness upon clay intercalation/exfoliation.
For example, while the tensile strength and modulus of
PP nanocomposites increased rapidly with increasing clay
content from 0 to 5wt.%, the notched Izod impact strength
was constant, within experimental error, in the clay con-
tent range between 0 and 7wt.% [158]. Another study
reports the impact properties for exfoliated nylon 6-based
nanocomposites prepared either by in situ intercalative
polymerization or by melt intercalation. In that study
marginal reductions in impact properties are reported,
whatever the exfoliation process used. In the case of in
situ intercalative polymerization, the Izod impact strength
is reduced from20.6 to 18.1J/mwhen 4.7wt.% clay is incor-
porated. Charpy impact tests showsimilar reduction in the
impact strength, with a drop from 6.21kJ/m
2
for the filler
free matrix, down to 6.06kJ/m
2
for the 4.7wt.% nanocom-
posite. Fig. 43 shows that the decrease in the Izod impact
strength of melt-intercalated nylon 6 nanocomposites is
not very pronounced over a relatively large range of filler
content [170].
Furthermore, toughness improvements upon clay dis-
persion have also been reported—a remarkable result,
1166 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 43. Effect of clay content on notched Izod impact strength of
nylon-6/clay nanocomposites obtained trough melt intercalation [170].
Reproduced fromLiu, Qi and Zhu by permission of John Wiley & Sons, Inc.
considering that conventional polymer–clay compos-
ites, containing aggregated nanolayer tactoids ordinarily
improve rigidity but sacrifice toughness and elongation [7].
As an example, Liu and Wu [146] observed a toughen-
ing effect in PA66CN. The notched Izod impact strength
increased from96 to 146J/mupon 5wt.% clay addition, and
remained higher than that of PA66, even with higher clay
content.
Suchresults are particularly surprising, considering that
from length-scale arguments it is known that toughen-
ing occurs over a specific size range; effective toughening
necessitates a filler size greater than 0.1␮m and may
not be energetically favorable at nano-length scales. Also,
the sizes of the nanoparticles are generally too small to
provide toughening through a crack-bridging mechanism
and cannot effectively enhance crack-trajectory tortuosity.
Therefore, the extremely reduced scale of a fully exfoli-
ated nanocomposite does not lend itself to a toughening
application. However, in an intercalated system there is
considerable interaction between silicate layers that might
alleviate this concern [45].
For example, Zerda and Lesser [45] showed that the
gross yielding behavior of a glassy thermoset was sub-
stantially modified upon the formation of intercalated
nanocomposites, with void formation within clay aggre-
gates leading to the evolution of a visible shear-banded
zone in compression samples. The fracture behavior
appears to be most dramatically improved in the interca-
lated system. The fracture energy of the composites was
increased by 100% at clay concentration of 5wt.%. By inves-
tigating the surface roughness andcrackpropagationunder
subcritical loading, it has been hypothesized that the cre-
ation of additional surface area on crack propagation is the
primary means for toughening intercalated systems. The
morphology of the system plays an important role in the
toughening mechanism because the spacing of regions of
intercalated clay is important to toughening. It is believed,
therefore, that the intercalated morphology can afford
some property improvements that are unavailable to the
fully exfoliated systems.
Concerning the fracture behavior of EVA-based
nanocomposites, Peeterbroeck et al. [167] concluded that
it is independent of the origin of the clay, while it appears
to be related to the nature of the clay organo-modifier and
the state of nanocomposite dispersion. On the other hand,
Kim et al. [44] attributed the enhanced toughness they
observed for intercalated PA12 nanocomposites to the
fact that some amount of applied energy is dissipated by
splitting, sliding or opening of the separated bundles in the
stacked layers. Also, LePluart et al. [136] reported that the
incorporation of a benzyl dimethyl tallowalkyl ammonium
montmorillonite in rubbery and glassy epoxy matrices
leads to promising improvement of mechanical properties.
They obtained an interesting stiffness/toughness balance
for very low filler contents and without reducing the T
g
of the matrix, which is particularly interesting consid-
ering how the brittleness of epoxies limits their use in
technological areas where their high T
g
is often highly
appreciated.
Quite interestingly, Fornes et al. [14] investigated how
the matrix molecular weight as well as the extension
rate during tensile tests affect the ductility of PA6-based
nanocomposites. Fig. 44 presents the relationship between
MMT content and elongation at break for PA6 matrices
of different molecular weights, for two different rates of
extension. As shown in Fig. 44a, the virgin polyamides are
very ductile at a test rate of 0.51cm/min. With increasing
claycontent, theductilitygraduallydecreases, however, the
HMW and MMW-based composites attain reasonable lev-
Fig. 44. Effect of MMT content on elongation at break for LMW, MMW, and HMW based nanocomposites at a crosshead speed of (a) 0.51cm/min and (b)
5.1cm/min [14]. Reproduced from Fornes, Yoon, Keskkula and Paul by permission of Elsevier Science Ltd., UK.
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1167
Table 28
Elongation at break of various PLS nanocomposites.
Nanocomposite Clay content (wt.%) Elongation at break (%) Ref.
PA6(LMW)/MMT 0 28 [14]
3.2 11
6.4 4.8
PA6(MMW)/MMT 0 101 [14]
3.1 18
7.1 5.0
PA6(HMW)/MMT (melt
intercalation)
0 129 [14]
3.2 27
7.2 6.1
EVA 0 1406 [167]
EVA/Cloisite Na 3 1403
EVA/Cloisite 20A 3 1231
EVA/Cloisite 25A 3 1259
EVA/Cloisite 30B 3 1266
EVA/Nanofil 757 3 1358
EVA/Nanofil 15 3 1291
EVA/Somasif ME100 3 1312
EVA/Somasif MAE 3 1270
Soft PU/30B (solution
intercalation)
0 1136 [88]
3 1109
7 1030
Soft PU/30B (melt
intercalation)
0 1445 [88]
3 1163
7 568
Hard PU/30B (solution
intercalation)
0 898 [88]
3 808
7 704
Hard PU/30B (melt
intercalation)
0 776 [88]
3 283
7 100
PU/MMT 0 950 [142]
5 1020
10 1065
21.5 1160
HDPE/o-MMT 0 36 [200]
0.9 25
1.8 20
2.8 14
4.0 15
els of ductility at MMT concentrations as high as 3.5wt.%,
while the elongationat break for the LMWbasednanocom-
posites decreases rapidly at low MMT content (around
1wt.%). Even though the opposite result could have been
anticipated, considering that high molecular weight matri-
ces favor clay exfoliation, the authors attribute the larger
reduction of elongation at break in the LMW-based sys-
tems to the presence of stacked silicate layers, as seen in
TEMphotographs. Ontheother hand, thehigher testingrate
of 5.1cm/min yields similar trends, as shown in Fig. 44b,
but the absolute level of elongation at break is significantly
lower. Interestingly, the strainat breakfor LMWcomposites
is relatively independent of the rate of extension, simi-
lar to what has been observed in glass fiber reinforced
composites. Even at the highest clay content, the HMW
composite exhibits ductile fracture, whereas the LMW and
MMW based nanocomposites fracture in a brittle manner
at the highest clay content.
As in the case of toughness, contradictory results have
also been presented concerning the effect of nanocom-
posite formation on the elongation at break, as can be
seen in Table 28. Even though in most cases this property
deteriorates whena layeredsilicate is dispersedintoa poly-
mer matrix, nanocomposites havebeenreportedexhibiting
similar or even higher elongations at break than the neat
matrices.
For example, in the case of EVA-12/MMT nanocompos-
ites, a significant increase of both the strength and the
elongation has been reported with the introduction of the
organoclay into the EVA-12 matrix. However, this enhance-
ment is a maximum when the clay concentration is only
2wt.%. Further increase of clay content causes reduction in
mechanical properties, probably due to aggregation of clay
layers, as already discussed [209]. Thellen et al. [152] con-
ducted tensile tests on PLA-based nanocomposite blown
films and recorded improvements up to 40% for both the
modulus and the elongation. Yao et al. [142] also reported
improvements in strain at break. Data of tensile strength
and strain-at-break vs. clay content are shown in Table 29.
The authors suggested that the improved elasticity is due
1168 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 29
Tensile strength and strain-at-break vs. the loading of layered clay.
Weight fraction
of the clay (%)
Tensile strength (MPa) Strain-at-break (%)
0 5.9 950
5 6.2 1020
10 6.5 1065
21.5 8.3 1160
in part to the plasticizing effect of gallery onium ions,
whichcontribute todanglingchainformationinthe matrix.
Accordingly, Chen and Evans [210] observed a dramatic
improvement in tensile elongation at break in the pres-
ence of clay. At low clay loadings, test pieces underwent
yielding during tension, similar to pristine PCL, but with
dramatic increases in ductility, quite the opposite of the
usual effect of adding a particulate filler toa polymer. When
the clay loading was high, typically higher than 20wt.%, the
composites becamebrittleanddidnot reachtheyieldpoint.
Finally, it is worth summarizing the work of Hong et
al. [185] on PP-based RTPO/clay nanocomposites, prepared
by using PP-MA as a compatibilizer. PP-based RTPO (or
in reactor made TPO) is a blend of PP and poly(ethylene-
co-propylene) (EPR), produced by the bulk polymerization
of propylene, followed by gas-phase copolymerization of
ethylene and propylene driven by the TiCl
4
/MgCl
2
-based
catalyst system. Such materials, like the conventional
blends of PP/EPR prepared by mechanical blending, exhibit
improved flexibility and toughness compared to neat PP.
Moreover, because the rubber phase can be dispersed uni-
formly and reacha highdegree of dispersioninthese insitu
blends, it is possible to achieve more intimate interaction
between the matrix and the rubber phase. The com-
positions and tensile properties of polypropylene-based
RTPO/clay nanocomposites are reported in Table 30. As can
be seen, the tensile moduli of the nanocomposites became
higher as the clay content increases. On the other hand, the
elongation at break decreases as the clay content increases,
but the value of nanocomposites containing 10wt.% clay is
437%, which is much higher than that of PP/clay nanocom-
posites reported elsewhere. As the authors claim, these
elongational properties of PP based RTPO/clay nanocom-
posites are unique and promising for many applications.
In fact, for reasons of comparison, Hong et al. also prepared
andtestednanocomposites using PP/EPRmechanical blend
matrix, modifiedwithPP-MA. For these materials, the elon-
gation at break values were about 50%, which are much
lower than those of RTPO clay nanocomposites and is not
suitable for industrial application. The authors attributed
this discrepancy to the difference of dispersion homogene-
ity and domain size of ethylene copolymer between RTPO
and PP/EPR mechanical blends.
Fig. 45. Stress–strain curves for nylon 6 and 95/05 composites at a
crosshead speed of 5.08cm/min [15]. Reproduced from Cho and Paul by
permission of Elsevier Science Ltd., UK.
6.1.4. Comparison and synergistic effects of clays and
conventional reinforcements
Typically, layeredsilicates areincorporatedinpolymeric
materials as the sole reinforcing element. However, several
studies have investigatedthe potential synergistic effects of
clays and conventional reinforcements, such as glass fibers.
In this context, Wu et al. [52] studied the effect of
adding glass fibers to PA6 and PA6-based nanocompos-
ites containing 3wt.%montmorillonite. They foundthat the
tensile strength of PA6/clay containing 30wt.% glass fibers
is 11% higher than that of PA6 containing 30wt.% glass
fibers, while the tensile modulus of the nanocomposites
increases by 42%. Bending strength and bending modulus
of neat PA6/clayare similar toPA6reinforcedwith20%glass
fibers. However, the notched Izod impact strength of the
nanocomposite is lower than that of neat polyamide 6, and
is further decreased with the addition of fibers.
In another study, typical stress-strain diagrams for
PA6 and composites containing 5wt.% of fillers are com-
pared, as shown in Fig. 45 (at 5.08cm/min) and Fig. 46
(at 0.5cm/min). A summary of the mechanical proper-
ties of these materials is shown in Table 31. As can be
seen from the table, regardless of the type of filler, the
strength and modulus are substantially increased relative
to the neat PA6, without significant variation in toughness
or impact strength, as measured by the standard Izod test.
Furthermore, nanocomposites show superior mechanical
properties, especially modulus, as compared with conven-
Table 30
Compounding formulations and tensile properties of PP-based RTPO/PpgMA/clay nanocomposites.
Sample PP-based RTPO (wt.%) PpgMA (wt.%) Clay (wt.%) Tensile strength
at yield (MPa)
Tensile strength
at break (MPa)
Elongation at
break (%)
Tensile modulus
(MPa)
RTPO 100 0 0 5.1 20.6 1390 46.0
RTPO NC3 88 9 3 6.4 16.6 980 71.2
RTPO NC5 80 15 5 8.1 16.8 859 78.3
RTPO NC10 60 30 10 14.2 16.6 437 251
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1169
Fig. 46. Stress–strain curves for nylon 6 and 95/05 composites at a
crosshead speed of 0.51cm/min [15]. Reproduced from Cho and Paul by
permission of Elsevier Science Ltd., UK.
tional PA6 composites formed by compounding with glass
fibers or untreated clay. The elongation at break for the
nanocomposites is more or less the same as that of the neat
PA6, whereas, values for the conventional composites are
dramatically decreased. Also, the elongation at break for
the nanocomposites is greatly affected by the crosshead
speed, as is the case for neat PA6. On the other hand, rate
of extension has little effect on the elongation of glass fiber
composites. It is noteworthy that the composite of PA6with
untreated Na
+
-MMT shows higher strength and modulus
than neat PA6, which is quite contrary to the results from
other investigators, who claimthat untreated clay compos-
ites with PA6 are inferior to neat polymer in terms of some
mechanical properties. Interestingly, a synergistic effect on
the tensile strength and modulus is again observed when
the exfoliated nanocomposite is used as the matrix for a
glass fiber reinforced composite. As shown in Table 31, the
modulus of the nanocomposite with 5wt.% loading of the
organoclay is improved about 38% relative to neat PA6 and
the glass fiber composite shows a 22% improvement. When
glass fibers are added to the nanocomposite, the modu-
lus is 81% higher than that of PA6. This exceeds what is
expected on the basis of simple additivity. Stiffness and
strengtharedramaticallyimprovedas theamount of organ-
oclay increases. On the other hand, the impact strength and
elongation at break remain at the levels of neat PA6 up to
about 5wt.%of theorganoclay, anddecreasethereafter [15].
6.2. Dynamic mechanical properties
Dynamic mechanical analysis (DMA) measures the
response of a material to a cyclic deformation (usually ten-
sionor three-point bendingtype deformation) as a function
of the temperature. DMA results are expressed by three
main parameters: (i) the storage modulus (E

or G

), cor-
responding to the elastic response to the deformation; (ii)
the loss modulus (E

or G

), corresponding to the plastic
response to the deformation and (iii) tanı, that is, the E

/E

(or G

/G

) ratio, useful for determining the occurrence of
molecular mobility transitions such as the glass transition
temperature [1].
Indicatively, the temperature dependence of G

, G

and
tanı of a nylon 6 matrix and various nanocomposites is
presented in Fig. 47. In the case of nanocomposites, the
main conclusion derived from dynamic mechanical stud-
ies is that the storage modulus increases upon dispersion
of a layered silicate in a polymer. This increase is generally
larger above the glass transition temperature, and for exfo-
liated PLS nanocomposite structures is probably due to the
creation of a three-dimensional network of interconnected
long silicate layers, strengthening the material through
mechanical percolation [1]. Above the glass transition tem-
perature, when materials become soft, the reinforcement
effect of the clay particles becomes more prominent, due to
the restrictedmovement of the polymer chains. This results
in the observed enhancement of G

[55]. For example, an
epoxy-based nanocomposite, containing 4vol.% silicates,
showed a 60% increase in G

in the glassy region, com-
pared to the unfilled epoxy, while the equivalent increase
in the rubbery region was 450% [135]. Similar results have
also been reported in the case of PP- [189], PCL- [80], SBS-
[211], PA- [64,212], PLA- [83,153,208,213], and epoxy-based
nanocomposites [135].
Enhancement of the loss modulus, G

, has also been
reported for nanocomposite materials, however this aspect
of dynamic mechanical performance is far less discussed in
the literature.
Finally, the tanı values are affected in different ways
by nanocomposite formation, depending on the polymer
matrix. For example, in PS based nanocomposites, a shift
of tanı to higher temperatures has been observed, accom-
panied by a broadening of this transition [205], while
the opposite effect was reported in the case of PP-based
nanocomposites [189]. Some authors observed a decrease
Table 31
Mechanical properties of polyamide 6 composites.
Polyamide composites Clay content (%) Izod impact
strength (J/m)
Modulus (GPa) Yield strength
(MPa)
Elongation at
break (%)
Crosshead speed
0.51cm/min
Crosshead speed
5.08cm/min
Polyamide 6 0 38 ± 4 2.66 ± 0.2 64.2 ± 0.8 200 ± 30 40 ± 8
PA6/glass fiber 5 53 ± 8 3.26 ± 0.1 72.6 ± 0.8 18 ± 1.3 14 ± 4
PA6/MMT 5 40 ± 2 3.01 ± 0.1 75.4 ± 0.3 22 ± 6.0 14 ± 3
PA6/organoclay 3.16 38 ± 3 3.66 ± 0.1 83.4 ± 0.7 126 ± 25 38 ± 19
PA6/organoclay/glass fiber 8 44 ± 3 4.82 ± 0.1 95.0 ± 0.9 8 ± 0.5 7 ± 4
1170 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 47. . Temperature dependence of G

; G

and tanı for N6 matrix and
various N6CNs [55]. Reproduced from Ray and Okamoto by permission of
Elsevier Science Ltd., UK.
of tanı peaks, andconsideredthis indicative of a glass tran-
sition suppression by the presence of the clay. However,
Fornes and Paul [64] pointed out that this conclusion is a
misinterpretation, since the low values for the nanocom-
posites are simply the result of dividing the relatively
constant loss modulus values in the T
g
region, by larger and
larger storage modulus values.
Quite surprisingly, DMAshowedthat above T
g
, the mod-
uli for the pure PU and the PU/o-MMT nanocomposites
show no obvious difference, while below T
g
, addition of
o-MMT strongly influences the modulus values. Interest-
ingly, the authors found that E

and E

of the PU/o-MMT
decrease in comparison with values for the PU, for unclear
reasons. On the other hand, significant enhancements of
E

and E

were seen for the nanocomposite prepared using
a particular modified clay [202]. In the case of PLA-based
nanocomposites, it was observed that PLACNs with a very
small amount of o-PCL as a compatibilizer exhibited a very
large enhancement of mechanical properties compared to
that of PLACN with comparable clay loading [153]. Kriko-
rian and Pochan [83] also studied the dynamic mechanical
properties of neat PLA and nanocomposites prepared with
OMLS. These authors found that at high temperatures the
reinforcement effect of OMLS weakens, and suggested that
Fig. 48. Proposed model for the torturous zigzag diffusion path in an
exfoliated polymer–clay nanocomposite when used as a gas barrier [85].
Reproduced fromYano, Usuki, Okada, Kurauchi and Kamigaito by permis-
sion of John Wiley & Sons Inc.
this indicates a weakening of the thermomechanical stabil-
ity of these materials at high temperature.
6.3. Barrier properties
Generally, polymer/layered silicate nanocomposites are
characterized by very strong enhancements of their bar-
rier properties. Polymers ranging from epoxies and good
sealants (like siloxanes) to semi-permeable (e.g. polyureas)
and highly hydrophilic (e.g. PVA) are all improved up to an
order of magnitude by low clay loadings [31].
The dramatic improvement of barrier properties can be
explained by the concept of tortuous paths. That is, when
impermeable nanoparticles are incorporated into a poly-
mer, the permeating molecules are forced to wiggle around
them in a random walk, and hence diffuse by a tortuous
pathway, as shown in Fig. 48 [4,7,55,206,214–216].
The tortuosity factor is defined as the ratio of the actual
distance, d

, that the penetrant must travel to the shortest
distance d that it would travel in the absence of barriers. It
is expressed in terms of the length L, the width W and the
volume fraction of the sheets ¢
s
as
z =
d

d
= 1 +
L
2W
¢
s
It becomes obvious from this expression that a sheet-like
morphology is particularly efficient at maximizing the path
length, due to the large length-to-width ratio, as compared
to other filler shapes [1,50,55].
According to the model proposed by Nielsen, the effect
of tortuosity on the permeability may, in turn, be expressed
as
P
PCN
P
p
=
1 −¢
s
z
where P
PCN
and P
P
represent the permeability of the
nanocomposite and the pure polymer, respectively and ¢
s
is the clay content [50,55,217].
Although the above equations were developed to model
the diffusion of small molecules in conventional compos-
ites, they have also been used in reproducing experimental
results for the relative permeability in PLS nanocompos-
ites. Discrepancies between the experimental data and the
theoretical line may be attributed either to inadequacies
of the model or to incomplete orientation of the particles
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1171
within the nanocomposite film plane [50,162]. In fact, the
key assumption of the Nielsen model is that the sheets are
placed in an arrangement such that the direction of dif-
fusion is normal to the direction of the sheets. Clearly, this
arrangement results inthe highest tortuosity, andany devi-
ation from it would, in fact, lead to deterioration of the
barrier properties [50,55].
Moreover, the tortuous path theory, including the
Nielsen equation as well as other phenomenological rela-
tions (e.g. the Cussler [218] formula, the Barrel [219]
formula and the power law equation [220]), is grounded
on the assumption that the presence of nanoparticles does
not affect the diffusivity of the polymer matrix. However,
experimental observations demonstrate that molecular
mobility in a polymer matrix, which is intimately con-
nectedto the mass transport properties, diminishedby clay
incorporation. This reduction should be accompanied by
a decrease in diffusivity of small molecules, which is not
considered in the concept of tortuous paths.
Messersmith and Giannelis [118] studied the perme-
ability of liquids and gases in nanocomposites and they
observed that water permeability in PCL nanocomposites
is dramatically reduced compared to the unfilled polymer.
They also noted how the decrease in permeability is much
more pronouncedinthe nanocomposites comparedto con-
ventionally filledpolymers withmuchhigher filler content.
Liu and Wu [146], recorded the water absorption curves
of PA66 and corresponding nanocomposites. They found
that with increasing clay content, the water absorption at
saturation decreases rapidly from 7.6% for PA66 to 5.2% for
the nanocomposite containing 5wt.% clay. They attributed
this reduction to the presence of immobilized polymer in
the amorphous phase. However, above 5wt.% clay content,
the decrease in the saturation amount of water is not so
obvious, probably because of aggregation of silicate layers.
Also, the diffusion coefficient values decrease greatly with
increasing clay loading, but after 5wt.% clay content, the
amplitude of the decrease is obviouslyslower. Inadditionto
theimmobilizedphaseexplanation, andtheincreasedaver-
age diffusion path length, since an epoxy-co-intercalated
clay was used in their study, the authors assumed that the
epoxy groups between silicate layers have a strong inter-
action with amino and amide groups of the PA66 matrix,
to some extent preventing them from forming hydrogen
bonds with water.
Significant reductions in diffusivity and maximum
water uptake were alsoreportedby Liuet al. [130] inepoxy-
based nanocomposites. Here, however, the decreased
maximum water uptake was attributed to the low maxi-
mumwater uptakeof thenanoclays (ca. 2.8wt.%) compared
to the epoxy resin system (ca. 7.5wt.%).
Drozdov et al. [221] conducted moisture diffusion tests
on vinylester resin-MMT clay nanocomposites and demon-
strated that the clay content affects in a similar way
the diffusion coefficient and the constants expressing
the elastoplastic behavior, indicating that moisture diffu-
sion and elastoplasticity may reflect the same phenomena
at the microlevel, associated with molecular mobility of
the polymeric matrix. Moreover, their experimental data
demonstrated that moisture diffusion in the neat polymer
resin is nearly Fickian, but is transformed to an anoma-
Fig. 49. Equilibriumconcentration of water vapor, C
eq
(g/100g), as a func-
tionof activitya =p/p
0
for samples OMont ( ), NPU0(᭹), NPU4(), NPU20
(), NPU40 (♦) [204]. Reproduced from Tortora, Gorrasi, Vittoria, Galli,
Ritrovati and Chiellini by permission of Elsevier Science Ltd., UK.
lous mode of transport of the penetrant molecules with
an increase in clay concentration. The authors explained
the anomalous moisture uptake byimmobilizationof water
molecules on the surfaces of the hydrophilic MMT clay lay-
ers. In fact, they pointed out that, after a nanocomposite
plate is immersed in water, three processes occur in the
nanocomposite: (1) sorption of water molecules on the
samplesurfaces, (2) diffusionof water intotheplate, and(3)
adsorption of water molecules on the hydrophilic surfaces
of clay layers, where these molecules become immobilized.
Many studies reported in the literature have focused on
nanocomposite barrier properties against gases andvapors.
As an example, Tortora et al. [204] measured the trans-
port properties of PU/o-MMT nanocomposites (prepared
using a PCL nanocomposite “master-batch”) using water
vapor as hydrophilic permeant and dichloromethane as
hydrophobic one. For both vapors, the sorption behavior
changed in the presence of the clay, as can be seen for
example in Fig. 49, where the equilibrium concentration,
C
eq
(g/100g), of water vapor is represented as a function
of the vapor activity for all nanocomposites and for the o-
MMT. The sorption curve of water vapor for o-MMT follows
the Langmuir sorption isotherm, in which the sorption of
solvent molecules occurs at specific sites; therefore, when
all the sites are saturated, a plateau is reached. On the other
hand, the sorption of neat PU shows a linear dependence
of equilibrium concentration on activity, while nanocom-
posites show a dual sorption shape, that is a downward
concavity, an inflection point and an upward curvature.
The prevailing mechanism in the first zone is the sorption
of solvent molecules on specific sites, due to interacting
groups. Tortora et al. inferred that this type of sorption
is due to the presence of clay in the polymers. At higher
activities, the plasticization of the polymeric matrix deter-
mines a more than linear increase of vapor concentration
and a transition in the curve is observed, from a dual type
to a Flory-Huggins behavior. From the calculated values of
1172 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 50. The O
2
permeability of PET/o-MMT [222]. Reproduced from Ke
and Yongping by permission of Elsevier Science Ltd., UK.
the sorption parameters, defined as: S =d(C
eq
)/dp, and the
zero-concentration diffusion coefficients for water sorp-
tion and dichloromethane vapor, the authors concluded
that the sorption did not drastically change on increasing
the clay content, whereas the zero-concentration diffusion
coefficient D
0
strongly decreased with increasing inor-
ganic content. The permeability calculated as the product
SD
0
, was largely dominated by the diffusion parameter; it
showed a remarkable decrease up to 20wt.% of clay and a
levelling off at higher contents.
Ke and Yongping [222] tested the O
2
permeability
of intercalated PET nanocomposites. As demonstrated in
Fig. 50, a small amount of clay effectively reduced the per-
meability of the PET film. When the content of o-MMT
reached 3wt.% the permeation of O
2
was reduced to half
that of the pure PET film. Further examples of barrier prop-
erty improvement for PET nanocomposites designated for
packaging applications are given in Table 32 [216].
Ogasawara et al. [223] reported on improved heliumgas
barrier properties of epoxy/MMT nanocomposites, com-
pared to the pure resin. The estimated diffusivity, D,
solubility, S, and permeability P are shown in Figs. 51–53,
as functions of montmorillonite weight fraction. Dispers-
ing MMT particles in the epoxy decreased the diffusion
coefficient D. For example, the diffusion coefficient of the
nanocomposite with 6wt.% clay was approximately one-
tenth that of the base polymer. On the other hand, the
solubility increased with montmorillonite dispersion and
permeability remained almost constant due to the balance
of diffusivity and solubility.
On the other hand, Ray et al. [208] found that the O
2
gas
permeability of PLA nanocomposites with 4, 5 and 7wt.%
Table 32
Relative barrier performance of newly developed rigid packaging based
on PET.
Container composition (supplier) Relative oxygen
transmission rate
at 23

C 50% RH
PET 1
PET nanocomposite (Tetrapak) <0.3
PET/PA nanocomposite (Eastman) 0.4–0.7
Fig. 51. Effect of montmorillonite weight fractionondiffusivityDof mont-
morillonite/epoxy nanocomposites [223]. Reproduced from Ogasawara,
Ishida, Ishikawa, Aoki and Ogura by permission of Elsevier Science Ltd.,
UK.
Fig. 52. Effect of montmorillonite weight fraction on solubility, S, of
montmorillonite/epoxy nanocomposites. The numerical curve based on
rule-of-mixture is superimposed [223]. Reproduced from Ogasawara,
Ishida, Ishikawa, Aoki and Ogura by permission of Elsevier Science Ltd.,
UK.
Fig. 53. Effect of montmorillonite weight fraction on permeability, P,
of montmorillonite/epoxy nanocomposites [223]. Reproduced from Oga-
sawara, Ishida, Ishikawa, Aoki and Ogura by permission of Elsevier Science
Ltd., UK.
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1173
Table 33
Oxygen gas permeabilities of the PLA/OMLS hybrid films.
Clay (wt.%) O
2
gas (cm
3
/(m
2
day))
C16MMT DTA-MMT C25A
0 777 777 777
4 449 455 –
6 340 353 430
10 327 330 340
clay, was reduced to 88, 85 and 81% compared to that of
neat PLA.
Similarly, Chang et al. [84] reported the oxygen gas
permeability of PLA nanocomposites prepared with three
different kinds of OMLS using a melt intercalation tech-
nique. Table 33 summarizes the results for O
2
gas
permeability. The results show that O
2
gas permeability of
nanocomposites systematically decreased with increasing
clay content; and when the clay loading was as much as
10wt.%, the permeability for nanocomposite decreased to
half the PLA permeability, regardless of the nature of the
OMLS employed for the nanocomposite preparation.
Finally, Fig. 54 presents water vapor and oxygen per-
meation results for PLA-based nanocomposite films. In
all cases the nanocomposite films were better oxygen
barriers than the pure PLA films (Fig. 54a), exhibiting a
15–48% reduction in oxygen permeation rate. It is worth
noticing that the oxygen permeation rate of the nanocom-
posite films was essentially independent of screw speed
and feed rate, whereas the oxygen barrier properties
of the neat PLA homopolymer were quite sensitive to
Fig. 54. MOCON permeation data (a) oxygen and (b) water vapor trans-
mission [152]. Reproduced from Thellen, Orroth, Froio, Ziegler, Lucciarini,
Farrell, D’ Souza and Ratto by permission of Elsevier Science Ltd., UK.
processing, suggesting that the need to optimize process-
ing parameters is more critical when working with the
PLA homopolymer than with the PLA/OMLS nanocompos-
ites. The PLA/OMLS nanocomposites also exhibited much
improved barrier properties to water vapor relative to
the neat films (Fig. 54b). In general, clay incorporation
decreased the permeation rate of the resulting films to
water vapor by about 40–50%, again independently of pro-
cessing [152].
Summarizing: although a decrease of diffusivity is a
well-established result of nanocomposite formation, con-
tradictory results are reported concerning the saturation
uptake values of various solvents or gases. Increases of
the saturation uptake level are usually attributed to clus-
tering phenomena. It is worth noticing, however, that in
nanocomposites the coexistence of phases with different
permeabilities can cause complex transport phenomena.
On the one hand, the organophilic clay gives rise to super-
ficial adsorption and to specific interactions with the
solvents. In turn, the polymer phase can be considered,
in most cases, as a two-phase, crystalline-amorphous sys-
tem, the crystalline regions being generally impermeable
to penetrant molecules. The presence of the silicate lay-
ers may be expected to cause a decrease in permeability,
due to the more tortuous path for the diffusing molecules
that must bypass impenetrable platelets [133]. Simultane-
ously, the influence of changes in matrix crystallinity and
chain mobility, induced by the presence of the filler, should
always be taken into consideration [10].
6.4. Thermal stability
The thermal stability of polymeric materials is usually
studied by thermogravimetric analysis (TGA). The weight
loss due to the formation of volatile products after degra-
dation at high temperature is monitored as a function of
temperature (and/or time). When heating occurs under an
inert gas flow, a non-oxidative degradation occurs, while
the use of air or oxygen allows oxidative degradation of the
samples [50,55].
Generally, the incorporation of clay into the polymer
matrixwas foundtoenhancethermal stabilitybyactingas a
superior insulator andmass transport barrier to the volatile
products generated during decomposition, as well as by
assisting in the formation of char after thermal decompo-
sition [50,55,133,224].
Vyazovkin et al. [225] compared the thermal degrada-
tion of a PS nanocomposite with that of the virgin polymer
under nitrogen and air. As seen in Fig. 55 in both nitrogen
and air the decomposition temperature of nanocompos-
ites increased by 30–40

C. The authors also observed that
the virgin polymer degrades without forming any residue,
whereas the nanocomposite (as expected) leaves some
residue.
Zanetti et al. [226] reported TGA curves of a nanocom-
posite PE/EVA/o-MMT and the corresponding matrix
PE/EVA. Under nitrogen, these samples do not show great
differences of stability. However, in air, the PE/EVA blend
is subject to a marked weight loss above 350

C, to form a
5wt.% residue at 450

C, which is completely oxidized to
volatile products between 470 and 550

C. The nanocom-
1174 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 55. TGAcurves of thedegradationof PS100andnPS90at aheatingrate
5

Cmin
−1
in air and nitrogen [225]. Reproduced fromVyazovkin, Dranka,
Fan and Advincula by permission of Wiley-VCH, Germany.
posite, on the other hand, displays a different pattern. The
presence of 5wt.% o-MMT is enough to change the poly-
mer’s thermo-oxidative behavior and between 350 and
480

C the amount of residue is higher to that observed in
a nitrogen flow. According to the authors, the organoclay
shields the polymer fromthe actionof oxygen, dramatically
increasing the thermal stability under oxidative conditions.
Bandyopadhyay et al. [227] reported the first improved
thermal stability of biodegradable nanocomposites that
combined PLA and organically modified fluorohectorite or
montmorillonite. They showed that the PLA intercalated
between the galleries of FH or MMT clay resisted the ther-
mal degradation under conditions that would otherwise
completely degrade pure PLA. This conclusion has been
verified by a number of researchers in subsequent stud-
ies. Thellen et al. [152] presented TGA curves for the neat
polymer and corresponding nanocomposites (Fig. 56) and
reportedthat the onset of thermal degradationwas approx-
Fig. 56. TGA curves of neat PLA and nano-PLA/MLS [152]. Reproduced
from Thellen, Orroth, Froio, Ziegler, Lucciarini, Farrell, D’ Souza and Ratto
by permission of Elsevier Science Ltd., UK.
imately 9

C higher for the nanocomposite than for the neat
PLA.
The thermal stability of PCL-based nanocomposites has
also been studied by TGA. Generally, the degradation of
PCL fits a two-step mechanism. First, random chain scis-
sion through pyrolysis of the ester groups, with the release
of CO
2
, H
2
O and hexanoic acid, and in the second step, ␧-
caprolactone (cyclic monomer) formation as a result of an
unzipping depolymerization process. It has been reported
that the thermal stability of PCL/o-MMT nanocomposites
systematically increases with increasing clay, up to a load-
ing of 5wt.% [1,228].
On the other hand, contradictory results are found in
the literature concerning the thermal degradation of PA6-
based nanocomposites. Pramoda et al. observed that the
degradation onset temperature is 12

C higher for PA6 with
2.5% clay loading than that of virgin PA6 and that the
onset temperature for the higher clay loading remained
unchanged. Also, Dabrowski et al. [229] showed that pro-
tective barriers are formed during thermal degradation of
polyamide 6/clay nanocomposite, which slow down the
rate of degradation via a diffusion process (hindering the
escape of volatiles). However, TGA experiments by other
workers did not show significant changes in the onset of
degradation. For example, according to Jang and Wilkie
[230] the mass loss behavior of PA6/clay nanocomposites
is not significantly different from that of virgin PA6. Irre-
spective of formulation, the temperatures at 50% mass loss
were 471–476

C, which was within the error range of the
TGA instrument used. Moreover, other researchers found
that PA6 nanocomposites have somewhat lower stability
than neat nylon 6, and attributed such observations to
the degradation effect of the quaternary alkylammonium
treatment on the montmorillonite [15]. For example, Davis
et al. [192] studied the thermal stability of PA6 and PA6
nanocomposites, injection molded at 300

C, by
13
C NMR.
They found that PA6 does not degrade at processing tem-
perature, whereas there is significant decrease inmolecular
weight in nanocomposites under the same conditions. The
authors noted that the degradation might depend upon
water in the nanocomposites, which may cause hydrolytic
cleavage. The thermal degradation mechanismof PA6, pro-
posed by Levchik et al., is shown in Fig. 57 [231].
In fact, despite the general improvement of thermal
stability, decreases in the thermal stability of polymers
upon nanocomposite formation have also been reported,
and various mechanisms have been put forward to explain
the results. It has been argued, for example, that after the
early stages of thermal decomposition the stacked sili-
cate layers could hold accumulated heat, acting as a heat
source to accelerate the decomposition process, in con-
junction with the heat flow supplied by the outside heat
source [55]. Also, the alkylammoniumcations in the organ-
oclay could suffer decomposition following the Hoffmann
elimination reaction, and the product could catalyze the
degradation of polymer matrices. Moreover, the clay itself
can also catalyze the degradation of polymer matrices.
Thus, it becomes obvious that the organoclay may have two
opposing functions in thermal stability of nanocomposites:
a barrier effect, which should improve the thermal stability
and a catalytic effect on the degradation of the poly-
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1175
Fig. 57. Dominant PA-6 thermal degradation products in the absence of a nucleophile (a) and in the presence of a nucleophile, such as water (b) [192].
Reproduced from Davis, Gilman and VanderHart by permission of Elsevier Science Ltd., UK.
mer matrix, which should decrease the thermal stability
[184].
For example, Zhao et al. [184] investigated the thermal
stability of PE-based nanocomposites in a nitrogen atmo-
sphere and recorded the TGA and DTGA (derivative curve)
profiles presented in Fig. 58. As can be seen from this fig-
ure, at the initial stage of degradation (before 400

C), the
nanocomposites degrade faster than the pure matrix; this
was attributed to the Hoffmann elimination reaction and
the clay-catalyzed degradation. On the other hand, above
400

C nanocomposites appear to be more stable than pure
PE. The onset temperatures for nanocomposites are all
higher than that of pure PE, but decrease with increas-
ing clay loading. Thus, the authors suggested that when
a low clay fraction is added to the polymer, the clay dis-
perses well and the barrier effect is predominant, but with
increasing loading, the catalyzing effect rapidly increases
and becomes dominant, so that the thermal stability of the
nanocomposite decreases.
Other researchers have studied the effect of clay
concentration on the thermal stability of EVA-based
nanocomposites. It has been found, for example, that the
thermal stability of EVA-12 (12wt.% VA) increases with
the introduction of o-MMT. With an increase in the o-
MMT loading over 2wt.%, however, the hybrids show a
decreasing trend in their initial thermal decomposition
temperature. Thesefindings wereattributedtothefact that,
at low filler contents homogenous exfoliation and random
dispersionof clayis achievedonananometer level, whereas
the higher filler loading destabilizes the matrix, because
of the aggregation of silicate layers [232]. In fact, EVA/clay
nanocomposites containing more vinyl acetate maintain
this thermal stability improvement up to 6–8wt.% filler
loading, probably because of the degree of dispersion of
clay in the polymer matrix [209].
Similarly, Paul et al. [233] observed an increase in ther-
mal stability of PLA nanocomposites with increasing clay
content, with a maximum at a clay loading of 5wt.%. With
further increase of filler content, a decrease in thermal sta-
bility was observed—an effect explained by the relative
extent of exfoliation as a function of the amount of OMLS.
Phang et al. [147] found that the thermal stability of
PA12 is significantly enhanced as the clay concentration
increases; for instance, by about 20

C with incorporation
1176 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 34
Thermal properties of PET hybrid fibers (DR
a
=1).
Organoclay (wt.%) n
inh
b
T
m
(

C) ^H
m
c
(J/g) 1
i
D
d
(

C) wt
600
R
e
0 (pure PET) 1.02 245 32 370 1
1 1.26 247 32 375 8
2 0.98 245 33 384 15
3 1.23 246 32 386 21
a
Draw ratio.
b
Inherent viscosities measured at 30

C by using 0.1g/100ml solutions in a phenol/1,1,2,2-tetrachloroethane (w/w) mixture.
c
Enthalpy change of fusion.
d
Initial weight reduction onset temperature.
e
Weight percent of residue at 600

C.
of only 5wt.% clay into the matrix. For PA12/organoclay
nanocomposites with lower clay contents (<2wt.%) only
limited improvement in thermal stability was observed.
This was attributed to the fact that the exfoliated struc-
ture formed at low clay content is probably not enough to
trigger the thermal and gas barrier properties effectively
in the matrix, because of the short tortuous path formed.
This result is consistent with reports claiming that opti-
mumthermal stability is usually achieved for clay loadings
between 2.5 and 5wt.%. For lower clay fractions, exfoli-
ated morphology dominates, but this lowclay content does
not enable the barrier effect. At much higher clay content,
on the other hand, particle agglomeration occurs. There-
fore, intercalated and exfoliated structures usually coexist,
which again does not allow maximization of the tortuous
path.
As shown in Table 34, PET nanocomposites exhibit
improved thermal stability, with the initial thermal degra-
Fig. 58. TGA and DTGA curves of PE and PE/clay nanocomposites in nitro-
gen atmosphere [184]. Reproduced fromZhao, Qin, Gong, Feng, Zhang and
Yang by permission of Elsevier Science Ltd., UK.
dation temperature 1
i
D
increasing with the amount of
organoclay. A maximum increase of 16

C was recorded in
the case of 3wt.% clay. Also, the weight of residue at 600

C
increased, ranging from 1 to 21%, with clay loading from 0
to 3wt.% [193].
An optimumclay loading for thermal stability enhance-
ment was also reported for PS-based nanocomposites.
When dimethylbenzyloctadecyl-ammonium cation was
used for MMT modification, the threshold was reached at a
surprisingly low MMT content of only 0.3wt.% [35].
Berta et al. [144] did TGA under nitrogen and air for
PUand the corresponding nanocomposite. Under nitrogen,
the nanocomposite shows the same TGA and DTGA profiles
as PU, but displaced by 10

C, a change attributed to the
barrier effect. On the contrary, when tested under air, the
nanocomposites showed very different behavior than pure
PU. For pure PU, most of the polymer volatilizes in the first
stepof PUdecompositionandthesecondstepis diminished
in the TGA/DTGA curves in air compared to those obtained
in nitrogen; thus only a relatively small shoulder appears
at 350

C in air. However, in the nanocomposites the lower
temperature degradation is significantly suppressed and
the secondDTGApeak around395

Cis clearly present. This
behavior was again attributed to greatly retarded thermal
oxidation due to the shielding of the material fromoxygen.
The thermal properties of EVA-based nanocomposites
have been widely studied, mainly by means of TGA. It
has been well established by different research groups
that EVAs exhibit two-step decomposition. The first step,
which is identical in both oxidative and non-oxidative
conditions, occurs from 350 to 400

C and corresponds
to the deacetylation reaction, with production of gaseous
acetic acid and formation of carbon–carbon double bonds
along the polymer backbone. The second step, between
400 and 500

C, involves thermal decomposition of the
unsaturated backbone, either by further radical scission
(non-oxidative decomposition) or by thermal combustion
(oxidative decomposition) [35,81,167].
Riva et al. [234] observed accelerated acetic acid loss
of EVA–clay nanocomposites and speculated that this pro-
cess can be catalyzed by acidic sites of the nanodispersed
clay. For the second step of EVA degradation, Maurin et al.
[235] foundas products 1-butene, carbondioxide, ethylene,
methane and carbon monoxide, while McGrattan [236]
identified hydrocarbons ranging from C8 to C26, grouped
in a series of ␣,␻-dienes, 1-alkenes and n-alkenes. By thor-
oughly studying both the first and second steps, Costache
et al. [237] investigated the possibility that the presence of
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1177
Fig. 59. Possible radical recombination reactions for EVA nanocompos-
ites [237]. Reproduced from Costache, Jiang and Wilkie by permission of
Elsevier Science Ltd., UK.
nanodispersed clay can change the degradation pathway
of EVA. In the early stages of the EVA degradation, the loss
of acetic acid seems to be catalyzed by the hydroxyl groups
present onthe edges of the clay lamellae. The TGA–FTIRand
GC–MS results of thermal degradation of EVA in the pres-
ence and in the absence of clay show that even though the
two processes are very similar, subtle changes occur, lead-
ing to the formation of products that differ both in quantity
andidentity. It has beensuggestedthat these products form
as a result of radical recombination reactions that occur
because the degrading polymer is containedwithinthe clay
layers for sufficient time to permit the reactions (Fig. 59).
In cases where there are multiple degradation pathways,
the presence of the clay can promote one of these at the
expense of another, and thus lead to different products and
hence a different rate of volatilization.
In another study, the thermal decomposition of EVA
nanocomposites has beeninvestigatedusing TGAinhelium
and in air. In helium, EVA nanocomposites exhibit a neg-
ligible reduction in thermal stability compared to virgin
EVA or EVA microcomposite. In contrast, when decom-
posed under air, the same nanocomposites exhibit a rather
large increase in thermal stability, as the maximum of the
second degradation peak is shifted 40

C to higher temper-
ature, while the maximum of the first decomposition peak
remains unchanged (see Table 35). The explanation for the
improved thermal stability is the formation of protective
char under oxidative conditions [238].
Finally, several studies have focused on the effect of
clay organic modification on thermal stability of nanocom-
posites. More specifically, it has been suggested that the
thermal stability of the nanocomposites is directly related
to the stability of the OMLS used for their preparation [84].
Table 35
Maximum temperature at the main degradation peak as measured under
air at 20

C/min for EVA and EVA-nanocomposites with different organ-
oclay contents.
Organoclay content (wt.%) Maximum temperature at the
main degradation peak (

C)
0 452.0
1 453.4
2.5 489.2
5 493.5
10 472.0
15 454.0
Fig. 60. TGA curves of (a) pure PU, (b) PU/3wt.% C16-MMT and (c)
PU/3wt.% MO-MMT [202]. Reproduced from Xiong, Liu, Yang and Wang
by permission of Elsevier Science Ltd., UK.
In a typical example, Xiong et al. [202] studied the ther-
mal stability of PU and nanocomposites prepared using
MMT modified either by a quaternary alkyl ammoniumsalt
(C
16
-MMT) or by anaromatic modifier (MO-MMT). The TGA
curves obtained (Fig. 60) show that the degradation rates
of the nanocomposites were slightly slower compared to
that of PU, indicating an improvement of thermal stability.
Comparing the quaternary alkyl ammonium salt and the
aromatic amine modifier they used, the authors found the
degradation onset temperature of PU/C
16
-MMT at 316.3

C,
thus lower than that of the PU/MO-MMT (331.6

C), show-
ing the latter to have the higher thermal stability. The main
reason is that the aromatic chain of the modifier in MO-
MMThas higher thermal stabilitythanthe alkyl chainof the
modifier in C
16
-MMT. The authors also noted that the aro-
matic amine modifier can react with the pre-polyurethane
matrixused, further strengtheningthe interactionbetween
inorganic and organic phases.
In another interesting study, Yei et al. [115] used TGA to
characterize PS-based nanocomposites prepared from clay
treated with cetylpyridinium chloride (CPC) and CPC/␣-
cyclodextrin (CPC/␣-CD) inclusion complex, as already
described in Section 5.3.1. Fig. 61 shows the TGA curves
of pure CPC and the CPC/␣-CD inclusion complex. As is
clearly evident, the CPC/␣-CD inclusion complex decom-
poses at higher temperature (284

C) than the pure CPC
(220

C). Thus, the formation of an inclusion complex
between CPD and ␣-CD improved the thermal stability of
the CPC surfactant; the presence of the ␣-CD protects CPC
from earlier decomposition. Table 36 summarizes the TGA
results for the nanocomposites and the pure polymer. Both
nanocomposites display higher decomposition tempera-
tures than the virgin PS, with the CPC/␣-CD intercalated
clay nanocomposite being the most thermally stable of the
three samples.
As deduced from the previous examples, even though
contradictory results are sometimes found in the lit-
1178 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Table 36
Results of TGA and DSC data for the polystyrene nanocomposites.
Sample Clay content (wt.%) T
g
(

C)
a
T
0.05
(

C)
b
T
0.5
(

C)
c
Char at 600

C (%)
PS 0 100 390 424 0
CPC/Clay/PS 3 102 408 424 2.9
a-CD/CPC/Clay/PS 3 106 423 452 5.8
a
Glass transition temperature (T
g
).
b
5% degradation temperature (T
0.05
).
c
50% degradation temperature (T
0.5
).
Fig. 61. TGAcurves of (a) pureCPCand(b) theCPC/a-CDinclusioncomplex
[115]. Reproduced from Yei, Kuo, Fu and Chang by permission of Elsevier
Science Ltd., UK.
erature concerning the thermal stability of polymeric
nanocomposites, the opportunity of achieving a significant
improvement in thermal stability through low filler con-
tent is particularly attractive because end-products can be
made cheaper, lighter and easier to process [35].
6.5. Flame retardance
6.5.1. Flame retardance of polymer–layered silicate
nanocomposites
Polymers are being used in more and more applications
where flame retardant behavior is of critical importance.
Traditionally, flame retardancy has been achieved either by
using intrinsically flame retardant polymers, such as fluo-
ropolymers or PVC, or by incorporating flame retardants
(FRs), such as aluminumtrihydrate, magnesiumhydroxide,
organic brominated compounds or intumescent systems.
However, such FRs exhibit significant disadvantages. For
example, aluminum trihydrate and magnesium hydroxide
need to be applied at very high loadings to be effec-
Fig. 62. Schematic view of the cone calorimeter [35]. Reproduced from Beyer by permission of Elsevier Science Ltd., UK.
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1179
Table 37
Cone calorimeter data of various polymers and nanocomposites with OMLS.
Sample PHRR (kW/m
2
) HRR
ave
(kW/m
2
) SEA
ave
(m
2
/kg) Ref.
PA6 1010 603 197 [240]
PA6/2% OMLS 686 390 271
PA6/5% OMLS 378 304 296
PS 1120 703 1460 [240]
PS silicate mix 3% 1080 715 1840
PS nanocomposite 3% 567 444 1730
PSw/DBDPO/Sb
2
O
3
30%) 491 318 2580
PS 1230 1315 [159]
PS/MAST-Hect 1% 1011 1336
PS/MAST-Hect 3% 894 1332
PS/MAST-Hect 5% 728 1327
PPgMA 1525 536 704 [240]
PPgMA nanocomposite 2% 450 322 1028
PPgMA nanocomposite 4% 381 275 968
EVA/Na
+
5% 1200 [163]
EVA/Cloisite 30B 3% 860
EVA/Cloisite 30B 5% 780
EVA/Cloisite 30B 10% 630
EVA 2303 430 [237]
EVA/30B 1174 670
EVA/30BHect 1289 593
EVA/30BMag 2010 476
EVA/MMT 1959 517
PU (I) 2561 741 176 [144]
PU (I)/o-MMT 918 344 305
PU (II) 2254 637 235 [144]
PU (II)/o-MMT 641 363 412
PU (III) 2647 768 165 [144]
PU (III)/o-MMT 848 444 172
PU (IV) 2664 775 235 [144]
PU (IV)/o-MMT 797 435 412
PE 1470 510 [184]
PE/JS 2% 670 440
PE/JS 5% 320 450
PE/JS 10% 540 380
PE/JS 15% 390 280
tive, resulting in high density and lack of flexibility of
the end-products, as well as low mechanical properties
and problems in compounding. On the other hand, con-
cerns over the environmental impact have made halogen
containing materials a less popular option in many coun-
tries. Moreover, the addition of many FRs increases the
production of soot and carbon monoxide during combus-
tion. Finally, intumescent systems are relatively expensive
and electrical requirements can restrict their application
[35,56].
Among test methods developed for the evaluation of
flame retardant properties, the one most commonly used
by researchers is cone calorimetry (Fig. 62), as it provides
valuable information and may even indicate the flame
retardancy mechanism. The measuring principle in this
test, which is standardized as ASTME 1354 and ISO5660, is
that of oxygen consumption. This states that there is a con-
stant relationship between the mass of oxygen consumed
from the air and the amount of heat released during poly-
mer combustion. In a typical cone calorimeter experiment
the sample is exposed to a defined heat flux, usually 35
or 50kW/m
2
; properties such as heat release rate (HRR),
peak of heat release (PHRR), time to ignition (TTI), total
heat released (THR), mass loss rate (MLR), mean CO yield
and mean specific extinction area can be simultaneously
measured [35,41]. The HRR is considered to be the most
important variable characterizing a fire. A high HRR causes
fast ignition and flame spread, while the PHRR represents
the point in a fire where heat is likely to propagate further,
or ignite adjacent objects [35,239].
As can be seen from Table 37, where cone calorime-
ter data are presented for various nanocomposites and
the corresponding neat polymers, the incorporation of lay-
ered silicates results in significant reductions of PHRR and
average HRR. Moreover, it has been demonstrated that the
reduction in PHRR is proportional to the fraction of clay,
and it also depends on its aspect ratio and surface charge
density.
In the literature it is reported that the primary param-
eter responsible for the lower HRR of nanocomposites is
the MLR during combustion, which, in turn, is also sig-
nificantly reduced compared to the values observed for
the pure polymer. This difference comes into effect shortly
after the initial combustion, when the nanocomposite has
1180 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 63. Residues after cone calorimeter experiment for EVA, EVA/30B-5 and EVA/Na
+
-5 [163]. Reproduced from Duquesne, Jama, Le Bras, Delobel, Recourt
and Gloaguen by permission of Elsevier Science Ltd., UK.
had time to form a char on its surface [56,177]. In fact, it
is generally considered that the formation of a thermal
insulating and low permeability char on the outer sur-
face of a nanocomposite during combustion is the key to
understanding improvement in flame retardant properties
[35,56]. More specifically, heat transfer from an external
source or froma flame promotes thermal decomposition of
the organoclay and the polymer. This results in accumula-
tion and reassembly of clay platelets on the surface of the
burning material [226]. Therefore, the carbonaceous char
formed superficially during combustion is rich in silicates
and can be viewed as a sort of ceramic char–layered silicate
nanocomposite [31,178,226]. In fact, XRD and TEM exami-
nationof suchresidues has revealedintercalatedstructures
[241]. Actually, it is exactly its own nanocomposite struc-
ture that allows the residue formed to act as a protective
barrier by reducing the heat and mass transfer between the
flame andthe polymer. That is, the char insulates the under-
lying polymer fromheat and also slows oxygen uptake and
the escape of volatile gases produced by polymer degra-
dation. Both these actions interfere with the combustion
cycle by reducing the amount of fuel available for burning
[31,35,56,178,241,242].
This mechanism has been put forward in most
studies reporting on the flame retardant properties of
nanocomposites. For example, combustion experiments on
EVA-based nanocomposites showed that the HRR and MLR
were reduced by 70–80% in a nanocomposite with low sil-
icate loadings (2–5%) presumably because of a refractory
char-clay surface layer formed by the reassembling of the
clay layers and catalyzed charring of the polymer [177].
Duquesneet al. [163] alsoreportedonthefireretardancy
of EVA-based nanocomposites, using two montmoril-
lonites: Cloisite Na
+
and Cloisite 30B. While the PHRR
was clearly reduced when either clay was added to the
polymer (relative decreases of 25% for Cloisite Na
+
and
50% for Cloisite 30B), the authors noted that the TTI was
also reduced and that the THR was similar for pure poly-
mer and the clay-containing polymer. Comparison of the
residues after the cone calorimeter experiment (Fig. 63)
demonstrates the different behavior of the three materi-
als. The pure polymer does not give a residue, whereas the
EVA/Na
+
-5 gives a powdery grey “ash,” and the EVA/30B-5
system gives a fragile, carbonaceous residue around 3mm
thick.
In the case of PE/clay nanocomposites significant reduc-
tions of PHRR were reported, whereas the TTI results were
somewhat more complicated. For low clay contents, TTI
was increased, due to the barrier effect of the clay. How-
ever, with increasing clay content a reduction of TTI was
attributed to catalytic effects. Again, a large reduction of
flammability in nanocomposites compared to pure PE was
attributed to the formation of char [184].
Table 38 summarizes the results of the cone calorime-
try tests performed on PU and PU-based nanocomposites.
The data show that the average HRR and PHRR were
greatly reduced for the nanocomposites as compared with
the reference materials. However the TTI was similar or
slightly reduced for the nanocomposites and the initial
rate of weight loss/heat release was higher, probably due
to early decomposition of the organic modifier of the
clay and subsequent clay-catalyzed polymer degradation.
As shown by the “fire performance index” (PHRR/TTI),
the nanocomposites perform much better than pure PUs.
However, they showed higher rates of smoke emission
than their pure PU counterparts, presumably because of
a greater degree of secondary condensed phase chemistry
in an oxygen-depleted environment, leading to the forma-
tion and evolution of aromatic and carbonaceous species.
Finally, Berta et al. [144] conducted vertical burn tests,
where a flame was applied twice for 10s to the base of
the test specimens and the burning behavior was observed.
Table 38
Cone calorimetry results for PU nanocomposites and reference materials.
PU TTI (s) PHRR (kW/m
2
) PI (PHRR/TTI) HRR
ave
(kW/m
2
) SEA
ave
(m
2
/kg)
PU NC-PU PU NC-PU PU NC-PU PU NC-PU PU NC-PU
I 29 29 2561 918 88 32 741 344 176 305
II 35 33 2254 641 64 19 637 363 235 412
III 26 17 2647 848 102 50 768 444 165 172
IV 22 25 2664 797 102 50 775 435 235 412
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1181
Fig. 64. HRR measured with a cone calorimeter (heat flux 35kW/m
2
) for
various PP-based RTPO materials: (a) PP-based RTPO (neat resin), (b) PP-
based RTPO/clay microcomposite, containing 10wt.% clay, (c) PP-based
RTPO/PPgMA/claynanocomposite, containing10wt.%clay, 30wt.%PPgMA
[185]. Reproduced fromHong, Lee, Bae, Jho, Nam, Namand Lee by permis-
sion of John Wiley & Sons, Inc.
Pure PU materials dripped heavily upon ignition, whereas
for the PU nanocomposites dripping was strongly sup-
pressed or eliminated.
HRRplots of PP basedRTPOneat resin, microcomposites
and nanocomposites are shown in Fig. 64. The PHRR of the
nanocomposite containing 10wt.% clay is 37% lower than
that of neat resin, while the microcomposite and the neat
resin showvery similar behavior. At the end of combustion,
the neat resin leaves no residue and the microcompos-
ite leaves only a little powder, while the nanocomposite
leaves a consistent char-like residue. Generally, PP ther-
mally degrades to volatile products above 250

C through
a radical chain process, propagated by carbon centered
radicals created by carbon–carbon bond scission. In neat
resin, thermal degradation continues during the combus-
tion, and all intermediate degradation products volatilize
completely. Onthe other hand, there maybe physicochemi-
cal adsorption of the intermediate degradation products on
clay surfaces in clay nanocomposites. This adsorption may
delay volatilization of the degradation products and pro-
moteaccumulationof theincompletedegradationproducts
on the clay [185].
Zanetti and Costa [177] also found that the nanodis-
persed morphology in PE/EVA nanocomposites leads to
a substantial decrease of combustion rate of the poly-
mer matrix, whereas the microcomposite shows a smaller
decrease of the rate of combustion.
However, a quite interesting observation is that,
although the clay must be nanodispersed to affect the
flammability of nanocomposites, it does not need to be
completely delaminated. Inother words, it has beenargued
that the flame retardancy obtained in nanocomposites
when merely intercalation has occurred is at least as
good as when complete exfoliation is achieved. In fact,
excellent performance has been observed when the clay
layers have remained separated by only approximately
3nm, which is considered to be in the “intercalation” zone
[55,135,231,243].
Fig. 65. Effects of clay content onmass burning rate of PA6 (8mmthick) at
50kW/m
2
[242]. Reproduced fromKashiwagi, Harris, Zhang, Briber, Cipri-
ano, Ragharan, Awad and Shields by permission of Elsevier Science Ltd.,
UK.
At this point, it is worth summarizing a very inter-
esting study by Kashiwagi et al. [242], aiming to further
elucidate the nanocomposite flame retardancymechanism.
The authors performed cone calorimeter tests on PA6 and
nanocomposites containing2and5%clay. Theynoticedthat
the MLR (burning) curve (Fig. 65) of each sample is propor-
tional to the HRR curve (Fig. 66). Thus, the specific heat
of combustion (H
c
), obtained from the HRR divided by the
MLR remains unchanged for the three samples, implying
that the observed reduction in HRR (and MLR) tends to be
due to chemical and physical processes in the condensed
phase, rather than in the gas phase. To prove this conjec-
ture, the authors exposed samples to the same external
flux as in the cone calorimeter, but in nitrogen, to avoid
Fig. 66. Effects of clay content on HRR of PA6 (8mm thick) at 50kW/m
2
[242]. Reproduced fromKashiwagi, Harris, Zhang, Briber, Cipriano, Ragha-
ran, Awad and Shields by permission of Elsevier Science Ltd., UK.
1182 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 67. Selected video images at 100, 200, and 400s in nitrogen at 50kW/m
2
[242]. Reproduced fromKashiwagi, Harris, Zhang, Briber, Cipriano, Ragharan,
Awad and Shields by permission of Elsevier Science Ltd., UK.
any gas phase effects. Despite the quantitative difference in
MLR between the two cases, the overall differences among
the three samples were very similar between the burn-
ing case and the gasification case. Given that the burning
behavior depends on processes in both the gas and the con-
densedphase, while the gasificationbehavior depends only
on those in the condensed phase, the authors suggested
that the observed improvement in the flammability resis-
tance of nanocomposites is due to chemical and physical
processes in the condensed phase. During gasification, the
nanocomposites appearedto be more viscous thanthe neat
PA6 sample and dark floccules appeared on their surfaces,
grew with time (Fig. 67) and were left at the bottom of
the container at the end of the test. Similar carbonaceous
floccules were also observed in the residues of the burnt
samples tested in the cone calorimeter. Further analysis
showed that up to 80% of the protective floccules consist
of clay particles, while the remaining 20% consist of ther-
mally stable organic components with possible graphitic
structure. The authors attributed the accumulation of clay
particles on the burning/gasifying sample surface to two
possible mechanisms. One is the recession of the polymer
resin fromthe surface by pyrolysis with dewetted clay par-
ticles left behind, and the other is the transportation of clay
particles pushed by numerous rising bubbles of degrada-
tion products.
The development of the aforementioned radiative gasi-
fication technique (Fig. 68) is expected to increase the
understanding of the condensed phase decomposition pro-
cesses of pyrolysis, since the mechanismof nanocomposite
flame retardancy can be looked at in more detail through
such techniques. With apparatus similar to the to cone
calorimeter, this method allows pyrolysis in a nitrogen
atmosphere at heat fluxes similar to those found in fires
[35,56,242].
Summarizing: nanocomposites could offer significant
advantages in the area of polymers flame retardancy
and these advantages become even more evident when
nanocomposites are compared with conventional FRs. First
of all, only very lowconcentrations of silicate are necessary
in nanocomposites, resulting in commercial advantages
such as low density, lower cost and ease of preparation.
Moreover, these materials are an environmentally friendly
alternative to some types of fire retardants, as they con-
tain no halogens, phosphates or aromatics other than those
that may be present in the polymer matrix; and they
do not produce increases in the carbon monoxide and
soot levels during combustion like those associated with
conventional FRs. Also, while traditional fillers very often
severely degrade the physical properties of the polymer
or discolor it, an important feature of nanocomposites is
the simultaneous improvement in many physical proper-
ties, without any change in the polymer color [3,35,56,178].
Finally, unlike some FRs, silicates provide physical integrity
to the material burning in configurations (e.g. vertical
upward combustion) in which dripping of flaming mate-
rial could occur, which constitutes an additional hazard of
fire propagation to surrounding materials [231].
However, even though flame retardancy is one of the
most promising properties of nanocomposites, and despite
the fact that these materials have shown to perform very
well in laboratory tests concerning their resistance to fire,
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1183
Fig. 68. A schematic view of the “radiative gasification” apparatus [35]. Reproduced from Beyer by permission of Elsevier Science Ltd., UK.
much more research needs to be carried out to establish
their applications and limitations. The potential synergy
between traditional flame retardants and nanocomposites,
whichis discussedinthefollowingparagraph, couldfurther
extend the uses of nanocomposites in this field [56].
6.5.2. Synergism between nanocomposites and flame
retardants
Fromthepoint of viewof fireretardancy, themost signif-
icant advantage offered by nanocomposite formation is the
reduction in PHRR (fromcone calorimeter measurements).
However, compared to the virgin polymer, the TTI is usu-
ally lowered while the THR remains the same. This means
that the nanocomposite ignites faster than the virgin poly-
mer and that, like the virgin polymer, the nanocomposite
is eventually completely combusted [239,244,245]. More-
over, a major limitation of nanocomposites is that they only
work in the condensed phase and do nothing to inhibit the
flame in the gas phase [246]. Therefore, even though these
materials can be considered to be flame retarded by defi-
nition, they performpoorly when tested under industrially
significant or regulatory fire safety tests, such as UL-94V.
In fact, it is believed that the excess quaternary ammo-
nium surfactants used to disperse the clays, also increase
the probability of early ignition [239,246]. Considering also
the disadvantages of traditional FRs, described in the pre-
vious paragraph, it becomes obvious that it is necessary
to develop novel synergistic flame retardant systems with
high efficiency and acceptable environmental impact.
In fact, as will be demonstrated in the following
examples, polymer nanocomposites work in a synergistic
manner with other FRs. Since a portion of the FR is replaced
by the nanocomposite in a less than 1:1 replacement ratio,
products with improved fire performance and a better bal-
ance of properties can be obtained [239].
Despite the existing regulatory concerns in the area of
halogenated FRs, polymer nanocomposites combined with
such additives are reported in the literature. For example,
Zanetti et al. [247] described a PP-based nanocomposite
incorporating decabromodiphenyl ether (DBE) and anti-
mony oxide (AO) as the FR system. The cone calorimeter
results obtained are presented inTable 39. It is worth notic-
ing that while the reference system (PP-MA+DBE+AO)
showed two peaks in HRR (one at 90s followed by a sec-
ond larger one at 170s), the addition of 5wt.% organoclay
eliminated the secondary peak, indicating a more uni-
form flammability behavior. The average HRR was lowered
by 58% and the PHRR by 70%. Also, the nanocompos-
ite significantly increased the burn time for the sample
when compared to the flame retardant control sam-
ple.
Si et al. [246] demonstrated that self-extinguishing
PMMA-based nanocomposites, which can pass the strin-
gent UL 94 V0 standard, can be successfully prepared by
combining organoclays with halogenated FRs. The authors
mixed PMMA, a highly combustible polymer, with DBE,
AO and o-MMT. Both neat PMMA and the control flame
retarded material failed the UL 94 V0 standard, while
Table 39
Cone calorimeter data (35kW/m
2
) for PP nanocomposites [247].
Formulation PHRR (kW/m
2
) PHRR, time (s) Average HRR
PP-MA+22wt.% DBE+5wt.% Sb
2
O
3
300, 650 90, 170 254
PP-MA+22wt.% DBE+5wt.% Sb
2
O
3
+5wt.% organoclay 200 85 107
PP-MA+organoclay 350 85 188
PP-MA 600 180 279
1184 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 69. Optical images of PMMA composites after the combustion of UL
94 V0 test: (a) PMMA/DB/AO(75/20/5) and (b) PMMA/DB/AO/Cloisite 20A
(70/20/5/5) [246]. Reproduced from Si, Zaitsev, Goldman, Frenkel, Peiffer,
Weil, Sokolov and Rafailovich by permission of Elsevier Science Ltd., UK.
the sample where both FR and clay were added self-
extinguished in 1s after the application of the flame
without dripping. Optical images of the samples are shown
in Fig. 69, where it can be seen that the PMMA sample con-
taining both FR and clay is blackened by the smoke of the
flame, but remains unchanged in shape. It was also noticed
that the samples with all three components, clay, DBE and
AO show a lower PHRR and average MLR than those with
only clay or the FRs.
Chigwada et al. [244] conducted a study aiming to
explore if any improvements in the TTI and THR, while
maintaining the reduction in PHRR, can be achieved
by the incorporation of a small amount of bromine
chemically attached to the clay cation. The authors first
prepared an organically modified clay using ammonium
salts with added oligomeric material consisting of vinyl-
benzyl chloride, styrene and dibromostyrene. Then they
prepared intercalated nanocomposites by bulk polymer-
ization. They found that the dibromostyrene enhances the
flame retardancy of PS nanocomposites as compared with
both the virgin polymer and nanocomposites prepared
from non-halogen containing, organically modified clays.
More specifically, with the bromine-containing organoclay,
nanocomposites were obtained exhibiting reduced PHRR,
THRand improved thermal stability. The reductioninPHRR
is due to nanocomposite formation and not to the presence
of bromine, which, however, is important in the reduction
of the THR, i.e. the presence of bromine, even at less than
4%, prevents the PS burning.
Another interesting study was carried out by Tang et
al. [248]. They did clay modification and intercalation
simultaneously during melt mixing. More specifically, they
melt compounded PP, Na-MMT and hexadecyltrimethy-
lammoniumbromide to yield a nanocomposite, suggesting
that clay modification occurred in the molten polymer
matrix. Therefore, the sodium bromide produced by the
ion-exchange reaction remained in the nanocomposite.
Subsequently, the authors combined the nanocompos-
ites obtained with an intumescent system consisting
of pentaerythritol and ammonium polyphosphate, with
melamine phosphate sometimes added. Even though syn-
ergismwas observed between the nanocomposites and the
intumescent FRs, the interpretation of the data is com-
plicated by the presence of NaBr, which acts as a vapor
phase FR. In fact, it remains unclear whether the improved
flammability properties reported are due to the nanocom-
posite or to NaBr. In any case, as Morgan [239] noted in
his review on nanocomposite–FR synergism, this novel
method of nanocomposite formation should be investi-
gated further, especially if the NaBr can be removed, to
produce a truly non-halogenated flame retardant formu-
lation.
Tang et al. [183] also observed that when MMT and
intumescent FRs are combined in a polymer matrix, their
synergistic effect is related to their composition ratio. It
was anticipated that the reassembling of silicate layers
on the surface of the nanocomposite during combustion
may hinder NH
3
from swelling, leading to a negative
effect on the fire retarding properties. NH
3
is the main
gaseous product; it volatilizes and makes the mixture of
thecarbonaceous residueandphosphocarbonaceous mate-
rials swell, leading to the formation of the intumescent
residuechar. Therefore, whenthemass of MMTis increased,
the negative effect may exceed the positive effect on the
fire retarding property, which explains why the syner-
gistic effect was no longer demonstrated at high MMT
loadings.
In another study dealing with the synergism of
nanocomposites and intumescent systems, the polyol
(carbonization agent) was replaced by PA6. More specif-
ically, a PA6 nanocomposite was compounded with EVA
and ammonium polyphosphate (acid source). The results
showed that the PHRR and THR were decreased by the PA6
nanocomposite, while the mechanical performance was
significantly improved [249].
Another important group of FRs which exhibit syner-
gismwithnanocomposites are the phosphorous-basedFRs.
For example, Chigwada et al. [245] observed reduction in
the PHRR, THR and MLR, when phosphorous-containing
FRs were incorporated in vinylester nanocomposite. The
authors reported that these reductions were directly pro-
portional to the amount of phosphate added.
Zheng and Wilkie [250] investigated the synergistic
action of phosphates and nanocomposites by incorporat-
ing the phosphate in the organic treatment of the clay.
They treated Na-MMT with a styrenic oligomer that con-
tained ammonium pendant groups and copolymerized
vinylphenyl phosphate. Then, PSnanocomposites werepre-
pared, either by melt intercalation or intercalation from
solution. TGA/FTIR showed that the phosphate is released
during thermal decomposition, and acts in the gas phase as
anFR. Theconecalorimeter data, ontheother hand, showed
that in the presence of the phosphate, the average HRR and
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1185
PHRR can be significantly reduced while the time to PHRR
is increased up to ca. 40s.
Quite similarly, Kim et al. [251] intercalated triph-
enylphosphate (TPP) in the galleries of an organo-modified
montmorillonite (Cloisite 30B). The clay obtained was sub-
sequently melt mixed with ABS yielding nanocomposite
structures. The key advantage of intercalating the phos-
phate in the organoclay is that the normally volatile TPP is
protected during melt compounding, allowing for a grater
range of melt processing without TPP loss.
On the other hand, Hussain et al. [252] introduced
organophosphinate into the backbone of an epoxy resin,
which was subsequently crosslinked in the presence of
o-MMT. Quite surprisingly, flame retardant antagonism
was observed with the PHRR and THR increasing for
the nanocomposite +FR system, as compared with the
epoxy+FRcontrol sample. No clear reasonwas giveninthis
study; but in a later review article, Morgan [239] indicated
that the observed antagonism could have been due to the
lack of uniform clay dispersion.
Another example where flame retardant antagonism
may be observed is the case of FR systems that achieve
flame retardancy by dripping away fromthe flame. As Mor-
gan [239] noticed, since nanocomposites inhibit polymer
flowanddrippingduringflamingcombustion, suchFRs will
not work with a polymer nanocomposite system.
In general, however, the synergism reported between
clays and conventional FRs provides an alternative for
improving fire performance without seriously deteriorat-
ing appearance and mechanical behavior, and even opens
the possibility of formulating self-extinguishing polymer-
based materials.
6.6. Heat distortion temperature
Heat distortion temperature or heat deflection temper-
ature (HDT) is the temperature at which a polymer sample
deforms under a specifiedload. Thus, it is anindexof a poly-
meric material’s heat resistance towards applied load and
is assessed by the procedure given in ASTM D-648 [55].
In general, improvements of HDT are reported by
nanocomposite formation. Usually, a significant increase
is achieved for clay contents of approximately 5wt.%,
and then HDT values level off for higher clay loadings
[94,208,253].
For example, Kojima et al. [94] showed that the HDT
of pure PA6 increases up to 90

C after nanocomposite
preparation with OMLS, and they reported the clay content
dependence of HDT of PA6/MMT nanocomposites. More
specifically, they showed that there is a marked increase
in HDT from 65

C for neat PA6 to 152

C for 4.7wt.%
nanocomposite. Beyond that MMT loading, the HDT of the
nanocomposites levels off. Moreover, the HDTvalues of var-
ious PA6 nanocomposites prepared with clay lamellae of
different lengths showed that the HDT also depends on the
aspect ratio of dispersed clay particles.
Similarly, nanodispersion of MMT in a PP matrix has
been found to promote a higher HDT (Table 40). In the case
of PP/f-MMT there is a marked increase of the HDT, from
109

C for the neat polymer to 152

C for a 6wt.% of clay,
after whichtheHDTof thenanocomposites levels off. When
Table 40
HDT of PP/MMT nanocomposites and the respective unfilled PP.
Organically modified MMT (wt.%) HDT
PP-f-MMT PP/alkyl-MMT
0 109 109
3 144 130
a
6 152 141
b
9 153
a
C18-MMT filler, extruder processed.
b
2C18-MMT filler, twin head mixer.
the same neat PP polymer is filled with alkylammonium
modified MMT, the HDT is also increased but to a smaller
extent, reflectingthelower exfoliationlevel of theinorganic
fillers [254].
It should be emphasized that the increase of HDT due
to clay dispersion is very important, not only fromapplica-
tion or industrial point of view, but also because it is very
difficult to achieve similar HDT enhancements by chem-
ical modification or reinforcement by conventional fillers
[31,50,55].
6.7. Rheological properties
The measurement of the rheological properties of any
polymeric material is crucial to gain fundamental under-
standing of the processibility of that material and is
usually conducted by either dynamic oscillatory shear
or steady shear measurements [50,55]. In the case of
polymer–layeredsilicate nanocomposites, the studyof rhe-
ological properties is instructive for two reasons: First,
these properties are indicative of melt processing behavior
in unit operations, such as injection molding. Second, since
the rheological properties of particle-filled materials are
sensitive to the structure, particle size, shape and surface
characteristics of the dispersed phase, rheology potentially
offers a means to assess the state of dispersioninnanocom-
posites, directly in the melt state. Thus, rheology can be
envisaged as a tool that is complementary to traditional
methods of materials characterization [15,37,50].
It is generally established that when nanocomposites
are formed, the viscosity at low shear rates increases with
filler concentration [15]. Very often, solid-like behavior is
observed, which is attributed to the physical jamming or
percolation of the randomly distributed silicate layers, at
surprisingly low volume fraction, due to their anisotropy
[55]. On the other hand, at high shear rates, shear thinning
behavior is usuallyobserved[15]. It has beensuggestedthat
this is the result of the alignment of silicate layers towards
the direction of flow at high shear rates. Such observa-
tions support the percolation argument used in the case of
nanocomposite rheological behavior under low shear [55].
Typical shear viscosity curves as a function of shear are
presented in Fig. 70 for PBS-based nanocomposites with
various clay loadings.
Shear thinningbehavior at highshear rates has alsobeen
observed for a PA6 nanocomposite. In fact, this behavior
is similar to that of neat PA6 and the composites with the
same amount of glass fiber or unmodifiedMMT. It is of great
interest to note that the absolute value of the melt viscos-
1186 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 70. Shear viscosity as a function of shear rates [55]. Reproduced from
Ray and Okamoto by permission of Elsevier Science Ltd., UK.
ity of the nanocomposite is significantly lower than that of
neat nylon 6 or the other composites—which implies good
melt processibility over a wide range of processing condi-
tions. One possible reason for reduction of melt viscosity
in the nanocomposite is slip between the PA6 matrix and
the exfoliated organoclay platelets during high shear flow.
Another possibility is a reduced molecular weight of the
nylon 6 due to degradation (e.g. hydrolysis) in the presence
of clay[15]. Similarly, capillarydatarevealedthat nanocom-
posites based on medium and low molecular weight PA6
exhibited lower viscosities than the corresponding pure
polymers [14].
6.8. Crystallinity
Crystal formation includes two stages, namely nucle-
ation and crystal growth. However, although it is well
established that nanometer sized clay platelets are effec-
tive nucleating agents, different effects have been reported
onthelinear growthrateandtheoverall crystallizationrate,
depending on the type of polymer [97].
For example, Maiti et al. [175] found that although clay
particles act as nucleating agents for the crystallization of
a PP-MA matrix, the linear growth rate and the overall
crystallization rate are not significantly influenced by the
presence of clay.
Similarly, Di Maio et al. [255] studied the isothermal
crystallizationof PCL/claynanocomposites andnoticedthat
the dispersed clay platelets act as nucleating agents in the
PCL matrix, remarkably reducing the crystallization half-
time t
1/2
. By DSC analysis after isothermal crystallization
(Fig. 71), the authors observed a reduction of the melting
temperature with the increase of clay content, indicat-
ing a reduced degree of crystals perfection and degree
of crystallinity. This was attributed to the confinement of
chains and segments in the presence of clay, hindering
the segmental rearrangement during crystallization and
restricting the formation of perfect crystals in the polymer
matrix.
Ke and Yongping [222] conducted DSC analysis on
intercalated PET/o-MMT nanocomposites. They found a
reduction of T
g
in the composite compared to the pure
matrix, which they attributed to the plasticizing effect of o-
Fig. 71. DSC thermograms of PCL and of selected PCL/clay nanocompos-
ites after isothermal crystallization at 45

C. Number refers to clay weight
concentration; 0* is the DSC thermogram of non-isothermal crystallized
(−10

C/min) pure PCL [255]. Reproduced from Di Maio, Iannace, Sorren-
tini and Nicolais by permission of Elsevier Science Ltd., UK.
MMT. However, they noticed that by increasing the o-MMT
content the T
g
is increased, as shown in Fig. 72. Further,
theyobservedthat the coldcrystallizing point of pure PETis
150

C, while for the nanocomposite it decreases to 130

C.
This result shows that adding o-MMT into PET is favorable
to its crystallization.
For the effect of nanocomposite preparation on EVA
crystallinity, contradictory results have been reported. For
example, Chaudhary et al. [171] found that the crystal-
lization process for EVA-28 is significantly affected by the
presence of clays, while Gelfer et al. [256] argued that
the effect of clay on the crystalline phase in EVA-3 is
insignificant. They observed the same crystalline structure
(orthorhombic) and similar melting behavior, as well as
transitiontemperatures inpureEVA-3andnanocomposites
containing 10wt.%clay. Gelfer et al. consideredthis to be an
anticipated result, since it is known that in ethylene-based
copolymers side chains (short branches) larger than the
methyl groupare excluded fromthe crystalline domainand
are aggregated into the amorphous phase. Consequently,
Fig. 72. The relationship between o-MMT content and Tg of composite
[222]. ReproducedfromKe andYongpingbypermissionof Elsevier Science
Ltd., UK.
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1187
the amorphous domains in EVA are enriched by the polar
VA units. It was hypothesized that the organoclay particles
dispersed in the EVA matrix have higher affinity with the
polar VA units; hence they are predominantly confined to
the amorphous phase where the VA content is high, with-
out significantly affecting the crystalline domainformedby
the non-polar ethylene segments.
While further work needs to be done to elucidate
crystallization phenomena in nanocomposites based on
different polymers, the effect of layered silicates on
polyamide crystallinity has been far more investigated. In
fact, a number of researchers have focused on the effect of
clay addition on the crystal morphology of polyamides, as
well as on the melting, glass transition, crystallization tem-
perature and crystallization rate. In semi-crystalline PA6,
two phases generally exist at room temperature. The ␣-
phase and the ␥-phase are monoclinic, but the latter can
be represented as a pseudo-orthotropic lattice.
In general, it has been observed that upon prepara-
tion of nanocomposites the crystallography of the PA6
matrix changes. Maiti and Okamoto [257] found that in the
presence of clay particles, PA6 crystallizes faster and exclu-
sively in the ␥-phase (Fig. 73). The nucleation and growth
processes of PA6 in the nanocomposites are presented in
Fig. 74, as deduced from direct observation by TEM.
Similarly, Lincoln et al. [12] showed through simulta-
neous SAXS and WAXS analyses at elevated temperature
that the presence of silicate layers provides a confined
environment for crystallization and disrupts crystallite for-
mation, ultimately resulting in the predominance of the
␥-phase in quenched samples. They noted that the more
ductile ␥-phase that is formed may contribute greatly to
the observed changes in properties of the material, specifi-
cally the toughness. Evidence has also been found that the
layers affect not only the formation of the lamellae, but
also of spherulites, which may also be the root of some of
the property enhancements. Moreover, certain processes
involved in nanocomposite preparation affect the global
orientation of the crystal phase. That is, X-ray diffraction
of PA/MMT nanocomposites has indicated that the chain
axes are normal to the silicate layers in the interior of an
injection molded component, while they are parallel to the
Fig. 73. Typical TEMimages of PA6CN3.7 crystallizedat (a) 170 and210

C.
The enlarged part shown (a) is form the indicated lamella in the original
image. The black strip inside the white part is clay. (b) Shows the typical
shish-kebab type of structure [257]. Reproduced fromMaiti and Okamoto
by permission of Wiley-VCH, Germany.
Fig. 74. Schematic view of the nucleation and growth mechanism in nylon-6 nanocomposite [257]. Reproduced from Maiti and Okamoto by permission of
Wiley-VCH, Germany.
1188 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 75. The heat flow vs. the time during isothermal crystallization of
nylon 1012 (spectrum a) and nylon 1012/clay nanocomposite (spectrum
b) by DSC [97]. Reproduced from Wu, Zhou, Qi and Zhang by permission
of John Wiley & Sons, Inc.
layers in the near surface region of molded and extruded
components.
Varlot et al. [5] suggested that the overall crystallinity of
the polyamide matrix remained unchanged with the addi-
tion of montmorillonite, even though the proportion of the
␥-phase was higher.
Concerning the glass transition, a decrease in T
g
has been found for PA6/clay nanocomposites; this was
attributed to an increase in the amorphous volume frac-
tion due to the surface/volume ratio of the crystallites, the
number of nuclei and the perfection of the crystal lamel-
lae [139]. However, DSC measurements conducted by other
researchers, indicate that the presence of layered silicate
filler does not affect the T
g
of the PA6 matrix, which occurs
at approximately 53

C. The melting peak of the compos-
ites is at a slightly lower temperature than that of neat PA6,
due toa slight reductionof crystallite size inthe presence of
fillers. All thefillers causeanincreaseincrystallizationtem-
perature relative to neat PA6. To various degrees, fillers may
act as nucleating agents, causing a higher crystallization
rate than that of the neat PA6 [15]. The same phenomena
have also been observed in PA66 based nanocomposites
[146].
Finally, Wuet al. [97] reportedDSCcurves for isothermal
crystallization of PA1012 and PA1012/clay nanocompos-
ites (Fig. 75). The crystallization exothermic peak of
the PA1012/clay nanocomposites is narrower than that
of PA1012, indicating that the nanocomposites have a
higher crystallization rate. The heat of crystallization
of the nanocomposite is less than that of the PA1012,
implying that the clay platelets decrease the polymer crys-
tallinity. The higher crystallizationrate recordedfor PA1012
nanocomposites was attributed to the nucleating action of
clayplatelets. Ontheother hand, theauthors suggestedthat
the confinement of the chains and segment movement will
hinder segmental rearrangement duringcrystallizationand
restrict the formation of perfect crystals in the PA1012/clay
nanocomposite, thus resulting in decreased crystallinity.
6.9. Biodegradation
An interesting aspect of nanocomposite technology is
the enhancement in biodegradability, often reported after
nanocomposite formation. Tetto et al. [258] first presented
results onthe biodegradabilityof nanocomposites basedon
PCL, reporting that the PCL/OMLS nanocomposites showed
improved biodegradability compared with pure PCL.
Biodegradabilityimprovements havealsobeenreported
in the case of PLA-based nanocomposites. As an example,
Ray et al. [208] presented photographs of the recovered
samples of neat PLA and PLACN4 from compost with time
(Fig. 76(a)). The decreased M
w
and residual weight R
w
per-
centage of the initial test samples with time is also shown
in Fig. 76(b). Obviously, the biodegradability of neat PLA
is significantly enhanced after nanocomposite preparation.
For a month, both the extent of M
w
loss and weight loss
are almost the same for neat PLA and PLACN4.5 However,
after 1 month, a sharp change occurs in weight loss of
PLACN4, and within 2 months, it is completely degraded by
compost. The degradation of PLA in compost is a complex
process involving: water absorption, ester cleavage andfor-
mation of oligomer fragments, solubilization of oligomer
fragments, andfinallydiffusionof solubleoligomers. There-
fore, any factor that increases the hydrolysis tendency of
neat PLA, ultimately controls the degradation. However,
from Fig. 76(b) it is evident that the hydrolysis tendencies
of PLA and PLACN4 are almost the same.
Ray et al. suggest that the presence of terminal hydrox-
ylated edge groups of the silicate layers may be one of the
factors responsible for this behavior. InPLACN4, the stacked
and intercalated silicate layers are homogeneously dis-
persed in the PLAmatrix, and these hydroxy groups initiate
heterogeneous hydrolysis of the PLAmatrix after absorbing
water from the compost. This process takes some time to
start. For this reason, according tothese authors, the weight
loss and degree of hydrolysis of PLA and PLACN4 is almost
same up to 1 month (Fig. 76(b)). However, after 1 month
there is a sharp weight loss in the case of PLACN4 as com-
pared with that of PLA. This means that 1 month is a critical
time to start heterogeneous hydrolysis, and due to this type
of hydrolysis the matrix degrades intovery small fragments
and is eliminated with the compost. This assumption was
confirmedby conducting the same type of experiment with
PLACN prepared by using dimethyl dioctadecylammonium
salt modifiedsynthetic mica whichhas noterminal hydrox-
ylated edge group; in that case the degradation tendency
was almost the same as that of PLA.
However, contradictory results concerning the effect
of clay dispersion on polymer biodegradability are also
found in the literature. In fact, Lee et al. [259] prepared
nanocomposites based on aliphatic unsaturated polyester
and found a decrease in biodegradability under compost-
ing with intercalation. They assumed that due to the high
aspect ratio and better dispersion of clay in the matrix a
more tortuous path formed for penetration of microorgan-
isms into the bulk and hindered their diffusion. Similarly,
Maiti et al. [195] attributed the suppressed biodegradation
tendency, whichtheyobservedinthecaseof PHBnanocom-
posites, to an improvement of the barrier properties of
the matrix after nanocomposite formation, even though
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1189
Fig. 76. (a) Real pictures of biodegradability of neat PLA and PLACN4 recovered from compost with time. Initial shape of the crystallized samples was
3cm×10cm×0.1cm. (b) Time dependence of residual weight, Rw and of matrix, Mw of PLA and PLACN4 under compost [208]. Reproduced from Ray,
Yamada, Okamoto and Ueda by permission of Elsevier Science Ltd., UK.
they did not report on the permeability. This explanation
contradicts the results of Ray et al. [260], who found no
relation between biodegradability and barrier properties
in PLA/OMLS nanocomposites.
From the aforementioned contradictory results, it
becomes obvious that the increase or the decrease in
nanocompositebiodegradationis still under discussionand
noconclusioncanbe drivenabout mechanisms onthe basis
of the current literature [231].
6.10. Photo-degradation
The degradability of nanocomposites under UV light
is a serious problem that may limit their applications. In
the few studies addressing this issue, it has been found
that nanocomposites exhibit lower stability than the cor-
responding neat polymers [231].
For example, Huaili et al. [261] studied the photo-
oxidative degradation of PE/MMT nanocomposites com-
pared with neat polyethylene. Since it is well established
that the degradationof hydrocarbonchains leads to the for-
mationof hydroxyl andketogroups, theystudiedthe extent
of photo-degradation by FTIR observations. As is shown in
Fig. 77, the degradation of PE/o-MMT nanocomposite was
greater than that of pure PE polymer after 200h irradia-
tion. Fig. 78 shows FTIR spectra in the carbonyl region upon
UV irradiation. Obviously, there is a considerable increase
in the intensity of the carbonyl region with an increase of
irradiation time in PE/o-MMT, which means that the mate-
rial is undergoing degradation. In the pure PE, on the other
hand, the intensity in the carbonyl region was significantly
less, which indicates less degradation.
Morlat [262] and Mailhot et al. [263] studied the
effect of compatibilizers on photo-degradation and its
kinetics by comparing PP nanocomposites with neat poly-
mer. The increase in the absorbance at 3200–3600 and
1600–1800cm
−1
was rapid in nanocomposites in compar-
ison with neat polymer. It was observed that the induction
period decreased from 8 to 4h by using PP-g-MA as com-
patibilizer and a two-phase degradation mechanism was
observed. In the first stage (up to 40h) there was no evi-
dence for hydroxyl band formation in the IR spectra, which
implies the absence of degradation on polymer backbone,
whereas in the second stage a dramatic increase in the rate
1190 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
Fig. 77. (a) FTIR spectra of PE/o-MMT nanocomposites before and after
200h irradiation. (b) FTIR spectra of pure PE before and after 200h UV
irradiation [261]. Reproduced from Huaili, Chungui, Shimin, Guangming
and Mingshu by permission of Elsevier Science Ltd., UK.
of photo-oxidation was found. The degradation products
were the same in the composite and the neat polymer.
According to Patterson et al. [264], the incorporation
of layered silicates in polycarbonate appeared to increase
the rate at which chain scission occurs. Furthermore, these
carbonate scissions produced a yellowing of the polycar-
bonate, which could inhibit its use in applications where
optical clarity is important.
However, in another study, the effect of accelerated
weathering of polycarbonate nanocomposites was inves-
tigated. The silicate content used ranged from0 to 3.5wt.%.
A UV-accelerated weathering tester programmed to cycle
for 8h of UV radiation and 4h of dark condensation was
selected for the exposure study. The materials were charac-
terizedbyUV/vis spectroscopyandFTIRspectroscopyandit
was concluded that the degradation of the nanocomposite
was less than that of the neat polymer [265].
Fig. 78. FTIR spectra of PE/nanocomposite at carbonyl region during
photo-degradation [261]. Reproduced from Huaili, Chungui, Shimin,
Guangming and Mingshu by permission of Elsevier Science Ltd., UK.
In any case, although no explanation has so far been
given for the differences in photo-degradation stability
between the nanocomposites and the pure polymers, it
has been suggested that the best way to increase the out-
door durability would be to develop nanocomposites by
modification of the clay rather than functionalization of
thermoplastics [231].
6.11. Optical clarity
Microsized particles used as reinforcing agents scatter
light, thus reducing light transmittance and optical clarity
[266]. On the other hand, layered silicate platelets, albeit
their micron lateral size, are just 1nm thick. Thus, when
single layers are dispersed in a polymer matrix, the result-
ing nanocomposite is optically clear in the visible region,
whereas, there is a loss of intensity in the UV region (for
z<250nm) mostly due to scattering by the MMT parti-
cles. There is no marked decrease in the clarity due to the
nanodispersed fillers (e.g. one has to load 20wt.% of C18-
MMT in 3mm thick film of PP before there develops haze
observable by the eye). This is a general behavior in UV/vis
transmittance for thick films (3–5mm) of polymer/MMT
nanocomposites basedonPVA, PP, andseveral epoxies [31].
7. Nanocomposites: advantages and applications
As described above, polymer nanocomposite materials
often exhibit properties superior to conventional com-
posites, such as strength, stiffness, thermal and oxidative
stability, barrier properties, as well as flame retardant
behavior [267]. These improved properties are generally
attained at lower filler content in comparison with conven-
tionally filled systems. Therefore, polymer–layered silicate
nanocomposites are far lighter in weight than a conven-
tional composite, which makes them quite competitive for
specific applications [55].
Moreover, for systems with favorable thermodynamics
of mixing, the organoclay can be incorporated in the final
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1191
Table 41
Selected commercial nanoclays.
Product Characteristics Applications Producer
Cloisite Organophilic Additives to enhance flexural and tensile
modulus, barrier properties and flame
retardancy of thermoplastics
Southern Clay Products
Nanomers Microfine powder Nylon, epoxy, unsaturated polyester,
engineering resins
Nanocor
Masterbatches Pellet Thermoplastic olefin and urethane,
styrene-ethylene butylene-styrene, ethylene
vinyl acetate
PolyOne Corporation, Clariant
Corporation, RTP Company
Bentone With a broad range of polarity Additives to enhance mechanical, flame
retardancy and barrier properties of
thermosets and thermoplastics
Elementis Specialties
Nanofil Improve the mechanical, thermal and
barrier properties
Thermoplastics and thermosets Sud-Chemie
Planomers Additive, enhance mechanical barrier
properties, thermal stability and flame
resistance
Electric and electronic, medical and health
care, adhesive, building and construction
materials
TNO
PlanoColors Nanopigments, e.g., blue, red, green,
yellow, high UV-stability
Decorative coloring, UV-stable coloring, heavy
metal free coloring
TNO
PlanoCoatings Additive, excellent transparency and
improved barrier properties
Transparent packaging materials, protective
coatings, transparent barrier coatings
TNO
stages of polymer processing (e.g. extrusion, injection or
compression molding) to obtain nanocomposite materials.
Thus, polymer nanocomposites are amenable to most of
the common processing techniques in today’s industrial
practice—which will lower the barriers to their commer-
cialization [31].
Another unique aspect of nanocomposites is the lack
of property trade-offs. Traditionally, blend or composite
formulations require trade-offs between desired perfor-
mance, mechanical properties, cost and processibility.
However, polymer nanocomposite technology provides a
route around these traditional limitations, and offers, for
the first time, the opportunity to design materials without
the compromises typically found in conventionally filled
polymers [267,268].
The aforementioned attractive characteristics of
polymer–layered silicate nanocomposites already suggest
a variety of possible industrial applications: automo-
tive (gas tanks, bumpers, interior and exterior panels),
construction (building sections and structural panels),
aerospace (flame retardant panels and high performance
components), food packaging, textiles, etc. [269].
It is for this reason that many companies have taken a
strong interest and have invested in developing nanoclays
(Table 41) and polymer nanocomposites (Table 42) [270].
Amongthese, thefirst commercial product of clay-based
polymer nanocomposites was the timing-belt cover made
from PA6 nanocomposites by Toyota Motors in the early
1990s. This timing-belt cover exhibitedgoodrigidity, excel-
lent thermal stability and no wrap. It also saved weight by
up to 25% [270]. Later, General Motors and partners Basell,
SouthernClay Products andBlackhawk Automotive Plastics
announced external automotive body parts (step-assist)
made fromthermoplastic, olefin layered silicate nanocom-
posites. A TPO nanocomposite with as little as 2.5% layered
silicate is as stiff and much lighter than parts with 10 times
Table 42
Selected commercial polymer nanocomposites.
Product Characteristics Applications Producer
Nylon nanocomposites Improved modulus, strength, heat
distort temperature, barrier properties
Automotive parts (e.g., timing-belt
cover, engine cover, barrier fuel line),
packaging (e.g., cosmetics, food,
medical, electronics), barrier film
Bayer, Honeywell Polymer, RTP
Company, Toyota Motors, Ube, Unitika
Polyolefin
nanocomposites
Stiffer, stronger, less brittle, lighter,
more easily recycled, improved flame
retardancy
Step-assist for GMC Safari and
chevrolet Astro vans, heavy-duty
electrical enclosure
Basell, Blackhawk Automotive Plastics,
General Motors, Gitto Global
Corporation, Southern Clay Products
M9
TM
High barrier properties Juice or beer bottles, multi-layer films,
containers
Mitsubishi Gas Chemical Company
Durethan KU2-2601
(nylon 6)
Doubling of stiffness, high gloss and
clarity, reduced oxygen transmission
rate, improved barrier properties
Barrier films, paper coating Bayer
Aegis
TM
NC (nylon
6/barrier nylon)
Doubling of stiffness, higher heat
distort temperature, improved clarity
Medium barrier bottles and films Honeywell Polymer
Aegis
TM
OX Highly reduced oxygen transmission
rate, improved clarity
High barrier beer bottles Honeywell Polymer
SET
TM
nanocomposite
nylon 12
Improved stiffness, permeability, fire
retardancy, transparency and recycling
Catheter shafts and balloons, tubing,
film and barriers, flexible devices
Foster Corporation
Forte
TM
nanocomposite Improved temperature resistance and
stiffness, very good impact properties
Automotive, furniture, appliance Noble Polymer
1192 S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198
the amount of conventional talc filler. Thus, the weight sav-
ings can reach 20%, depending on the part and the material
that is being replaced by the TPO nanocomposite [268].
WilliamWindscheif, Basell’s Global Business VicePresident
for Advanced Polyolefins, called this application “a small
step, but a giant one for nanocomposites” and added that it
heralds a broader shift to nano-PP in automotive technol-
ogy [271].
Consultant Kenneth Sinclair, head of STA Research in
Sndiomish, Wash., estimated that in the near future the
application of PP-based nanocomposites in the automotive
industry will expand, with nano-PP mostly cannibilizing
existing PP applications. However, replacement of metals
and engineering thermoplastics will follow. In this context,
a long term goal for Dow Plastics is in-reactor compound-
ing of nano-PP by using nano-clays as the catalyst support
for in-situpolymerizationof PP homopolymer. Dow’s effort
is focused on highly loaded (up to 10% clay) nano-PPs for
semi-structural automotive uses [271].
Meanwhile, a role for nanocomposites in polycarbonate
automotive glazing is being explored by Exatec of Wixon,
Mich., a joint venture of Bayer and GE Plastics, that is
dedicated to PC auto-glazing development, considered for
the exterior coating needed to achieve weatherability and
abrasion resistance without reducing clarity. A Bayer coat-
ing containing nanoparticles is one of several promising
approaches being pursued [271].
It is worth noticing that the weight advantage of poly-
mer nanocomposites could have a significant impact on
environmental protection and material recycling. It is pre-
dicted that widespread use of polymer nanocomposites
would save 1.5 billion liters of gasoline over the life of 1
year’s production of vehicles and reduce related CO
2
emis-
sions by more than 5 billion kilograms [270].
Next to the automotive industry, polymer nanocom-
posites are expected to find wide applications as barrier
materials. In fact, the excellent barrier properties of
clay-based polymer nanocomposites could result in con-
siderable enhancement of shelf-life for many types of
packaged food. Meanwhile, the optical transparency of
polymer nanocomposite film is generally similar to their
pristine counterparts, which is impossible with conven-
tional polymer composites. Therefore, the above property
advantages wouldmake themwidely acceptable inpackag-
ing industries as wrapping films and beverage containers.
For example, Bayer has developed a new grade of plastic
films for food packaging, which are made from PA6 exfoli-
ated nanocomposites [270]. Honeywell is also developing
nano-PA materials that can beat the cost of high-barrier
plastics or even glass. Nanocor’s Imperm compound sup-
plements the inherent gas barrier of amorphous MDX6
nylon from Mitsubishi Gas Chemical with the addition of
nanoclay. Used as the core of a three-layer PET bottle,
Imperm reportedly ensured a 28.5-week beer shelf-life.
Imperm is said to adhere to PET without tie layers, while
sufficient clarity is retained to meet requirements for the
amber bottle [271].
Meanwhile, Ube America is developing nanocomposite
barriers for automotive fuel systems, using up to 5% nan-
oclay in PA6 and PA6/66 blends [271].
Also quite interesting are potential applications of
nanocomposites based on biodegradable polymers. Such
polymers have become indispensable in a wide range
of applications. However, despite their attractive degra-
dation characteristics and significant demand for such
materials, the lack of structural and functional stability
prevents currently available biodegradable polymers from
having widespread commercial impact [267]. Therefore,
biodegradable polymer-based nanocomposites appear to
have a very bright future for a wide range of applications
as high-performance biodegradable materials [55].
Layered silicate nanoparticles, when distributed within
the matrix of a fiber-reinforced polymer (FRP), can retard
the diffusion of environmental moisture and other chemi-
cals to the fiber–matrix interface where their presence can
result indelaminationandfiber weakening. Thus, the use of
nanoparticles helps to preserve the integrity of FRPs and to
prolong the service life of composites when these are used
Fig. 79. Possible growth paths for nanocomposites applications.
S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1193
in outdoor applications such as bridges and utility poles
[272].
Other potential nanocomposite applications include
nano-pigments that are believed to be an environment-
friendly alternative to toxic cadmium and palladium
pigments, as well as controlled drug delivery systems, etc.
[270].
However, despite the current optimism surround-
ing polymer–nanocomposite materials, the mechanical
performance benchmarks set by highly loaded short-
fiber composites are still beyond the capabilities of low
concentration nanocomposites. Manufacturing costs also
remain a significant factor restricting the growth of
polymer–nanocomposite applications [200]. In fact, some
early application development programs have lapsed for
cost reasons. Such casualties include the timing-belt cover
based on nylon 6 nanocomposite [271].
According to Silberglitt, there are two possible paths or
trends—a high-growth path, under which nanocomposite
materials are pervasively applied throughout society and a
low-growth path, under which the use of nanocomposites
leads to incremental improvements in specific technology
areas (Fig. 79) [269].
8. Summary
Polymer–layered silicate nanocomposites, although
known for many years, have attracted recent attention due
to the report of the Toyota research group on the improved
properties of PA6 nanocomposites and also due to the
observation by Giannelis and co-workers that their prepa-
ration is possible by simple melt-mixing of the polymer
with the layered silicate. Other preparation routes include
intercalation of polymer or prepolymer from solution, in
situintercalativepolymerizationandtemplatesynthesis. In
most cases, layered silicates first need to be modified with
cationic-organic surfactants, in order to become miscible
with polymeric matrices. Then, whether a nanocomposite
will form or not, and whether this will be intercalated or
exfoliated, depends on a variety of factors. These include
the type of polymer, layered silicate and organic modi-
fier, the preparation technique and processing conditions.
In general, nanocomposite materials, particularly those
with exfoliated structures present significant improve-
ments of modulus and strength, whereas contradictory
results are reportedconcerningtheir elongationandtough-
ness. Improvements of storage and loss moduli are also
reportedby many authors. Other interesting characteristics
of this class of materials include improved barrier proper-
ties, thermal stability and flame retardance. Despite some
contradictory results reported in the literature and pre-
sentedhere, concerningcertainaspects of polymer–layered
silicate nanocomposite technology, we hope this review
will be a useful tool for those conducting research in this
field.
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6.

7. 8.

5.4.3. Compatibility issues in non-polar polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4.4. Degradation problems encountered during melt intercalation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Nanocomposite properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1. Mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1.1. The reinforcing mechanism of layered silicates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1.2. Modulus and strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1.3. Toughness and strain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1.4. Comparison and synergistic effects of clays and conventional reinforcements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2. Dynamic mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3. Barrier properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.4. Thermal stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.5. Flame retardance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.5.1. Flame retardance of polymer–layered silicate nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.5.2. Synergism between nanocomposites and flame retardants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.6. Heat distortion temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.7. Rheological properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.8. Crystallinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.9. Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.10. Photo-degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.11. Optical clarity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Nanocomposites: advantages and applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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1. Introduction Traditionally, polymeric materials have been filled with synthetic or natural inorganic compounds in order to improve their properties, or simply to reduce cost. Conventional fillers are materials in the form of particles (e.g. calcium carbonate), fibers (e.g. glass fibers) or plate-shaped particles (e.g. mica). However, although conventionally filled or reinforced polymeric materials are widely used in various fields, it is often reported that the addition of these fillers imparts drawbacks to the resulting materials, such as weight increase, brittleness and opacity [1–5]. Nanocomposites, on the other hand, are a new class of composites, for which at least one dimension of the dispersed particles is in the nanometer range. Depending on how many dimensions are in the nanometer range, one can distinguish isodimensional nanoparticles when the three dimensions are on the order of nanometers, nanotubes or whiskers when two dimensions are on the nanometer scale and the third is larger, thus forming an elongated structure, and, finally, layered crystals or clays, present in the form of sheets of one to a few nanometers thick and hundreds to thousands nanometers in extent [1,4]. Among all the potential nanocomposite precursors, those based on clay and layered silicates have been most widely investigated, probably because the starting clay materials are easily available and because their intercalation chemistry has been studied for a long time [6]. Polymer–layered silicate nanocomposites, which are the subject of the present contribution, are prepared by incorporating finely dispersed layered silicate materials in a polymer matrix [2]. However, the nanolayers are not easily dispersed in most polymers due to their preferred faceto-face stacking in agglomerated tactoids. Dispersion of the tactoids into discrete monolayers is further hindered by the intrinsic incompatibility of hydrophilic layered sil-

icates and hydrophobic engineering plastics. Therefore, layered silicates first need to be organically modified to produce polymer–compatible clay (organoclay). In fact, it has been well-demonstrated that the replacement of the inorganic exchange cations in the cavities or “galleries” of the native clay silicate structure by alkylammonium surfactants can compatibilize the surface chemistry of the clay and a hydrophobic polymer matrix [7]. Thereafter, different approaches can be applied to incorporate the ion-exchanged layered silicates in polymer hosts by in situ polymerization, solution intercalation or simple melt mixing. In any case, nanoparticles are added to the matrix or matrix precursors as 1–100 m powders, containing associated nanoparticles. Engineering the correct interfacial chemistry between nanoparticles and the polymer host, as described previously, is critical but not sufficient to transform the micron-scale compositional heterogeneity of the initial powder into nanoscale homogenization of nanoparticles within a polymeric nanocomposite [8]. Therefore, appropriate conditions have to be established during the nanocomposite preparation stage. The resulting polymer–layered silicates hybrids possess unique properties – typically not shared by their more conventional microscopic counterparts – which are attributed to their nanometer size features and the extraordinarily high surface area of the dispersed clay [1,4]. In fact, it is well established that dramatic improvements in physical properties, such as tensile strength and modulus, heat distortion temperature (HDT) and gas permeability, can be achieved by adding just a small fraction of clay to a polymer matrix, without impairing the optical homogeneity of the material. Most notable are the unexpected properties obtained from the addition of stiff filler to a polymer matrix, e.g. the often reported retention (or even improvement) of the impact strength. Since the weight fraction of the inor-

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Nomenclature AIBN N,N -azobis(isobutyronitrile) CEC cation exchange capacity CX-clay X is the number of carbon atoms in clay organic modifier d spacing between diffractional lattice planes D diffusivity DETDA diethyl toluene diamine DGEBA diglycidyl ether of bisphenol A DM dioctadecyldimethyl ammonium chloride DMA dynamic mechanical analysis DSC differential scanning calorimetry DTGA differential thermogravimetric analysis E storage modulus under bending mode E loss modulus under bending mode EVA ethyl-vinyl-acetate copolymer FTIR Fourier transform infrared spectroscopy fwhm full-width-at-half-maximum G storage modulus under tensile mode G loss modulus under tensile mode GPC gas-permeation chromatography HDPE high density polyethylene HDT heat distortion temperature HRR heat release rate MMT montmorillonite NMR nuclear magnetic resonance o-Clay organo-modified clay OMLS organo-modified layered silicate, organosilicate, or organoclay P permeability PA polyamide PAA poly(acrylic acid) PBO polybenzoxale PCL polycaprolactone PCN polymer–clay nanocomposite PDMS polydimethylsiloxane PE polyethylene PEI poly(ether imide) PEO poly(ethylene oxide) PET poly(ethylene terephthalate) PHB poly(3-hydroxybutyrate) PHRR peak heat release rate PI polyimide PA polylactide PLS polymer–layered silicate nanocomposite PMMA polymethyl methacrylate PP polypropylene PP-MA or PP-g-MA maleic anhydride-grafted polypropylene PS polystyrene PSF polysulfone PU polyurethane PVA poly(vinyl acetate) PVC poly(vinyl chloride) PVE poly(vinyl ethylene) PVOH poly(vinyl alcohol) PVP poly(vinyl pyrrilidone) S solubility SBS SEA Tan ı Tc TEM Tg TGA TGAP TGDDM poly(styrene-butadiene-styrene) specific extinction area G /G crystallization temperature transmission electron microscopy glass transition temperature thermogravimetric analysis triglycidyl p-aminophenol tetrafunctional tetraglycidyldiaminodiphenylmethane TPO thermoplastic olefin UP unsaturated polyester WAXD or WAXS wide angle X-ray diffraction or scattering XRD X-ray diffraction

ganic additive is typically below 10%, the materials are also lighter than most conventional composites [2,9–12]. These unique properties make the nanocomposites ideal materials for products ranging from high-barrier packaging for food and electronics to strong, heat-resistant automotive components [11]. Additionally, polymer–layered silicate nanocomposites have been proposed as model systems to examine polymer structure and dynamics in confined environments [12,13]. However, despite the recent progress in polymer nanocomposite technology, there are many fundamental questions that have not been answered. For example, how do changes in polymer crystalline structure induced by the clay affect overall composite properties? How does one tailor organoclay chemistry to achieve high degrees of exfoliation reproducibility for a given polymer system? How do process parameters and fabrication affect composite properties? Further research is needed that addresses such issues [14]. The objective of this work is to review recent scientific and technological advances in the field of polymer–layered silicate nanocomposite materials and to develop a better understanding of how superior nanocomposites are formed. 2. Milestones in the research on polymer–layered silicate nanocomposites The incorporation of layered silicates into polymer matrices has been known for over 50 years [15]. In fact, one of the earliest systematic studies of the interaction between a clay mineral and a macromolecule dates back to 1949, when Bower [16] described the absorption of DNA by montmorillonite. Even in the absence of X-ray diffraction (XRD) evidence, this finding implied insertion of the macromolecule in the lamellar structure of the silicate. In 1950, Carter et al. [17] developed organoclays with several organic onium bases to reinforce latex-based elastomers and in 1958, Hauser and Kollman [18] were granted a patent for “clay complexes with conjugated unsaturated aliphatic compounds of four to five carbon atoms”. Uskov [19], in 1960, found that the softening point of poly(methyl methacrylate) derived by polymerization of

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methyl methacrylate was raised by montmorillonite modified with octadecylammonium, while in the following year Blumstein [20] obtained a polymer inserted in the structure of a montmorillonite by polymerizing a previously inserted vinyl monomer. Two years later, Greenland [21] used a poly(vinyl alcohol)/montmorillonite system to show that a polymer could be directly inserted in a clay in an aqueous solution. The same year, the incorporation of organoclay into a thermoplastic polyolefin matrix was disclosed by Nahin and Backlund [22] of Union Oil Co. They obtained organoclay composites with strong solvent resistance and high tensile strength by irradiation-induced cross linking. However, they did not focus on the intercalation characteristics of the organoclay or the potential properties of the composites. In 1975, Tanihara and Nakagawa [23] reached a similar result by intercalating polyacrylamide and poly(ethylene oxide) from an aqueous solution. In 1976 Fujiwara and Sakamoto [24] of the Unichika Co. described the first organoclay hybrid polyamide nanocomposite. However, it was not until Toyota researchers began a detailed examination of polymer–layered silicate composites that nanocomposites became more widely studied in academic, government and industrial laboratories [25–28]. The Toyota research group disclosed improved methods for producing nylon 6 clay nanocomposites using in situ polymerization similar to the Unichika process. They reported that these polymer–clay nanocomposites exhibit superior strength, modulus, heat distortion temperature, water and gas barrier properties, with comparable impact strength as neat nylon 6. They also reported on various other types of polymer–clay hybrid nanocomposites based on epoxy resin and polystyrene, acrylic polymer, rubber, and polyimides formed using a similar approach. On the other hand, work by Giannelis and co-workers [29,30] revealed that intercalation of polymer chains into the galleries of an organoclay can occur spontaneously on heating a mixture of polymer and silicate clay powder above the polymer glass transition or melt temperature. Once sufficient polymer mobility is achieved, chains diffuse into the host silicate clay galleries, thereby producing an expanded polymer–silicate structure. To summarize: although the intercalation chemistry of polymers when mixed with appropriately modified layered silicates and synthetic layered silicates has long been known, two major findings have stimulated the revival of interest in polymer–layered silicate nanocomposite materials. First, the report from the Toyota research group on a nylon 6/montmorillonite nanocomposite, in which very small amounts of layered silicate loadings resulted in pronounced improvements of thermal and mechanical properties; and second, the observation by Giannelis and his co-workers that it is possible to melt-mix polymers with layered silicates, without the use of organic solvents. Since then, the high promise for industrial applications has motivated vigorous research, and today efforts are being conducted globally, using almost all types of polymer matrices. In fact, nanocomposites have been demonstrated with many thermoplastic and thermosetting polymers of different polarities including, among others, polystyrene, polycaprolactone, polypropylene, poly(ethylene oxide), epoxy resin, polysiloxane and polyurethane [7,14,15,31–33].

It must be noted, however, that so far most of these materials have been produced only on the laboratory scale; and until a short time ago, research tended to center on proof of exfoliation of the clay [32]. 3. Layered silicates 3.1. Structure and characteristics of layered silicates Layered silicates used in the synthesis of nanocomposites are natural or synthetic minerals, consisting of very thin layers that are usually bound together with counter-ions. Their basic building blocks are tetrahedral sheets in which silicon is surrounded by four oxygen atoms, and octahedral sheets in which a metal like aluminum is surrounded by eight oxygen atoms. Therefore, in 1:1 layered structures (e.g. in kaolinite) a tetrahedral sheet is fused with an octahedral sheet, whereby the oxygen atoms are shared [34]. On the other hand, the crystal lattice of 2:1 layered silicates (or 2:1 phyllosilicates), consists of two-dimensional layers where a central octahedral sheet of alumina is fused to two external silica tetrahedra by the tip, so that the oxygen ions of the octahedral sheet also belong to the tetrahedral sheets, as shown in Fig. 1. The layer thickness is around 1 nm and the lateral dimensions may vary from 300 Å to several microns, and even larger, depending on the particulate silicate, the source of the clay and the method of preparation (e.g. clays prepared by milling typically have lateral platelet dimensions of approximately 0.1–1.0 m). Therefore, the aspect ratio of these layers (ratio length/thickness) is particularly high, with values greater than 1000 [1,35–37]. The basic 2:1 structure with silicon in the tetrahedral sheets and aluminum in the octahedral sheet, without any substitution of atoms, is called pyrophyllite. Since the layers do not expand in water, pyrophyllite has only an external surface area and essentially no internal one. When silicon in the tetrahedral sheet is substituted by aluminum, the resulting structure is called mica. Due to this substitution the mineral is characterized by a negative surface charge, which is balanced by interlayer potassium cations. However, because the size of the potassium ions matches the hexagonal hole created by the Si/Al tetrahedral layer, it is able to fit very tightly between the layers. Consequently, the interlayers collapse and the layers are held together by the electrostatic attraction between the negatively charged tetrahedral layer and the potassium cations. Therefore, micas do not swell in water and, like pyrophyllite, have no internal surface area [38]. On the other hand, if in the original pyrophyllite structure the trivalent Al-cation in the octahedral layer is partially substituted by the divalent Mg-cation, the structure of montmorillonite is formed, which is the best-known member of a group of clay minerals, called “smectites” or “smectite clays”. In this case the overall negative charge is balanced by sodium and calcium ions, which exist hydrated in the interlayer [39]. A particular feature of the resulting structure is that, since these ions do not fit in the tetrahedral layer, as in mica, and the layers are held together by relatively weak forces, water and other polar molecules can enter between the unit layers, causing the lattice to expand [33].

the larger is their internal surface and hence their tendency to agglomerate rather than to disTable 1 Chemical structure of commonly used 2:1 phyllosilicatesa [1].D. The reason why these materials have received a great deal of attention recently.. Similarly. This can be readily achieved through ion-exchange reactions that render the clay organophilic [42]. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1123 Fig.39. in order to render them miscible with other polymers. are on the order of 10 nm and are composed of stacks of parallel lamellae. C. primary particles. being only 1 nm thick. Micro-aggregates are formed by lateral joining of several primary particles.36]. Alkylammonium ions are mostly used.2. one must exchange the alkali counter-ions with a cationic-organic surfactant. and aggregates are composed of several primary particles and micro-aggregates [40]. x: degree of isomorphous substitution (between 0. Pavlidou. 1.7 TPa!). Their chemical formula is given in Table 1 [1]. in their pristine state layered silicates are only miscible with hydrophilic polymers. In order to obtain the exchange of the onium ions with the cations in the galleries.S. Analysis of layered silicates has shown that there are several levels of organization within the clay minerals. However. 2. UK. For example. Organic modification of layered silicates Since. called an “interlayer” or “gallery” [1. The smallest particles. carbon nanotubes display the so far highest known values of elastic modulus (ca. 3. Along with montmorillonite. the silicate layers have the tendency to organize themselves to form stacks with a regular van der Waals gap between them.35. In general. as shown in Fig. display a perfect crystalline structure. it is well established that structural perfection is more and more nearly reached as the reinforcing elements become smaller and that the ultimate properties of reinforcing composite elements may be expected if their dimensions reach atomic or molecular levels. hectorite and saponite are the layered silicates that are most commonly used in nanocomposite materials. In fact.41]. as reinforcing materials for polymers. 2:1 Phyllosilicates Montmorillonite Hectorite Saponite General formula Mx (Al4−x Mgx )Si8 O20 (OH)4 Mx (Mg6−x Lix )Si8 O20 (OH)4 Mx Mg6 (Si8−x Alx )O20 (OH)4 perse homogeneously in a matrix [2]. The interlayer dimension is determined by the crystal structure of the silicate (for dehydrated Na–montmorillonite this dimension is approximately 1 nm) [37].3).5 and 1. 1. water a M: monovalent cation. although other “onium” salts can be used. The structure of a 2:1 layered silicate [35]. is their potentially high aspect ratio and the unique intercalation/exfoliation characteristics that will be discussed later [15]. such as poly(ethylene oxide) and poly(vinyl alcohol). Reproduced from Beyer by permission of Elsevier Science Ltd. individual clay sheets. such as sulfonium and phosphonium [1. the smaller the reinforcing elements are. .

Reproduced from Fischer by permission of Elsevier Science Ltd. even if a small part of the charge balancing cations is located on the external crystallite surface.1124 S.% [48]. Schematic picture of an ion-exchange reaction. packing density.85 and 2. the majority of these exchangeable cations are located inside the galleries [1].. This is expected since both of these parameters contribute to increasing the volume occupied by the intragallery surfactant [7]. leaving the organic tail radiating away from the surface [1. C18 M (with 12. Sometimes. 1.39]. on the basis of the CEC of the clay. UK. This property is highly dependent on the nature of the isomorphous substitutions in the tetrahedral and octahedral layers and therefore on the nature of the soil where the clay was formed. as they are not structural. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Fig. dried clays that have been subjected to organo-modification along with a sample of the corresponding untreated clay are ignited at 1000 ◦ C. and must rather be considered as an average value over the whole crystal. In general. appropriate to the intercalation of polymer molecules [46]. The alkali cations. the longer the surfactant chain length. enabling polymer chains to move in between them and secondly. The charge of the layer is not locally constant. swelling of the silicate is needed. From the differences in the loss on ignition of the sample and blank and the molecular weight of the alkylammonium salt. 2. 1. resulting in an increase of the gallery height [44]. polymers or prepolymers) to diffuse between the layers and eventually separate them [42./g [39. the hydrate formation of monovalent intergallery cations is the driving force for water swelling.2 mequiv. Conclusively.42]. The microchemical environment in the galleries is. Proportionally. the milliequivalents of the organic substance retained by the clays are calculated and those values are taken as their CEC. The inorganic. the long organic chains of such surfactants.9–1. with positively charged ends.41]. That is. The excess negative charge of layered silicates and their capability to exchange ions can be quantified by a specific property known as the cation-exchange capacity (CEC) and expressed in mequiv.42]. Moreover. the interlayer distance also depends on the way the onium ion chains organize themselves in the organoclay. Cloisite 20A. one way to measure the clay CEC is by determining the amount of alkylammonium salt retained by the organoclays. can be easily replaced by other positively charged atoms or molecules. prepared organoclays with different alkylammonium chain lengths and also used an organophilic clay.47]. The interlayer spacings of C12 M. as the negative charge originates in the silicate layer./g [1. In order to describe the structure of the interlayer in organoclays. Wang et al. why montmorillonites from different origins show differences in CEC. Alternatively. the organo-modified layered silicates (OMLSs. the surface modification both increases the basal spacing of clays and serves as a compatibilizer between the hydrophilic clay and the hydrophobic polymer [45]. They found that the interlayer spacing increases with the increase in size of alkylamine chain length. organosilicates or organoclays) may be engineered to optimize their compatibility with a given polymer [43. ranging from approximately 0. C16 M. This explains. Indeed.D. chemical analysis of the clay can also be applied for CEC determination [42]. the surface properties of each single sheet are changed from being hydrophilic to hydrophobic [2]. which has two long alkyl chains. the gap between the single sheets is widened. and the higher the charge density of the clay. the further apart the clay layers will be forced. Depending on the functionality. C. Pavlidou.45]. as it varies from layer to layer. respectively [49]. . The organic cations lower the surface energy of the silicate surface and improve wetting with the polymer matrix [4. therefore. the cationic head group of the alkylammonium molecule preferentially resides at the layer surface. the content of the surfactant is usually about 35–45 wt. It is worth noticing that. However. relatively small (sodium) ions are exchanged against more voluminous organic onium cations. It then becomes possible for organic species (i.47 nm.79. This ion-exchange reaction has two consequences: firstly.36. and thus are called exchangeable cations [43]. the alkylammonium cations may even provide functional groups that can react with the polymer or initiate polymerization of monomers [33]. For this reason alkali cations are preferred in the galleries because 2-valent and higher valent cations prevent swelling by water. Actually. 16 and 18 carbon atoms in the alkylammonium chain) and 20 A were 1.e. for example. Natural clays may contain divalent cations such as calcium and require exchange procedures with sodium prior to further treatment with onium salts [41]. one has to know that. and length of the organic modifiers. are tethered to the surface of the negatively charged silicate layers. For example.

They further analyzed the data by expressing the mass of organic material per unit volume of gallery. WAXS results for organoclays: mass of organic per unit mass of montmorillonite [51]. from a disordered to more ordered monolayer. Reproduced from Alexandre and Dubois by permission of Elsevier Science Ltd. By monitoring frequency shifts of the asymmetric CH2 stretching and bending vibrations. they showed that alkyl chains can vary from liquid-like to solid-like. organic component per unit mass of inorganic MMT for each organoclay. UK. Alkyl chain aggregation in layered silicates: (a) lateral monolayer. or as the temperature increases.. UK. indicated the coexistence of ordered trans and disordered gauche conformations [50]. as shown in Fig. depending on the packing density and the chain length.D. conducted WAXS scans for different organoclays and for pristine sodium montmorillonite. the interlayer structure appears to evolve in a stepwise fashion. or gallery density. 3 [1. the chains are not completely disordered but retain some orientational order similar to that in the liquid crystalline state (Fig. the mass of Fig.. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1125 Fig. according to which the organic chains have been long thought to lie either parallel to the silicate layer. Yoon. As the chain length increases. 3. Reproduced from Alexandre and Dubois by permission of Elsevier Science Ltd. 4). C. 4. (c) paraffin-type monolayer and (d) paraffin-type bilayer [1]. as gallery = mass organic 1 mass organic/mass MMT = gallery volume d − d0 (area/side)/mass MMT Fig. Initially.S. an NMR study reported by Wang et al. 5. to radiate away from the surface. liquid crystalline-type environment [1]. based on FTIR experiments. A more realistic description has been proposed by Vaia et al. lateral monolayer. Alkyl chain aggregation models: (a) short alkyl chains: isolated molecules. Hunter. with the liquid-like structure dominating as the interlayer density or chain length decreases..7]. then “jumping” to a more disordered pseudo-bilayer. . Reproduced from Fornes. UK. and plotted basal spacing values obtained vs. forming mono or bilayers or.. Keskkula and Paul by permission of Elsevier Science Ltd. Fornes et al. the orientation of surfactant chains was deduced from infrared and XRD measurements. When the available surface area per molecule is within a certain range. forming mono or even a bimolecular tilted “paraffinic” arrangement. (b) lateral bilayer. Pavlidou. In addition. (b) intermediate chain lengths: in-plane disorder and interdigitation to form quasi bilayers and (c) longer chain length: increased interlayer order. as shown in Fig. 5.

%). In immiscible systems.33.4.44. where the geometrically imposed mean distance between the layers becomes less than the lateral dimensions of the silicate layers. separation into discrete phases normally takes place. Intercalated structures are formed when a single (or sometimes more) extended polymer chain is intercalated between the silicate layers. a phase-separated composite is obtained. Since dispersing a layered silicate can be pictured like opening a book. in general the material possesses a layered structure. as indicated by Fig.1. The first is the ability of the silicate particles to disperse into individual layers.44]. Therefore. At this point.35]. This should lead to the most significant changes in mechanical and physical properties [35]. Intercalation ´ ˚ causes less than 20–30 A separation between the platelets [1. The complete dispersion of clay nanolayers in a polymer optimizes the number of available reinforcing elements for carrying an applied load and deflecting cracks. the majority of the polymer chains in the hybrids are tethered to the surface of the silicate layers. the poor physical attraction between the organic and the inorganic components leads to relatively poor mechanical properties. In most cases. Thus.35]. produces a calculated density of 1.D. suggesting that organoclay galleries exhibit molecular environments ranging from solid. indeed with few exceptions. • Particle–particle correlation (orientation and position) arising at low volume fractions. 0. it can be expected that there are domains in these materials. of course. This is because the silicate layers are highly anisotropic. Summarizing this section. the polymer sepa´ ˚ rates the clay platelets by 80–100 A or more [52]. These two types of polymer–layered silicate nanocomposites are depicted in Fig.6 Å. layered silicate and organic cation [1.1126 S. when delaminated) cannot be placed completely randomly in the sea of polymer.e.52].33. This long-range order and domain structure is likely to become better defined at the higher silicate contents. However. with lateral dimensions ranging from 100 to 1000 nm. C. determines aspect ratio. The second characteristic is the ability to fine-tune their surface chemistry through ion exchange reactions with organic and inorganic cations. exfoliated or delaminated structures are obtained when the clay layers are well separated from one another and individually dispersed in the continuous polymer matrix [1. Nanocomposite structures Any physical mixture of a polymer and silicate (or inorganic material in general) does not necessarily form a nanocomposite. allowing for mechanical property improvements [35. with a repeat distance between them. Pavlidou. in turn. when the polymer is unable to intercalate between the silicate sheets.4. These characteristics. depending on the preparation method and the nature of the components used.1–2 vol. which are attributed to the nanoscopic dimensions and the extreme aspect ratios of layered silicates. The exfoliation or delamination configuration is of particular interest because it maximizes the polymer–clay interactions making the entire surface of layers available for the polymer. interrelated since the degree of dispersion in a given matrix that. the densities calculated in that work agree with conclusions made by Vaia et al. particle agglomeration tends to reduce strength and produce weaker materials [4]. On the other hand. are [8]: • Low percolation threshold (ca.40]. even above the melting temperature of the constituent polymers. 4. In fact. about the conformation and structure of the organic interlayer of similar organoclays. The coupling between the tremendous surface area of the clay and the polymer matrix facilitates stress transfer to the reinforcement phase.53]. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 where d − d0 is the gallery height. thus forcing some preferential orientation between the layers. there might be considerable polydispersity effects in terms of the orientation and the distance between the silicate layers. . two types of nanocomposites can be obtained. there are two particular characteristics of layered silicates that are exploited in polymer–layered silicate nanocomposites. Forcing the fit through an intercept d0 = 9. 6 [50]. the majority of the polymer nanocomposites reported in the literature were found to have intercalated or mixed intercalatedexfoliated nanostructures [33]. Thus. depends on the interlayer cation [4. These two characteristics are. The situation is analogous to polymer blends. it is generally accepted that exfoliated systems give better mechanical properties than intercalated ones [5.33]. as in the case of intercalated hybrids [4]. 5. Thus. The result is a well ordered multilayer structure of alternating polymeric and inorganic layers. it is not easy to achieve complete exfoliation of clays and. wherein some long-range order is preserved and the silicate layers are oriented in some preferred direction. the interlayer expansion is comparable to the radius of gyration of the polymer rather than that of an extended chain. it is worth mentioning six interrelated structural characteristics. That is. In this case. Furthermore. gallery . whose properties are in the same range as for traditional microcomposites [1. which is the basal spacing of pristine sodium montmorillonite. an aspect ratio as high as 1000 for fully dispersed individual layers can be obtained (contrast that to an aspect ratio of about 10 for undispersed or poorly dispersed particles). This range of densities encompasses what might be expected for organic liquids or solids.to liquid-like [51]. Many such randomly oriented grains make up the entire sample leading to the presence of disordered material. including polymer matrix. The slope of the linear relation between gallery height and the second quantity in the above equation gives the density of the organic material in the gallery. with grains wherein the silicate layers are oriented in a preferred direction leading to the presence of grain boundaries and concomitant defects [54]. However. Furthermore. distinguishing polymer–silicate nanocomposites from conventional filled systems. Nanocomposite structures and characterization 4.07 g/cm3 .35. Beyond this traditional class of polymer-filler composites. and even when separated by large distances (i.

• Large number of particles per particle volume (106 –108 particles/ m3 ). C. An increase in the degree of coherent layer stacking (i. By monitoring the position. Additionally. Nanocomposite structural characterization Two complementary techniques are generally used to characterize the structures of nanocomposites: XRD and transmission electron microscopy (TEM) [1.56]. the characteristics of the OMLS basal reflections do not change. the nanocomposite structure may be identified [55]. d the spacing between diffractional lattice planes and  is the measured diffraction angle or glancing angle [1.35. Pavlidou. some layered silicates initially do not exhibit well-defined basal reflections. • Comparable size scales among the rigid nanoparticle inclusions. The influence of polymer intercalation on the order of the OMLS layers may be monitored by changes in the fullwidth-at-half-maximum (fwhm) and intensity of the basal reflections. a more disordered system) results in peak broadening and intensity loss [47].D. for exfoliated structures no more diffraction peaks are visible in the XRD diffractograms either because of a much too large spacing between the layers (i. Therefore. the intercalation of the polymer chains increases the interlayer spacing. 7). allowing the interlayer spacing to be determined (Fig.. (b) PS + organoclay → intercalated nanocomposite. a decrease in the degree of coherent layer stacking (i. shape and intensity of the basal reflections from the distributed silicate layers. • Extensive interfacial area per volume of particles (103 –104 m2 /ml). 4. Reproduced from Ray and Bousima by permission of Elsevier Science Ltd. the structure of the silicate is not affected. 6. XRD is most commonly used to probe the nanocomposite structure and occasionally to study the kinetics of polymer melt intercalation [55]. For immiscible polymer/OMLS mixtures..%). little can be said about the spatial distribution of the silicate layers or any structural inhomogeneities in nanocomposites. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1127 Fig. In such intercalated nanocomposites. In contrast. the extensive layer separation associated with exfoliated structures disrupts the coherent layer stacking and results in a featureless diffraction pattern.S.2.55. Thus. On the other hand. according to Bragg’s law. . although XRD offers a conventional method to determine the interlayer spacing of the silicate layers in the original layered silicates and the intercalated nanocomposites (within 1–4 nm). UK. (c) siloxane + organoclay → delaminated nanocomposite [35]. UK. Due to its ease of use and availability. On the other hand.e. exceeding 8 nm in the case of ordered exfoliated structure) or because the nanocomposite does not present ordering [1. peak broadening and intensity decreases are very difficult to study systematically. Thus. distance between particles. However. 7.47]. and thus. Schematic illustration of two different types of thermodynamically achievable polymer/layered silicate nanocomposites [50]. where corresponds to the wave length of the X-ray radiation used in the diffraction experiment. a more ordered system) results in a relative decrease in the fwhm of the basal reflections upon hybrid formation. • Short distances between particles (10–50 nm at ∼ 1–8 vol. This technique allows the determination of the spaces between structural layers of the silicate utilizing Bragg’s law: sin  = n /2d.35. conclusions concerning the mechanism of nanocomposite Fig. and the relaxation volume of polymer chains. Reproduced from Beyer by permission of Elsevier Science Ltd. in comparison with the spacing of the organoclay used. the repetitive multilayer structure is well preserved.e.e. Typical XRD patterns from polymer/layered silicates: (a) PE + organoclay → no formation of a nanocomposite. leading to a shift of the diffraction peak towards lower angle.56].

surface chemistry. if that mechanism is efficient. the dynamics of exfoliated polymer clay nanocomposites. TEM micrographs of poly(styrene)-based nanocomposites: (a) intercalated nanocomposite and (b) exfoliated nanocomposite [1]. more importantly. Some authors also used Fourier transform infrared spectroscopy (FTIR) to elucidate the structure of the nanocomposites [62. by Fe3+ . and at such distances. of proton (and 13 C nuclei) with the quality of clay dispersion [55]. They were especially interested in developing NMR methods to quantify the level of clay exfoliation. a broadening of the diffraction peak is often observed and one must rely on TEM observation to define the overall structure [1]. measuring 1 nm thick. and the average paramagnetic contribution to T1 H is weaker. when nanocomposites are formed. Thus the paramagnetically induced relaxation will influence the overall measured T1 H to an extent that will depend both on the Fe concentration in the clay layer and.60. UK. while the central plane of the layers contains octahedrally coordinated Al3+ with frequent non-stoichiometric substitutions. TEM allows a qualitative understanding of the internal structure and can directly provide information in real space. Therefore. somewhat less frequently. As already mentioned. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 formation and structure based solely on XRD patterns are only tentative. and to a very limited extent. Reproduced from Alexandre and Dubois by permission of Elsevier Science Ltd. but as these variations are Fig. VanderHart et al. Since the silicate layers are composed of heavier elements (Al. relaxation will also propagate into the bulk of the polymer by spin diffusion. they appear darker in bright-field images. The latter dependence suggests a potential relationship between measured T1 H values and the quality of the clay dispersion.D. Fig. Characterization of polymer/layered silicate nanocomposites by 13 C solid-state nuclear magnetic resonance (13 C NMR) has also been proposed. The spectral density of these fluctuations is important because the T1 H of protons (and 13 C nuclei) within about 1 nm of the clay surface can be directly shortened.58]. the spin-exchange interaction between the unpaired electrons on different Fe atoms is expected to produce magnetic fluctuations in the vicinity of the Larmor frequencies for protons or 13 C nuclei. . FTIR may be able to identify differences between the bonding in a mixture and the bonding in a related nanocomposite. the intersections of the silicate sheets are seen as dark lines which are the cross sections of the silicate layers..61]. Si and O) than the interlayer and surrounding matrix (C. T1 s. Pavlidou.57]. For protons. in a localized area. first used this technique as a tool for gaining greater insight about the morphology. 8. a very important facet of nanocomposite characterization [59]. also employed the same arguments in order to understand the stability of a particular OMLS under different processing conditions [55. 8 shows the TEM micrographs obtained for an intercalated and an exfoliated nanocomposite. However. H and N). besides these two well defined structures other intermediate organizations can exist presenting both intercalation and exfoliation. In this case.0–1. VanderHart et al. On the other hand. on morphology and defect structures [57. The concentration of the later ion is very important because Fe3+ is strongly paramagnetic in this distorted octahedral environment. the average distances between polymer/clay interfaces are greater.4 nm. C. on the average distances between clay layers. The main objective in solid-state NMR measurement is to connect the measured longitudinal relaxations. where an Al3+ is replaced by Mg2+ and. special care must be exercised to guarantee a representative cross-section of the sample [56.63]. Typical concentrations of Fe3+ in naturally occurring clays produce nearest-neighbor Fe–Fe distances of about 1.1128 S. If the clay particles are stacked and poorly dispersed in the polymer matrix. The surfaces of naturally occurring layered silicates such as MMT are mainly made of tetrahedral silica.

the polymer aids the nucleation and growth of the inorganic host crystals and gets trapped within the layers as they grow. it should be mentioned that several workers have suc- . Reproduced from Zanetti. without reporting properties of the products. Introduction At present there are four principal methods for producing polymer–layered silicate nanocomposites: (1) in situ template synthesis. the aforementioned subsidiary methods have only been used to confirm the evidence from the primary methods. and PSintercalated OLS [41]. Concerning the evaluation of other nanocomposites structural characteristics. the clay minerals are synthesized within the polymer matrix. where restrictions on its mobility increase its glass transition temperature (Tg ). Clay platelets intrinsically have a distribution of lateral dimensions. although widely used for the synthesis of double-layer hydroxide-based nanocomposites.D. even when intercalation has taken place. 9 presents DSC traces of polystyrene (PS). 5.44. The many interactions the intercalated chains of the polymer form with the host species greatly reduce their rotational and translational mobility. DSC traces of pure PS. In addition to being an interesting analytical datum. but in principle could indicate novel methods of synthesis [56]. It becomes obvious from this section that a major issue when synthesizing polymer–layered silicate nanocomposites is the characterization of the product. Lomakin and Camino by permission of Wiley-VCH. This effect is readily detected by DSC. The recovery. However. as illustrated in Fig. However. and post-treatment of these clays may contribute to the variation in filler geometry. extrusion of these clays with polymer and any additional melt processing steps that follow. 900 ◦ C for approx- imately 45 min. unlike conventional fiber composites. First of all. without needing the presence of the onium ion. 10. 9. which decompose the polymers. i. 9.1. During the process. However.65]. the considerable increase in Tg is an important property of these materials that enables them to be employed at higher temperatures compared with the original polymer and thus extends their fields of application [41]. injection molding. it should be noted that the amount of clay present in a sample may be estimated. a PS/OMLS mixture and an intercalated PS/OMLS nanocomposite. (2) intercalation of polymer or prepolymer from solution.14. Fig. at present FTIR is an unreliable method of characterization in most cases [56]. refinement. as it not only helps to characterize the material. An exception is the synthesis of hectorite-type clay minerals which can be performed under relatively mild conditions. Finally. 10 depicts various complications of calculating an aspect ratio from TEM photomicrographs that arise from variations in both length/diameter. Preparation of nanocomposites 5. To date. the synthesis of clay minerals generally requires high temperatures. a physical mixture of PS/OLS. Finally. using an aqueous solution (or gel) containing the polymer and the silicate building blocks.35. Germany. In fact. building a clearer picture of the changes that occur when a nanocomposite forms is important. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1129 Fig. Pavlidou. Furthermore. A similar increase is anticipated to occur in a nanocomposite due to elevation of the energy threshold needed for the transition. Fig. Template synthesis (sol–gel technology) In this technique.S. The resulting ash is then weighed and corrected for loss of structural water [64].g. Another problem is the aggregation tendency of the growing silicate layers.e. will amplify the range of particle shapes and sizes. is far less developed for layered silicates and will not be considered in the following discussion. this technique. The presence of this peak in the mixture is evidence of the absence of interactions between the organic and the inorganic phases.52. Although theoretically this method has the potential of promoting the dispersion of the silicate layers in a one-step process. e. by placing pre-dried nanocomposite pellets in a furnace at ca. the determination of filler aspect ratio for layered silicate nanocomposites is not straightforward.1. Good estimates require a thorough analysis of TEM photomicrographs at different magnifications. chemical treatment. differential scanning calorimetry (DSC) provides further information concerning intercalation. minute.1. as for conventional composites. Therefore. 5. particularly when the layered silicate is not completely exfoliated. C. it presents serious disadvantages. many of the studies conducted so far in this field are solely dedicated to structural characterization of the nanocomposites. As precursors for the clay silica sol. and thickness. microtoming of the nanocomposite sample into thin sections for TEM analysis will also result in an apparent distribution of observed particle sizes even if all disk-like platelets were the same size [64]. The PS and PS/OMLS mixture curves clearly display the characteristic peak due to glass transition of the polymer. The situation is similar to that in a reticulated polymer. magnesium hydroxide sol and lithium fluoride are used. (3) in situ intercalative polymerization and (4) melt intercalation [1. The transition is absent in the nanocomposite curve and in fact occurs at temperatures higher than those shown in Fig.

owing to the weak forces that stack the layers together can be easily dispersed in an adequate solvent. the entropy gained by desorption of solvent molecules is the driving force for polymer intercalation from solution [66–71]. usually under vacuum. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Fig. Melt intercalation This technique consists of blending the layered silicate with the polymer matrix in the molten state.2. The reaction can be initiated either by heat or radiation. lithium fluoride and polymers like poly(vinyl alcohol). After the organoclay has swollen in the solvent. the modified layered silicate is swollen by a liquid monomer or a monomer solution. Polymerization produces long-chain polymers within the clay galleries.4. or by precipitation. The final step consists of removing the solvent. Upon solvent removal the sheets reassemble.3. but most of them remained uniformly distributed in the polymer matrix [1. Under this process are also gathered the nanocomposites obtained through emulsion polymerization where the layered silicate is dispersed in the aqueous phase.. .D. such as polyimide) is soluble. by the diffusion of a suitable initiator or by an organic initiator or catalyst fixed through cationic exchange inside the interlayer before the swelling step by the monomer. is especially of practical interest. in situ polymerization and melt intercalation are considered as commercially attractive approaches for preparing polymer/clay nanocomposites. the solvent approach is difficult to apply in industry owing to problems associated with the use of large quantities of solvents [1. Melt intercalation. previously intercalated solvent. so that the polymerization reaction can occur between the intercalated sheets. Examples of complications in the determination of the aspect ratio of layered silicate fillers within polymer nanocomposites [64]. UK.2. the clay layers are delaminated and the resulting material possesses a disordered structure [1.35]. either by vaporization.1. the polymer is added to the solution and intercalates between the clay layers. For example.and extra-gallery polymerization rates are properly balanced. However.1130 S. The major advantage of this method is that intercalated nanocomposites can be synthesized that are based on polymers with low or even no polarity. the layered silicate is exfoliated into single layers using a solvent in which the polymer (or prepolymer in case of insoluble polymers. The monomer migrates into the galleries of the layered silicate.37].35. since it presents significant advantages that will be discussed in the corresponding paragraph. Among the aforementioned methods. Reproduced from Fornes and Paul by permission of Elsevier Science Ltd.35. 5. Intercalation of polymer or prepolymer from solution Following this technique. Pavlidou. In situ intercalative polymerization In situ-polymerization was the first method used to synthesize polymer–clay nanocomposites based on polyamide 6. sandwiching the polymer to form a nanocomposite structure. In this technique. 10. 5. Intercalation of polymer from solution Intercalation of a polymer from a solution is a two-stage process in which the polymer replaces an appropriate.1. magnesium hydroxide. Under conditions in which intra. in particular. 5. some silicate layers aggregated. cessfully applied it for the preparation of nanocomposite materials.3. Such a replacement requires a negative variation in the Gibbs free energy. Under such conditions – if the layer surfaces are sufficiently compatible with the chosen polymer – the polymer can crawl into the interlayer space and form either an intercalated or an exfoliated nanocomposite [1. 11. It is well known that such layered silicates. In other words. C. as shown in Fig. and Carrado and Xu synthesized hectorites from gels consisting of silica.41] 5.1. It is thought that the diminished entropy due to the confinement of the polymer is compensated by an increase due to desorption of intercalated solvent molecules. Evidently. polyaniline and polyacrylonitrile.37]. Carrado et al.

6. 8.N -dimethylacetamide (DMA). C. Summarizing the above: although a number of nanocomposites have been produced by intercalation from solution (representative examples are presented in Table 2). 13 represents the conceptual view of the swelling behavior of . -amino acid (COOH–(CH2 )n−1 –NH2 + . Chang et al. The nanocomposite was then recovered by precipitation from THF [79]. this method may involve the copious use of organic solvents. due to the favorable enthalpic interaction between these diols and the C O bonds in the PLA backbone. Even though this technique has been mostly used with water soluble polymers. Moreover.3.50]. indicating that the extent of intercalation of -caprolactam monomer is high when the number of carbon atoms in the -amino acid is large [93].85]. 11. In the case of polymeric materials that are infusible and insoluble even in organic solvents. PVE. intercalation from non-aqueous solutions has also been reported [78–81]. it is important to note that. 12-aminolauric acid-modified MMT (12-MMT) was Table 2 PLS nanocomposites prepared by intercalation from solution. Krikorian and Pochan [83] prepared PLA nanocomposites using dichloromethane as the polymer solvent and as the OMLS dispersion medium. intercalation only occurs for certain polymer/clay/solvent systems. Fig. HDPE-based nanocomposites have been prepared by dissolving HDPE in a mixture of xylene and benzonitrile with dispersed OMLS. 5.1. In situ intercalative polymerization of thermoplastic polymers The Toyota research group first reported the ability of . from the industrial point of view. 12. in using this method. involved dissolving the polymer in hot chloroform in the presence of organomodified MMT. However. TEM and WAXD analyses revealed that only microcomposites were formed and that an intercalated morphology was not achieved. Nanocomposite PVOH/Na -MMT PVA/Na+ -MMT TPU/OMLS PEO/Na+ -MMT or Na+ -hectorite PEO/MMT PLA/OMLS PLA/OMLS HDPE/protonated dodecylamine modified MMT PSF/OMLS PI/dodecylammonium modified MMT + Solvent(s) Water Water Toluene/DMAc Acetonitrile Chloroform Dichloromethane DMAc Xylene/benzonitrile (80/20 wt. exfoliated nanocomposites were formed when diols were present in the organic modifier of the clay. 4. by mixing pure PS and organophilic clay with adsorbed cetyl pyridium chloride [82]. meaning that for a given polymer one has to find the right clay. with n = 2. That is. depending on the type of OMLS used. Similarly. several studies have focused on the preparation of PLA-layered silicate nanocomposites using intercalation from solution.3. -amino acid was found to have a strong effect on the swelling behavior as reported in Fig. The authors obtained intercalated or exfoliated nanocomposites.D. For example. Schematic representation of PLS obtained by intercalation from solution. Moreover. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1131 Fig. In a typical synthesis. [86] [87] [88] [89] [90] [83] [84] [91] [92] [85] . PVP and PAA [3. 12.21. it was found from a comparison of different types of inorganic silicates that clays having higher CEC lead to more efficient exfoliation of the silicate platelets [51]. In situ intercalative polymerization 5.S. 5.72–77]. The first attempts by Ogata [78]. such as PEO. In a later study. [84] reported the preparation of PLA-based nanocomposites with different kinds of OMLS via solution intercalation using N. 3. which is usually environmentally unfriendly and economically prohibitive [50]. the only possible route to produce nanocomposites with this method is to use polymeric precursors that can be intercalated in the layered silicate and then thermally or chemically converted to the desired polymer [1. PS/OMLS exfoliated nanocomposites have also been prepared by the solution intercalation technique. 11.%) DMAC DMAC Ref. Pavlidou. 18) modified Na+ -MMT to be swollen by -caprolactam monomer at 100 ◦ C and subsequently initiate ring opening polymerization to obtain PA6/MMT nanocomposites [25]. The number of carbon atoms in the . -amino acid modified Na+ -MMT by -caprolactam [93]. organic modifier and solvents [1.

%) or intercalated structures (from 15 to 70 wt. One can also point out that an intercalated structure is obtained even if no acid is added [95]. Kojima. Further work demonstrated that intercalative polymerization of -caprolactam could be realized without modifying the MMT surface. for unclear reasons.%) were obtained. Pavlidou. Kawasumi. Kurauchi and Kamigaito by permission of Materials Research Society. XRD intensity curve of injection molded nylon-6 nanocomposite as obtained by the one-pot intercalation polymerization process in the presence of acetic acid [95]. Table 3 gives results obtained for different acids in relation to the intensity (Im ) of the XRD intercalation peak that might be present in the nanocomposites obtained (Fig. XRD patterns of -amino acid [NH2 (CH2 )n−1 COOH] modified Na+ MMT [93]. Usuki. using 12MMT as a catalyst (when the relative amount of 12-MMT in the mixture was less than 8 wt. USA. Swelling behavior of -amino acid modified MMT by caprolactam [93]. has also been reported to form nanocomposites via in situ intercalative polymerization. They first studied by XRD the dependence of the clay swelling process on ALA concentration in HCl. Fig. Indeed. allowing the ring opening polymerization to proceed at 260 ◦ C when 6-aminocaproic acid is added as an accelerator. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 3 Peak intensity (Im ) and interlayer spacing (d) of nylon-6-based nanocomposites prepared in presence of different acid derivatives by the one-pot technique [95].%. USA. Another polyamide. Okada. as proved by the increase in interlayer spacing from 10 to 15. Inc. Kurauchi and Kamigaito by permission of John Wiley & Sons.1132 S. ./100 g). this monomer was able to directly intercalate the Na+ -MMT in water in the presence of hydrochloric acid. Kurauchi and Kamigaito by permission of Materials Research Society. The resulting composite does not present a diffraction peak in XRD. Reproduced from Usuki. Reichert et al. only phosphoric acid allows for the preparation of a truly exfoliated nanocomposite. Kojima.2 19. the other acids tending to promote the formation of partially exfoliated-partially intercalated structures.D. nylon 12. Okada. Reproduced from Usuki. Kawasumi. Kawasumi. Okada. In attempts to carry out the whole synthesis in one pot.3 21. in the presence of excess -caprolactam. Depending on the amount of 12-MMT introduced. and TEM observation agrees with a molecular dispersion of the silicate sheets [94].3 18. as evidenced by XRD and TEM. 12. have led to the conclusion that the COOH end groups present along the 12-MMT surface are responsible for the polymerization initiation [25]. Comparison of the titrated amounts of COOH and NH2 end groups present in the synthesized nanocomposites with given values. mixed with -caprolactam and the mixture was heated at 250–270 ◦ C for 48 h to polymerize -caprolactam. either exfoliated (for less then 15 wt. 14. and found that it can be separated in two regimes: a cation-exchange of inorganic cations by protonated ALA at low ALA concentra- Fig.7 20. These results show that. Acid Phosphoric acid Hydrochloric acid Isophtalic acid Benzenesulfonic acid Acetic acid Trichloroacetic acid No acid Im (cps) 0 200 255 280 555 585 1840 d (Å) 0 21. At high temperature (200 ◦ C).6 Fig. the clay so modified can be swollen again.3 20. Reproduced from Kojima. 14). 13. C.1 Å. [96] used 12-aminolauric acid (ALA) as both the layered silicate modifier and the monomer. 6-aminocaproic acid was added as a polymerization accelerator and the heating profile was slightly modified). the system proved to be sensitive to the nature of the acid used to promote the intercalation of -caprolactam. such as the CEC of the montmorillonite used (119 mequiv.

In one of these studies. 20 bar) with both types of swollen clay. The glass tube was then cooled to room temperature and the resulting PA1012/organoclay hybrid was obtained as a white solid. Pavlidou. due to ineffective control of stoichiometry. a large increase in intragallery distance is hard to obtain. the organomodified montmorillonite is reported to react with PET comonomers (ethylene glycol and terephthalic acid derivatives) to form an intercalated nanocomposite [106]. [97] investigated the preparation of PA1012 nanocomposite by polycondensation polymerization. few publications focused on the preparation of polyamide from diamine and diacid. In the last step a vacuum (<0. and the reaction was continued for another 2 h. Kressler. Mulhaupt and Stoppelmann by permission of Wiley-VCH. this mixture was added to an absolute alcohol solution of 1. H2 SO4 . presumably due to the high viscosity of PET polymer. 16. . cyclic oligomers of PET have much lower solution and melt viscosities than the corresponding polymer. the authors proposed and successfully applied the ring-opening polymerization of ethylene terephthalate cyclic oligomers (ETCs) with organically modified MMT. It was then added with a slight excess of diaminodecane to a U-shaped glass tube which was purged with nitrogen before the reaction. ALA was then polymerized at high temperature (280 ◦ C) and under elevated pressure (ca. Then. Thomann. polystyrene (PS) [100]. The swelling was found to be independent of the swelling temperature. polyolefins (PP and PE) [102–105]. C. However. Schematic representation of the swelling behavior of the fluoro-modified talc ME 100 in presence of aminolauric acid [96]. including polymethyl methacrylate (PMMA) [98. the temperature was increased to 225 ◦ C. and polyethylene terephthalate (PET) [106]. Because of low molecular weight and cyclic molecular architecture. coupled with energy dispersive X-ray (EDX). polybenzoxale (PBO) [101]. The in situ polymerization technique has also been applied for the preparation of nanocomposites based on thermoplastic polymers other than polyamides.1 atm) was applied to remove the water and residual monomer. A dispersion of organoclay in absolute alcohol was added to 1. although in situ polymerization was successfully applied for the preparation of PA6 and PA12/clay nanocomposites. Mulhaupt and Stoppelmann by permission of Wiley-VCH. 15 and 16).10-decanedicarboxylic acid under vigorous stirring. when clay intercalation is intended by mix- Fig. Reproduced from Reichert. the layered silicate concentration and the type of acid used to protonate ALA (HCl. as an alternative approach to the preparation of PET-based nanocomposites. Wu et al.10 diaminodecane in absolute alcohol. For example. 15. Reproduced from Reichert. Thomann. Germany. The absence of peaks in the XRD pattern indicated the exfoliation of the clay platelets in the PA1012 matrix. attempts to prepare PET nanocomposites through melt intercalation have resulted in limited intercalation of guest molecules. Therefore. The glass tube was flushed with nitrogen each time to remove the water produced in polycondensation. After maintaining the autoclave for 2 h at 200 ◦ C.D.99]. as well as atomic force microscopy (AFM). according to Lee et al. in a study discussing the synthesis of PET nanocomposites using in situ polymerization. H3 PO4 ). resulting in the immediate precipitation of a diaminodecane–decanedicarboxylic acid salt. when the ALA concentration exceeds the amount of HCl in the medium (Figs. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1133 Fig. The tube was immersed in an oil bath and the temperature was quickly raised to 200 ◦ C to start the reaction. However. On the other hand. XRD and TEM. and thus. Kressler. Germany. so it may be expected that. the temperature was increased to 215 ◦ C and held for 1. tion and a further diffusion of zwitterionic 12-aminolauric acid into the interlayer space. [107] endeavors to prepare PET nanocomposites using direct condensation polymerization of diol and diacid result in formation of oligomers with significantly low molecular weight.S. Interlayer distance of fluoro-modified talc (ME 100) in function of an increasing amount of aminolauric acid used as the organic modifier [96].5 h under these conditions. confirmed that the resulting structures were partially exfoliated and otherwise intercalated nanocomposites. The salt was recrystallized from a mixture of alcohol and water and was obtained as a white powder.

The clay dispersion was then surface-treated with MAO.2 P(H2 )b (bar) 0 0 0. Filler h m h a b c d MAO (10−3 mol) 33. for 1 h to form the active catalyst species. problems such as precise control of stoichiometry and high vacuum requirements. Schematic representation of nanocomposite formation by ringopening reaction of cyclic oligomers in between silicate layers [107]. Reproduced from Lee. It has to be pointed out that no ion exchange reaction was required. the silicate layers were contacted with a metallocene pre-catalyst.%) 4. [103] used a palladium-based complex and synthetic fluorohectorite as the polymerization catalyst and inorganic component respectively for the synthesis of polyethylene nanocomposites.75 Catalyst (10−6 mol) 15. rubbery polymer formed. The polymerization was carried out by adding ethylene to the medium.000 h: hectorite and m: montmorillonite. the complete absence of diffraction peaks in the XRD patterns strongly suggests the formation of an exfoliated nanocomposite.6 12. Over a 2 h period. C.1134 S. 30 wt.20 23.3 Filler loadingc (wt. Some typical in situ intercalation experiments are gathered in Table 4. Pavlidou. Moreover. easier diffusion and a higher degree of intercalation or exfoliation would be obtained. layered silicate/UHMWPE was produced. Measured by thermogravimetric analysis (TGA). They used organic salts with hydroxyl groups for the mod- Table 4 Synthesis and composition of PE-based nanocomposite produced by in situ intercalative polymerization of ethylene (P(C2 H4 ) = 10 bar) in non-organomodified layered silicatesa [1]. Rather. The fluffy materials obtained could then be nicely dispersed in non-polar solvents such as heptane or toluene. Rhee and Kim J by permission of Elsevier Science Ltd. and after solvent removal by evaporation.4 HDPE Mn (g/mol) –d –d 77. UK. this strategy relied on the immobilization of the active species through electrostatic interactions with surface anchored MAO. ing with cyclic oligomer instead of linear polymer. Hydrogen partial pressure at start. .5 16.00 27.D. while after 12 h a large mass of colorless. can be effectively avoided through ring opening reaction of cyclic oligomers (Fig. HDPE nanocomposites have been synthesized by the so-called polymerization-filling technique (PFT). very difficult to melt (Table 4. In addition.3 3. Jin et al. a high temperature treatment at 150 ◦ C was applied to modify the layered silicate. layered silicates in aqueous colloidal suspension were made less hydrophilic through elimination of water by freeze drying. even at high filler content (ca. entries 1 and 2). 17).. Analysis of the tolueneextracted polyethylene by GPC revealed a high molecular weight.2 3. Examination of the TEM pictures reveals partial exfoliation. which is an extremely viscous material. Similarly. When ethylene polymerization was carried out in the absence of molecular hydrogen (thus without any transfer agent). strictly required in preparation of PET by conventional condensation polymerization of difunctional monomers. Addition of hydrogen to the polymerization medium allows molecular weight to be reduced with substantial improvement of melt processability (Table 4. Ma. In order to apply this technique to nanofillers.e. they observed monomer consumption and a dramatic increase in the size of the silicate-catalyst composite. They first intercalated palladium catalyst into the galleries of modified fluorohectorite (C14N-2) and exposed the dry powder to ethylene gas. (tert-butylamido)dimethyl(tetramethylZ5-cyclopentadienyl) silane titanium dimethyl. which involves anchoring in a first step a Ziegler-Natta type or any other coordination catalyst onto a filler surface and then in situ polymerizing ethylene directly from the surfacetreated fillers. 17. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Fig. entry 3). Insoluble UHMWPE that cannot be eluted by SEC. After removal of unreacted MAO. [105] also applied the in situ exfoliation method during ethylene polymerization by fixing a Tibased Ziegler-Natta catalyst at the inner surface of MMT.% montmorillonite) [108–110]. i. Bergman et al.

18 represents the TiCl4 fixation mechanism between silicate layers of MMT–OH. polymerization was quenched with a dilute HCl solution in methanol. Park. Pavlidou. In a study by Shin et al. ification of MMT (MMT–OH) since hydroxyl groups in intercalation agents offer facile reactive sites for anchoring catalysts between silicate layers. Following the in situ intercalative polymerization technique. Schematic illustration of the modification and ion exchange of laponite with [Zr(n–C5 H5 )2 Me(thf)]BPh4 and propene polymerization [104].D. Doh and Cho [113] compared the ability of several tetraalkylammonium cations incorporated into Na+ -MMT to promote the intercalation of PS through the free radical polymerization of styrene. The polymerization of ethylene was conducted by injecting ethylene into the catalyst slurry (30–50 ◦ C. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1135 Fig. while formation of polyethylene inside the galleries leads to the exfoliation of layered silicates. The intercalation process allows the transition metal catalyst and the activator methylaluminoxane to enter the clay galleries and polymerize ethylene. respectively. Reproduced from Jin. [112] carried out ethylene polymerizations in the presence of layered silicates. [111] montmorillonite was intercalated with triisobutylaluminum and -undecylenyalcohol. the authors assumed that intercalation occurs in this case also. O’Hare and Royan by permission of The Royal Society of Chemistry. The authors noted that two types of polymerization are possible: (a) the homopolymerization of ethylene. affording HDPE and ethylene–octene copolymers (zirconium-based catalyst) and branched polyethylene (nickel and palladium-based catalysts). however this is not evident from the d-spacings because such hydrogenated tallow alkyl chains should be long enough (mainly C18 chains) to easily accommodate the PS. where hydrogenated tallow alkyl corresponds to a mixture of mainly octadecyl chains together with small amounts of lower linear homologs and R may be either another hydrogenated tallow alkyl (Ta). 2-ethyl hexyl (Eh) or benzyl (Bz) group. This is probably due to a better affinity between styrene and benzyl groups spread all along the layered MMT surfaces. The so-modified o-MMTs were coded as TaMMT. Tudor et al. Layer spacings obtained for the three MMTs and corresponding composites are presented in Table 5 and reveal that the best intercalation occurs for Bz-MMT. Three tetraalkylammonium cations were tested. Im. Mechanistic representation of the fixing of TiCl4 between the silicate layers of MMT–OH [105]. It is worth mentioning that even though the interlayer spacing for Ta-MMT does not change much. Eh-MMT and Bz-MMT. [104] treated a synthetic hectorite with methylaluminoxane (MAO) to remove the acidic protons and to prepare the interlayer spacing to receive the transition metal catalyst. . 19. UK. while Ni-and Pd-based catalysts were much less affected by the nature of the clay. Kwak and Kwak by permission of Wiley-VCH. Heinemann et al. 18. However. and (b) the copolymerization of ethylene and the vinyl ends of alcohol modifier connected to the surface during intercalation. After predetermined reaction times. all based on the following formula: (CH3 )2 N·(hydrogenated tallow alkyl)R. while in situ polymerization with unmodified silicates gave microcomposite structures. separated by filtration and dried in vacuum. 4 bars). Different catalysts were used. without the need of MAO treatment. using 1-octene as comonomer. such as organo-modified bentonite and unmodified hectorite and fluoromica. Sun and Garces [102] also reported the preparation of PPCN by in situ polymerization with metallocene/clay catalysts. C. Using a synthetic fluorinated mica-type layered silicate deprived of protons in the galleries. Fig. PP/clay nanocomposites have also been prepared by in situ intercalative polymerization. Willington.S. initiated by AIBN at 50 ◦ C. which produces polyethylene chains. Reproduced from Tudor. Germany. nanocomposites formed only in the case of organo-modified clays. Details of the preparation route are shown in Fig. 19. The polymer was precipitated in methanol. WAXD analysis again revealed exfoliation of MMT layers in both the powdery reaction product and the HDPE matrix. the catalyst was intercalated directly within the silicate layers. chemically connected to the silicate surface. Even though this technique allows for extensive intercalation of PS chains through the choice of Fig. It appeared that the modified bentonites had a dramatic negative effect on the polymerization activity of the zirconium-based catalyst due to its high sensitivity towards any kind of polar functionality. The powder was then used as the master batch and mixed with HDPE by melt extrusion.

b It was judged by the appearance of the montmorillonite dispersion in styrene monomer (++) fully dispersible. l. Yei et al. by suspending the clay in styrene monomer. KOH and SDS were added to the solution and the temperature was raised to 50 ◦ C. an appropriate alkylammonium cation. The clay C30B led to fully exfoliated structure. the clay was thoroughly dried and placed in the polymerization vial.27 nm. CDs comprise a series of -1. The cavities of CDs are hydrophobic.1136 S.6 Å). Pavlidou.D. The same researchers also modified a Na+ -MMT by the protonated aminolauric acid and dispersed this modified clay in liquid -caprolactone before polymerizing it at high temperature. after 1 h of clay swelling in the monomer melt. Upon cooling to room temperature the reaction mixture solidified. which showed an increase in the silicate d-spacing from 1. Messersmith and Giannelis [117] reported the first preparation of PCL nanocomposites. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 5 Interlayer spacings of organo-modified montmorillonites (X-MMT) and as-obtained PS-based nanocomposites and the clay dispersibility within the polymerization medium [113].e. substantially higher than that caused by CPC alone. The d0 0 1 spacing observed prior to polymerization was found to be consistent with the orientation of the CL ring perpendicular to the silicate layers. as presented in Fig. the polymerization was co-initiated by AlEt3. XRD analysis of the nanocomposites after polymerization indicates a reduction in the silicate d-spacing from 1. (+) partly dispersible and (−) non-dispersible. Styrene monomer and K2 S2 O8 were added slowly and polymerization was performed at 50 ◦ C for 8 h.46 to 1. On the other hand. exfoliated PLA/clay nanocomposites were prepared by in situ coordination-insertion polymerization method [116]. acetone was added to break the emulsion. aliphatic chain within the CPC/ -CD cannot bend within the galleries of the clay. in contrast to what is usually observed in in situ intercalative polymerization. i.8 19. XRD patterns indicate that the CPC surfactant is intercalated successfully into the galleries of the clay. Eh (2-ethylhexyl).l-Lactide solution in dried THF was then transferred to the vial under nitrogen and the solvent was eliminated under reduced pressure. The absence of WAXD peaks together with TEM observations of silicate layers randomly dispersed within the PS matrix attest to the complete exfoliation of the layered silicate. Polymerizations were conducted in bulk at 120 ◦ C for 48 h. neither exfoliation nor control over the molecular weight of PS produced has been observed. The modified clays were also obtained as white precipitate after adding a solution of the surfactant (CPC or CPC/ -CD inclusion complex) in a Na+ -MMT suspension. 20. The decrease in the d-spacing is consistent with the dimensional change accompanying polymerization of CL monomer. [115] prepared PS/clay nanocomposites through emulsion polymerization.1 20. The authors assumed that the monomer intercalates in the gaps between the aminolauric acid chains so that no gallery expansion could be seen. increasing their spacing from 1. followed by the ring opening polymerization at 170 ◦ C for 48 h. [114]. Furthermore. Akelah and Moet [100] modified MMT with vinylbenzyltrimethyl ammonium cation.12 nm. in 1993. who modified Na+ -MMT by anchoring an ammonium cation bearing a nitroxide moiety known for its ability to mediate the free radical polymerization of styrene in bulk.5% aqueous aluminum sulfate was added to the polymerized emulsion. followed by dilute HCl with stirring. with the extent of intercalation depending upon the nature of the solvent used. For the preparation of an inclusion complex.43 to 2.% of the modified clay with -caprolactone at room temperature for two h. Intercalation of the CL monomer was revealed by XRD. although PS is well intercalated. Interestingly enough.4 32. the d-spacing caused by the inclusion complex is 5. The clay was treated with either cetyl-pyridinium chloride (CPC) or the inclusion complex of CPC in -cyclodextrin (CPC/ -CD).l-lactide in the presence of C25A. such as acetonitrile or acetonitrile/toluene under N2 . intercalated PS/MMT nanocomposites were produced. In this way. In another study. C. Styrene polymerizations were carried out in presence of AIBN at 80 ◦ C for 5 h. whereas C25A-based nanocomposites exhibited an intercalated morphology.46 nm. 2. After stirring for 4 h. The PCL nanocomposites were prepared by mixing up to 30 wt.7 In PS/X-MMT 14.28 to 1. Xa -MMT Interlayer spacing (Å) In X-MMT Sodium MMT BZ-MMT Eh-MMT Ta-MMT 11. In a typical synthetic procedure. After cooling. However. This was the first study reporting cyclodextrins (CDs) as surfactants for intercalation in clay. Emulsion polymerization was performed as follows: a surfactant solution (CPC or CPC/ -CD inclusion complex) was added to an aqueous suspension of clay. one drawback of this procedure is that the macromolecule produced is not a pure PS. CPC was mixed with a saturated solution of -CD in water and the complex was obtained as a white crystalline precipitate.2 34. no peak was detected in the XRD patterns for polymer/clay nanocomposites prepared from the CPC and CPC/ -CD treated clays which implies that they all possess exfoliated structures. a mixture of Cr3+ FH and CL was heated at 100 ◦ C for 48 h. When C30B was used. In a typical synthesis. This was explained by the authors considering that the linear.5 32. using Cr3+ exchanged fluorohectorite (FH). where the . or Ta (hydrogenated tallow alkyl). but rather a copolymer between styrene and surfactant. In another study. Finally.0 28. while Sn(Oct)2 was used to catalyze the polymerization of l. XRD patterns of the modified clay after contact with -caprolactone at room temperature do not show any significant increase in the layer spacing (13. The authors used two different kinds of OMLS (C30B and C25A) for the preparation of nanocomposites. thus CDs have the ability to include hydrophobic molecules within their cavities. A similar approach has been applied by Weimer et al. by in situ intercalative polymerization. and they dispersed and swelled the modified clay in various solvent and co-solvent mixtures.9 − ++ + + Dispersibilityb a Organo-modifiers: (CH3 )2 N+ (hydrogenated tallow alkyl)R with R = Bz (benzyl).37 nm.4-linked cyclic oligosaccharides with shapes resembling hollow truncated cones.

suggesting that the PCL is indeed intercalated within the silicate layers of the clay in the blend that. they added a suspension of an intercalated PCL nanocomposite (prepared by intercalative polymerization of -CL and having a basal spacing of 24 Å) in chloroform to a chloroform solution of PCL and after stirring for 15 h. It can be inferred. Pantoustier et al. exfoliation will not be reached. it is worth mentioning that. Powder XRD of the composite before (solid line) and after (dashed line) polymerization. since such nanocomposites obviously cannot be synthesized by melt intercalation. including the catalytic effect on the curing reaction. the miscibility with the curing agent. [6] suggested that the low molecular weight of PCL synthesized by in situ polymerization in the presence of layered silicate may be responsible for the high brittleness of the resulting nanocomposites. and meaning weaker attractive forces between the silicate layers [33. C. respectively. meaning a greater amount of intragallery resin preload and a completed organization of the clay. a number of research groups have studied the effect of various parameters on the exfoliation of clays in epoxy resins. however. Even though the polymerization mechanism of -caprolactone in the presence of clay generally remains unclear and different assumptions have been made [121–123].S. the authors also conducted the same experiment without MMT. consequently. it is thought that the modifiers introduced into the galleries of the clay sheets would promote the reaction between the epoxy in the gallery with the cur- . the exfoliation ability of the organoclays is determined by their nature. In situ intercalative polymerization of thermosetting polymers Despite the aforementioned disadvantages of in situ intercalative polymerization. That is. the long alkyl-chain of the organo-cation. the good penetrating ability of curing agent to clay. as the curing agent is mixed into the clay/epoxy mixture. that factors promoting the curing reaction of intragallery resin will facilitate the exfoliation of the clay. Interfacial modifiers. not only to compatibilize the inorganic aluminosilicate and organic resin. therefore. the extragallery resin will gel before the intragallery resin produces enough curing heat to drive the clay to exfoliate. and (3) the process is available only to the resin manufacturer who is able to dedicate a production line for this purpose [124].D. These results demonstrate the ability of MMT to catalyze and control CL polymerization.120] compared PCL nanocomposites prepared by intercalative polymerization using both pristine MMT and -aminododecanoic acid modified MMT.2. this is the only viable technique for the preparation of thermoset-based nanocomposites. For comparison. In contrast. the authors assumed that CL is activated through interaction with the acidic site on the clay surface. Therefore.%) of clay. In this case. 20.3. Pioneering studies by Pinnavaia and coworkers [129] on MMT/epoxy systems established the initial conceptual methodology. etc. and the platelets may re-aggregate during subsequent processing steps. USA. important drawbacks of this technique have also been pointed out: (1) it is a time-consuming preparation route (the polymerization reaction may take more than 24 h). Another possibility may be that intercalation of the monomer occurs only during the heating step of the solution. More specifically. The polymerization of CL with pristine and modified MMT gives PCL with a molar mass of 4800 and 7800 g/mol.128]. Such factors include the catalytic effect of organoclay on the curing reaction. underwent partial restructuring during the blend formation. at least in terms of a molecular weight distribution that remains remarkably narrow. The XRD patterns of this product 5. and a narrow distribution. even though in situ intercalative polymerization has proved successful in the preparation of various polymer–layered silicate nanocomposites. (2) exfoliation is not always thermodynamically stable. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1137 showed a peak corresponding to a basal spacing of 18 Å. if the extragallery polymerization is more rapid than the intragallery diffusion and polymerization or if intragallery polymerization is retarded. the curing heat produced is enough to overcome the attractive forces between the silicate layers and an exfoliated nanocomposite structure can be formed. indicating that exfoliation occurred [118]. Since there is a curing competition between intragallery and extragallery resin. monomer insertion within the silicate gallery induces an increase in the interlayer spacing. [119. Pavlidou. such as primary ammonium alkyls are intercalated between the MMT layers. they obtained the final composite by precipitation into hexane.125–127]. they proposed the preparation of blends of high molecular weight PCL with different amounts of o-MMT/PCL nanocomposite prepared via in situ polymerization and containing a high amount (30 wt. Reproduced from Messersmith and Giannelis by permission of the American Chemical Society. Insets are schematic illustrations (not drawn to scale) corresponding to the intercalated monomer (left) and intercalated polymer (right) [117]. but found no CL polymerization. In fact. XRD patterns of the obtained composites did not show a diffraction peak. as long as the intragallery polymerization occurs at a rate comparable to the extragallery polymerization. Fig. which is the other commercially important preparation method [42. Gorrasi et al. After polymerization. At this point. but also to accelerate the crosslinking reaction between the layers through acid catalysis. On the other hand.

such as methylene dianiline. [131] found that the clays with primary and secondary onium ions formed exfoliated nanocomposites. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 6 d-Spacing of tixogel and OPTC18 at 5 phr in epoxy/amine systems at the beginning and at the end of polymerization. Similarly. but they do not seem to offer any significant long-term advantage. Epoxy system + 5 phr Tixogel DGEBA/MCDEA d-Spacing when reaction starts (Å) d-Spacing at the end of the reaction (Å) 33. a benzyl dimethyl tallow alkyl ammonium MMT. producing a new hydroxyl that subsequently reacts with free DGEBA via a similar base-catalyzed oxirane ring opening to build up the epoxy network. BDMA can catalyze the reaction between the hydroxyl groups of the alkylammonium and the oxirane of the monomer. Lower viscosity resins lead to faster pre-intercalation. The first MMT is Tixogel MP250. Le Pluart et al. Study of the curing reactions tended to prove that the particular alkylammonium used (that bears two hydroxyl functions) could play an active role. They found that when primary and secondary amines. indicating some partial intercalation. However. for unclear reasons the authors could not determine a gel time in the presence of OPTC18. An MMT with a low CEC is exfoliated already during swelling in the epoxy resin prior to curing. the curing agent controls the rate of cure. Messersmith and Giannelis [135] analyzed the effect of different curing agents on the formation of nanocomposites based on DGEBA and a montmorillonite modified by bis(2-hydroxyethyl)methyl hydrogenated tallow alkyl ammonium cation. delamination during heating of the reaction mixture occurred. In this context.6-diethylaniline] (MCDEA) as well as two montmorillonites modified with different alkyl ammonium ions having the same chain length. Hackman and Hollaway [134] noted that the epoxy resin component of the nanocomposite has little effect on the exfoliation of the clay layers.5 110 ing agent. It was also found that the length of alkyl chains of modified MMT may determine whether an intercalated and partially exfoliated or a totally exfoliated nanocomposite will be obtained. In the case of . This was attributed to either the bridging of the silicate layers by the bifunctional amine molecules. again modified with a wide variety of surfactants. For the diglycidyl ether of bisphenol A (DGEBA).7 35.D. such as nadic methyl anhydride (NMA). the d-spacings of the clays at the beginning and the end of polymerization are presented in Table 6. which determines the amount of surfactant ions present between the clay layers and therefore controls the space available for diffusion of epoxy molecules during mixing with the organoclay. while the second is OPTC18. using a mixture of two diethyltoluene diamine (DETDA) isomers as the hardener and a commercially available octadecyl ammonium ion modified MMT as the clay. A possible mechanism explaining this phenomenon is homopolymerization of the epoxy resin during the swelling phase.0 Epoxy system + 5 phr OPTC18 DGEBA/MCDEA 33. an octadecylammonium ion modified MMT. They used two different curing agents: an aliphatic diamine with a polyoxypropylene backbone (D2000) and 4. It has been established that the highest CEC provides the minimum space. especially when BDMA or NMA were added as the curing agents. only intercalated epoxy–clay structures could be obtained. Concerning the influence of network formation on organoclay dispersion. The same kind of study was also conducted by Zilg et al. Another parameter of the clay that greatly affects the outcome of nanocomposite processing is the cation exchange capacity (CEC). On the other hand. the duration of swelling of the clay with high CEC is shown to be critical for the synthesis of an exfoliated nanocomposite [42]. or to the strong polarity of the N–H groups in the primary and secondary amines that causes a reaggregation of dispersed silicate layers. This would make the intragallery curing reaction faster than the extragallery reaction. Interestingly.0 70 DGEBA/D2000 54. For example. triglycidyl p-aminophenol (TGAP) and tetrafunctional tetraglycidyldiamino diphenylmethane (TGDDM). Recently. causing diffusion of new epoxy molecules into the clay galleries. With further heating. [133] prepared nanocomposites of three different epoxy resins: diglycidyl ether of bisphenol A (DGEBA). although it is the basic unit. C.9 DGEBA/D2000 33. which prevents further expansion of the layers from taking place. boron trifluoride monomethylamine (BTFA) or benzyldimethylamine (BDMA) were added. Lan et al. The large amount of space available between the layers favors the diffusion. For example. the swelling phase is of critical importance to the final nanocomposite structure. The authors noticed that gel time was decreased in the presence of Tixogel for both the DGEBA/D2000 and the DGEBA/MCDEA systems. When other curing agents.4 -methylenebis[3chloro-2. Becker et al. Pavlidou.1138 S. thus facilitating the expansion of the clay sheets and helping to achieve exfoliation [130]. crosslinked with m-phenylene diamine (MPDA) and containing 5% modified MMT. Other researchers investigated the effect of the polymer resin. disappearance of the interlayer spacing reflection indicated that delamination had occurred. much research has focused on the effect of curing agent on the intercalation/exfoliation of clays in epoxy resins. were used. It was argued that acidic alkyl ammonium ions tend to favor exfoliation by catalyzing homopolymerization of DGEBA molecules inside the clay galleries. whereas those with tertiary and quaternary onium ions retained an intercalated structure. All epoxy resin systems intercalated the organically modified layered silicate and increased the d-spacing from 23 up to 80 Å. [136] investigated the influence of curing agent and clay organophilic treatment on the reactivity and cure behavior of epoxy networks and on the morphology of the final composites. [132] who cured DGEBA with hexahydrophthalic acid anhydride in the presence of different types of clays. Addition of the curing agent induced first an increase of the interlayer spacing from 36 to 39 Å.2 33.

uniform dispersion and a high degree of exfoliation is possible in systems that typically only show intercalated morphologies after traditional cure cycles. both reactive mixtures have swelled the organoclay already at the beginning of the reaction. resulting in intercalated nanocomposites. Then. Again the initial state of dispersion is good. solution rheometry and melt rheometry. This may generate higher styrene monomer concentration in . reducing the cost of the nanocomposites. Acetone was then evaporated and a stoichiometric quantity of the curing agent was added. The most significant feature of this technique is that very little (<5 wt. Conceptually. where in the first step. due to the high viscosity of the system. the mixtures of UP and modified MMT) are prepared. Using TGDDM as the matrix. a curing agent was added into the hybrid and mixed thoroughly. the synthesis of unsaturated polyester (UP)/layered silicate nanocomposites involves two steps: first the mixing process. involving clay processing in solvent (acetone) under high pressure and also against solid obstacles. prepared epoxy/crude clay nanocomposites using the “slurry-compounding” technique. pre-intercalates of the UP and MMT nanocomposites (i. As for epoxy-based nanocomposites. whereas in order to investigate the formation mechanism of UP/MMT nanocomposites. Suh et al. High shear forces. In another study. XRD patterns indicated that intercalation was realized irrespective of the mixing method applied. nanocomposites of up to 7. Among the various parameters. The structures of UP/MMT nanocomposites were investigated by XRD and TEM. is added with varying mixing times from 15 to 180 min.4 -diaminodiphenyl sulfone (DDS) as the hardener and an octadecyl amine modified MMT. The synthesis of nanocomposites based on montmorillonite and UP has been reported by different research groups. C. as the curing agent concentration increased. and then the styrene monomer. An important finding was that the intercalated hybrids were quite stable for storage. The formation of exfoliated nanocomposites was confirmed by XRD and TEM. In a typical example. containing dimethyl dehydrogenated tallow ammonium as an organic modifier. the effect of processing has also been investigated. the extragallery crosslinking dominated. during which the crosslinking reaction takes place by decomposing the initiators [139]. Koerner et al. [128] intercalated an organically modified MMT by epoxy resin by both direct or solution mixing. However.S.% clay loading were successfully synthesized with the HPM method. Pavlidou. 4. simultaneous mixing or sequential mixing. leading to the formation of ordered exfoliated nanocomposites. [139] reported on the formation mechanism of UP nanocomposites. has been applied by Liu et al. This demonstrates the possibility of improving the quality of dispersion at the nanometer scale during the polymerization of the network. Furthermore. acting as the curing agent. [33] confirmed the formation of exfoliated nanocomposites when DGEBA was auto-polymerized with MMTs. Jiankun et al. The so-called “high pressure mixing” (HPM) method. They used two different kinds of MMT: a dodecyl ammonium bromide MMT and Cloisite 20A.%) organic modifier is required to facilitate the exfoliation and dispersion of the clay. Similarly. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1139 Tixogen. It was also concluded that prolonging the stirring time above a certain level or using solution intercalation would not further improve the intercalation. The observations are very different in the case of OPTC18. this is achieved by maximizing epoxy viscosity by halting cure before gelation and by compounding at sub-ambient temperatures near the resin’s glass transition. [140] described the preparation of crosslinked polyester/clay nanocomposites by dispersing organically modified MMT in pre-promoted polyester resin and subsequently crosslinking the system using methyl ethyl ketone peroxide (MEKP) catalyst at several clay concentrations. Using this method.e. wherein the UP linear chains are mixed with the curing agent and layered silicate and second the curing process. [137] studied the impact of shear during epoxy nanocomposite processing and demonstrated that with proper mechanical processing conditions.D. UP was polymerized by the free radical polymerization with the modified montmorillonite dispersed in it. In order to prepare nanocomposites.e. the “slurry compounding” approach has been developed for epoxy/clay nanocomposite preparation using sodium MMT [138]. The authors noted that such improvement is not only due to the kind of organoclay used nor to the epoxy system chosen. Finally. as well as with reaction and diffusion kinetics of the reactive systems. The results led the authors to suggest the following mechanism of UP/silicate nanocomposite formation: The styrene monomer moves more easily than uncured UP chains. In another study. whatever the curing agent used. and used two different ways of mixing in order to prepare UP-based nanocomposites. During the polymerizations the d-spacing remains the same. based on XRD and TEM findings [127]. The mixture was degassed and dried. Chin et al. The authors claimed the formation of exfoliated structure. i. montmorillonite was treated with methacrylate-silane coupling agent in order to rend the filler hydrophilic and reactive. the authors used DMTA. but the d-spacing further increases during isothermal reaction of both reactive mixtures. The results indicated that if the organoclays can be exfoliated at all. nanoclays can be dispersed in acetone and an epoxy solution to form a stable suspension. facilitate homogenization of the layered silicate nanocomposite. TEM images show that the agglomerates of nanoclays were bro- ken down to form small particles consisting of several clay platelets. Exfoliated nanocomposites were also observed with DGEBA cured with MPDA of less than equimolar concentration. To further reduce the cost of polymer/clay nanocomposites Wang et al. since the d-spacing increased from 20.2 up to 34 Å. demonstrating that the polymerization of the epoxy/amine systems does not modify the dispersion of Tixogen. Bharadwaj et al. [130] for the preparation of epoxy nanocomposites. the exfoliation will be finished before the gel point of the epoxy. but rather is linked with interactions and chemical affinities between the organoclay and the network precursors. A clay–acetone slurry was mixed with required quantities of epoxy resin at 50 ◦ C.5 wt. in which the basal spacing of the nanoclay is increased. all mixtures were cured at 80 ◦ C for 3 h and post-cured at 120 ◦ C for 4 h.

Therefore. the styrene monomers are more easily dispersed inside and outside the silicate layers as mixing time increases. The approach of Wang and Pinnavaia to form polyurethane nanocomposites.5%) nanocomposites. and crosslinking density reaches the degree of crosslinking density of the cured pure UP. a known amount of Na+ -MMT was blended with a known amount of MMDI and cured at 78 ◦ C for 168 h. Berta et al. In the sequential mixing method. Mulhaupt and co-workers [143] prepared PU nanocomposites from modified reactive fluoromica clay. Acclaim 2220 Acclaim 4220 Daltocel F435 Arcol 1374 the MMT gallery than in any other part in a simultaneous mixing system. Yao et al. the gallery spacing of the layered clay is 1. the crosslinking reaction takes place homogeneously inside and outside the silicate layers. The dried organophilic mica was dispersed by means of a high shear mixer in trihydroxyterminated oligo-propylene-oxide. Pavlidou.1140 Table 7 Polyurethane characteristics. As measured through XRD. Interestingly.N-dimethyl-benzyl-amine.5 2. 21. Table 8 summarizes the d-spacings determined by SAXS for the PU/clay nanocomposites. indicating that in these nanocomposites there is no longer sufficient ordering of the clay platelets to produce a scattering peak. EO = ethylene oxide. because of the low concentration of styrene in uncured UP linear chains. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 PU nanocomposite Polyol Name Calculated Mn 2000 4000 4000 6000 Functionalitya 2 2 2. the desired weights of polyol and organoclay were mixed and then butanediol (chain extender). using polyols with different molecular weight and functionality (see Table 7) as well as methylenediphenylene diisocyanate (MDI). PU reference S. Hence.3 Wt. Reproduced from Berta. The first examples of elastomeric PU/clay nanocomposites with improved properties compared to the pristine polymer were reported by Wang and Pinnavaia [141]. More recently. C. focused on the solvation of the organoclay by polyols. 21. UK. it is thought that crosslinking density and Tg of UP/silicate nanocomposite increase to some extent.% N. If polymerization occurs in these conditions. Preparation of PU/clay nanocomposites [144]. The system was cured at 120 ◦ C for 3 h and 80 ◦ C for 24 h.. The authors Fig.4 -diphenyl methylate diisocyanate (MMDI). they found that montmorillonites exchanged with long chain onium ions (carbon number > 12) are easily solvated by several polyols that are commonly used in polyurethane chemistry. modified polyether polyol (MPP) and Na+ -MMT. Pans and Camino by permission of Elsevier Science Ltd.1 nm and increases to 1. Lindsay. On the other hand. catalyst and MDI were added in appropriate amounts. It is clear that all the PU/clay materials are nanocomposites. [142] reported the preparation of a novel kind of PU/MMT nanocomposite using a mixture of modified 4. the styrene monomer diffuses into the gallery of MMT intercalated with UP as time goes on.D. Conventional PU microcomposites are usually formulated by premixing the inorganic component with the polyol and then curing the mixture with the diisocyanate. indicating that the PU chains were intercalated between the layers of the clay. Therefore. [144] synthesized elastomer polyurethane nanocomposites showing several degrees of dispersion. as the 18 Å d-spacing. In a typical synthetic route. No peaks associated with clay gallery spacings were observed for NC-II and NC-IV.6 nm for the PU/clay (21. The synthesis of the PU/clay nanocomposites is schematically illustrated in Fig.6 wt. the total crosslinking density of the sample decreases. associated with the base organoclay has disappeared. For the preparation of nanocomposites. A number of researchers have synthesized polyurethane (PU)-based nanocomposites by the in situ polymerization method. .% EOb end 15 15 17 15 I II III IV a b NC-I NC-II NC-III NC-IV Approximated. Stable and transparent polyol dispersions were obtained and then cured with diisocyanatophenylmethane and accelerated with 0. therefore.

By XRD analysis it was found that the basal spacing of the organoclay increased compared to MMT (d0 0 1 = 1. Finally. However.S.43 nm when MMT–OH was further modified by DBDMT—an effect attributed to conjugation of hydroxyl groups from different layers. TEM analysis revealed that nanocomposites containing both MMT–OH and MMT–Tin exhibited good clay dispersion. The authors studied the effect of the clay–monomer mixing sequence on clay dispersion and found that the two-step process offered better clay dispersion than the one-step approach. The mixture of all ingredients was mixed and foaming occurred in a closed plastic container with fixed volume at ambient temperature. the d-spacing decreased from 1. 22 shows SEM images of the freeze fractured surface of PU foams. the hybrid was post-cured at 100 ◦ C for 4 h. Material Cloisite 30B (organoclay) NC-I NC-II NC-III NC-IV Clay d-spacing 18 65 None 102 none 1141 postulated that this is due to the higher equivalent Mw (Mn /functionality) of the polyols in these nanocomposites. because the gallery of MMT was expanded by molecular chains of the modifier. thus. Catalyst was always added with polyol. According to the authors. Gao et al. clay was first mixed with one monomer and then the second monomer was added. . Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 8 d-Spacings for organoclay and PU/clay nanocomposites.4 -diisocyanate (MDI) and two trifunctional polyester polyols. however MMT–Tin showed better exfoliation and more uniform dispersion.D. since it means that the dimensions of the polyol molecule control the gallery spacing in the initial step of dispersing the clay in polyol. Pavlidou. wherein all ingredients were mixed simultaneously. [145] prepared PU nanocomposites. the authors used a polymeric aromatic isocyanate based on diphenylmethane 4. MMT was modified by dibutyldimethoxytin (DBDMT) and. denoted as MMT–Tin. probably due to the intragallery catalysis of organotin. Widya and Macosko by permission of Elsevier Science Ltd. For the synthesis of PU nanocomposites and foams. Turning to the reactive foaming of PU nanocomposites. a surfactant as well as pentane (blowing agent) were also used. For reactive foaming of PU. In fact. was obtained. causing an increase of gallery spacing of clay. After polymerization under ambient conditions. organophilic montmorillonite with a catalytic function. SEM micrographs of PU foams at cross-sections parallel to foam rising direction [145].77 to 1. Reproduced from Gao. as well as their foams by in situ polymerization and batch foaming with different modified MMTs. which was attributed to the reaction between the isocyanate monomers and the hydroxyl groups on alkyl chains of MMT–OH. For PU nanocomposites.16 nm). premixing the functional clays with isocyanate provides better clay dispersion. UK. 22.. In the XRD spectra no diffraction peak was observed for PU nanocomposite with MMT–Tin. this is of particular importance. It is clearly observed that the neat PU foam has fewer cells and a larger cell size than PU nanocomposite foams with 5 wt. Fig. followed by curing at 100 ◦ C. Lee. Especially.% organoclay. whereas there is little difference Fig. C.

UK.1142 S.D. polymer chains diffuse from the bulk polymer melt into the galleries between the silicate layers. TGDDM Unsaturated polyester Polymerization conditions Ring opening. AIBN Ref. giving end-use manufacturers many degrees of freedom with regard to final product specifications (e. thermoplastic polyurethane [88]. 23 [13..99] [100] [106] [125] [126] [127] Crosslinking. C.146]. the detailed mechanism of how nanoparticles influence cell morphology needs further investigation. diamine curing agent DETDA curing agent Free radical crosslinking between MMT–Tin/PU and MMT–OH/PU nanocomposite foams in terms of cell size and density. melt processing is environmentally sound since no solvents are required [14.36. 9. usually under shear.99] [98. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 9 PLS nanocomposites prepared by in situ polymerization. it is worth describing Fig.46. both in situ polymerization and intercalation from solution are limited because neither a suitable monomer nor a compatible polymer–silicate solvent system is always available. rendering this technique a promising new approach that would greatly expand the commercial opportunities for nanocomposites technology [14. [25] [44] [117] [118] [105] [98. That is. without the necessary involvement of resin production.15. 23.147]. melt compounding would be significantly more economical and simpler than in situ polymerization. As already mentioned. A list of representative thermoset and thermoplastic – based nanocomposites prepared through in situ polymerization is given in Table 9. Before discussing in detail the factors affecting clay delamination during melt blending as well as the degradation issues involved in this technique. the majority of thermoplastic polymers.47].g. choice of organoclay.150].. The advantages of forming nanocomposites by melt processing are quite appealing.47]. 80 ◦ C. Thus. 48 h 30–50 ◦ C. 80 ◦ C. 5 h Free radical. The ‘melt intercalation’ process [35]. TGAP. etc.151].15. These disadvantages drive the researchers to the direct melt intercalation method. 48 h 280 ◦ C. 100 ◦ C. it shifts nanocomposite production downstream. 20 bar. as the authors noted.1. 16 h Free radical.4. Introduction and advantages of the technique For most technologically important polymers. PET [148] (and recycled PET [149]). including PA [14. as shown in Fig. etc. 4 bars Free radical. selection of polymer grade. and it enhances the specificity for the intercalation of polymer. level of reinforcement. polyolefins [111. Pavlidou. At the same time. Moreover. by eliminating the competing host-solvent and polymer–solvent interactions [29].15]. During annealing. which is the most versatile and environmentally benign among all the methods of preparing polymer–clay nanocomposites (PCNs) [4.156]. 170 ◦ C.). PLA [152–154].5 h (after an initial swelling stage) Ring opening.4.51. 48 h 100 ◦ C. 5 h. EVA [81. of a mixture of polymer and layered silicate above the softening point of the polymer. have been used to study nanocomposite formation by melt intercalation. terephthalic acid derivatives DGEBA DGEBA. . they are not always compatible with current polymer processing techniques. 250–270 ◦ C. Reproduced from Beyer by permission of Elsevier Science Ltd. melt processing allows nanocomposites to be formulated directly using ordinary compounding devices such as extruders or mixers. 5. nanocomposite synthesis via polymer melt intercalation involves annealing. The appearance of a shoulder at very low angle in the XRD patterns of nanocomposite foams implies that clay orientation and dispersion is somewhat affected by the foaming process. Polymer melt intercalation 5. However. Therefore. PCL [155. It minimizes capital costs because of its compatibility with existing processes. If technically possible. Nanocomposite PA6/12-aminolauric acid modified MMT PA12/Somasif ME 100 PCL/aminolauric acid modified MMT PCL/Cr3+ exchanged fluorohectorite PE/MMT with fixed Ti-based Ziegler-Natta catalyst PMMA/OMLS PS/OMLS PS/vinylbenzyl-trimethyl-ammoniumMMT PET/o-MMT Epoxy/o-MMT Epoxy/octadecylammonium modified MMT UP/MMT treated with a mathacrylate-silane coupling agent Monomer -Caprolactam -Amino dodecanoic acid (ADA) -Caprolactone -Caprolactone Ethylene MMA Styrene Styrene Ethylene glycol.

Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1143 a slightly modified approach aiming to facilitate exfoliation and consisting of melt processing the polymer with a pre-intercalated clay or slurry. which was collected and washed with hot water. PA12 and other polymer nanocomposites using similarly modified clay. thus the co-intercalated clay. The nanocomposites were prepared using a twin-screw extruder with a screw speed of 180 rpm operating at 200 ◦ C. Also in the case of polyolefins. Na-MMT showed a characteristic diffraction peak corresponding to the (0 0 1) plane at 1. the alkylammonium ion exchange enables conversion of the hydrophilic interior clay surface to hydrophobic and increases the layer distance as well. In addition. PrEMMT and epoxy resin GY 240 were mixed in a Haake Reocorder 40 mixer for 1 h. Present in small amounts.24 nm. The synthetic route for the formation of the terpolymer MAST [159]. epoxy resin then diffuses into the clay galleries to further increase the layer distance. allowing the organic matrix to be virtually any polymer [2]. Liu and Wu obtained well exfoliated nanocomposites when clay loading was less than 7 wt. to prepare PS/clay nanocomposites by melt blending. [157] modified a commercially available organo-ammonium-exchanged montmorillonite. dissolved in hot water. the swelling agent serves to swell the clay layers. Therefore. Similarly. C. [160] reported a novel compounding process for the preparation of PA6/MMT Fig. using a type of co-intercalated organophilic clay. using the aforementioned procedure. such as ethylene glycol. As an example. the use of a swelling agent (a monomer or polymer known to intercalate/exfoliate smectite clay) next to the surfactant placed at the clay surfaces after an ion-exchange reaction has allowed the preparation of nanocomposites. One of the co-intercalation monomers is unsaturated. by absorbing epoxide compound between the silicate layers. Na+ -MMT was dispersed in hot water using a homogenizer. dibenzoyl peroxide (BPO) and a donor agent were dissolved in epoxypropyl methacrylate. Jiang and Wilkie by permission of Elsevier Science Ltd. In XRD patterns. leading to the formation of nanocomposites.96 nm basal spacing in the XRD pattern. Then. This is the condition of PrEMMT. [159] used an oligomerically modified clay. 24. XRD measurements indicated a mixed intercalated/delaminated structure for the MAST modified clay. since Ishida had successfully prepared PA6. a better dispersion effect can be expected for EMMT. termed EMMT was obtained. In fact. the initiator for the grafting reaction. In this organophilic environment. Subsequently. Following such an approach. using an organic swelling agent (with boiling point between 100 and 200 ◦ C. naphtha or heptane) in order to increase the interlayer spacing. The synthetic route for the formation of the terpolymer MAST is depicted in Fig. a twin-screw extruder was used for the preparation of nanocomposites. The preparation of the new kind of co-intercalated organophilic clay used was as follows. a portion of MAST oligomer. prepared by ion-exchange with the oligomer prepared from maleic anhydride (MA). Wolf et al. PrE-MMT showed a 1. After thorough drying in a vacuum oven. Pavlidou. . Zheng et al. In another study. UK.D. Recently. 24. By combining XRD and TEM analyses the authors concluded that the hybrids formed were characterized by a mixed immiscible/intercalated/delaminated structure. Reproduced from Zheng. hexadecyltrimethylammonium bromide. was poured into the Na+ -MMT–water solution with vigorous stirring for 30 min to yield a white precipitate. dissolved in acetone was added drop-wise to a dispersion of clay in distilled water and acetone. Hexadecylammonium modified MMT (C16-MMT) was mixed with epoxypropyl methacrylate in a Haake mixer for 1 h..77 nm. whereas no peaks were observed for the PS/MAST. the co-intercalated clay also brings the active functional group into the PA66 system. Liu and Wu [146] prepared a co-intercalated clay.S. They expected strong interaction between PA66 and this new kind of modified clay. Nanocomposites were subsequently prepared by melt blending in a Brabender Plasticorder at 60 rpm and 190 ◦ C for 15 min. A precipitate (MAST hectorite clay) formed immediately. WAXD patterns and TEM observations established that the larger interlayer spacing and the strong interaction caused by grafting can improve the dispersion effect of silicate layers in the PP matrix. The swollen organo-modified clay was then compounded with PP in a twin-screw extruder at 250 ◦ C.%. herein called MAST. The swelling agent was volatilized during extrusion. while the basal spacing of E-MMT was 3. the precipitate was ground into a product termed PrEMMT. The co-intercalated organophilic clay (EM-MMT) was prepared as follows. Hasegawa et al. Thereafter. Before mixing with clay. The obviously larger layer distance of E-MMT demonstrates the advantage of cointercalated organophilic clay. styrene (ST) and vinylbenzyltrimethylammonium chloride (VBTACl) terpolymer. so it could tether on the PP backbone through a grafting reaction. As the authors pointed out. Liu and Wu [158] reported the preparation of PP nanocomposites via meltcompounding.

Factors affecting polymer melt intercalation Predicting whether or not a polymer–silicate nanocomposite will form through melt compounding is not straightforward. (b and c) the clay slurry reduces to finer drops during blending and. With a view to improving predictability. charge of the silicate or specific groups on the polymer (or the alkyl chains) affect hybrid formation and miscibility? How does temperature or shear affect processing? And finally. for example. Usuki and Sato by permission of Elsevier Science Ltd. These include energy changes. . and those associated with intermolecular interaction among silicate surface. Reproduced from Hasegawa. The dispersion of silicate layers in this process is quite different from that of conventional compounding process using organophilic clay. Fig. In this process.D. at the same time. the exfoliated silicate layers are directly fixed in the polymer matrix without aggregation of the silicate layers. Pavlidou. UK.. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 nanocomposites. attempts have been made to model the behavior of hybrids that form as a result of direct melt intercalation with organically modified clays and to assess the parameters required to favor intercalation [56]. According to this study.e. why do certain polymer–silicate systems favor intercalated hybrids. the water of the slurry drops begins to evaporate in contact with the PA6 melt. 25. WAXD patterns and TEM observations clearly indicate the exfoliation of MMT layers in the PA6 matrix but the final properties of PA6/Na+ -MMT nanocomposites were nearly equal to those of conventional PA6/MMT nanocomposites prepared by dry compounding with MMT. where polymer chains first intercalate into the stacked silicate galleries and then exfoliate into the matrix. (d) the evaporated water is removed under vacuum.1144 S. and silicate layers are dispersed into the PA6 melt as monolayer or as a few layers. and yet others are immiscible. using a Na+ -MMT water slurry as an alternative for organically modified MMT. as a wide variety of factors influence the outcome. dipole–dipole. 5.4. Kato. C. tethered chain and polymer. hydrogen. the expansion of the spaces between the layers of the silicate. followed by removal of the water. leading to microcomposites? How does packing density and chain length of the alkylammonium chains in the organosilicate layer. Okamoto. Some of the questions that need to be addressed are. the Na+ -MMT slurry was blended with PA6 using an extruder. how does the type of bonding at the polymer/silicate interface (i. Schematic figures depicting dispersion of the Na+ -MMT slurry into nylon-6 during compounding [160]. the exfoliation of silicate layers into the PA6 matrix occurs as follows: (a) the clay slurry is first pumped into the melting matrix under vigorous shear. van der Waals or covalent in which the alkylammonium chains become part of the polymer chain) affect the properties of the hybrid [4]. 25 shows schematically dispersion of the Na+ -MMT silicate layers of the clay slurry into the PA6 matrix during compounding by an extruder. In this process.2. others delamination. Fig. arising from the confinement of the polymer within the silicate.

Thus. associated with layer separation and greater conformational energy of the aliphatic chains of the alkylammonium cations.147]. because an entropy gain. focused on the thermodynamics governing nanocomposite formation. where the number of contacts per lattice site is replaced by an interaction area per lattice site. Thus. 26. UK. In this case. C*: coco (product made from coconut oil. whether a mixture of polymer and OMLS produces an exfoliated or intercalated nanocomposite or a conventional microcomposite depends critically upon the characteristics of the polymer and the OMLS. . Hunter. For the enthalpic term a modified meanfield. is used. packing den- Fig. resulting in a net entropy change near zero. Yoon.11. this entropy loss. Reproduced from Fornes. HE: 2-hydroxy-ethyl.2. unlike the solution intercalation method. Keskkula and Paul by permission of Elsevier Science Ltd. associated with the confinement of a polymer melt is not prohibitive to nanocomposites formation. the outcome of hybrid formation via polymer melt intercalation depends on energetic factors which may be determined from the surface energies of the polymer and OMLS. HT: hydrogenated tallow. and H: hydrogen designate the substituents on the nitrogen. The confinement of the intercalated polymer chains is similarly approximated using a self-consistent field treatment of a random-flight polymer with excluded volume between two surfaces. Pavlidou. (b) Organoclays used to evaluate the effect of structural variations of the amine cations on nanocomposite morphology and properties [51]. of course. Thermodynamic aspects. consisting predominantly of chains with 12 carbons (∼48%)). In general. including the nature of the polymer as well as the type. they developed a mean-field. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1145 5. the conclusions of the mean-field model developed. (a) Molecular structure and nomenclature of amine salts used to organically modify sodium montmorillonite by ion exchange.. balances the entropy loss of polymeric intercalation. which is smaller than the radius of gyration of typical polymers.D. lattice-based thermodynamic model. site-fraction approach.1. from the theoretical model. However.4. R: rapeseed (consisting largely of chains with 22 carbons (∼45%)). Configurational changes of the silicate are determined using a modified FloryHuggins lattice model in which the occupation of the lattice is weighted to simulate the preferred orientations of the alkylammonium cations in the presence of two impenetrable surfaces (silicate layers). there is obviously a large entropic barrier that inhibits the polymer from penetrating this gap and intermixing with the clay [9.S. To that end.4]. which are widely accepted by other researchers. Since the spacing (or “gallery”) between the sheets is on the order of 1 nm. This modified approach allows one to express the interaction parameter as energy per area and may be approximated by interfacial or surface energies [1. C. To address some of these questions Giannelis et al. The entropic term is the sum of the configurational changes associated with the polymer and the silicate (including the alkylammonium chains in organosilicates). the decreased entropy due to the confinement of the polymer is not compensated by an increase due to desorption of solvent molecules. T: tallow (predominantly composed of chains with 18 carbons (∼65%)). may be summarized as follows. Assuming the configurations and interactions of the various constituents are independent. the free energy change of hybrid formation can be separated into independent enthalpic and entropic terms. The symbols M: methyl.

as presented in Fig. This means that the octadecyl ammonium ion is more compatible than ammoniumdodecanoic acid when intercalated in FH during the synthesis of EVA/FH nanocomposites [165]. during processing) to temperatures above the melting temperature. In a relevant study EVA was melt mixed with two clays: Cloisite Na+ and Cloisite 30B (modified with methyl-tallow-bis-2-hydroxyethyl ammonium ions). respectively. 5. as opposed to adding an excess. for both montmorillonites. in the case of PP or PE nanocomposite materials prepared by melt mixing of the polymers with surface modified clay using high shear forces. [164] also synthesized EVA/clay nanocomposites through a melt blending method. it is reasonable that. For example. the authors emphasized that these effects may be specific to nylon 6 matrices.1 sity and size of the organic modifiers on the silicate surface [1. In another study by Alexandre et al. abbreviated as EVA-12 and EVA19.9 16. These materials were melt-blended at 120 ◦ C in a twin screw microcompounder to obtain nanocomposites. Nanocomposites based on the organoclay having two alkyl chains are superior to the nanocomposites based on the organoclay having one alkyl chain. the system. XRD measurements revealed a decrease in clay interlayer spacing after blending with EVA.g. were processed into their nanocomposites with synthetic clay fluorohectorite (FH) organo-modified by octadecyl ammonium ion (ODA) and aminododecanoic acid.47. Therefore. C. In a detailed study. Moreover. the authors claimed that nanocomposites were formed in the case of Cloisite 30B. using different EVAs and octadecyltrimethyl ammonium. on the basis of TEM observations. EVA chains intercalated into the organo-modified MMT sheets. In this respect. as already mentioned in Section 3. The effect of clay organo-modification on the morphology of EVA-based nanocomposites has also been investigated. However. This was attributed to the relatively better affinity of LLDPE for the alkyl chains than for the silicate surface. the conditions favoring exfoliation may be quite different depending on the specific system investigated.2. As deduced from these findings. Among different variables. Code Cation Interlayer spacing In modified clay Mont-Na Mont-2CN2C18 Mont-NC11 COOH Mont-3CNC21 COOH Na (CH3 )2 N+ (C18 H37 )2 H3 N+ C11 H22 COOH (CH3 )3 N+ C21 H42 COOH + In EVA composite 12. such as montmorillonite exchanged with dimethyldioctadecyl ammonium (Mont- .2.2.161]. The selection of amines shown in Fig. Therefore. remains thermodynamically unstable. Mixing was performed in a Brabender Laboratory Mixer at 160 ◦ C. whereas ammonium dodecanoic acid intercalated FH formed a microcomposite. dioctadecyldimethyl ammonium. good dispersion of the particles may be achieved by the help of strong shear forces during the preparation and processing of the nanocomposite materials.D. microstructures were obtained in the case of Cloisite Na+ [163]. It is worth mentioning that even when the surfactant chains are miscible with the polymer matrix. Again.3 16. e.3 20. a complete layer separation depends on the establishment of very favorable polymer–surface interactions to overcome the penalty of polymer confinement.4. three surfactant structural issues were found to significantly affect nylon 6 nanocomposite morphology and properties: decreasing the number of long alkyl tails from two tallows to one. the type of surfactant. however. However.7 20. In fact. This can be observed. several exchanging cations bearing either simple alkyl chains or aliphatic chains terminated by a carboxylic group were studied for modifying montmorillonites as described in Table 10.6 40. two different EVAs containing 12 and 19% vinyl acetate. Even though. the interlayer structure of the OMLS should be optimized to maximize the configurational freedom of the functionalizing chains upon layer separation and to maximize potential interaction sites at the interlayer surface [47]. and use of an equivalent amount of surfactant with the montmorillonite.1 12. in this case. If such a mixture is heated (e. the organic modification of the clay is a very important factor affecting the resulting structures. the chain length and the packing density may play an important role. The effect of layered silicates and their organic modification. Octadecyl ammonium ion intercalated FH (FH-ODA) formed a delaminated nanostructure. Pavlidou. LLDPE and two organoclays in a co-rotating twin screw extruder with a barrel temperature set at 200 ◦ C and a screw speed of 280 rpm.76 mol% vinyl acetate).41. In order to achieve clay exfoliation.2. [166]. led to greater extents of silicate platelet exfoliation. Hotta and Paul [162] prepared PE/clay nanocomposites by melt compounding various combinations of LLDPE-g-MA. Zhang et al. and tricetadecymethyl ammonium ion exchange MMTs. quite surprisingly. If this is not the case. differences in the intercalation behavior have also been observed between clays modified with different surfactants.2 31. use of methyl rather than hydroxy-ethyl groups. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 10 Interlayer spacing of various modified montmorillonites and the resulting composites obtained with EVA (10.g. Nanocomposites were only formed when EVA copolymers were melt mixed with unfunctionalized organo-montmorillonites. 26a permitted the authors to make six structural comparisons. increasing the number of alkyl chains should lead to better dispersion of the organoclay.4.1146 S. but in the case of sodium montmorillonite (Na+ -MMT) there was no such intercalation. Fornes et al.147. a (partial) re-agglomeration of the particles takes place [2] immediately. in terms of clay dispersion. [51] used various amine compounds to exchange the sodium ion of native montmorillonite clay. 26b.

It is also worth noticing that.1 9. the polymer is unable to penetrate the gallery between the clay surfaces. for short surfactant molecules. In order to determine the effect of the nature of the clay and clay organic modifier on nanocomposite morphology and properties.2 31. and the equilibrium morphology becomes immiscible (two-phase) for most values of the Flory-Huggins parameter and the clay volume fraction. it is generally accepted that at low interlayer packing densities of the organic modifier. According to their work. and surfactant length. This better filler dispersion might arise from interactions between the acetate functions of EVA and the hydroxyl-bearing ammonium cations that modify Cloisite 30B.4 Interlayer distance variation (Å) 0. the optimal structure appears to exhibit a chain arrangement slightly greater than a pseudo-bilayer. EVA and clay (5 wt.3 . When comparing Cloisite 20A. at least for the polystyrene intercalation. independent of the interlayer spacing of the clays used or the amount of modifier. [167] used EVA copolymer containing 27 wt. As the packing density increases. the nanocomposites based on Cloisite 30B display the highest exfoliation and clay stacking destruction.7 36.9 20. Table 12 Interlayer spacing variation as obtained from diffraction peaks measured by XRD on clays and the resulting melt-blended EVA composites. there is an optimum interlayer structure favoring hybrid formation that is intermediate between a disordered monolayer and a solid-like paraffinic arrangement of aliphatic chains. The difference between primary and quaternary ammonium head groups did not appear to be a predominant factor. whatever the clay nature. calculated phase diagrams and showed that as the length of the grafted chains and/or their density is increased. Next to these studies.S. Evidently.5 12. which they examined [47]. the use of ammonium cations functionalized with carboxylic groups did not lead to the formation of an intercalated structure. characterized by clays of various origins but modified by the same ammonium cation.2 40. b Determined by X-ray diffraction on as-received clays. Filler Cloisite Na Cloisite 20A Cloisite 25A Cloisite 30B Nanofil 757 Nanofil 15 Somasif ME100 Somasif MAE Clay type Montmorillonite Montmorillonite Montmorillonite Montmorillonite Montmorillonite Montmorillonite Fluoromica Fluoromica Interlayer cations Na+ (CH3 )2 N+ (CH3 )2 N+ (CH3 )2 N+ Na+ (CH3 )2 N+ Na+ (CH3 )2 N+ (hydrogenated tallow)2 (hydrogenated tallow)(2-ethylhexyl) (tallow)(CH2 CH2 OH)2 (hydrogenated tallow)2 (hydrogenated tallow)2 Ammonium contenta (wt.2 Ca 29 (broad) 12.3 40. the chains adopt more extended conformations (and thus larger initial gallery heights). Nanofil 757 or Somasif ME100) in EVA is characterized by the formation of microcomposites.4 20.2 31.1 16. very high degrees of surfactant coverage on the silicate surface make intercalation and exfoliation unfavorable [168].5 12.%) 0 29. a Determined by thermogravimetric analysis under helium atmosphere. since no significant increase in the basal spacings recorded for these materials can be observed.%) were compounded in a two-roll mill for 12 min at 140 ◦ C. dispersion of unmodified clays (Cloisite Na.9 0 40. whereas with the same EVA matrix. indicating that functionalization of the clay interlayer is detrimental to the intercalation process. C.1 – 0 Ca 11 0. Concerning the conformation of surfactant chains.7 18. one can remark that the final interlayer spacings are very close.1 Tallow: linear alkyl chains (C18 (65%). Nanofil 15 and Somasif MAE. 2CNC18). Pavlidou.2 12.1 20. Ginzburg et al.2 26.% VA and various commercial organoclays. However. presented in Table 11. the chains adopt a disordered monolayer arrangement. surfactant coverage. The results of XRD analysis are reported in Table 12.3 16. the miscibility between the clay sheets and the polymer is improved and the resulting mixture can exhibit exfoliated structure for a range of clay volume fractions.1 22. Only in the limit of large negative (strong attraction between grafted chains and polymer melt) can such a composite become exfoliated [9].8 – 12.2 38. Balazs and co-workers proposed a theoretical model that uses numerical self-consistent field calculations to study the effect on morphological behavior of varying the surfactant–matrix enthalpic interaction. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 11 Characteristics of the various studied clays. Filler Cloisite Na Cloisite 20A Cloisite 25A Cloisite 30B Nanofil 757 Nanofil 15 Somasif ME100 Somasif MAE Filler interlayer distance (Å) 12.7 18. ultimately resulting in a solidlike paraffinic arrangement of the chains [47].D. while all the tested organo-modified clays result in both intercalated and exfoliated structures. C14 (5%) with ∼40% mono-unsaturated chains. According to Vaia and Giannelis. The model indicated that longer surfactants (clay organic modifiers) promote intercalation of matrix molecules in the modified clay galleries by providing a reduction in the entropic penalty to the intercalating polymer.3 0 28. That is.1 22. characterized by the absence of a characteristic XRD peak.8 1147 Interlayer distanceb (Å) 12. Peeterbroeck et al.1 Composite interlayer distance(Å) 12.2 ∼29 (broad) 12. C16 (30%).

the surface now can be thought of as being comprised of the dense brush. one has effectively a short surfactant at high coverage. As the molecular weight difference between the two surfactants increases. Pavlidou. Fig. 27a. and reduced enthalpic interaction with the clay surface. XRD data indicated that the samples remained in a phase-separated morphology. the long alkyl tail displays only a limited compatibility with the polymer chains. In the bimodal brush. polymer–surface interactions are also important for a complete and stable dispersion. This was explained within the framework of well-established theories of dewetting from dense polymer brushes [169]. the situation may become something like that illustrated in Fig. 27c. This is the scenario for typical surfactant-modified clay at very low coverage. Alternatively. but still it is possible that it does not actually assist in the wetting and intercalation processes. Unfortunately. Therefore. it is still possible that the brush is still effectively dense (only 17% of the exchangeable cations were replaced by the longer surfactant and the remaining 83% by the short surfactant). the surfactant present in lesser amount becomes effectively longer. the clay compatible block could be PEO. of one possible outcome on longer surfactant conformation of the densely packed brush of a shorter surfactant [169]. despite the bimodal nature of the brushes in this experiment. a long surfactant is illustrated at low coverage over a surface that is repulsive to the polymer matrix (PS homopolymer). These authors initially prepared organically modified clays by exchanging most cation exchange positions in Na+ -MMT with custommade quaternary ammonium ion terminated PS surfactants of five different molecular weights. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Fig. an ion-exchange reaction may not even be necessary. Phase-separated morphologies were observed in all cases. Texturing of the silicate surface was expected to allow intercalation of matrix molecules in the galleries by providing a favorable entropic gain to the intercalating polymer through interaction with the longer grafted molecules. which is applied to enhance the adhesion between the fiber and polymer matrix [11]. Second. This last conclusion is consistent with that from the experimental work of Kurian et al. surfactants fulfill only partly this requirement. making the long surfactant fraction ineffective in fostering wetting and intercalation. but the conformation of the longer sur- factant must also be considered. one has to simultaneously consider different factors. better compatibilization should be expected from “macro-surfactants” like block or graft copolymers combining blocks which can interact with the solid particle surface and with the matrix polymer – thus meeting most of the requirements listed above (Fig. in a later study the authors described a new scheme termed mixed coverage. This work clearly demonstrates that when tailoring the silicate characteristics that favor intercalation or exfoliation. because there is now no enthalpic repulsion causing the surfactant to stretch away from the silicate surface. Thus. for a bimodal surfactant brush. 28) [2]. Reproduced from Kurian. C. 27b. This is because an ideal compatibilization agent between two intrinsically incompatible components should have (combined in one molecule) parts which mix thermodynamically stable and easily with both components [2]. regardless of surfactant molecular weight. however. For example. However. That is. Therefore. the ionic part interacts certainly in a favorable way with the charged surface of the sheet-like clay particles. 27 shows a schematic of this scenario. the surfactant chain length and packing density. When a small fraction of those surfactants are replaced with longer surfactants. If the mixed surfactants used to create the textured surface do not differ much in their lengths.1148 S. the simple organic modification of the clay through ion-exchange reactions is not always enough to achieve nanocomposite formation. To explain this result. As illustrated in Fig. the block copolymer may also be used as a “co-surfactant” with the surfactant on the surface of organo-clays. Beyer and Galvin by permission of John Wiley & Sons Inc.D. Dasgupta. Illustration. to create a silicate surface grafted with a bimodal brush. Balazs et al. 27c. In this case. as stated above. the surfactant will stretch away from the surface until the energy required to stretch is no longer less than that of the repulsive enthalpic interactions. the shorter surfactant at full coverage (83%) effectively replaces the silicate surface. The length of the longer surfactant is still important. They showed that high levels of modification resulted in dense polymer brushes on the clay surfaces. e. the authors suggested that. In Fig. thus fine-tuning the thermodynamic . preventing intercalation of PS homopolymer molecules. with no indication of intercalation or exfoliation of the layered silicate in the PS matrix. Summarizing the above. The PEO block acts as a complexing group for the sodium ions located between the sheets of the inorganic clay. wherein the silicate is modified with a mixture of PS-based surfactants of different lengths. In fact. The clay substrate represents the surface of a fiber and the “surfactants” represent a coating. 27. where the longer surfactant now remains close to the brush of chemically similar molecules and does not aid intercalation by interacting with matrix polymer molecules [169]. likened the situation found in nanocomposites to the behavior of fiber-reinforced composites.g. This would result in the scenario illustrated in Fig.

which lowered the thermodynamic energy barrier for clay–polymer interaction. Early work by Vaia and Giannelis showed that. which is more suitable for the less polar EVA9 due to long aliphatic chains in C15A.170]. clay delamination typically requires the use of compatibilizers.%. characteristics of the clay surface with respect to the polymer matrix material.000 at 160 ◦ C.49]. The average number of platelets per stacks was shown to decrease with increasing molecular weight. Polymer matrix parameters may also determine the outcome of melt blending a polymer and a layered silicate. For example.2. the authors noted that additional experimental work examining the intercalation behavior of a broader range of polymer molecular weights coupled with dynamic blending of constituents to enhance equilibrium mixing would be required to further explore this issue [47]. However. medium and high) using a co-rotating twin screw extruder. while in the case of apolar polymer matrices. Therefore. suitable for the more polar polymers. most probably due to percolation phenomena [2. Finally.3. it is often reported that while low clay loadings favor exfoliation. the amount of clay incorporated in the polymer matrix also plays a determining role. inducing the formation of intercalated to exfoliated nanostructures. It is well established that the presence of polar groups (ester groups of the vinyl acetate moieties) all along the chains improves the ability of these polymers to intercalate in organo-modified montmorillonites [1]. Further dispersion of clay platelets is hindered. Chaudhary et al. Reproduced from Fischer by permission of Elsevier Science Ltd. like EVA18 or EVA28. The effect of the polymer matrix.%) allow only intercalation of polymer chains in the layered silicate galleries to occur. favor the intercalation of macromolecular chains into the silicate galleries [47. the authors concluded that an increase in the content of polar VA groups in EVA 18 and EVA28 as compared to EVA9. apart from the clay chemistry. a first ion-exchange step with double tailed ammonium cations is followed by a further incorporation of end-group modified (grafted) oligomeric polypropylene between the organically modified sheets and a subsequent mixing with the matrix polymer. possibly allowed a relatively higher number of polymer chains to migrate and stabilize within the clay platelet and form partially exfoliated and/or disordered intercalated states. such as Lewis acid-base interactions or hydrogen bonding. for example. for statically annealed PS samples. Therefore. As a result. WAXD and TEM results collectively reveal a mixed structure for the LMW based nanocom- posites. as discussed in the following paragraph.S. This process relies on the compatibilizing action of the functionalized oligomers [2]. However. [171] prepared EVA-based nanocomposites via melt intercalation using an intermeshing counter-rotating twin screw extruder. Toyota. having regions of intercalated and exfoliated clay platelets. They prepared composites with filler level varying from 2. going from 6 h for Mw of 30. In general. 5. is the presence of polar type interactions (i.e. tensile tests revealed superior performance for the higher molecular weight nylon 6 composites. and subsequently characterized the structures obtained by WAXD and TEM. Only the time needed for intercalation to proceed was different. the final hybrid structure is independent of the molecular weight of the polymer. polymer compatibilizers have been used in the preparation of EVA-based nanocomposites.5 wt. In another study. [14] prepared nanocomposites based on three different molecular weight grades of nylon 6 (low. In a representative study. Therefore. high Mw PS decreases the kinetics of intercalation by decreasing the diffusivity of the polymer in the interlayer. probably the most critical condition for the formation of intercalated and especially exfoliated hybrids via polymer melt intercalation. other than Van der Waals forces). the effect of the matrix molecular weight has been considered.4. 28. thereby revealing larger extents of clay platelet exfoliation for the nanocomposites in the order HMW > MMW > LMW composites. while the clay was exfoliated in the more polar EVA18 and EVA28.5 to 7. several studies have focused on the effect of the vinyl acetate content on the dispersion of clay nanoplatelets. It is worth mentioning that despite the presence of polar groups in EVAs. In this procedure. The results indicated that only intercalation occurred in the case of the less polar EVA9. Schematic picture of the action of block copolymer for an exfoliation of clay sheets within a polymeric matrix [2]. and Cloisite 30B (C30B). it has been observed that the higher the vinyl acetate content the larger is the basal spacing increase of the clay.. They used EVA copolymers with 9. developed such a process for the incorporation of MMT sheets into PP. In fact. UK. Clearly. 18 and 28% VA (vinyl acetate) and two organo-modified clays: Cloisite 15A (C15A). C. In this context. particularly those based on HMW. it is important to note that. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1149 Fig. A good example demonstrating the importance of polar interactions is the formation of EVA-based nanocomposites via melt intercalation. polar polymers containing groups capable of associative type interactions.D. Pavlidou.000 and 48 h for 400. Fornes et al. as will be discussed in Section 6. higher amounts of clay (usually above 10 wt.1.000 to 24 h for 90.2. Li and Ha [172] selected a maleic anhydride grafted EVA containing 18 mol% VA to process its nanocomposites with organo-modified Cloisite through melt blending at 175 ◦ C and found that the dispersion of Cloisite in the maleic anhy- . Qualitative TEM observations were supported by a quantitative analysis of high magnification TEM images.

). there is no apparent compatibility of the clay chemical treatment and the polymer. on the other hand. by controlling intercalation through crystallization at a suitable temperature. Melt processing conditions play a key role in achieving high levels of exfoliation. Conclusively. but shear elsewhere is very low. total shear is lower than in single-screw extruders and in co-rotating twin-screw extruders. The effect of melt intercalation processing conditions. McNally et al. Often. However. They used the ultrasonic oscillation extrusion system developed to prepare polymer/MMT nanocomposites. for the aforementioned reason. among which twin screw extruders have proven to be most effective for the exfoliation and dispersion of silicate layers [14]. In the co-rotating pattern the screws rotate in the same direction and the material is passed from one screw to another and follows a path over and under the screws. the screws rotate counter to each other and the material is brought to the junction of the two screws. there appears to be an optimum extent of back mixing and an optimum shear intensity. Okamoto and co-workers [175. When the clay chemical treatment and the resin are compatible. for example. Li et al. even for a given extruder.e. showed that the clay particles are well dispersed at low Tc and that segregation of silicate layers occurs at high Tc . This implies that. internal mixers (i. nanocomposites have been formed using a variety of shear devices (e. More specifically. observed directly by TEM. However. and also reduce the size and size distribution of dispersed particles in polymer blends. in case 3. [52] presented a simplified scheme to underline the conditions under which clay exfoliation into a polymer occurs during melt blending. other researchers have reported on nanocomposite preparation using single-screw extruders. though only for specific matrices. consisting of an extruder and a cylinder die connected to a generator of ultrasonic oscillations in the direction parallel to the flow of the polymer melt. The microstructure of the nanocomposites. 5. in the case of PEI matrix [46. which organically combines extruder and ultrasound power. although it is often stated that twin screw extruders favor intercalation when compared to single screw systems. a number of factors affect the outcome of melt intercalation. batch mixing devices where mixing occurs in a closed chamber) may also be successfully used for the preparation of exfoliated nanocomposites. excessive shear intensity or backmixing apparently causes poorer delamination and dispersion [52]. clay chemical treatment and polymer are marginally compatible. thus in the co-rotating case there is less likelihood that material will become stagnant. as demonstrated. mixers. As the material passes between the screws. [174] developed an ultrasonic extrusion technology.176] observed through X-ray analyses that the intergallery spacing of PP-MA based nanocomposites increases with the crystallization temperature Tc for any amount of clay content in the nanocomposites. apart of the various extrusion systems. Finally. Pavlidou. However. building up in what is called the material bank on the top of the junction.D. The first case is chemistry-dependent. almost any set of processing conditions can be used to form an exfoliated nanocomposite. It should be noted at this point that. On the other hand. including provisions for additional mixing. etc.4. Two different patterns for intermeshing twin-screw extruders are possible. one can control the fine structure. extruders. It distinguishes three cases. They found that for the composite prepared by single screw extrusion. this may not be the case for counter-rotating extrusion systems.2. these devices appear to be much less popular in nanocomposite preparation. Indeed. The screws in twin screw extruders intermesh so that the relative motion of the flight of one screw inside the channel of the other acts as a paddle that pushes the material from screw to screw and from flight to flight.4. is the crystallization temperature. it is important to notice that. was found to improve the exfoliation of the clay. the morphology—and thus the properties of crystalline polymer/clay nanocomposites. increasing the mean residence time in the extruder generally improves the delamination and dispersion. In this situation. Cho and Paul [15] prepared nylon 6/o-MMT nanocomposites using either an intermeshing corotating twin screw extruder or a single screw extruder. 29a) is based on the relationship between the compatibility of the chemistry of the clay treatment and the matrix and the process conditions used to make a nanocomposite. This gives high contact with the extruder barrel. Focusing on the effect of the extrusion system on the degree of intercalation. The path also ensures that most of the resin will be subjected to the same amount of shear as it passes between the screws and the barrel. The proposed scheme (Fig. the organoclay chemical treatment and the matrix are compatible enough that processing conditions can be tailored to optimize delamination and dispersion. The self-wiping nature of the co-rotating screws is much more complete than in the counter-rotating system. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 dride grafted EVA was much better than in the simple EVA matrix. or static mixers at the end of the screw are used to enhance mixing and thus the silicate dispersion [173]. which was attributed to insufficient amount of shear and short residence time. The authors claimed that the introduction of ultrasonic irradiation in extrusion processing of polymer can improve the processibility of polymer materials. [36] successfully prepared PA12/clay nanocomposites using conventional single-screw melt blending. In the counter-rotating pattern. On the other hand. Processing conditions can be optimized to . For example. by mixing in the twin screw extruder. full exfoliation is not achieved. The system. In this context. Dennis et al.g. co-rotating systems are more effective than either counter-rotating or single-screw extruders [173].52]. This buildup of material is conveyed along the length of the screw by the screw flights. Another factor affecting the resulting structures in the case of crystalline polymer matrices. Therefore. special screw designs. In case 2. C. Since only a small amount of material passes between the screws. the process conditions can be optimized to give an exfoliated nanocomposite. high shear is created. That is. For example. the organoclay is uniformly dispersed into nylon 6 and the individual layers are aligned along the flow axis. which improves the efficiency of heating.1150 S. Moreover. ultrasonicators. processing conditions may determine the outcome.

. The authors mixed pristine MMT with the surfactant (C16) and PP with or without PP-MA using a high speed mixer. since their increasing concentrations will reduce the free energy of the system. As more polymer enters and goes further in between clay platelets. since they are able to bend [14.177–179].49. The results of this study showed that the structure of PPclay nanocomposites is sensitive to the compatibilizer and the surfactant. In fact. leading up to the formation of a graft copolymer in which maleic anhydride units are attached to the PE chains. However. Pathway 2 shows polymer chains entering the clay galleries pushing the ends of platelets apart.D. such that the maleated polyolefin can serve as a “compatibilizer” between the matrix and the filler [162. like polyamides. stacks of platelets are decreased in height by sliding platelets apart from each other. However. Wang et al. For the PE/o-MMT system the intercalate effect is limited and the dispersion of clay is unsatisfactory. Proposed mechanism of how the organoclay particles disperse into polymers during melt processing. Reproduced from Dennis. respectively. a pathway that requires shear intensity. as testified by both XRD and TEM. [49] prepared several types of nanocomposites with different compositions of the organically modified clay and maleated polyethylene by melt compounding at 140 ◦ C using a Brabender mixer operating at 60 rpm for 20 min. such as the most widely used polyolefins.181]. the authors suggested that there is some . some surfactant remains in the polymer matrix. 29b) to demonstrate that increasing shear intensity is not enough to achieve exfoliation.52]. for non-polar polymers. the platelets appear to peel from the edge. 29. Zhang and Wilkie [182] obtained PEorganoclay nanocomposites by adding maleic anhydride directly as a compatibilizer during the melt blending.1 wt. ways to resolve the difference in polarity between polyolefins and clays. Therefore. because these polymers are so hydropho- bic and lack suitable interactions with the clay surface. Compatibility issues in non-polar polymers In contrast to polar polymers. Tang et al. in order to prepare nanocomposites by conventional melt compounding. The mixed powder was then processed in a twin screw extruder and nanocomposites were obtained. At first. facilitated by residence time in the mixing device.4. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1151 Fig. The dispersion mechanism proposed is the following. [179] showed that two kinds of hybrids are formed by melt mixing: an o-MMT with PE and with PE-g-MA. which is favorable for thermodynamic stability. They found that the alkylammonium chain length may change the degree of interaction between clay and polyethylene and that the original basal reflection peak of the clay disappeared completely above a certain grafting level of MA. Pavlidou.3. MMT was exfoliated in the matrix. White.%.180.162. which may enhance the compatibility when the matrix is intercalated into the interlayer. As the authors suggested. the maleic anhydride probably reacted with PE during the high temperature blending in air. However. that can effectively exfoliate organically modified clays using conventional melt processing techniques. Quite interestingly. C. the development of polyolefin/clay nanocomposites is a field of rapidly growing industrial relevance due to their promise of improved performance in packaging and engineering applications [111].S. UK. The most promising strategy at the present time is to add a small amount of a maleic anhydride grafted polyolefin that is miscible with the base polyolefin. about 0. It is believed that the polar character of the anhydride has an affinity for the clay materials. Kim. have been proposed. Cho and Paul DR by permission of Elsevier Science Ltd. for the PE-g-MA/o-MMT nanocomposites. [183] described the preparation of PP-based nanocomposites through a successful combination of clay modification and intercalation in one step. These authors also presented possible clay delamination paths (Fig. In fact. PE or PP. This pathway does not require high shear intensity. More specifically. Chang. Part (a) shows three cases involving the interplay between chemistry and process conditions in the mixing device. some surfactant chains diffuse into the interlayer under physical absorption and shear. Part (b) illustrates schematically how platelets peel apart under the action of shear [52]. even after it has been organically modified [49. synthesis of well exfoliated nanocomposites appears to be more difficult. thus. initial attempts to create non-polar polymer/clay nanocomposites by simple melt mixing were based on the introduction of a modified oligomer to mediate the polarity between the clay surface and the polymer [2. 5. but involves diffusion of polymer into the clay galleries (driven by either physical or chemical affinity of the polymer for the organoclay surface) and is. give intercalants or tactoids that are minimized in size. especially near the edge of the clay galleries. but even partial exfoliation does not occur.177]. Hunter. Zhai et al. rendering the clay organophilic. In another study. In pathway 1.

Zhao et al. it has been suggested that the relative . whereas intercalation of the organoclay occurred in the presence of the four polar polymers. For example. so that the chemical reaction with hydroxyl groups at the edge of the clay layers and the interlayer ion exchange were carried out in one step. [184] investigated chlorosilane-modified montmorillonites and their results showed that intercalated PE nanocomposites were obtained by melt intercalation using common alkylammonium intercalated clay. the authors used directly a reactive intercalating agent (N. a more disordered system). However. after the surfactant makes the clay sufficiently organophilic. Polymer Structure LDPE EMA (y = 0.-trimethoxyl-silanepropyl) octadecyldimethylammonium chloride (abbreviated JSAc) to modify the montmorillonite clay. which was pretreated with chlorosilane. the authors concluded that no interaction was likely between the LDPE and the silicate. poly(ethyleneco-methyl acrylate-co-acrylic acid) (EMAAA). Through XRD measurements.1152 S.% caused a decrease in the degree of coherent layer stacking (i.177.28) EMAAA (y = 0. At the same time. One typical example is the PP/clay nanocomposite system described by Toyota. Composites were prepared by melt mixing in a twin screw extruder operating at 380 rpm with a screw configured for intensive mixing. It is also worth mentioning the work of Preston et al. some PP-MA may be intercalated into the interlayer of MMT. PP also is usually modified with polar oligomers prior to introduction of modified clay. Zanetti and Costa [177] prepared several types of composites with different PE/EVA ratios and 5 wt.18. In fact. just as in the interaction between the surfactant and the silicates. poly(ethylene-co-methyl acrylate) (EMA).18.215) EVA −18. EVA has also been used as a compatibilizer to prepare PE-based nanocomposites. In a later work.D. In addition to maleic anhydride and maleic anhydride grafted PE.e.185]. As in the case of PE. who prepared nanocomposites using the following matrices: two EVAs with different vinyl acetate contents.% EVA was enough to intercalate all the organoclay. and pointed out that the miscibility between maleated oligomer and matrix polymer played a key role in composite properties [2. due to its low polarity. whereas only microcomposites were formed when using common intercalating agent. in order to achieve nanometric dispersion of the clay [161]. 0. 1 wt. Pavlidou. Consequently. it is difficult to get exfoliated and homogenous dispersion of the silicate layer at the nanometer level in polypropylene. No interaction was obtained by compounding the PE with the clay in absence of a compatibilizer. and a blend of LDPE with maleated ethylene copolymer (PE-g-MA). C. PP-MA may act as a high molecular weight surfactant. in the presence of a maleic anhydride grafted PP (PP-g-MA).% organoclay by melt compounding at 150 ◦ C using a Brabender internal mixer with a screw speed of 60 rpm for 10 min.06) PE-g-MAH (y ≈ 0. The organoclay they used was organically modified bentonite clay. They added three times as much PP-g-MA as the clay by weight to prepare well mixed PP/clay nanocomposites. the exfoliation of intercalated MMT should take place. −28 (x = 0. [178]. The Toyota research group prepared PP/clay nanocomposites by direct melt compounding of PP with organo-modified MMT. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 13 Structures of the polar polymers used as composite matrices.% VA. PE/clay nanocomposites were then directly prepared by melt inter- calating PE and the above mentioned clay in a twin screw extruder at 180 ◦ C and 200 rpm. if the miscibility of PP-MA with PP is good enough to allow dispersion at the molecular level. On the other hand. Further increasing the amount of EVA above 10 wt.02) interaction between the polymer matrix and the surfactant. z = 0. The polymer EVA contained 19 wt. Structures for each of these materials are given in Table 13.49. The interlayer spacing of the clay increases and.

differences in mechanical properties when using different clays are smaller if DEM is used instead of MAH. When too many carboxyl groups were spread along the polyolefin chains. concluded that clay and matrix modification are synergistic factors which need to be properly modulated in order to obtain the desired final properties in this kind of non-polar polymer-based nanocomposite. using a twin screw extruder. because of its high thermal stability. According to the authors. Maleic anhydride was used as reference. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1153 Fig. DEM has a lower polarity compared to MAH. Okamoto et al. In fact. DEM was chosen as the compatibilizing agent. such as PS. compatibilization is a critical issue also for other polymers. when the PP-g-MA fraction was increased.5 wt. [189] prepared PP/MMT nanocomposites. Hasegawa et al.D. Okamoto. and good compatibilization with polyolefins. Kato. i. The authors also noticed that intercalation increased with the polymer-toclay ratio. in order to retain some miscibility between PP-MA and PP chains. Reproduced from Hasegawa. 30 shows a schematic representation of the clay dispersion process in PP-MA-based nanocomposites. Schematic illustration of OMLS dispersion process in PP-g-MA matrix [187]. Fig. [186] reported the preparation of exfoliated PP-based nanocomposite by melt blending PP-g-MA and organically modified MMT at 200 ◦ C. The authors mixed PP-g-MA (0.% MA) and different amounts (2.e. 4 and 7. the low homopolymerization behavior of DEM allows better control of the functionalization reaction.%) of C18-MMT in a twin screw extruder at 200 ◦ C and obtained nearly exfoliated structures when 2 wt. This is a consequence of the very low degree of compatibilization between the polymer matrix and the clay. The results showed that although the commercial clay outperforms the octadecylammonium treated bentonite. indicating that a minimal functionalization of PP chains has to be reached for intercalation to proceed. Wang and Wilkie [190] prepared PS/clay nanocomposites by in situ reactive blending with both the organically modified clays and the pristine inorganic clay in the presence of maleic anhydride.% clay led to disordered intercalated nanocomposites and ordered intercalated structures. content in maleic anhydride cannot exceed a given value. respectively. high boiling point. Lopez et al. [188] prepared PP-based nanocomposites by the melt intercalation of PP chains modified by either maleic anhydride (PP-g-MA) or hydroxyl groups (PP-OH) in o-MMT. For both matrices. Similarly.% clay was added. this study proves that clay dispersion and interfacial adhesion are greatly affected by the kind of matrix modification. Finally. leading rather to the dispersion of PP-g-MA intercalated clay in the PP matrix [1]. However. Hasegawa et al. Germany. C. Using the same method. a PP-g-MA matrix with a lower maleic anhydride content did not intercalate under the same conditions.2 wt. . The authors therefore.5 wt. commercial modified montmorillonite and sodium bentonite modified with octadecylammonium ions. Furthermore. intercalated nanocomposites were recovered after melt blending at 200 ◦ C for 15 min. since it has been widely used as compatibilizer for this kind of system. compared to other compatibilizing agents. [161] used two different polar coupling agents. addition of 4 and 7. providing a less effective interaction with the polar components of the clay. Pavlidou. Kawasumi. Tsukigase and Usuki by permission of Wiley-VCH. However. namely poly(styrene-co-methyl vinyl oxazoline). Kato et al. Therefore. Also. no further increase in the interlayer spacing was obtained in PP/PP-g-MA/clay blends.S. as in the case of PE and PP matrices. the driving force of exfoliation originates from the strong hydrogen bonding between the MA groups and the polar clay surface. [191] produced partially exfoliated PS/clay nanocomposites by compounding in a twin-screw extruder organically modified MMT with an blend of PS and ≥50% of another compatibilizer. The PP/clay hybrids were prepared by melt compounding with two different clays. diethyl maleate grafted PP (PP-g-DEM) and commercial maleic anhydride grafted PP (PP-g-MA) to prepare PP-based nanocomposites. and found that maleic anhydride increases the possibility of nanocomposite formation. 30.

Hunter and Singh by permission of Elsevier Science Ltd. Virgin PA6 did not degrade under identical processing conditions. they conducted an investigation on the processing degradation of PA6/MMT nanocomposites and clay organic modifier. the thermal degradation of organically modified montmorillonite is quite different compared to that of pure montmorillonite.7 2.1154 Table 14 Molecular weight of host polymers. The results led them to the following conclusions: 1. it was found that the number average molecular weight (Mn ) of PU significantly decreases during melt compounding and. [43] focused on the effect of organic modifiers on the thermal decomposition of OMLSs and found that.8 1. as shown in Table 14. since polymer processing is normally done above 150 ◦ C. but in different relative amounts. Another distinguishing difference between sodium montmorillonite and the organically modified montmorillonite is in the temperature range from 800 to 1000 ◦ C. Also. if the processing temperature to make the PLS is beyond the thermal stability of the organic treatment on the OMLS. the need for an optimized processing route is diminished. In OMLS sample the free water disappears by 40 ◦ C. UK. however. (b) the region where organic substances evolve in the tempera- Fig. Pavlidou.000 82. apart from the polymer matrix degradation.000 121. a particular quaternary alkyl ammonium treatment of the montmorillonite clay degraded it to an extent correlated with extruder residence time. There is no interlayer water in OMLS as the quaternary ammonium salt has been exchanged for the hydrated sodium cation. but drying at 80 ◦ C resulted in no water loss. on the basis of previous research. which illustrates that if there is a good driving force for intercalation between the polymer and organosilicate.9 5. The authors employed two TPUs: a soft elastomer (SPU) and a hard elastomer (HPU) consisting of the same soft and hard segments. Pan. drying at 120 ◦ C rather than 80 ◦ C prior to processing had little effect on the degree of degradation. (c) the structural water region in the temperature range 500–800 ◦ C. Davis et al. Moreover. Although melt compounding offered slightly better silicate dispersion than solvent casting. as the organic constituent in the organo-clay starts to decompose somewhat above 200 ◦ C. the authors suggested that solvent casting must be the preferred processing route for these materials.D. To address this issue. The catalytic activity of MMT was not investigated in this particular study. Heating at 120 ◦ C for 4 h thoroughly dried virgin PA6. 3. 31 for the OMLS was considered in four parts: (a) the free water region below 200 ◦ C.0 2. [88] prepared TPU nanocomposites by both twin screw extrusion and solvent casting. [192] found that during melt blending MMT/PA6 nanocomposites in a twin-screw extruder at 240 ◦ C.0 Mn 85. Degradation problems encountered during melt intercalation Despite the aforementioned advantages of polymer melt intercalation. C. a certain temperature is needed in the processing. SPU Mn As-received PU Solvent cast Melt compounded 216. when preparing clay/polymer nanocomposites using melt blending. The most distinguishing difference between the sodium montmorillonite and the organically modified montmorillonite is in the temperature range 200–500 ◦ C. while different long alkyl substituents have no effect or very little effect. during solvent casting (due to an ultrasonic probe that was applied). important in the process to make a polymer/clay nanocomposite. In this particular case. For example. both processing routes led to delaminated structures.1 1. it appeared that MMT could be involved in PA6 thermal degradation.4. owing to elimination of PU and surfactant degradation. therefore. in order to compare the outcomes of these methods. ture range 200–500 ◦ C. The DTGA thermal curve shown in Fig. Gao. the degradation issues encountered during melt intercalation have been addressed in several studies. some decomposition will take place. Xie et al.4. 31. Comparison of DTGA curves of various OMLS [43]. Longer drying times and . Finnigan et al. Sodium montmorillonite is very stable when the temperature is higher than 800 ◦ C. to a smaller extent. this technique may involve polymer degradation problems since. In fact. Vaia.000 PDI 2.000 66. PA6 nanocomposites significantly degraded during processing at 300 ◦ C. Thermal decomposition of PA6 nanocomposite may have resulted from hydrolytic peptide scission. Therefore. (d) a region between 800 and 1000 ◦ C where organic carbon reacts in some yet unknown way.000 S. The onset temperature of decomposition of the organic modifier is. in addition to common detrimental aspects of degradation. Within experimental uncertainty. The amount of volatile water in PA6 nanocomposites was greater than was observed in virgin PA-6.000 59. 2. As demonstrated by WAXD analysis.. the authors identified as additional causes of thermal degradation the small size of the extruder (and thus the large surface to volume ratio) as well as the absence of additives to reduce degradation. Liu. the OMLS continues to lose weight and a larger amount of CO2 is released at temperatures over 800 ◦ C. the resulting products may play a major but yet to be determined role in the formation of exfoliated nanostructures [43]. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 HPU PDI 1. however. Reproduced from Xie.

In this context. as mentioned above. which catalyze the Mixing device and conditions Co-rotating twin screw extruder. MMT and water are responsible for the degradation of PA6 nanocomposites. 80 ◦ C. Chang et al. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1155 Fig. Synthesis of the thermally stable organoclay [193]. In addition to the aforementioned studies. Some combinaTable 15 PLS nanocomposites prepared by melt intercalation. C. The obvious solutions are to reduce the heat or to increase the extrusion speed. Kim. 6 h Twin screw extruder. Gilman et al. 250 ◦ C 130 ◦ C Co-rotating mini twin screw extruder. 190 ◦ C Twin screw extruder. Nanocomposite PA6/[(HE)2 M1 R1 ] modified MMT PA6/Na+ -MMT water slurry PS/alkylammonium modified MMT PEI/hexadecylamine modified MMT PEO/Li+ or Na+ -MMT PLA/C18-MMT PP/stearylammonium modified clay PP-MA/C18-MMT PP/o-MMT modified using an organic swelling agent (Tb = 100–200 ◦ C) EVA/dimethyl-dioctadecyl ammonium modified MMT PET/1. 285 ◦ C ◦ Ref. processing conditions may affect the morphology of the resulting material. a number of researchers have developed and applied clays exhibiting high thermal stability. although darker streaks may also be present. 200 ◦ C Twin screw extruder. 32. when an organically modified MMT was used. On the other hand. little degradation was observed. [194] described the preparation of PA6-based nanocomposites of MMT modified with trialkylimidazolium cations to obtain high stability OMLS at high processing temperatures. however. Reproduced from Chang. Even though there is no explanation on how organically modified fluoromica acted to protect the system. [193] developed a thermally stable montmorillonite through an ion exchange reaction between Na+ -MMT and dodecyl triphenyl phosphonium chloride (C12 PPh-Cl− ) (Fig.S. 5. when a material is subjected to extrusion. A surprising result reported in another study was that poly(3-hydroxybutyrate) (PHB) nanocomposites prepared via melt intercalation showed severe degradation as testified by GPC. (c) clay and water are a special catalyst combination and/or (d) clay is a source of high-temperature reactive water or hydroxyls. others are exploring ways to overcome or limit degradation during polymer melt intercalation.. whereas no degradation was found with nanocomposites based on organically modified fluoromica. 25 h Internal mixer. 280 rpm Extrusion and drying Statically heating at 165 ◦ C. higher temperatures resulted in drier PA6 nanocomposites. that is. A strong odor may also indicate degradation. 240 C. In general. 30 min Statically annealing.D. the authors suggest that the presence of Al Lewis acid sites. which focus mainly on the degradation mechanism. UK. 370 ◦ C. If the degradation is general. This means that: (a) water itself may not be sufficient to cause degradation. (b) water escapes from PA-6 faster than from the nanocomposite. the entire extrudate is affected. [14] [160] [29] [46] [196] [153] [197] [186] [166] [166] [148] . this needs to be done carefully since. Joo and Im by permission of Elsevier Science Ltd. Pavlidou. When PA6 was processed at 300 ◦ C some water was present. the most likely cause is that the heat is too high for the speed of extrusion. 32).2-dimethyl-3-N-alkyl imidazolium salt modified MMT tion of these two variables are likely feasible since the speed of the extruder affects mechanical heating of the material [173]. vacuum. However. 4. PP-MA compatibilizer Twin screw extruder. as shown by discoloration throughout. degradation is detected as discoloration and lowered physical or mechanical properties.

the modulus increases linearly with the filler volume fraction. Therefore.e. 33. may be one reason [195]. some authors have argued that the dramatic improvement of modulus for such extremely low clay concentrations (i. such as fibers.5 29.1. and is thus stiffened through its affinity for and adhesion to the filler surface. No. Fornes and Paul [64] used an analytical approach to elucidate how incomplete exfoliation influences nanocomposite stiffness. A proposed theoretical approach assumes a layer of affected polymer on the filler surface.7 7. In fact.5 15. gallery is the volume fraction of gallery space and Egallery is the modulus of the material in the gallery. very few authors have used stabilization systems in the preparation of polymeric nanocomposites. and thus it is expected that the enhancement of modulus will become much less dramatic [198]. of platelets per stack Reinforcing factor (RF) Halpin–Tsai equation d0 0 1 = 0. Mechanical properties 6. whereas for nanocomposites much lower filler concentrations increase the modulus sharply and to a much larger extent [55]. In most conventionally filled polymer systems.0 25.1. when a relatively softer matrix is reinforced with such fillers. Reinforcement mechanism in composite materials. Obviously. The reinforcing mechanism of layered silicates The first mechanism that has been put forward to explain the reinforcing action of layered silicates is one also valid for conventional reinforcements.3 14. beyond the percolation limit.6 hydrolysis of ester linkages at high temperature. C.6 11.6 16. From this mechanism it becomes obvious that the larger the surface of the filler in contact with the polymer.5 d0 0 1 = 1.3 7. the surface area exposed to the polymer is huge and. when the number of platelets in a stack is equal to one. it is worth noting at this point that. which is schematically depicted in Fig.1 17.1 9. gallery can be expressed in terms of X-ray d-spacings. by using the rule of mixtures: Estack = + MMT EMMT gallery Egallery where MMT is the volume fraction of silicate layers in the stack.7 9. that the bonding between the two phases is adequate [64]. d0 0 1 is the repeat spacing between silicate particles.96 nm 34.8 23. which is expected to be much less than EMMT . 33. In Table 15 several PLS nanocomposites prepared via melt intercalation are presented as typical examples. 6.1. This could partly explain why layered silicates.8 16. therefore. the additional silicate layers are incorporated in polymer regions that are already affected by other silicate layers. The volume fraction occupied by gallery space. where n is the number of platelets per stack.3 d0 0 1 = 1. the polymer. the system represents an individual exfoliated platelet. rigid fillers are naturally resistant to straining due to their high moduli. becomes highly restrained mechanically.8 nm 34. of course. Obviously.9 12. the significant increases in the modulus with very low filler content are not surprising.96 nm 1 2 3 4 5 10 49.2 27. 2–5 wt. Table 16 shows how the number of platelets in a stack affects the reinforce- . the greater the reinforcing effect will be.8 4. as gallery = (n − 1)(d0 0 1 − tplatelet ) d0 0 1 (n − 1) + tplatelet Fig. despite the aforementioned degradation problems encountered during melt intercalation. is probably their most distinguishing characteristic. the low silicate loading required in nanocomposites to effect significant property improve- ments. for such high aspect ratio fillers as the layered silicate layers.8 18. Pavlidou. However.7 33. having an extremely high specific surface area (on the order of 800 m2 /g) impart dramatic improvements of modulus even when present in very small amounts in a polymer. and tplatelet is the thickness of a silicate platelet. particularly that adjacent to the filler particles.5 21.D. Nanocomposite properties 6.%) cannot be attributed simply to the introduction of the higher modulus inorganic filler layers. This affected polymer can be thought of as a region of the polymer matrix that is physisorbed on the silicate surface.8 nm 49. EMMT is the modulus of MMT.3 Mori–Tanaka theory d0 0 1 = 0. In order to prove the effect of degree of exfoliation on nanocomposite mechanical properties. That is. with a much higher modulus than the bulk equivalent polymer. Finally. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 16 Predicted reinforcing factors per number of platelets per stack. Furthermore. assuming.1156 S. This enables a significant portion of an applied load to be carried by the filler. They expressed the modulus of a simple clay stack in the direction parallel to its platelets.2 39.

To explain this phenomenon. it should be emphasized that the effect of nanocomposite formation on tensile strength is not as clear as in the case of the modulus since reductions of tensile strength upon nanocomposite formation have also been reported. which lists the tensile strengths of a number of nanocomposite materials and compares them with the corresponding values for the neat polymers. Reproduced from Bharadawaj. indicating that the crosslinking density is inversely proportional to the degree of exfoliation [140]. the effects shown separately in Fig. C. polymerization within protonated -caprolactam swollen montmorillonite or polymerization within natural montmorillonite in the presence of -caprolactam and an acid catalyst [45]. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1157 Fig. Young’s modulus was increased from 120 to 445 MPa with addition of 8 wt. the drop for the 2. [156] reported an increase from 216 to 390 MPa for a PCL nanocomposite containing 10 wt.% nanocomposites may be traced to the morphology. Fan.% clay. This plot of Young’s modulus of nylon 6 nanocomposite vs. [32] reported a 175% improvement in yield stress accompanied by a 200% increase in tensile modulus for a nylon 6 nanocomposite containing 5 wt. UK. 34. the modulus decreases with increasing clay content. especially for the intercalated clay. such as modulus. in the case of nylon 6 nanocomposites obtained through the intercalative ring opening polymerization of -caprolactam. shows a Fig. the largest drop in reinforcement is experienced when going from one to two platelets per stack. As shown in Fig.96 nm) as well as in an intercalated or organically modified clay (d0 0 1 = 1.2. as a function of clay content [31].. Such examples are included in Table 18. Mehrabi. Apart from the modulus. Tensile modulus vs. Overall. as can be seen in Table 17 for a number of different materials.8 nm).% ammonium treated clay in PCL. the addition of OMLS in a polymer matrix usually also increases the tensile strength compared to that of the neat polymer material. Interestingly. whatever the method of preparation: polymerization within organo-modified montmorillonite. For example. a large increase in the Young’s modulus at rather low filler content has been reported. 36. .5 wt. Similarly. Modulus and strength In general. it was observed that the sam- ple showed exfoliation on a global scale compared to the nanocomposite containing 10 wt. Hamilton. exceptions to this general trend have been reported.1. as in Fig. in fact. the trends in Table 16 show the high sensitivity of nanocomposite stiffness to the level of exfoliation.S. it was proposed that the intercalation and exfoliation of the clay in the polyester resin serve to effectively decrease the number of crosslinks from a topological perspective. 35. However. UK. clay concentration for crosslinked polyester nanocomposites [140].% clay. Chavira and Thompson by permission of Elsevier Science Ltd. Most polymer–clay nanocomposite studies report tensile properties. For example. concluded that stacks of platelets reduce stiffness of nanocomposites through lower effective filler moduli and reduced aspect ratio. Increasing n in both stacking scenarios leads to lower reinforcement efficiencies. Pavlidou..D.% ammonium-treated montmorillonite. Trujillo. The effect of the number of platelets per stack on the (a) modulus and (b) aspect ratio for the simplified arrangement of platelets [64]. filler weight content. in crosslinked polyester/OMLS nanocomposites. 6.5 wt.e. ment factor (RF in an unexchanged. Fornes et al. Gorrasi et al. However. Murga. while in another study [201]. the addition of an organically modified layered silicate in a polymer matrix results in significant improvements of Young’s modulus.% nanocomposite was greater than expected. The origin of the greater drop in properties of the 2. Shelley et al. non-expandable clay (d0 0 1 = 0. 35. i. Reproduced from Fornes and Paul by permission of Elsevier Science Ltd. 34.

11 1.250 1.55].0122 0.010 0.0122 0.081 0.134 0.061 0.0072 0.1 0 3.119 1.2 6.0124 0.024 0. Nanocomposite PA6/MMT (in situ polymerization) PA6(LMW)/MMT (melt intercalation) PA6(MMW)/MMT (melt intercalation) PA6(HMW)/MMT (melt intercalation) PP(7.7 5.0122 0.0240 0.0122 0.D.0122 0.71 3.050 0.021 0. The tensile strength increases rapidly from 78 MPa for PA66 up to 98 MPa for PA66CN5.1158 S.8 4.0249 0.3 0 3.65 4.0122 0. Liu and Wu [146] studied the mechanical performance of PA66 nanocomposites prepared via melt intercalation.2 7.4 0 3. In another study.0122 0.0135 0.2 0 7.0122 0.714 0. C.% clay and above).82 3.0193 0.70 0. This change corresponds to the passage from totally exfoliated structure (below 10 wt. 10 wt.060 1.0075 0.04 2. A similar phenomenon is observed in the dependence of tensile .086 0.1 7.75 3.360 Ref.87 2.8 2. using epoxy co-intercalated clay.2 0 7.% of nanoclay.0 Young modulus (GPa) 1.0228 0.61 2.%) to partially exfoliated—partially intercalated structure (for 10 wt.380 1.9 1.92 5.92 2.%. [199] [14] [14] [14] [186] [186] [167] [167] [167] [167] [167] [167] [167] [167] [88] [88] [88] [88] [200] constant large rate of increase of modulus up to ca. as determined by XRD and TEM [1. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 17 Young modulus of various PLS nanocomposites.66 5.020 1. but the increasing amplitude decreases when the clay content is above 5 wt.2 0 3 0 3 0 3 0 3 0 3 0 3 0 3 0 3 0 3 7 0 3 7 0 3 7 0 3 7 0 0.760 1.838 0. Pavlidou.0220 0. whereas above this threshold the aforementioned levelling-off of Young’s modulus is observed.0114 0.2% PP-g-MA)/OMLS PP(21.6% PP-g-MA)/OMLS EVA/Cloisite Na EVA/Cloisite 20A EVA/Cloisite 25A EVA/Cloisite 30B EVA/Nanofil 757 EVA/Nanofil 15 EVA/Somasif ME100 EVA/Somasif MAE Soft PU/30B (solution intercalation) Soft PU/30B (melt intercalation) Hard PU/30B (solution intercalation) Hard PU/30B (melt intercalation) HDPE/o-MMT Clay content (wt.0138 0.0116 0.%) 0 4.

7 27.2 24.9 62.5 25.2 0 12.%) 0 4. suggesting that the relative amount of intercalation/exfoliation of the clay morphology gradually increases with increasing clay content. while lim- ited improvement of the tensile strength was observed by incorporating clay in the matrix.9 6.6 70.6 0 17.7 84. C. Another example (Fig.5 8. .% was again attributed to the inevitable aggregation of the layers at high clay content.2 86.6 97.1 45 31 21 58 44 34 5.2 7.6 28. The smaller increase in amplitude observed with a clay loading above 5 wt.6 26. since the tensile strength is usually sensitive to the degree of dispersion [147].4 0 3.3 22 25 27 28 22 21 23 24 27 26 26 26 25 Ref.2 30.2 69.9 97.9 25.5 0 5 10 15 0 5 10 15 0 0. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 18 Tensile strength of various PLS nanocomposites.4 25.% of clay. Again.2 97.1 0 3.3 69. Compared to the virgin polymer. 37) shows both the tensile modulus and the yield strength of neat PA12 and the nanocomposites.9 83.3 0 3.S. With further increase in clay loading a moderate decrease of tensile strength was observed.6 95.2 6.8 2.7 23. the tensile modulus of PA12/clay systems was improved by about 40% upon adding only 5 wt.D.6 53.7 5.9 1.6 0 3 3 3 3 3 3 3 3 0 3 7 0 3 7 0 5 10 21. which increased steadily with increasing organoclay loading.8 4. [199] 1159 [14] [14] [14] [1] [1] EVA EVA/Cloisite Na EVA/Cloisite 20A EVA/Cloisite 25A EVA/Cloisite 30B EVA/Nanofil 757 EVA/Nanofil 15 EVA/Somasif ME100 EVA/Somasif MAE Soft PU/30B (solution intercalation) Hard PU/30B (solution intercalation) PU/MMT [167] [88] [88] [142] PE/JS [184] PE/DM [184] HDPE/o-MMT [200] modulus of PA66CN on clay content.2 78.0 Tensile strength (MPa) 68.7 24. Pavlidou. it was suggested that there is an optimum clay concentration for nanocomposite tensile strength improvement.4 16. Nanocomposite PA6/MMT (in situ polymerization) PA6(LMW)/MMT (melt intercalation) PA6(MMW)/MMT (melt intercalation) PA6(HMW)/MMT (melt intercalation) PMMA/OMLS PS/OMLS Clay content (wt.2 6.8 26.1 7.0 28.

of organo-modified montmorillonite/nylon-6-based nanocomposite obtained by melt intercalation [170]. processing conditions need to be optimized to allow greater exfoliation of the clay platelets and. Mohamed. having a smaller aspect ratio. play a rather minor role [1. Pramoda. Chen. On the other hand. . Shen. For an increase in Im . how- Fig. Effect of clay content on tensile modulus. other factors that influence the degree of exfoliation. Similarly. Keskkula and Paul by permission of Elsevier Science Ltd. LMW. respectively). Effect of MMT content on tensile modulus for LMW. This explains the variations observed in moduli of PA6 nanocomposites prepared by intercalative ring opening polymerization of -caprolactam. MMW and HMW (low. Even after a second pass through this extruder.. 39). Interestingly. The final nanocomposite properties are almost independent of the barrel temperature over the range of typical nylon 6 processing.67 Fig. UK. 38. Fig. MMW. which is inversely related to the amount of exfoliated layers in the nanocomposite. while intercalated particles.D. The WAXD peak intensity Im .55]. The effect of PA6 molecular weight and MMT content on nanocomposite tensile modulus is shown in Fig. with different kinds of acids to catalyze the polymerization (Table 19). thus. Lu and Hu by permission of John Wiley & Sons Ltd.e. also have an impact on nanocomposite modulus and strength. but they are slightly improved by increasing the screw speed or by a second pass through the extruder.25 2. Reproduced from Liu. apart from the clay content. 37. indicating that exfoliated layers are the main factor responsible for the improvement in stiffness. and HMW based nanocomposites [14]. Reproduced from Fornes. Acid Phosphoric acid Hydrochloric acid Isophtalic acid Benzenesulfonic acid Acetic acid Trichloroacetic acid Im (cps) 0 200 255 280 555 585 Young’s modulus (GPa) 2. C. Yield strength increases with MMT content. In the case of composites formed by single-screw extrusion. a parallel decrease in Young’s modulus is observed.74 1. the stiffness increases with increasing matrix molecular weight at any given concentration.1160 S.05 1. undispersed tactoids are still easily observed with naked eye. He.74 1. Chow. Tensile modulus and yield strength of PA12/clay nanocomposites as a function of clay concentration [147]. the tensile strength and modulus were slightly improved by the second pass. Liu.63 1. 36. medium and high molecular weight. on behalf of the SCI. 38. Similar trends with respect to the level of organoclay content and molecular weight are evident in the yield strength results (Fig. measured at room temperature. even though the moduli of the neat PA6s are all quite similar. Therefore. i. The addition of organoclay leads to a substantial improvement in stiffness for the composites based on each of the three PA6 samples examined. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 19 XRD peak intensity (Im ) and Young’s modulus of various nylon-6-based nanocomposites obtained by a one-step in situ intercalative polymerization of -caprolactam with Na–montmorillonite in the presence of different acids. Pavlidou. also depends on the nature of the acid used to catalyze the polymerization process. Qi and Zhu by permission of John Wiley & Sons. greater improvement in mechanical properties. However. nylon 6 nanocomposites with good properties can be obtained over a broad range of processing conditions in the twin screw extruder. the exfoliation of the clay platelets is not extensive. Inc. Cho and Paul [15] studied the effect of mixing device and processing parameters on the mechanical properties of polyamide nanocomposites. Reproduced from Phang. Yoon.

The increase in modulus with addition of MMT is much stronger for the organoclay with two alkyl tails than for the one with a single tail. and HMW based nanocomposites [14].6 0 7.6 1161 Young’s modulus (MPa) 780 714 760 830 838 964 1010 a PP = polypropylene. 39. Effect of MMT content on yield strength for LMW. As can be seen the ultimate strength increased dramatically with clay content and reached a maximum at 5 wt. Similar trends were observed also for nanocomposite yield strength. PPCH y/z = polypropylene based nanocomposite (y/z = weight ratio between y parts of filler and z parts of PP-MA). In another study.2 14. MMW. These differences with respect to molecular weight are attributed to the better exfoliation achieved for the higher molecular weight matrices [14]. Hotta and Paul [162] performed tensile tests on various PE and PE-MA nanocomposites based on organoclays with one or two alkyl tails. as would be expected on the basis of the much better dispersion of clay platelets for the surfactant with two alkyl tails. and C16 -MMT. Other factors that may play a crucial role in improvement of nanocomposite mechanical properties include the organic modification of the clay and the addition of compatibilizers to the polymer matrix.% MMT. the authors noted that there is no advantage in adding PE-MA for building modulus or strength at low MMT content (≤2. treated with a thermally stable. Sample PE PE/JS5 PE/JS10 PE/JS15 PE/DM5 PE/DM10 PE/DM15 Tensile strength (MPa) 22 25 27 28 21 23 24 Flexural strength (MPa) 26 28 33 38 26 31 30 Flexural modulus (MPa) 710 780 1050 1330 750 980 1030 Izod impact strength (J/m) 20 16 16 12 22 16 14 . which presents the ultimate strength of PUnanocomposites with different contents of two organically treated montmorillonites: MO-MMT. UK.%) 0 7. Both strength and modulus are higher in the case of the reactive intercalating agent.%) 0 0 0 6. Sample PP PP/PP-MA 7 PP/PP-MA 22 PPCC PPCH 1/1 PPCH 1/2 PPCH 1/3 Filler content (wt. there is a clear advantage in adding PE-MA at higher MMT contents.. Keskkula and Paul by permission of Elsevier Science Ltd.2 7. PP-MA x: polypropylene modified by maleic anhydride (x = wt. where the ultimate strength of Table 21 Mechanical properties of PE and PE/clay composites.2 PP-MA content (wt. in which the initial montmorillonite was modified by two intercalating agents: the commonly used dioctadecyldimethyl ammonium chloride (DM) and the reactive N.5 wt.%. It is readily observed that increasing the amount of PP-MA increases the modulus. Pavlidou. The effect of clay organic modification on nanocomposite mechanical properties is also demonstrated in Fig.2 7.9 7. owing to the better dispersion of the organoclay [184]. Interestingly. On the contrary. Reproduced from Fornes. C. Even though the benefit for modulus is not as great as might be expected.S. As a representative example. while the HMW and MMW-based nanocomposites show a steady increase in strength with clay content.-trimethoxysilanepropyl octadecyldimethyl ammonium chloride (JS). the LMW-based nanocomposites show a less pronounced effect.D.2 21.4 21.%). while comparison of PP with the simple PP-MA/PP blends rules out any possible effect of matrix modification due to the presence of increasing amounts of PP-MA [1]. in the absence of PE-MA.5 wt. in spite of the morphological differences seen. Yoon. aromatic amine modifier containing active groups. 40. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 20 Influence of maleic anhydride-modified polypropylene content on the stiffness of PP matrices and PP/clay nanocompositesa . Fig.% of PP-MA in the blend). treated with a quaternary alkyl ammonium salt. PPCC = polypropylene-based microcomposite. Young’s modulus values of PP/PP-MA nanocomposites are listed in Table 20 and compared with the corresponding microcomposite as well as simple PP-MA/PP polymer blends. the yield strength actually decreases on addition of MMT beyond 2. ever. Table 21 lists the strength and modulus values for PE-based nanocomposites.

5 Average tensile modulus (N/mm2 ) 2565 ± 11 2796 ± 31 3075 ± 56 Relative ultimate stress 1. while the polarity increases (and will increase the intercalation). the degree of crystallinity must also be considered. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 22 Tensile test results of Polypox H205 nanocomposites processed with low shear. Gopakumar et al.% clay in PE-MA increased Young’s modulus by 30 and 53%.000 1. Quite interestingly. the ultimate tensile stress decreased with increasing clay content. However. However.000 0. i. Since in EVA with increasing VA content the crystallinity of the polymer decreases (and will lower the stiffness).203]. Reproduced from Xiong. Pavlidou.D. the nanocomposites increased by about 450% for C16 -MMT and 600% for MO-MMT.8 2.920 0. it has been suggested that neither intercalated nor exfoliated nanosilicates lead to an improvement of the tensile stress at break.4 ± ± ± ± 1.6 54.034 1. the flexural modulus and ultimate flexural stress increased by 19.055 1. since this determines their aspect ratio and.. [171] studied the tensile properties of nanocomposites based on EVAs with various VA contents and two alternative organoclays. although the variation was large.090 1. up to a maximum of 15% for the 10 wt. because EVAs of different vinyl acetate contents have been processed into the nanocomposites with different clays and different modifying agents by different methods [81]. As can be seen.000 1. their surface area [55. 40. respectively. The results of tensile tests conducted by Hackman and Hollaway [134] on epoxy nanocomposites conventionally prepared under low-shear (stirring for 5 h at 90 ◦ C) are highlighted in Table 22. a relation not observed with EVA-28.1 Relative flexural modulus 1. a linear proportionality was found between clay concentration and tensile modulus for EVA-9 and EVA-18. [151] found that the exfoliation of 5 and 10 wt.909 Relative tensile modulus 1. Flexural tests were also conducted and the results are outlined in Table 23.199 Fig.2 53.6 and Average ultimate flexural stress (N/mm2 ) 95.5% I30E 10% I30E Average flexural modulus (N/mm2 ) 2755 2966 3101 3294 ± ± ± ± 83 90 85 76 the extent of filler reinforcement. hence. Specimen 0% I30E 5% I30E 10% I30E Average ultimate tensile stress (N/mm2 ) 59. UK.e. Liu.2 102. given that the mechanical properties of a filled system depend on two principal factors. Experimental results showed that the influence of increasing clay concentration on the tensile behavior of EVA matrices was significant only with a low or moderately polar EVA matrix (9 and 18% VA).3 ± 9. In another study dealing with the effect of matrix variations on mechanical properties of nanocomposites. The extent of improvement of nanocomposite mechanical properties will also depend directly upon the average length of the dispersed clay particles. it is very difficult to compare the extent of the improvement of the mechanical properties of different EVA/clay nanocomposites reported so far. At this point we note that several authors have also pointed out factors that have an adverse effect on nanocomposite modulus and/or strength and need to be taken into consideration when preparing nanocomposite materials.000 1.0 3. Yang and Wang by permission of Elsevier Science Ltd. In fact.0 and 19.126 1. In the case of high Tg thermosets. C. crystallinity of the polymer matrix and Table 23 Flexural test results of Polypox H205 nanocomposites processed with low shear. The authors noted that the greatly enhanced interfacial area derived from exfoliation of the clay improves the mechanical reinforcement potential of the filler. indicating that the improved mechanical strength depends on the characteristics of the modifier [202].% clay composition. Specimen 0% I30E 5% I30E 7.076 1. whereas the tensile stress at yield showed only a marginal increase.% clay loading respectively. Effect of organic-MMT loading on the tensile strength of (a) PU/MO-MMT and (b) PU/C16-MMT [202].196 Relative flexural stress 1.6 ± 6. compared with that of pure PU. but rather make the materials more brittle. Thus.077 .1162 S. The tensile modulus increased by 9.2 3. This effect appears to be generally more pronounced for intercalated structures than for exfoliated ones [1]. the stiffness and toughness responses would reflect an interplay of two factors: (a) an increase in the “rigid” amorphous phase due to polymer–clay intercalation and (b) an increase in the “mobile” amorphous phase due to the increasing VA content.0 ± 0.3 102. The authors attributed this phenomenon to the fact that large clay particles act as impurities and increase stress concentrations. Chaudhary et al.9% with 5 and 10 wt.0 97. the authors suggested that in their system.

the tensile modulus and ultimate tensile stress increased by 18.8 24 50 86 134 Tensile strength (MPa) 45 31 21 58 44 34 Fail strain (%) 1136 1109 1030 898 808 704 Melt compounded Young’s modulus (MPa) 7.24 2.b 3 3 3 2 3 3 3 3 3 3 3 3 3 3 2 3 1 2 3 Draw ratio. On the other hand. for specimens containing 10 wt.2 11.63 2.31 2. in PS intercalated nanocomposites the ultimate tensile stress was found to decrease compared to that of the PS matrix and dropped further at higher filler content.D. [204].% clay. [6]. C. contrary to other compositions in which polar interactions may prevail.%) Solvent cast Young’s modulus (MPa) SPU 0 3 7 HPU 0 3 7 7. when 5 wt. in the same study.12 3. Pegoretti et al.7 and 9. Elongation percent at break. however.28 2.29 4. strengthening the matrix interface [205].88 2. respectively. because the materials often become brittle and fail before reaching the yield point. who conducted tensile tests on PCL nanocomposite. which however were accompanied by a decrease in tensile strength and elongation [88]. Organoclay (wt.3 61 81 119 Tensile strength (MPa) 21 22 7 44 20 15 1163 Fail strain (%) 1445 1163 568 776 283 100 7.7%. a slight decrease of stress at break and a dramatic reduction of strain were reported. Pavlidou. it has been argued that in the presence of polar or ionic interactions between the polymer and the silicate layers. [149] found that the yield strength was not reduced by the addition of clay to recycled PET and considered Table 25 Tensile properties of PET hybrid fibers.10 3. In general. upon silicate addition large improvements in stiffness were observed. prepared by either solvent casting or melt compounding. It should be noted that several authors have reported inability to measure nanocomposite yield stress.51 2. the improvement in ultimate tensile strength was attributed to the smaller particles not generating stress concentrations leading to premature failure.S. the stress at break is usually increased. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 24 Summary of tensile properties of thermoplastic PU-based nanocomposites.47 3. Such remarks were made by Gorrasi et al. In this case. This lack of strength was attributed to the fact that only weak interactions exist at the PS/clay interface. however. [193] who prepared PET-based nanocomposites through in situ intercalative polymerization.4 19. containing 30 wt. while lower clay concentrations in the blend led to better mechanical properties in terms of flexibility and drawability.08 E.%) 0 (Pure PET) DRa 1 3 10 16 1 3 10 16 1 3 10 16 1 3 10 16 a b this to be a sign of good interfacial adhesion. it was not even possible to draw the sample because of its brittleness.63 2. Both exfoliated and intercalated PU/o-MMT nanocomposites showed an improvement in the elastic modulus upon increasing the clay content. Similar trends have been reported by Tortora et al.B. An interesting study was performed by Chang et al. respectively.5 13. and subsequently pro- Ultimate strength (MPa) 46 47 51 51 58 56 50 48 68 55 54 51 71 68 62 55 Modulus (GPa) 2.% clay only the elastic modulus could be evaluated since the sample did not reach the yield point. but a decrease in the stress and strain at break. 30B content (wt. For nanocomposites processed under high shear.% clay loading was applied. no or very slight tensile strength enhancement is recorded [1]. For the initial nanocomposite. . whereas when there is lack of interfacial adhesion.80 2.40 3.39 2. As can be seen. For the blend containing 15 wt.3%.% clay. is provided in Table 24.21 2. and also on blends of this nanocomposite with HMW PCL. A summary of the tensile properties of soft (SPU) and hard (HPU) polyurethane elastomers and of the corresponding nanocomposites.

3. Finally.98 1.%) 0 4 5 7 0 5 10 15 0 5 10 15 obtained by bending tests on nanocomposite materials are presented in Tables 26 and 27.10 GPa. the fracture surface became smoother compared with that of neat PA12. nanocomposite fibers did not follow this trend. as shown in Fig.78 1. 41(a) shows a typical fracture morphology in virgin nylon 12 and a ductile fracture as evidenced by plastic deformation.% clay (Fig.% clay addition (Fig.1164 S. Nanocomposite PLA/OMLS Clay content (wt. In fact.21 to 4.39 GPa. This study clearly illustrates that nanocomposite materials may have a different response to mechanical loads than the corresponding neat polymer matrices. 41(b) and (c) show fracture surfaces of the nanocomposites containing 1 and 5 wt. For 1 wt. 6. 41(d). On the other hand. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 26 Bending modulus of various PLS nanocomposites. An increase in the mechanical tensile strength with increasing DR is very common for engineering plastics and is usually observed in flexible coil-like polymers. as the DR was increased from 1 to 16.181]. microvoids are formed around the large inhomogeneities. Usually. As shown in Table 25. respectively.71 0. However. 41(d)) verifies the formation of microvoids due to the debonding of clay platelets from the matrix.75 0. for pure PET. Fig.% in hybrids at DR = 1. the tensile properties of the fibers formed increased with increasing amount of organoclay at DR = 1.% was observed in Fig. Chang et al. 41(c).330 0. The hot extrudates were stretched through the die of a capillary rheometer at 270 ◦ C and immediately drawn to various draw ratios (DR). Bending strength (MPa) 86 134 122 105 26 28 33 38 26 26 31 30 Ref.% clay. the strength and modulus increased from 46 to 51 MPa and 2. the observation of nanocomposite fracture surfaces is quite interesting. which become evident especially at high clay loadings. These microvoids will coalesce with formation of larger cracks causing embrittlement. Careful inspection of the fracture surface at higher magnification of nanocomposite with 5 wt. [208] PE/JS [184] PE/DM [184] . ultimately resulting in reduced toughness [147]. even though nanocomposite researchers are generally interested in the tensile properties of the final materials. which reduce the tensile mechanical properties. No distinct clay agglomerates are observed by scanning electron microscopy (SEM) even at high magnification. the ultimate strength and modulus of the hybrid fibers decreased markedly with increasing DR.030 Ref. However. [208] PE/JS [184] PE/DM [184] duced nano-hybrid fibers by extrusion through the die of a capillary rheometer.71 0.207]. the strength linearly improved from 46 to 71 MPa.D.8 0. When the organoclay was increased from 0 to 3 wt. it is quite interesting to note the effect of DR on the tensile strength and modulus of PET and PET nanocomposite fibers. an even more brittle feature for clay concentration of 5 wt. Some results Table 27 Bending strength of various PLS nanocomposites.21 to 2. Nanocomposite PLA/OMLS Clay content (wt. respectively.6 5. This has been testified through careful inspection of fracture surfaces and is also correlated to observations by in situ deformation experiments using TEM [147. Pavlidou. and the modulus from 2. Toughness and strain The brittle behavior often exhibited by nanocomposites probably originates from the formation of microvoids due to debonding of clay platelets from the polymer matrix upon failure.8 5.050 1. 41(b)).%) 0 4 5 7 0 5 10 15 0 5 10 15 Bending modulus (GPa) 4. suggested that higher stretching of the fiber leads to debonding and creation of voids in the hybrid. As is evident from Table 25.1. Fig. C. there are a few reports concerning the flexural properties of PLS nanocomposites [206.5 5.

SEM images showing fracture surfaces after impact tests: (a) neat PA12. respectively. C.% clay is incorporated. In the case of in situ intercalative polymerization. the Izod impact strength is reduced from 20. toughness improvements upon clay dispersion have also been reported—a remarkable result. Furthermore.%. Reproduced from Phang.21 kJ/m2 for the filler free matrix.1 J/m when 4. Izod impact strength of PA12/clay nanocomposites as a function of clay concentration [147]. Chen. in the clay content range between 0 and 7 wt. within experimental error. (b) and (c) PA12 nanocomposites containing 1 and 5 wt. Liu. Pramoda. Lu and Hu by permission of John Wiley & Sons Ltd. Charpy impact tests show similar reduction in the impact strength. 43 shows that the decrease in the Izod impact strength of melt-intercalated nylon 6 nanocomposites is not very pronounced over a relatively large range of filler content [170]. He. For example. vations of reduction in impact strength are also reported in nylon 6/clay nanocomposites and PE-based nanocomposites. Lu and Hu by permission of John Wiley & Sons Ltd. down to 6. . 42 shows that the Izod impact strength monotonically decreases as the clay concentration increases. Pavlidou. Pramoda. the aforementioned embrittlement effect from clay addition [147]. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1165 Fig. 41. Mohamed. Chow.% [158]. Similar obser- Fig.D.% nanocomposite. Reproduced from Phang. Shen. Shen. Liu. Mohamed.7 wt. i. indicating that the incorporation of clay into semicrystalline thermoplastics usually results in toughness reduction. The toughness (representing the energy absorption during the fracture process) decreases by about 25% with 5 wt. In that study marginal reductions in impact properties are reported. on behalf of the SCI.% clay.S. Fig. 42. on behalf of the SCI. while the tensile strength and modulus of PP nanocomposites increased rapidly with increasing clay content from 0 to 5 wt. He. Another study reports the impact properties for exfoliated nylon 6-based nanocomposites prepared either by in situ intercalative polymerization or by melt intercalation. In the case of nylon 12 nanocomposites. On the other hand. the notched Izod impact strength was constant.e. Fig. whatever the exfoliation process used.06 kJ/m2 for the 4.7 wt. some studies report little or no change of toughness upon clay intercalation/exfoliation. Chow. (d) high magnification of (c) [147].6 to 18.% of clay. with a drop from 6. Chen.

Fornes et al. 44. in an intercalated system there is considerable interaction between silicate layers that might alleviate this concern [45]. Reproduced from Liu. effective toughening necessitates a filler size greater than 0. Such results are particularly surprising. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Fig. They obtained an interesting stiffness/toughness balance for very low filler contents and without reducing the Tg of the matrix. Reproduced from Fornes. considering that conventional polymer–clay composites. considering that from length-scale arguments it is known that toughening occurs over a specific size range. sliding or opening of the separated bundles in the stacked layers. Quite interestingly. For example. The morphology of the system plays an important role in the toughening mechanism because the spacing of regions of intercalated clay is important to toughening. the HMW and MMW-based composites attain reasonable lev- Fig. By investigating the surface roughness and crack propagation under subcritical loading. [14] investigated how the matrix molecular weight as well as the extension rate during tensile tests affect the ductility of PA6-based nanocomposites. the sizes of the nanoparticles are generally too small to provide toughening through a crack-bridging mechanism and cannot effectively enhance crack-trajectory tortuosity. the extremely reduced scale of a fully exfoliated nanocomposite does not lend itself to a toughening application. and HMW based nanocomposites at a crosshead speed of (a) 0. 43. while it appears to be related to the nature of the clay organo-modifier and the state of nanocomposite dispersion. 44 presents the relationship between MMT content and elongation at break for PA6 matrices of different molecular weights. Effect of clay content on notched Izod impact strength of nylon-6/clay nanocomposites obtained trough melt intercalation [170]. for two different rates of extension. . UK. Also. and remained higher than that of PA66. Kim et al.%. Effect of MMT content on elongation at break for LMW. On the other hand. Liu and Wu [146] observed a toughening effect in PA66CN. The fracture behavior appears to be most dramatically improved in the intercalated system. that the intercalated morphology can afford some property improvements that are unavailable to the fully exfoliated systems. Fig. however.51 cm/min. containing aggregated nanolayer tactoids ordinarily improve rigidity but sacrifice toughness and elongation [7]. [44] attributed the enhanced toughness they observed for intercalated PA12 nanocomposites to the fact that some amount of applied energy is dissipated by splitting. Concerning the fracture behavior of EVA-based nanocomposites. even with higher clay content.% clay addition. The notched Izod impact strength increased from 96 to 146 J/m upon 5 wt. Peeterbroeck et al. With increasing clay content. it has been hypothesized that the creation of additional surface area on crack propagation is the primary means for toughening intercalated systems. which is particularly interesting considering how the brittleness of epoxies limits their use in technological areas where their high Tg is often highly appreciated. The fracture energy of the composites was increased by 100% at clay concentration of 5 wt. with void formation within clay aggregates leading to the evolution of a visible shear-banded zone in compression samples.51 cm/min and (b) 5. [167] concluded that it is independent of the origin of the clay. therefore. Yoon. 44a. MMW. It is believed.1 cm/min [14]. the ductility gradually decreases. Qi and Zhu by permission of John Wiley & Sons. LePluart et al..1 m and may not be energetically favorable at nano-length scales.1166 S. [136] reported that the incorporation of a benzyl dimethyl tallow alkyl ammonium montmorillonite in rubbery and glassy epoxy matrices leads to promising improvement of mechanical properties. Also. Keskkula and Paul by permission of Elsevier Science Ltd.D. C. As an example. As shown in Fig. However. Inc. the virgin polyamides are very ductile at a test rate of 0. Zerda and Lesser [45] showed that the gross yielding behavior of a glassy thermoset was substantially modified upon the formation of intercalated nanocomposites. Pavlidou. Therefore.

[14] 1167 PA6(MMW)/MMT [14] PA6(HMW)/MMT (melt intercalation) EVA EVA/Cloisite Na EVA/Cloisite 20A EVA/Cloisite 25A EVA/Cloisite 30B EVA/Nanofil 757 EVA/Nanofil 15 EVA/Somasif ME100 EVA/Somasif MAE Soft PU/30B (solution intercalation) Soft PU/30B (melt intercalation) Hard PU/30B (solution intercalation) Hard PU/30B (melt intercalation) PU/MMT [14] [167] [88] [88] [88] [88] [142] HDPE/o-MMT [200] els of ductility at MMT concentrations as high as 3. whereas the LMW and MMW based nanocomposites fracture in a brittle manner at the highest clay content. considering that high molecular weight matrices favor clay exfoliation. Even at the highest clay content.1 1406 1403 1231 1259 1266 1358 1291 1312 1270 1136 1109 1030 1445 1163 568 898 808 704 776 283 100 950 1020 1065 1160 36 25 20 14 15 Ref. the authors attribute the larger reduction of elongation at break in the LMW-based systems to the presence of stacked silicate layers. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 28 Elongation at break of various PLS nanocomposites.%.0 Elongation at break (%) 28 11 4. However. Yao et al. as already discussed [209]. probably due to aggregation of clay layers.1 0 3. as shown in Fig.8 2. Further increase of clay content causes reduction in mechanical properties. 44b. this enhancement is a maximum when the clay concentration is only 2 wt. [152] conducted tensile tests on PLA-based nanocomposite blown films and recorded improvements up to 40% for both the modulus and the elongation. Even though in most cases this property deteriorates when a layered silicate is dispersed into a polymer matrix. as can be seen in Table 28. On the other hand. the higher testing rate of 5. clay content are shown in Table 29.2 7.0 129 27 6.8 4. but the absolute level of elongation at break is significantly lower. nanocomposites have been reported exhibiting similar or even higher elongations at break than the neat matrices. contradictory results have also been presented concerning the effect of nanocom- posite formation on the elongation at break.1 cm/min yields similar trends. [142] also reported improvements in strain at break.%) 0 3.D.%. Thellen et al.2 6.9 1.2 0 3 3 3 3 3 3 3 3 0 3 7 0 3 7 0 3 7 0 3 7 0 5 10 21. Data of tensile strength and strain-at-break vs.4 0 3. Even though the opposite result could have been anticipated.S.%). Nanocomposite PA6(LMW)/MMT Clay content (wt. The authors suggested that the improved elasticity is due . the HMW composite exhibits ductile fracture. For example.8 101 18 5.5 wt. while the elongation at break for the LMW based nanocomposites decreases rapidly at low MMT content (around 1 wt.1 7. As in the case of toughness. the strain at break for LMW composites is relatively independent of the rate of extension. Pavlidou. C.5 0 0. a significant increase of both the strength and the elongation has been reported with the introduction of the organoclay into the EVA-12 matrix. in the case of EVA-12/MMT nanocomposites. Interestingly. similar to what has been observed in glass fiber reinforced composites. as seen in TEM photographs.

A summary of the mechanical properties of these materials is shown in Table 31. it is possible to achieve more intimate interaction between the matrix and the rubber phase.D.5 Tensile strength (MPa) 5. these elongational properties of PP based RTPO/clay nanocomposites are unique and promising for many applications. exhibit improved flexibility and toughness compared to neat PP. the notched Izod impact strength of the nanocomposite is lower than that of neat polyamide 6.2 Tensile strength at break (MPa) 20. but the value of nanocomposites containing 10 wt. quite the opposite of the usual effect of adding a particulate filler to a polymer. which are much lower than those of RTPO clay nanocomposites and is not suitable for industrial application. On the other hand. Stress–strain curves for nylon 6 and 95/05 composites at a crosshead speed of 5. PP-based RTPO (or in reactor made TPO) is a blend of PP and poly(ethyleneco-propylene) (EPR).1 14.4 8. but with dramatic increases in ductility.% glass fibers is 11% higher than that of PA6 containing 30 wt.1168 S.%) 0 9 15 30 Clay (wt. For these materials. followed by gas-phase copolymerization of ethylene and propylene driven by the TiCl4 /MgCl2 -based catalyst system.9 6.08 cm/min [15]. As the authors claim. The authors attributed this discrepancy to the difference of dispersion homogeneity and domain size of ethylene copolymer between RTPO and PP/EPR mechanical blends.1. Hong et al. Chen and Evans [210] observed a dramatic improvement in tensile elongation at break in the presence of clay.. because the rubber phase can be dispersed uniformly and reach a high degree of dispersion in these in situ blends. as shown in Fig. similar to pristine PCL. However. which is much higher than that of PP/clay nanocomposites reported elsewhere.%) 100 88 80 60 PpgMA (wt.5 cm/min). In fact. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 29 Tensile strength and strain-at-break vs.% montmorillonite. also prepared and tested nanocomposites using PP/EPR mechanical blend matrix. UK.5 8. At low clay loadings. They found that the tensile strength of PA6/clay containing 30 wt. the composites became brittle and did not reach the yield point. Fig. the loading of layered clay. modified with PP-MA. Reproduced from Cho and Paul by permission of Elsevier Science Ltd. test pieces underwent yielding during tension. while the tensile modulus of the nanocomposites increases by 42%. prepared by using PP-MA as a compatibilizer. several studies have investigated the potential synergistic effects of clays and conventional reinforcements. typically higher than 20 wt. [52] studied the effect of adding glass fibers to PA6 and PA6-based nanocomposites containing 3 wt. [185] on PP-based RTPO/clay nanocomposites. Accordingly. Weight fraction of the clay (%) 0 5 10 21.% of fillers are compared. C. for reasons of comparison.4. Finally. regardless of the type of filler.1 6. Pavlidou.2 6.6 Elongation at break (%) 1390 980 859 437 Tensile modulus (MPa) 46. Comparison and synergistic effects of clays and conventional reinforcements Typically. When the clay loading was high.3 Strain-at-break (%) 950 1020 1065 1160 in part to the plasticizing effect of gallery onium ions.6 16. the strength and modulus are substantially increased relative to the neat PA6.3 251 . typical stress-strain diagrams for PA6 and composites containing 5 wt. Wu et al. the elongation at break values were about 50%. the tensile moduli of the nanocomposites became higher as the clay content increases. such as glass fibers.%. and is further decreased with the addition of fibers. The compositions and tensile properties of polypropylene-based RTPO/clay nanocomposites are reported in Table 30. like the conventional blends of PP/EPR prepared by mechanical blending. 45 (at 5.0 71. 46 (at 0.2 78. which contribute to dangling chain formation in the matrix. Such materials.%) 0 3 5 10 Tensile strength at yield (MPa) 5. it is worth summarizing the work of Hong et al.08 cm/min) and Fig. In this context. the elongation at break decreases as the clay content increases. as compared with conven- Table 30 Compounding formulations and tensile properties of PP-based RTPO/PpgMA/clay nanocomposites. produced by the bulk polymerization of propylene. without significant variation in toughness or impact strength. layered silicates are incorporated in polymeric materials as the sole reinforcing element. However. Furthermore. As can be seen. especially modulus.8 16. In another study. nanocomposites show superior mechanical properties. 6.% glass fibers. Sample RTPO RTPO NC3 RTPO NC5 RTPO NC10 PP-based RTPO (wt. Bending strength and bending modulus of neat PA6/clay are similar to PA6 reinforced with 20% glass fibers.% clay is 437%. as measured by the standard Izod test.6 16. 45. As can be seen from the table. Moreover.

This exceeds what is expected on the basis of simple additivity. 6.66 ± 0. a synergistic effect on the tensile strength and modulus is again observed when the exfoliated nanocomposite is used as the matrix for a glass fiber reinforced composite. PCL. On the other hand. PA.4 ± 0.51 cm/min [15].[189]. Similar results have also been reported in the case of PP.[83. who claim that untreated clay composites with PA6 are inferior to neat polymer in terms of some mechanical properties.3 83.153. G and tan ı of a nylon 6 matrix and various nanocomposites is presented in Fig. a shift of tan ı to higher temperatures has been observed. has also been reported for nanocomposite materials. SBS[211]. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1169 elongation at break remain at the levels of neat PA6 up to about 5 wt. when materials become soft.. rate of extension has little effect on the elongation of glass fiber composites.2 ± 0. the tan ı values are affected in different ways by nanocomposite formation. and decrease thereafter [15]. This increase is generally larger above the glass transition temperature.208. the elongation at break for the nanocomposites is greatly affected by the crosshead speed. the modulus of the nanocomposite with 5 wt. It is noteworthy that the composite of PA6 with untreated Na+ -MMT shows higher strength and modulus than neat PA6. while the equivalent increase in the rubbery region was 450% [135]. however this aspect of dynamic mechanical performance is far less discussed in the literature. Reproduced from Cho and Paul by permission of Elsevier Science Ltd. corresponding to the elastic response to the deformation.[80].2 3. strengthening the material through mechanical percolation [1]. showed a 60% increase in G in the glassy region. Polyamide composites Clay content (%) Izod impact strength (J/m) Modulus (GPa) Yield strength (MPa) Elongation at break (%) Crosshead speed 0. DMA results are expressed by three main parameters: (i) the storage modulus (E or G ). Enhancement of the loss modulus. In the case of nanocomposites.26 ± 0.16 8 38 53 40 38 44 ± ± ± ± ± 4 8 2 3 3 2.% of the organoclay.S. containing 4 vol.0 25 0. and for exfoliated PLS nanocomposite structures is probably due to the creation of a three-dimensional network of interconnected long silicate layers.01 ± 0. PLA. that is.08 cm/min 40 14 14 38 7 ± ± ± ± ± 8 4 3 19 4 Polyamide 6 PA6/glass fiber PA6/MMT PA6/organoclay PA6/organoclay/glass fiber 0 5 5 3. the modulus is 81% higher than that of PA6.D. When glass fibers are added to the nanocomposite.2. in PS based nanocomposites. values for the conventional composites are dramatically decreased. which is quite contrary to the results from other investigators.% loading of the organoclay is improved about 38% relative to neat PA6 and the glass fiber composite shows a 22% improvement.4 ± 0. The elongation at break for the nanocomposites is more or less the same as that of the neat PA6. (ii) the loss modulus (E or G ).1 64. As shown in Table 31. whereas. G .5 . Finally. 46. depending on the polymer matrix.[64. useful for determining the occurrence of molecular mobility transitions such as the glass transition temperature [1].0 ± 0.3 6. Interestingly.212].51 cm/min Crosshead speed 5. compared to the unfilled epoxy.% silicates. the E /E (or G /G ) ratio.8 75. accompanied by a broadening of this transition [205]. corresponding to the plastic response to the deformation and (iii) tan ı. For example.8 72. tional PA6 composites formed by compounding with glass fibers or untreated clay. Stiffness and strength are dramatically improved as the amount of organoclay increases.82 ± 0. C. Indicatively.66 ± 0.1 3. the main conclusion derived from dynamic mechanical studies is that the storage modulus increases upon dispersion of a layered silicate in a polymer. Dynamic mechanical properties Dynamic mechanical analysis (DMA) measures the response of a material to a cyclic deformation (usually tension or three-point bending type deformation) as a function of the temperature. while the opposite effect was reported in the case of PP-based nanocomposites [189]. the temperature dependence of G . For example.6 ± 0. On the other hand. Pavlidou.213]. This results in the observed enhancement of G [55].1 4.1 3. an epoxy-based nanocomposite. UK.7 95. the impact strength and Table 31 Mechanical properties of polyamide 6 composites. Above the glass transition temperature. and epoxy-based nanocomposites [135]. 47. as is the case for neat PA6.9 200 18 22 126 8 ± ± ± ± ± 30 1. the reinforcement effect of the clay particles becomes more prominent. Stress–strain curves for nylon 6 and 95/05 composites at a crosshead speed of 0. Also. due to the restricted movement of the polymer chains. Some authors observed a decrease Fig.

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Fig. 48. Proposed model for the torturous zigzag diffusion path in an exfoliated polymer–clay nanocomposite when used as a gas barrier [85]. Reproduced from Yano, Usuki, Okada, Kurauchi and Kamigaito by permission of John Wiley & Sons Inc.

this indicates a weakening of the thermomechanical stability of these materials at high temperature. 6.3. Barrier properties Generally, polymer/layered silicate nanocomposites are characterized by very strong enhancements of their barrier properties. Polymers ranging from epoxies and good sealants (like siloxanes) to semi-permeable (e.g. polyureas) and highly hydrophilic (e.g. PVA) are all improved up to an order of magnitude by low clay loadings [31]. The dramatic improvement of barrier properties can be explained by the concept of tortuous paths. That is, when impermeable nanoparticles are incorporated into a polymer, the permeating molecules are forced to wiggle around them in a random walk, and hence diffuse by a tortuous pathway, as shown in Fig. 48 [4,7,55,206,214–216]. The tortuosity factor is defined as the ratio of the actual distance, d , that the penetrant must travel to the shortest distance d that it would travel in the absence of barriers. It is expressed in terms of the length L, the width W and the volume fraction of the sheets s as = L d =1+ 2W d
s

Fig. 47. . Temperature dependence of G ; G and tan ı for N6 matrix and various N6CNs [55]. Reproduced from Ray and Okamoto by permission of Elsevier Science Ltd., UK.

of tan ı peaks, and considered this indicative of a glass transition suppression by the presence of the clay. However, Fornes and Paul [64] pointed out that this conclusion is a misinterpretation, since the low values for the nanocomposites are simply the result of dividing the relatively constant loss modulus values in the Tg region, by larger and larger storage modulus values. Quite surprisingly, DMA showed that above Tg , the moduli for the pure PU and the PU/o-MMT nanocomposites show no obvious difference, while below Tg , addition of o-MMT strongly influences the modulus values. Interestingly, the authors found that E and E of the PU/o-MMT decrease in comparison with values for the PU, for unclear reasons. On the other hand, significant enhancements of E and E were seen for the nanocomposite prepared using a particular modified clay [202]. In the case of PLA-based nanocomposites, it was observed that PLACNs with a very small amount of o-PCL as a compatibilizer exhibited a very large enhancement of mechanical properties compared to that of PLACN with comparable clay loading [153]. Krikorian and Pochan [83] also studied the dynamic mechanical properties of neat PLA and nanocomposites prepared with OMLS. These authors found that at high temperatures the reinforcement effect of OMLS weakens, and suggested that

It becomes obvious from this expression that a sheet-like morphology is particularly efficient at maximizing the path length, due to the large length-to-width ratio, as compared to other filler shapes [1,50,55]. According to the model proposed by Nielsen, the effect of tortuosity on the permeability may, in turn, be expressed as PPCN 1− = Pp
s

where PPCN and PP represent the permeability of the nanocomposite and the pure polymer, respectively and s is the clay content [50,55,217]. Although the above equations were developed to model the diffusion of small molecules in conventional composites, they have also been used in reproducing experimental results for the relative permeability in PLS nanocomposites. Discrepancies between the experimental data and the theoretical line may be attributed either to inadequacies of the model or to incomplete orientation of the particles

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within the nanocomposite film plane [50,162]. In fact, the key assumption of the Nielsen model is that the sheets are placed in an arrangement such that the direction of diffusion is normal to the direction of the sheets. Clearly, this arrangement results in the highest tortuosity, and any deviation from it would, in fact, lead to deterioration of the barrier properties [50,55]. Moreover, the tortuous path theory, including the Nielsen equation as well as other phenomenological relations (e.g. the Cussler [218] formula, the Barrel [219] formula and the power law equation [220]), is grounded on the assumption that the presence of nanoparticles does not affect the diffusivity of the polymer matrix. However, experimental observations demonstrate that molecular mobility in a polymer matrix, which is intimately connected to the mass transport properties, diminished by clay incorporation. This reduction should be accompanied by a decrease in diffusivity of small molecules, which is not considered in the concept of tortuous paths. Messersmith and Giannelis [118] studied the permeability of liquids and gases in nanocomposites and they observed that water permeability in PCL nanocomposites is dramatically reduced compared to the unfilled polymer. They also noted how the decrease in permeability is much more pronounced in the nanocomposites compared to conventionally filled polymers with much higher filler content. Liu and Wu [146], recorded the water absorption curves of PA66 and corresponding nanocomposites. They found that with increasing clay content, the water absorption at saturation decreases rapidly from 7.6% for PA66 to 5.2% for the nanocomposite containing 5 wt.% clay. They attributed this reduction to the presence of immobilized polymer in the amorphous phase. However, above 5 wt.% clay content, the decrease in the saturation amount of water is not so obvious, probably because of aggregation of silicate layers. Also, the diffusion coefficient values decrease greatly with increasing clay loading, but after 5 wt.% clay content, the amplitude of the decrease is obviously slower. In addition to the immobilized phase explanation, and the increased average diffusion path length, since an epoxy-co-intercalated clay was used in their study, the authors assumed that the epoxy groups between silicate layers have a strong interaction with amino and amide groups of the PA66 matrix, to some extent preventing them from forming hydrogen bonds with water. Significant reductions in diffusivity and maximum water uptake were also reported by Liu et al. [130] in epoxybased nanocomposites. Here, however, the decreased maximum water uptake was attributed to the low maximum water uptake of the nanoclays (ca. 2.8 wt.%) compared to the epoxy resin system (ca. 7.5 wt.%). Drozdov et al. [221] conducted moisture diffusion tests on vinylester resin-MMT clay nanocomposites and demonstrated that the clay content affects in a similar way the diffusion coefficient and the constants expressing the elastoplastic behavior, indicating that moisture diffusion and elastoplasticity may reflect the same phenomena at the microlevel, associated with molecular mobility of the polymeric matrix. Moreover, their experimental data demonstrated that moisture diffusion in the neat polymer resin is nearly Fickian, but is transformed to an anoma-

Fig. 49. Equilibrium concentration of water vapor, Ceq (g/100 g), as a function of activity a = p/p0 for samples OMont ( ), NPU0 ( ), NPU4 ( ), NPU20 ( ), NPU40 (♦) [204]. Reproduced from Tortora, Gorrasi, Vittoria, Galli, Ritrovati and Chiellini by permission of Elsevier Science Ltd., UK.

lous mode of transport of the penetrant molecules with an increase in clay concentration. The authors explained the anomalous moisture uptake by immobilization of water molecules on the surfaces of the hydrophilic MMT clay layers. In fact, they pointed out that, after a nanocomposite plate is immersed in water, three processes occur in the nanocomposite: (1) sorption of water molecules on the sample surfaces, (2) diffusion of water into the plate, and (3) adsorption of water molecules on the hydrophilic surfaces of clay layers, where these molecules become immobilized. Many studies reported in the literature have focused on nanocomposite barrier properties against gases and vapors. As an example, Tortora et al. [204] measured the transport properties of PU/o-MMT nanocomposites (prepared using a PCL nanocomposite “master-batch”) using water vapor as hydrophilic permeant and dichloromethane as hydrophobic one. For both vapors, the sorption behavior changed in the presence of the clay, as can be seen for example in Fig. 49, where the equilibrium concentration, Ceq (g/100 g), of water vapor is represented as a function of the vapor activity for all nanocomposites and for the oMMT. The sorption curve of water vapor for o-MMT follows the Langmuir sorption isotherm, in which the sorption of solvent molecules occurs at specific sites; therefore, when all the sites are saturated, a plateau is reached. On the other hand, the sorption of neat PU shows a linear dependence of equilibrium concentration on activity, while nanocomposites show a dual sorption shape, that is a downward concavity, an inflection point and an upward curvature. The prevailing mechanism in the first zone is the sorption of solvent molecules on specific sites, due to interacting groups. Tortora et al. inferred that this type of sorption is due to the presence of clay in the polymers. At higher activities, the plasticization of the polymeric matrix determines a more than linear increase of vapor concentration and a transition in the curve is observed, from a dual type to a Flory-Huggins behavior. From the calculated values of

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Fig. 50. The O2 permeability of PET/o-MMT [222]. Reproduced from Ke and Yongping by permission of Elsevier Science Ltd., UK.

Fig. 51. Effect of montmorillonite weight fraction on diffusivity D of montmorillonite/epoxy nanocomposites [223]. Reproduced from Ogasawara, Ishida, Ishikawa, Aoki and Ogura by permission of Elsevier Science Ltd., UK.

the sorption parameters, defined as: S = d(Ceq )/dp, and the zero-concentration diffusion coefficients for water sorption and dichloromethane vapor, the authors concluded that the sorption did not drastically change on increasing the clay content, whereas the zero-concentration diffusion coefficient D0 strongly decreased with increasing inorganic content. The permeability calculated as the product SD0 , was largely dominated by the diffusion parameter; it showed a remarkable decrease up to 20 wt.% of clay and a levelling off at higher contents. Ke and Yongping [222] tested the O2 permeability of intercalated PET nanocomposites. As demonstrated in Fig. 50, a small amount of clay effectively reduced the permeability of the PET film. When the content of o-MMT reached 3 wt.% the permeation of O2 was reduced to half that of the pure PET film. Further examples of barrier property improvement for PET nanocomposites designated for packaging applications are given in Table 32 [216]. Ogasawara et al. [223] reported on improved helium gas barrier properties of epoxy/MMT nanocomposites, compared to the pure resin. The estimated diffusivity, D, solubility, S, and permeability P are shown in Figs. 51–53, as functions of montmorillonite weight fraction. Dispersing MMT particles in the epoxy decreased the diffusion coefficient D. For example, the diffusion coefficient of the nanocomposite with 6 wt.% clay was approximately onetenth that of the base polymer. On the other hand, the solubility increased with montmorillonite dispersion and permeability remained almost constant due to the balance of diffusivity and solubility. On the other hand, Ray et al. [208] found that the O2 gas permeability of PLA nanocomposites with 4, 5 and 7 wt.%
Table 32 Relative barrier performance of newly developed rigid packaging based on PET. Container composition (supplier) Relative oxygen transmission rate at 23 ◦ C 50% RH 1 <0.3 0.4–0.7

Fig. 52. Effect of montmorillonite weight fraction on solubility, S, of montmorillonite/epoxy nanocomposites. The numerical curve based on rule-of-mixture is superimposed [223]. Reproduced from Ogasawara, Ishida, Ishikawa, Aoki and Ogura by permission of Elsevier Science Ltd., UK.

PET PET nanocomposite (Tetrapak) PET/PA nanocomposite (Eastman)

Fig. 53. Effect of montmorillonite weight fraction on permeability, P, of montmorillonite/epoxy nanocomposites [223]. Reproduced from Ogasawara, Ishida, Ishikawa, Aoki and Ogura by permission of Elsevier Science Ltd., UK.

S. Pavlidou, C.D. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 33 Oxygen gas permeabilities of the PLA/OMLS hybrid films. Clay (wt.%) O2 gas (cm3 /(m2 day)) C16MMT 0 4 6 10 777 449 340 327 DTA-MMT 777 455 353 330 C25A 777 – 430 340

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clay, was reduced to 88, 85 and 81% compared to that of neat PLA. Similarly, Chang et al. [84] reported the oxygen gas permeability of PLA nanocomposites prepared with three different kinds of OMLS using a melt intercalation technique. Table 33 summarizes the results for O2 gas permeability. The results show that O2 gas permeability of nanocomposites systematically decreased with increasing clay content; and when the clay loading was as much as 10 wt.%, the permeability for nanocomposite decreased to half the PLA permeability, regardless of the nature of the OMLS employed for the nanocomposite preparation. Finally, Fig. 54 presents water vapor and oxygen permeation results for PLA-based nanocomposite films. In all cases the nanocomposite films were better oxygen barriers than the pure PLA films (Fig. 54a), exhibiting a 15–48% reduction in oxygen permeation rate. It is worth noticing that the oxygen permeation rate of the nanocomposite films was essentially independent of screw speed and feed rate, whereas the oxygen barrier properties of the neat PLA homopolymer were quite sensitive to

processing, suggesting that the need to optimize processing parameters is more critical when working with the PLA homopolymer than with the PLA/OMLS nanocomposites. The PLA/OMLS nanocomposites also exhibited much improved barrier properties to water vapor relative to the neat films (Fig. 54b). In general, clay incorporation decreased the permeation rate of the resulting films to water vapor by about 40–50%, again independently of processing [152]. Summarizing: although a decrease of diffusivity is a well-established result of nanocomposite formation, contradictory results are reported concerning the saturation uptake values of various solvents or gases. Increases of the saturation uptake level are usually attributed to clustering phenomena. It is worth noticing, however, that in nanocomposites the coexistence of phases with different permeabilities can cause complex transport phenomena. On the one hand, the organophilic clay gives rise to superficial adsorption and to specific interactions with the solvents. In turn, the polymer phase can be considered, in most cases, as a two-phase, crystalline-amorphous system, the crystalline regions being generally impermeable to penetrant molecules. The presence of the silicate layers may be expected to cause a decrease in permeability, due to the more tortuous path for the diffusing molecules that must bypass impenetrable platelets [133]. Simultaneously, the influence of changes in matrix crystallinity and chain mobility, induced by the presence of the filler, should always be taken into consideration [10]. 6.4. Thermal stability The thermal stability of polymeric materials is usually studied by thermogravimetric analysis (TGA). The weight loss due to the formation of volatile products after degradation at high temperature is monitored as a function of temperature (and/or time). When heating occurs under an inert gas flow, a non-oxidative degradation occurs, while the use of air or oxygen allows oxidative degradation of the samples [50,55]. Generally, the incorporation of clay into the polymer matrix was found to enhance thermal stability by acting as a superior insulator and mass transport barrier to the volatile products generated during decomposition, as well as by assisting in the formation of char after thermal decomposition [50,55,133,224]. Vyazovkin et al. [225] compared the thermal degradation of a PS nanocomposite with that of the virgin polymer under nitrogen and air. As seen in Fig. 55 in both nitrogen and air the decomposition temperature of nanocomposites increased by 30–40 ◦ C. The authors also observed that the virgin polymer degrades without forming any residue, whereas the nanocomposite (as expected) leaves some residue. Zanetti et al. [226] reported TGA curves of a nanocomposite PE/EVA/o-MMT and the corresponding matrix PE/EVA. Under nitrogen, these samples do not show great differences of stability. However, in air, the PE/EVA blend is subject to a marked weight loss above 350 ◦ C, to form a 5 wt.% residue at 450 ◦ C, which is completely oxidized to volatile products between 470 and 550 ◦ C. The nanocom-

Fig. 54. MOCON permeation data (a) oxygen and (b) water vapor transmission [152]. Reproduced from Thellen, Orroth, Froio, Ziegler, Lucciarini, Farrell, D’ Souza and Ratto by permission of Elsevier Science Ltd., UK.

the organoclay shields the polymer from the action of oxygen. This conclusion has been verified by a number of researchers in subsequent studies. and various mechanisms have been put forward to explain the results. 57 [231]. Reproduced from Vyazovkin. The presence of 5 wt. the temperatures at 50% mass loss were 471–476 ◦ C. Fan and Advincula by permission of Wiley-VCH. C. D’ Souza and Ratto by permission of Elsevier Science Ltd. [229] showed that protective barriers are formed during thermal degradation of polyamide 6/clay nanocomposite. Pavlidou. Pramoda et al. acting as a heat source to accelerate the decomposition process. The authors noted that the degradation might depend upon water in the nanocomposites. whereas there is significant decrease in molecular weight in nanocomposites under the same conditions. Dranka. is shown in Fig. injection molded at 300 ◦ C. For example. by 13 C NMR. TGA experiments by other workers did not show significant changes in the onset of degradation. displays a different pattern. Germany. observed that the degradation onset temperature is 12 ◦ C higher for PA6 with 2. Generally. posite. For example. They showed that the PLA intercalated between the galleries of FH or MMT clay resisted the thermal degradation under conditions that would otherwise completely degrade pure PLA.5% clay loading than that of virgin PA6 and that the onset temperature for the higher clay loading remained unchanged. Also. 56) and reported that the onset of thermal degradation was approx- Fig. Moreover. which slow down the rate of degradation via a diffusion process (hindering the escape of volatiles). proposed by Levchik et al. In fact. TGA curves of neat PLA and nano-PLA/MLS [152]. The thermal degradation mechanism of PA6. Farrell.. 56. the alkylammonium cations in the organoclay could suffer decomposition following the Hoffmann elimination reaction. On the other hand. the degradation of PCL fits a two-step mechanism. Bandyopadhyay et al.1174 S. in conjunction with the heat flow supplied by the outside heat source [55]. Reproduced from Thellen. Also. It has been reported that the thermal stability of PCL/o-MMT nanocomposites systematically increases with increasing clay. despite the general improvement of thermal stability. on the other hand. Froio. [152] presented TGA curves for the neat polymer and corresponding nanocomposites (Fig. imately 9 ◦ C higher for the nanocomposite than for the neat PLA. which was within the error range of the TGA instrument used. contradictory results are found in the literature concerning the thermal degradation of PA6based nanocomposites.D. They found that PA6 does not degrade at processing temperature. Thellen et al. and the product could catalyze the degradation of polymer matrices. it becomes obvious that the organoclay may have two opposing functions in thermal stability of nanocomposites: a barrier effect. Moreover. and attributed such observations to the degradation effect of the quaternary alkylammonium treatment on the montmorillonite [15]. decreases in the thermal stability of polymers upon nanocomposite formation have also been reported. that after the early stages of thermal decomposition the stacked silicate layers could hold accumulated heat. Irrespective of formulation.228]. which may cause hydrolytic cleavage. with the release of CO2 . which should improve the thermal stability and a catalytic effect on the degradation of the poly- . dramatically increasing the thermal stability under oxidative conditions. [192] studied the thermal stability of PA6 and PA6 nanocomposites..% [1. First. H2 O and hexanoic acid. up to a loading of 5 wt. TGA curves of the degradation of PS100 and nPS90 at a heating rate 5 ◦ C min−1 in air and nitrogen [225]. It has been argued. random chain scission through pyrolysis of the ester groups. 55. However.% o-MMT is enough to change the polymer’s thermo-oxidative behavior and between 350 and 480 ◦ C the amount of residue is higher to that observed in a nitrogen flow. caprolactone (cyclic monomer) formation as a result of an unzipping depolymerization process. Orroth. Ziegler. [227] reported the first improved thermal stability of biodegradable nanocomposites that combined PLA and organically modified fluorohectorite or montmorillonite. UK. The thermal stability of PCL-based nanocomposites has also been studied by TGA. other researchers found that PA6 nanocomposites have somewhat lower stability than neat nylon 6. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Fig. for example. Lucciarini. according to Jang and Wilkie [230] the mass loss behavior of PA6/clay nanocomposites is not significantly different from that of virgin PA6. Thus. According to the authors. Davis et al. Dabrowski et al. and in the second step. the clay itself can also catalyze the degradation of polymer matrices.

UK. Reproduced from Davis. however. On the other hand. with a maximum at a clay loading of 5 wt. a decrease in thermal stability was observed—an effect explained by the relative extent of exfoliation as a function of the amount of OMLS. Phang et al. Dominant PA-6 thermal degradation products in the absence of a nucleophile (a) and in the presence of a nucleophile. Similarly. by about 20 ◦ C with incorporation . at low filler contents homogenous exfoliation and random dispersion of clay is achieved on a nanometer level. With further increase of filler content. but decrease with increasing clay loading.D. [184] investigated the thermal stability of PE-based nanocomposites in a nitrogen atmosphere and recorded the TGA and DTGA (derivative curve) profiles presented in Fig. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1175 Fig. for example. this was attributed to the Hoffmann elimination reaction and the clay-catalyzed degradation. Gilman and VanderHart by permission of Elsevier Science Ltd.%. the authors suggested that when a low clay fraction is added to the polymer. the hybrids show a decreasing trend in their initial thermal decomposition temperature. These findings were attributed to the fact that. whereas the higher filler loading destabilizes the matrix. that the thermal stability of EVA-12 (12 wt. Paul et al.S.%. mer matrix. For example. the clay disperses well and the barrier effect is predominant. the catalyzing effect rapidly increases and becomes dominant. 58. probably because of the degree of dispersion of clay in the polymer matrix [209]. Thus. With an increase in the oMMT loading over 2 wt. for instance. It has been found. The onset temperatures for nanocomposites are all higher than that of pure PE. such as water (b) [192]. above 400 ◦ C nanocomposites appear to be more stable than pure PE.% VA) increases with the introduction of o-MMT. C. which should decrease the thermal stability [184]. so that the thermal stability of the nanocomposite decreases.. but with increasing loading. Pavlidou. [147] found that the thermal stability of PA12 is significantly enhanced as the clay concentration increases. [233] observed an increase in thermal stability of PLA nanocomposites with increasing clay content. the nanocomposites degrade faster than the pure matrix. In fact. because of the aggregation of silicate layers [232]. at the initial stage of degradation (before 400 ◦ C). As can be seen from this figure. EVA/clay nanocomposites containing more vinyl acetate maintain this thermal stability improvement up to 6–8 wt. Zhao et al. 57. Other researchers have studied the effect of clay concentration on the thermal stability of EVA-based nanocomposites.% filler loading.

PET nanocomposites exhibit improved thermal stability. particle agglomeration occurs.23 Tm (◦ C) 245 247 245 246 32 32 33 32 Hm c (J/g) i TD d (◦ C) wt600 e R 1 8 15 21 370 375 384 386 Draw ratio. a change attributed to the barrier effect. Costache et al. However. Also.81. most of the polymer volatilizes in the first step of PU decomposition and the second step is diminished in the TGA/DTGA curves in air compared to those obtained in nitrogen.02 1. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 34 Thermal properties of PET hybrid fibers (DRa = 1).2-tetrachloroethane (w/w) mixture. The thermal properties of EVA-based nanocomposites have been widely studied.1176 S. By thoroughly studying both the first and second steps. but displaced by 10 ◦ C. On the contrary.1 g/100 ml solutions in a phenol/1.167]. in the nanocomposites the lower temperature degradation is significantly suppressed and the second DTGA peak around 395 ◦ C is clearly present. grouped in a series of . It has been well established by different research groups that EVAs exhibit two-step decomposition. Gong. For the second step of EVA degradation. the nanocomposite shows the same TGA and DTGA profiles as PU. This result is consistent with reports claiming that optimum thermal stability is usually achieved for clay loadings between 2. the nanocomposites showed very different behavior than pure PU. the weight of residue at 600 ◦ C increased. which again does not allow maximization of the tortuous path. on the other hand. Riva et al. [144] did TGA under nitrogen and air for PU and the corresponding nanocomposite. UK. while McGrattan [236] identified hydrocarbons ranging from C8 to C26. i dation temperature TD increasing with the amount of organoclay. .%) only limited improvement in thermal stability was observed. C. When dimethylbenzyloctadecyl-ammonium cation was used for MMT modification. thus only a relatively small shoulder appears at 350 ◦ C in air. 1-alkenes and n-alkenes.1.%) 0 (pure PET) 1 2 3 a b c d e ninh b 1. Organoclay (wt. carbon dioxide. 58. Maurin et al. Qin.. with the initial thermal degra- Fig. when tested under air. between 400 and 500 ◦ C. involves thermal decomposition of the unsaturated backbone. intercalated and exfoliated structures usually coexist.26 0.98 1. Initial weight reduction onset temperature. Therefore. [235] found as products 1-butene. [234] observed accelerated acetic acid loss of EVA–clay nanocomposites and speculated that this process can be catalyzed by acidic sites of the nanodispersed clay. Pavlidou. Feng. Under nitrogen.% [193]. The second step. ethylene. This was attributed to the fact that the exfoliated structure formed at low clay content is probably not enough to trigger the thermal and gas barrier properties effectively in the matrix. with production of gaseous acetic acid and formation of carbon–carbon double bonds along the polymer backbone. mainly by means of TGA. the threshold was reached at a surprisingly low MMT content of only 0. occurs from 350 to 400 ◦ C and corresponds to the deacetylation reaction. For lower clay fractions.% clay. [237] investigated the possibility that the presence of of only 5 wt. Reproduced from Zhao. but this low clay content does not enable the barrier effect.% [35]. methane and carbon monoxide. The first step. At much higher clay content. As shown in Table 34. For PA12/organoclay nanocomposites with lower clay contents (<2 wt. Inherent viscosities measured at 30 ◦ C by using 0. Weight percent of residue at 600 ◦ C. exfoliated morphology dominates. either by further radical scission (non-oxidative decomposition) or by thermal combustion (oxidative decomposition) [35. This behavior was again attributed to greatly retarded thermal oxidation due to the shielding of the material from oxygen.2.5 and 5 wt. because of the short tortuous path formed. ranging from 1 to 21%.% clay into the matrix.D. Enthalpy change of fusion. which is identical in both oxidative and non-oxidative conditions.%. For pure PU. Berta et al. TGA and DTGA curves of PE and PE/clay nanocomposites in nitrogen atmosphere [184]. Zhang and Yang by permission of Elsevier Science Ltd. A maximum increase of 16 ◦ C was recorded in the case of 3 wt. with clay loading from 0 to 3 wt. An optimum clay loading for thermal stability enhancement was also reported for PS-based nanocomposites. -dienes.3 wt.

0 Fig.3 ◦ C. Possible radical recombination reactions for EVA nanocomposites [237]. Yei et al. Table 35 Maximum temperature at the main degradation peak as measured under air at 20 ◦ C/min for EVA and EVA-nanocomposites with different organoclay contents. while the maximum of the first decomposition peak remains unchanged (see Table 35). The main reason is that the aromatic chain of the modifier in MOMMT has higher thermal stability than the alkyl chain of the modifier in C16 -MMT. The authors also noted that the aromatic amine modifier can react with the pre-polyurethane matrix used.0 454.. Finally. Comparing the quaternary alkyl ammonium salt and the aromatic amine modifier they used. The TGA–FTIR and GC–MS results of thermal degradation of EVA in the presence and in the absence of clay show that even though the two processes are very similar. indicating an improvement of thermal stability. [115] used TGA to characterize PS-based nanocomposites prepared from clay treated with cetylpyridinium chloride (CPC) and CPC/ cyclodextrin (CPC/ -CD) inclusion complex.. In cases where there are multiple degradation pathways.3. C. As deduced from the previous examples. as already described in Section 5. the formation of an inclusion complex between CPD and -CD improved the thermal stability of the CPC surfactant. 60) show that the degradation rates of the nanocomposites were slightly slower compared to that of PU. Organoclay content (wt. The explanation for the improved thermal stability is the formation of protective char under oxidative conditions [238]. the CPC/ -CD inclusion complex decomposes at higher temperature (284 ◦ C) than the pure CPC (220 ◦ C). further strengthening the interaction between inorganic and organic phases. UK. In helium. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1177 Fig. TGA curves of (a) pure PU. the presence of the clay can promote one of these at the expense of another.6 ◦ C).% MO-MMT [202].%) 0 1 2. More specifically. and thus lead to different products and hence a different rate of volatilization.% C16-MMT and (c) PU/3 wt. even though contradictory results are sometimes found in the lit- . when decomposed under air. nanodispersed clay can change the degradation pathway of EVA. The TGA curves obtained (Fig.1. Thus. Both nanocomposites display higher decomposition temperatures than the virgin PS.5 5 10 15 Maximum temperature at the main degradation peak (◦ C) 452. 59). Reproduced from Xiong. with the CPC/ -CD intercalated clay nanocomposite being the most thermally stable of the three samples. showing the latter to have the higher thermal stability.5 472. Yang and Wang by permission of Elsevier Science Ltd. the same nanocomposites exhibit a rather large increase in thermal stability. Liu. the thermal decomposition of EVA nanocomposites has been investigated using TGA in helium and in air.2 493. Pavlidou.S. 60. it has been suggested that the thermal stability of the nanocomposites is directly related to the stability of the OMLS used for their preparation [84]. [202] studied the thermal stability of PU and nanocomposites prepared using MMT modified either by a quaternary alkyl ammonium salt (C16 -MMT) or by an aromatic modifier (MO-MMT). as the maximum of the second degradation peak is shifted 40 ◦ C to higher temperature.0 453. Fig. EVA nanocomposites exhibit a negligible reduction in thermal stability compared to virgin EVA or EVA microcomposite. thus lower than that of the PU/MO-MMT (331. subtle changes occur. As is clearly evident. UK. In the early stages of the EVA degradation. In another interesting study. several studies have focused on the effect of clay organic modification on thermal stability of nanocomposites. (b) PU/3 wt. 59. In contrast. the authors found the degradation onset temperature of PU/C16 -MMT at 316. Reproduced from Costache.D. In another study.4 489. Xiong et al. Table 36 summarizes the TGA results for the nanocomposites and the pure polymer. the loss of acetic acid seems to be catalyzed by the hydroxyl groups present on the edges of the clay lamellae. Jiang and Wilkie by permission of Elsevier Science Ltd. 61 shows the TGA curves of pure CPC and the CPC/ -CD inclusion complex. leading to the formation of products that differ both in quantity and identity. It has been suggested that these products form as a result of radical recombination reactions that occur because the degrading polymer is contained within the clay layers for sufficient time to permit the reactions (Fig. the presence of the -CD protects CPC from earlier decomposition. In a typical example.

magnesium hydroxide.%) 0 3 3 Tg (◦ C)a 100 102 106 T0. . the opportunity of achieving a significant improvement in thermal stability through low filler content is particularly attractive because end-products can be made cheaper.5 ). Reproduced from Yei. 6. 62. Kuo.05 ). 61. Fu and Chang by permission of Elsevier Science Ltd. For example. Fig. flame retardancy has been achieved either by using intrinsically flame retardant polymers. Traditionally. or by incorporating flame retardants (FRs). C. However.05 (◦ C)b 390 408 423 T0. such FRs exhibit significant disadvantages.9 5. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 36 Results of TGA and DSC data for the polystyrene nanocomposites.5. lighter and easier to process [35]. erature concerning the thermal stability of polymeric nanocomposites. such as aluminum trihydrate. Reproduced from Beyer by permission of Elsevier Science Ltd.. Sample PS CPC/Clay/PS a-CD/CPC/Clay/PS a b c Clay content (wt. such as fluoropolymers or PVC. aluminum trihydrate and magnesium hydroxide need to be applied at very high loadings to be effec- Fig.1178 S. TGA curves of (a) pure CPC and (b) the CPC/a-CD inclusion complex [115]. Schematic view of the cone calorimeter [35]. 5% degradation temperature (T0. UK.8 Glass transition temperature (Tg ). Pavlidou.D. organic brominated compounds or intumescent systems.1.5 (◦ C)c 424 424 452 Char at 600 ◦ C (%) 0 2. Flame retardance of polymer–layered silicate nanocomposites Polymers are being used in more and more applications where flame retardant behavior is of critical importance.5. 50% degradation temperature (T0. Flame retardance 6.. UK.

As can be seen from Table 37. On the other hand. as well as low mechanical properties and problems in compounding. Moreover. resulting in high density and lack of flexibility of the end-products. which.239]. Finally. Pavlidou. intumescent systems are relatively expensive and electrical requirements can restrict their application [35. Moreover. In a typical cone calorimeter experiment the sample is exposed to a defined heat flux. or ignite adjacent objects [35. it has been demonstrated that the reduction in PHRR is proportional to the fraction of clay. properties such as heat release rate (HRR). time to ignition (TTI). mean CO yield and mean specific extinction area can be simultaneously measured [35. and it also depends on its aspect ratio and surface charge density.S. mass loss rate (MLR). Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 37 Cone calorimeter data of various polymers and nanocomposites with OMLS. the incorporation of layered silicates results in significant reductions of PHRR and average HRR. as it provides valuable information and may even indicate the flame retardancy mechanism. C. [240] 1179 [240] [159] [240] [163] [237] [144] [144] [144] [144] [184] tive. The HRR is considered to be the most important variable characterizing a fire. total heat released (THR). peak of heat release (PHRR). while the PHRR represents the point in a fire where heat is likely to propagate further. in turn. The measuring principle in this test. the one most commonly used by researchers is cone calorimetry (Fig. This difference comes into effect shortly after the initial combustion. concerns over the environmental impact have made halogen containing materials a less popular option in many countries. Sample PA6 PA6/2% OMLS PA6/5% OMLS PS PS silicate mix 3% PS nanocomposite 3% PSw/DBDPO/Sb2 O3 30%) PS PS/MAST-Hect 1% PS/MAST-Hect 3% PS/MAST-Hect 5% PPgMA PPgMA nanocomposite 2% PPgMA nanocomposite 4% EVA/Na+ 5% EVA/Cloisite 30B 3% EVA/Cloisite 30B 5% EVA/Cloisite 30B 10% EVA EVA/30B EVA/30BHect EVA/30BMag EVA/MMT PU (I) PU (I)/o-MMT PU (II) PU (II)/o-MMT PU (III) PU (III)/o-MMT PU (IV) PU (IV)/o-MMT PE PE/JS 2% PE/JS 5% PE/JS 10% PE/JS 15% PHRR (kW/m2 ) 1010 686 378 1120 1080 567 491 1230 1011 894 728 1525 450 381 1200 860 780 630 2303 1174 1289 2010 1959 2561 918 2254 641 2647 848 2664 797 1470 670 320 540 390 741 344 637 363 768 444 775 435 510 440 450 380 280 430 670 593 476 517 176 305 235 412 165 172 235 412 536 322 275 HRRave (kW/m2 ) 603 390 304 703 715 444 318 SEAave (m2 /kg) 197 271 296 1460 1840 1730 2580 1315 1336 1332 1327 704 1028 968 Ref. where cone calorimeter data are presented for various nanocomposites and the corresponding neat polymers. A high HRR causes fast ignition and flame spread.D. usually 35 or 50 kW/m2 . This states that there is a constant relationship between the mass of oxygen consumed from the air and the amount of heat released during polymer combustion. Among test methods developed for the evaluation of flame retardant properties.41]. the addition of many FRs increases the production of soot and carbon monoxide during combustion. In the literature it is reported that the primary parameter responsible for the lower HRR of nanocomposites is the MLR during combustion. is that of oxygen consumption.56]. 62). when the nanocomposite has . is also significantly reduced compared to the values observed for the pure polymer. which is standardized as ASTM E 1354 and ISO 5660.

Both these actions interfere with the combustion cycle by reducing the amount of fuel available for burning [31. the char insulates the underlying polymer from heat and also slows oxygen uptake and the escape of volatile gases produced by polymer degradation. heat transfer from an external source or from a flame promotes thermal decomposition of the organoclay and the polymer. XRD and TEM examination of such residues has revealed intercalated structures [241].178. a large reduction of flammability in nanocomposites compared to pure PE was attributed to the formation of char [184]. For example. As shown by the “fire performance index” (PHRR/TTI).1180 S. TTI was increased. For low clay contents. Actually. While the PHRR was clearly reduced when either clay was added to the polymer (relative decreases of 25% for Cloisite Na+ and 50% for Cloisite 30B). [163] also reported on the fire retardancy of EVA-based nanocomposites. C. whereas the EVA/Na+ -5 gives a powdery grey “ash. Again. Jama. they showed higher rates of smoke emission than their pure PU counterparts. the authors noted that the TTI was also reduced and that the THR was similar for pure polymer and the clay-containing polymer.241. with increasing clay content a reduction of TTI was attributed to catalytic effects.178. UK. Delobel. combustion experiments on EVA-based nanocomposites showed that the HRR and MLR were reduced by 70–80% in a nanocomposite with low silicate loadings (2–5%) presumably because of a refractory char-clay surface layer formed by the reassembling of the clay layers and catalyzed charring of the polymer [177]. the carbonaceous char formed superficially during combustion is rich in silicates and can be viewed as a sort of ceramic char–layered silicate nanocomposite [31. Reproduced from Duquesne.” and the EVA/30B-5 system gives a fragile. it is generally considered that the formation of a thermal insulating and low permeability char on the outer surface of a nanocomposite during combustion is the key to understanding improvement in flame retardant properties [35. Comparison of the residues after the cone calorimeter experiment (Fig. Finally. the nanocomposites perform much better than pure PUs. Therefore. carbonaceous residue around 3 mm thick. whereas the TTI results were somewhat more complicated. However. 63) demonstrates the different behavior of the three materials. More specifically.D.56. Table 38 Cone calorimetry results for PU nanocomposites and reference materials. Pavlidou. This results in accumulation and reassembly of clay platelets on the surface of the burning material [226]. This mechanism has been put forward in most studies reporting on the flame retardant properties of nanocomposites. presumably because of a greater degree of secondary condensed phase chemistry in an oxygen-depleted environment. In the case of PE/clay nanocomposites significant reductions of PHRR were reported. However the TTI was similar or slightly reduced for the nanocomposites and the initial rate of weight loss/heat release was higher. However. 63. it is exactly its own nanocomposite structure that allows the residue formed to act as a protective barrier by reducing the heat and mass transfer between the flame and the polymer. Table 38 summarizes the results of the cone calorimetry tests performed on PU and PU-based nanocomposites. Recourt and Gloaguen by permission of Elsevier Science Ltd. where a flame was applied twice for 10 s to the base of the test specimens and the burning behavior was observed. In fact. The data show that the average HRR and PHRR were greatly reduced for the nanocomposites as compared with the reference materials. probably due to early decomposition of the organic modifier of the clay and subsequent clay-catalyzed polymer degradation. due to the barrier effect of the clay.35.242]. PU TTI (s) PU I II III IV 29 35 26 22 NC-PU 29 33 17 25 PHRR (kW/m2 ) PU 2561 2254 2647 2664 NC-PU 918 641 848 797 PI (PHRR/TTI) PU 88 64 102 102 NC-PU 32 19 50 50 HRRave (kW/m2 ) PU 741 637 768 775 NC-PU 344 363 444 435 SEAave (m2 /kg) PU 176 235 165 235 NC-PU 305 412 172 412 . The pure polymer does not give a residue.56].177]. [144] conducted vertical burn tests. had time to form a char on its surface [56. Duquesne et al. using two montmorillonites: Cloisite Na+ and Cloisite 30B. That is. In fact. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Fig. Berta et al.. Residues after cone calorimeter experiment for EVA. Le Bras. EVA/30B-5 and EVA/Na+ -5 [163]. leading to the formation and evolution of aromatic and carbonaceous species.226].

Effects of clay content on HRR of PA6 (8 mm thick) at 50 kW/m2 [242]. Bae.. UK. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1181 Fig. At this point. To prove this conjecture. Awad and Shields by permission of Elsevier Science Ltd. In fact. the specific heat of combustion (Hc ). Awad and Shields by permission of Elsevier Science Ltd. but in nitrogen. the authors exposed samples to the same external flux as in the cone calorimeter. PP thermally degrades to volatile products above 250 ◦ C through a radical chain process. Reproduced from Kashiwagi. The PHRR of the nanocomposite containing 10 wt. However. whereas for the PU nanocomposites dripping was strongly suppressed or eliminated. They noticed that the MLR (burning) curve (Fig. Fig. 66). Zanetti and Costa [177] also found that the nanodispersed morphology in PE/EVA nanocomposites leads to a substantial decrease of combustion rate of the polymer matrix.S. In neat resin. Cipriano. Ragharan. 65) of each sample is proportional to the HRR curve (Fig.% clay is 37% lower than that of neat resin. . implying that the observed reduction in HRR (and MLR) tends to be due to chemical and physical processes in the condensed phase. HRR measured with a cone calorimeter (heat flux 35 kW/m2 ) for various PP-based RTPO materials: (a) PP-based RTPO (neat resin). On the other hand. Pavlidou.% PPgMA [185]. The authors performed cone calorimeter tests on PA6 and nanocomposites containing 2 and 5% clay. rather than in the gas phase. it does not need to be completely delaminated. 64. Harris. 66. containing 10 wt. Jho. Pure PU materials dripped heavily upon ignition. This adsorption may delay volatilization of the degradation products and promote accumulation of the incomplete degradation products on the clay [185]. containing 10 wt. excellent performance has been observed when the clay layers have remained separated by only approximately 3 nm. Zhang. Nam. 30 wt.D.231. it has been argued that the flame retardancy obtained in nanocomposites when merely intercalation has occurred is at least as good as when complete exfoliation is achieved. Reproduced from Hong. [242].. whereas the microcomposite shows a smaller decrease of the rate of combustion. and all intermediate degradation products volatilize completely. the neat resin leaves no residue and the microcomposite leaves only a little powder. (c) PP-based RTPO/PPgMA/clay nanocomposite. C. 64. aiming to further elucidate the nanocomposite flame retardancy mechanism.% clay.243].% clay. a quite interesting observation is that. Cipriano. Nam and Lee by permission of John Wiley & Sons. Thus.135. which is considered to be in the “intercalation” zone [55. Inc. thermal degradation continues during the combustion. At the end of combustion. Reproduced from Kashiwagi. HRR plots of PP based RTPO neat resin. Generally. In other words. Ragharan. although the clay must be nanodispersed to affect the flammability of nanocomposites. propagated by carbon centered radicals created by carbon–carbon bond scission. Briber. to avoid Fig. Lee. (b) PPbased RTPO/clay microcomposite. there may be physicochemical adsorption of the intermediate degradation products on clay surfaces in clay nanocomposites. microcomposites and nanocomposites are shown in Fig. 65. Effects of clay content on mass burning rate of PA6 (8 mm thick) at 50 kW/m2 [242]. Harris. while the nanocomposite leaves a consistent char-like residue. Briber. UK. while the microcomposite and the neat resin show very similar behavior. Zhang. obtained from the HRR divided by the MLR remains unchanged for the three samples. it is worth summarizing a very interesting study by Kashiwagi et al.

while traditional fillers very often severely degrade the physical properties of the polymer or discolor it. grew with time (Fig. and despite the fact that these materials have shown to perform very well in laboratory tests concerning their resistance to fire. lower cost and ease of preparation. Similar carbonaceous floccules were also observed in the residues of the burnt samples tested in the cone calorimeter. while the remaining 20% consist of thermally stable organic components with possible graphitic structure. With apparatus similar to the to cone calorimeter. the overall differences among the three samples were very similar between the burning case and the gasification case. Moreover. UK. unlike some FRs. Finally.56. Pavlidou. Given that the burning behavior depends on processes in both the gas and the condensed phase. However. an important feature of nanocomposites is the simultaneous improvement in many physical properties. 200.. and they do not produce increases in the carbon monoxide and soot levels during combustion like those associated with conventional FRs.1182 S. During gasification. and the other is the transportation of clay particles pushed by numerous rising bubbles of degradation products. Awad and Shields by permission of Elsevier Science Ltd. these materials are an environmentally friendly alternative to some types of fire retardants. C. Ragharan. The authors attributed the accumulation of clay particles on the burning/gasifying sample surface to two possible mechanisms. . and 400 s in nitrogen at 50 kW/m2 [242].g. only very low concentrations of silicate are necessary in nanocomposites.56. as they contain no halogens. the nanocomposites appeared to be more viscous than the neat PA6 sample and dark floccules appeared on their surfaces. Zhang. since the mechanism of nanocomposite flame retardancy can be looked at in more detail through such techniques. without any change in the polymer color [3.D. Summarizing: nanocomposites could offer significant advantages in the area of polymers flame retardancy and these advantages become even more evident when nanocomposites are compared with conventional FRs. Despite the quantitative difference in MLR between the two cases. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Fig. vertical upward combustion) in which dripping of flaming material could occur.242]. Cipriano. Further analysis showed that up to 80% of the protective floccules consist of clay particles. silicates provide physical integrity to the material burning in configurations (e. 67) and were left at the bottom of the container at the end of the test. phosphates or aromatics other than those that may be present in the polymer matrix. Also. even though flame retardancy is one of the most promising properties of nanocomposites. resulting in commercial advantages such as low density. Briber. any gas phase effects. 68) is expected to increase the understanding of the condensed phase decomposition processes of pyrolysis. One is the recession of the polymer resin from the surface by pyrolysis with dewetted clay particles left behind. which constitutes an additional hazard of fire propagation to surrounding materials [231].178]. the authors suggested that the observed improvement in the flammability resistance of nanocomposites is due to chemical and physical processes in the condensed phase. while the gasification behavior depends only on those in the condensed phase. 67. Selected video images at 100. The development of the aforementioned radiative gasification technique (Fig. First of all.35. Reproduced from Kashiwagi. Harris. this method allows pyrolysis in a nitrogen atmosphere at heat fluxes similar to those found in fires [35.

AO and o-MMT. However. UK. the most significant advantage offered by nanocomposite formation is the reduction in PHRR (from cone calorimeter measurements).% Sb2 O3 PP-MA + 22 wt. The cone calorimeter results obtained are presented in Table 39. time (s) 90.% organoclay PP-MA + organoclay PP-MA PHRR (kW/m2 ) 300.. Also. 170 85 85 180 Average HRR 254 107 188 279 . C. polymer nanocomposites combined with such additives are reported in the literature.2. A schematic view of the “radiative gasification” apparatus [35]. with DBE. compared to the virgin polymer. Formulation PP-MA + 22 wt. Reproduced from Beyer by permission of Elsevier Science Ltd. also increase the probability of early ignition [239. the nanocomposite significantly increased the burn time for the sample when compared to the flame retardant control sample. much more research needs to be carried out to establish their applications and limitations. such as UL-94V. they perform poorly when tested under industrially significant or regulatory fire safety tests.245]. the addition of 5 wt. [247] described a PP-based nanocomposite incorporating decabromodiphenyl ether (DBE) and antimony oxide (AO) as the FR system. as will be demonstrated in the following examples. Considering also the disadvantages of traditional FRs. Zanetti et al. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1183 Fig. The average HRR was lowered by 58% and the PHRR by 70%. it becomes obvious that it is necessary to develop novel synergistic flame retardant systems with high efficiency and acceptable environmental impact. a highly combustible polymer. In fact. indicating a more uniform flammability behavior. like the virgin polymer. The authors mixed PMMA. Therefore. while Table 39 Cone calorimeter data (35 kW/m2 ) for PP nanocomposites [247]. can be successfully prepared by combining organoclays with halogenated FRs. For example. Moreover. which can pass the stringent UL 94 V0 standard. described in the previous paragraph.S. Si et al. Pavlidou. which is discussed in the following paragraph. Since a portion of the FR is replaced by the nanocomposite in a less than 1:1 replacement ratio. even though these materials can be considered to be flame retarded by definition. could further extend the uses of nanocomposites in this field [56]. 650 200 350 600 PHRR. products with improved fire performance and a better balance of properties can be obtained [239].% organoclay eliminated the secondary peak.D. the nanocomposite is eventually completely combusted [239. In fact. 6.244. The potential synergy between traditional flame retardants and nanocomposites.5. [246] demonstrated that self-extinguishing PMMA-based nanocomposites.246]. Synergism between nanocomposites and flame retardants From the point of view of fire retardancy.% Sb2 O3 + 5 wt. polymer nanocomposites work in a synergistic manner with other FRs.% DBE + 5 wt. the TTI is usually lowered while the THR remains the same. This means that the nanocomposite ignites faster than the virgin polymer and that. It is worth noticing that while the reference system (PP-MA + DBE + AO) showed two peaks in HRR (one at 90 s followed by a second larger one at 170 s). 68.% DBE + 5 wt. Both neat PMMA and the control flame retarded material failed the UL 94 V0 standard. it is believed that the excess quaternary ammonium surfactants used to disperse the clays. Despite the existing regulatory concerns in the area of halogenated FRs. a major limitation of nanocomposites is that they only work in the condensed phase and do nothing to inhibit the flame in the gas phase [246].

Tang et al. The results showed that the PHRR and THR were decreased by the PA6 nanocomposite. to produce a truly non-halogenated flame retardant formulation. however. this novel method of nanocomposite formation should be investigated further. Peiffer. NH3 is the main gaseous product. the sodium bromide produced by the ion-exchange reaction remained in the nanocomposite. The cone calorimeter data. The reduction in PHRR is due to nanocomposite formation and not to the presence of bromine. More specifically. [248]. the average HRR and . In fact. Zaitsev. which explains why the synergistic effect was no longer demonstrated at high MMT loadings. while the mechanical performance was significantly improved [249]. Optical images of the samples are shown in Fig. Zheng and Wilkie [250] investigated the synergistic action of phosphates and nanocomposites by incorporating the phosphate in the organic treatment of the clay. Na-MMT and hexadecyltrimethylammonium bromide to yield a nanocomposite.D. Chigwada et al. even at less than 4%. on the other hand. 69. In any case. nanocomposites were obtained exhibiting reduced PHRR. clay. can be achieved by the incorporation of a small amount of bromine chemically attached to the clay cation. organically modified clays. the authors combined the nanocomposites obtained with an intumescent system consisting of pentaerythritol and ammonium polyphosphate. [183] also observed that when MMT and intumescent FRs are combined in a polymer matrix. styrene and dibromostyrene. C. Then. Another important group of FRs which exhibit synergism with nanocomposites are the phosphorous-based FRs. Another interesting study was carried out by Tang et al. the sample where both FR and clay were added selfextinguished in 1 s after the application of the flame without dripping. Pavlidou. More specifically. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Fig. leading to a negative effect on the fire retarding properties. when phosphorous-containing FRs were incorporated in vinylester nanocomposite. THR and improved thermal stability. THR and MLR. Then they prepared intercalated nanocomposites by bulk polymerization. For example. especially if the NaBr can be removed. their synergistic effect is related to their composition ratio. while maintaining the reduction in PHRR.1184 S.. it remains unclear whether the improved flammability properties reported are due to the nanocomposite or to NaBr. [244] conducted a study aiming to explore if any improvements in the TTI and THR. In another study dealing with the synergism of nanocomposites and intumescent systems. They treated Na-MMT with a styrenic oligomer that contained ammonium pendant groups and copolymerized vinylphenyl phosphate. with the bromine-containing organoclay. which. Sokolov and Rafailovich by permission of Elsevier Science Ltd. as Morgan [239] noted in his review on nanocomposite–FR synergism. prevents the PS burning. they melt compounded PP. Chigwada et al. Optical images of PMMA composites after the combustion of UL 94 V0 test: (a) PMMA/DB/AO (75/20/5) and (b) PMMA/DB/AO/Cloisite 20A (70/20/5/5) [246]. Even though synergism was observed between the nanocomposites and the intumescent FRs. a PA6 nanocomposite was compounded with EVA and ammonium polyphosphate (acid source). and acts in the gas phase as an FR. 69. Therefore. either by melt intercalation or intercalation from solution. showed that in the presence of the phosphate. It was also noticed that the samples with all three components. The authors reported that these reductions were directly proportional to the amount of phosphate added. DBE and AO show a lower PHRR and average MLR than those with only clay or the FRs. Frenkel. the negative effect may exceed the positive effect on the fire retarding property. Weil. UK. where it can be seen that the PMMA sample containing both FR and clay is blackened by the smoke of the flame. They did clay modification and intercalation simultaneously during melt mixing. with melamine phosphate sometimes added. leading to the formation of the intumescent residue char. when the mass of MMT is increased. is important in the reduction of the THR. More specifically. Goldman. it volatilizes and makes the mixture of the carbonaceous residue and phosphocarbonaceous materials swell. i. the presence of bromine. [245] observed reduction in the PHRR.e. Therefore. the interpretation of the data is complicated by the presence of NaBr. TGA/FTIR showed that the phosphate is released during thermal decomposition. suggesting that clay modification occurred in the molten polymer matrix. the polyol (carbonization agent) was replaced by PA6. They found that the dibromostyrene enhances the flame retardancy of PS nanocomposites as compared with both the virgin polymer and nanocomposites prepared from non-halogen containing. which acts as a vapor phase FR. The authors first prepared an organically modified clay using ammonium salts with added oligomeric material consisting of vinylbenzyl chloride. It was anticipated that the reassembling of silicate layers on the surface of the nanocomposite during combustion may hinder NH3 from swelling. but remains unchanged in shape. Reproduced from Si. Subsequently. PS nanocomposites were prepared.

Second.D. [252] introduced organophosphinate into the backbone of an epoxy resin. the study of rheological properties is instructive for two reasons: First. and then HDT values level off for higher clay loadings [94. due to their anisotropy [55]. not only from application or industrial point of view. It is generally established that when nanocomposites are formed.50]. On the other hand. Organically modified MMT (wt. after which the HDT of the nanocomposites levels off. these properties are indicative of melt processing behavior in unit operations. In general. solid-like behavior is observed. Pavlidou. and they reported the clay content dependence of HDT of PA6/MMT nanocomposites. No clear reason was given in this study. Thus. the same neat PP polymer is filled with alkylammonium modified MMT. The clay obtained was subsequently melt mixed with ABS yielding nanocomposite structures.%.55]. they showed that there is a marked increase in HDT from 65 ◦ C for neat PA6 to 152 ◦ C for 4.%) HDT PP-f-MMT 0 3 6 9 a b PP/alkyl-MMT 109 130a 141b 109 144 152 153 C18-MMT filler. such as injection molding. Kim et al. C.253]. from 109 ◦ C for the neat polymer to 152 ◦ C for a 6 wt. but also because it is very difficult to achieve similar HDT enhancements by chemical modification or reinforcement by conventional fillers [31. Such observations support the percolation argument used in the case of nanocomposite rheological behavior under low shear [55]. at high shear rates. allowing for a grater range of melt processing without TPP loss. rheology can be envisaged as a tool that is complementary to traditional methods of materials characterization [15. Morgan [239] indicated that the observed antagonism could have been due to the lack of uniform clay dispersion. shear thinning behavior is usually observed [15]. this behavior is similar to that of neat PA6 and the composites with the same amount of glass fiber or unmodified MMT.S. improvements of HDT are reported by nanocomposite formation. the viscosity at low shear rates increases with filler concentration [15]. Shear thinning behavior at high shear rates has also been observed for a PA6 nanocomposite. as compared with the epoxy + FR control sample. at surprisingly low volume fraction. In the case of polymer–layered silicate nanocomposites. In the case of PP/f-MMT there is a marked increase of the HDT. It has been suggested that this is the result of the alignment of silicate layers towards the direction of flow at high shear rates.7 wt. 40 s. 6. Beyond that MMT loading. Similarly. reflecting the lower exfoliation level of the inorganic fillers [254].50.208.55]. and even opens the possibility of formulating self-extinguishing polymerbased materials. As Morgan [239] noticed. 70 for PBS-based nanocomposites with various clay loadings. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1185 PHRR can be significantly reduced while the time to PHRR is increased up to ca.% nanocomposite. the synergism reported between clays and conventional FRs provides an alternative for improving fire performance without seriously deteriorating appearance and mechanical behavior. Quite similarly. directly in the melt state. since nanocomposites inhibit polymer flow and dripping during flaming combustion.37. nanodispersion of MMT in a PP matrix has been found to promote a higher HDT (Table 40). a significant increase is achieved for clay contents of approximately 5 wt.% of clay. It should be emphasized that the increase of HDT due to clay dispersion is very important. The key advantage of intercalating the phosphate in the organoclay is that the normally volatile TPP is protected during melt compounding. On the other hand. Kojima et al. [251] intercalated triphenylphosphate (TPP) in the galleries of an organo-modified montmorillonite (Cloisite 30B). twin head mixer. Hussain et al. Another example where flame retardant antagonism may be observed is the case of FR systems that achieve flame retardancy by dripping away from the flame. Very often. extruder processed. For example. it is an index of a polymeric material’s heat resistance towards applied load and is assessed by the procedure given in ASTM D-648 [55]. Quite surprisingly. 2C18-MMT filler. Heat distortion temperature Heat distortion temperature or heat deflection temperature (HDT) is the temperature at which a polymer sample deforms under a specified load. [94] showed that the HDT of pure PA6 increases up to 90 ◦ C after nanocomposite preparation with OMLS. It is of great interest to note that the absolute value of the melt viscos- . particle size. Rheological properties The measurement of the rheological properties of any polymeric material is crucial to gain fundamental understanding of the processibility of that material and is usually conducted by either dynamic oscillatory shear or steady shear measurements [50. the HDT of the nanocomposites levels off. When Table 40 HDT of PP/MMT nanocomposites and the respective unfilled PP. which is attributed to the physical jamming or percolation of the randomly distributed silicate layers. In general. More specifically. shape and surface characteristics of the dispersed phase. Usually.7. Typical shear viscosity curves as a function of shear are presented in Fig. rheology potentially offers a means to assess the state of dispersion in nanocomposites. In fact. such FRs will not work with a polymer nanocomposite system. since the rheological properties of particle-filled materials are sensitive to the structure. the HDT is also increased but to a smaller extent. 6. which was subsequently crosslinked in the presence of o-MMT. flame retardant antagonism was observed with the PHRR and THR increasing for the nanocomposite + FR system. the HDT values of various PA6 nanocomposites prepared with clay lamellae of different lengths showed that the HDT also depends on the aspect ratio of dispersed clay particles. but in a later review article.6. however. Thus. Moreover.

as shown in Fig. hindering the segmental rearrangement during crystallization and restricting the formation of perfect crystals in the polymer matrix. although it is well established that nanometer sized clay platelets are effective nucleating agents. they observed that the cold crystallizing point of pure PET is 150 ◦ C. Similarly. 71. Reproduced from Ray and Okamoto by permission of Elsevier Science Ltd. . They observed the same crystalline structure (orthorhombic) and similar melting behavior. Iannace.D. Di Maio et al. while for the nanocomposite it decreases to 130 ◦ C. UK. since it is known that in ethylene-based copolymers side chains (short branches) larger than the methyl group are excluded from the crystalline domain and are aggregated into the amorphous phase. remarkably reducing the crystallization halftime t1/2 . However. indicating a reduced degree of crystals perfection and degree of crystallinity. [171] found that the crystallization process for EVA-28 is significantly affected by the presence of clays. the linear growth rate and the overall crystallization rate are not significantly influenced by the presence of clay. Chaudhary et al.. Maiti et al. 72. One possible reason for reduction of melt viscosity in the nanocomposite is slip between the PA6 matrix and the exfoliated organoclay platelets during high shear flow. 0* is the DSC thermogram of non-isothermal crystallized (−10 ◦ C/min) pure PCL [255]. ity of the nanocomposite is significantly lower than that of neat nylon 6 or the other composites—which implies good melt processibility over a wide range of processing conditions. They found a reduction of Tg in the composite compared to the pure matrix.8. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Fig. Shear viscosity as a function of shear rates [55]. 71). while Gelfer et al.g. contradictory results have been reported. C. hydrolysis) in the presence of clay [15]. Sorrentini and Nicolais by permission of Elsevier Science Ltd. 72. MMT.. Pavlidou. Crystallinity Crystal formation includes two stages. 70. Ke and Yongping [222] conducted DSC analysis on intercalated PET/o-MMT nanocomposites. Consequently.. For example. Another possibility is a reduced molecular weight of the nylon 6 due to degradation (e. By DSC analysis after isothermal crystallization (Fig. This result shows that adding o-MMT into PET is favorable to its crystallization. However. the authors observed a reduction of the melting temperature with the increase of clay content. capillary data revealed that nanocomposites based on medium and low molecular weight PA6 exhibited lower viscosities than the corresponding pure polymers [14]. as well as transition temperatures in pure EVA-3 and nanocomposites containing 10 wt. Gelfer et al. 6. different effects have been reported on the linear growth rate and the overall crystallization rate. The relationship between o-MMT content and Tg of composite [222]. Fig. For the effect of nanocomposite preparation on EVA crystallinity.% clay. Further. depending on the type of polymer [97]. Similarly. which they attributed to the plasticizing effect of o- Fig. This was attributed to the confinement of chains and segments in the presence of clay. namely nucleation and crystal growth. For example. considered this to be an anticipated result. [175] found that although clay particles act as nucleating agents for the crystallization of a PP-MA matrix. UK. [256] argued that the effect of clay on the crystalline phase in EVA-3 is insignificant. DSC thermograms of PCL and of selected PCL/clay nanocomposites after isothermal crystallization at 45 ◦ C. Reproduced from Ke and Yongping by permission of Elsevier Science Ltd.1186 S. UK. Reproduced from Di Maio. [255] studied the isothermal crystallization of PCL/clay nanocomposites and noticed that the dispersed clay platelets act as nucleating agents in the PCL matrix. they noticed that by increasing the o-MMT content the Tg is increased. Number refers to clay weight concentration.

while they are parallel to the Fig. 74.7 crystallized at (a) 170 and 210 ◦ C. PA6 crystallizes faster and exclusively in the -phase (Fig. the effect of layered silicates on polyamide crystallinity has been far more investigated. Similarly. which may also be the root of some of the property enhancements. a number of researchers have focused on the effect of clay addition on the crystal morphology of polyamides. Moreover. Germany. In semi-crystalline PA6. Lincoln et al. but also of spherulites. Maiti and Okamoto [257] found that in the presence of clay particles.S. The nucleation and growth processes of PA6 in the nanocomposites are presented in Fig. Reproduced from Maiti and Okamoto by permission of Wiley-VCH. 74. In general. Reproduced from Maiti and Okamoto by permission of Wiley-VCH. as deduced from direct observation by TEM. it has been observed that upon preparation of nanocomposites the crystallography of the PA6 matrix changes. It was hypothesized that the organoclay particles dispersed in the EVA matrix have higher affinity with the polar VA units. They noted that the more ductile -phase that is formed may contribute greatly to the observed changes in properties of the material. specifically the toughness. ultimately resulting in the predominance of the -phase in quenched samples. The enlarged part shown (a) is form the indicated lamella in the original image. . Fig. hence they are predominantly confined to the amorphous phase where the VA content is high. Schematic view of the nucleation and growth mechanism in nylon-6 nanocomposite [257]. crystallization temperature and crystallization rate.D. The black strip inside the white part is clay. (b) Shows the typical shish-kebab type of structure [257]. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1187 the amorphous domains in EVA are enriched by the polar VA units. Typical TEM images of PA6CN3. Germany. X-ray diffraction of PA/MMT nanocomposites has indicated that the chain axes are normal to the silicate layers in the interior of an injection molded component. two phases generally exist at room temperature. The phase and the -phase are monoclinic. While further work needs to be done to elucidate crystallization phenomena in nanocomposites based on different polymers. 73. [12] showed through simultaneous SAXS and WAXS analyses at elevated temperature that the presence of silicate layers provides a confined environment for crystallization and disrupts crystallite formation. In fact. Evidence has also been found that the layers affect not only the formation of the lamellae. certain processes involved in nanocomposite preparation affect the global orientation of the crystal phase. C. without significantly affecting the crystalline domain formed by the non-polar ethylene segments. as well as on the melting. glass transition. Pavlidou. 73). That is. but the latter can be represented as a pseudo-orthotropic lattice.

On the other hand.1188 S. C. DSC measurements conducted by other researchers. [259] prepared nanocomposites based on aliphatic unsaturated polyester and found a decrease in biodegradability under composting with intercalation. after 1 month. Ray et al. Tetto et al. the biodegradability of neat PLA is significantly enhanced after nanocomposite preparation. ester cleavage and formation of oligomer fragments. [195] attributed the suppressed biodegradation tendency. which they observed in the case of PHB nanocomposites. it is completely degraded by compost. Maiti et al. causing a higher crystallization rate than that of the neat PA6 [15]. Similarly. 76(a)). Zhou. Lee et al. any factor that increases the hydrolysis tendency of neat PLA. The melting peak of the composites is at a slightly lower temperature than that of neat PA6. and due to this type of hydrolysis the matrix degrades into very small fragments and is eliminated with the compost. even though Fig. 76(b) it is evident that the hydrolysis tendencies of PLA and PLACN4 are almost the same. thus resulting in decreased crystallinity.5 However. in that case the degradation tendency was almost the same as that of PLA. The heat of crystallization of the nanocomposite is less than that of the PA1012. Finally. As an example. Therefore. ultimately controls the degradation. the stacked and intercalated silicate layers are homogeneously dispersed in the PLA matrix. according to these authors. In PLACN4. implying that the clay platelets decrease the polymer crystallinity. and these hydroxy groups initiate heterogeneous hydrolysis of the PLA matrix after absorbing water from the compost. The heat flow vs. Varlot et al. The crystallization exothermic peak of the PA1012/clay nanocomposites is narrower than that of PA1012. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 6. the time during isothermal crystallization of nylon 1012 (spectrum a) and nylon 1012/clay nanocomposite (spectrum b) by DSC [97]. For a month. They assumed that due to the high aspect ratio and better dispersion of clay in the matrix a more tortuous path formed for penetration of microorganisms into the bulk and hindered their diffusion. Ray et al. and finally diffusion of soluble oligomers. All the fillers cause an increase in crystallization temperature relative to neat PA6. 76(b). this was attributed to an increase in the amorphous volume fraction due to the surface/volume ratio of the crystallites. Inc. often reported after nanocomposite formation. Obviously. The higher crystallization rate recorded for PA1012 nanocomposites was attributed to the nucleating action of clay platelets. Concerning the glass transition. [5] suggested that the overall crystallinity of the polyamide matrix remained unchanged with the addition of montmorillonite. [258] first presented results on the biodegradability of nanocomposites based on PCL. The same phenomena have also been observed in PA66 based nanocomposites [146]. The decreased Mw and residual weight Rw percentage of the initial test samples with time is also shown in Fig. The degradation of PLA in compost is a complex process involving: water absorption. which occurs at approximately 53 ◦ C.9. suggest that the presence of terminal hydroxylated edge groups of the silicate layers may be one of the factors responsible for this behavior. from Fig. layers in the near surface region of molded and extruded components. 75. indicating that the nanocomposites have a higher crystallization rate. the number of nuclei and the perfection of the crystal lamellae [139]. This process takes some time to start. both the extent of Mw loss and weight loss are almost the same for neat PLA and PLACN4. Biodegradability improvements have also been reported in the case of PLA-based nanocomposites. Biodegradation An interesting aspect of nanocomposite technology is the enhancement in biodegradability. the authors suggested that the confinement of the chains and segment movement will hinder segmental rearrangement during crystallization and restrict the formation of perfect crystals in the PA1012/clay nanocomposite. However. Wu et al. [97] reported DSC curves for isothermal crystallization of PA1012 and PA1012/clay nanocomposites (Fig. Pavlidou. . However. solubilization of oligomer fragments. fillers may act as nucleating agents. However. To various degrees. indicate that the presence of layered silicate filler does not affect the Tg of the PA6 matrix. This assumption was confirmed by conducting the same type of experiment with PLACN prepared by using dimethyl dioctadecylammonium salt modified synthetic mica which has no terminal hydroxylated edge group. after 1 month there is a sharp weight loss in the case of PLACN4 as compared with that of PLA. reporting that the PCL/OMLS nanocomposites showed improved biodegradability compared with pure PCL. a sharp change occurs in weight loss of PLACN4. However. Qi and Zhang by permission of John Wiley & Sons. 75). the weight loss and degree of hydrolysis of PLA and PLACN4 is almost same up to 1 month (Fig. This means that 1 month is a critical time to start heterogeneous hydrolysis. [208] presented photographs of the recovered samples of neat PLA and PLACN4 from compost with time (Fig. due to a slight reduction of crystallite size in the presence of fillers. contradictory results concerning the effect of clay dispersion on polymer biodegradability are also found in the literature. even though the proportion of the -phase was higher. 76(b)). a decrease in Tg has been found for PA6/clay nanocomposites. For this reason. In fact. to an improvement of the barrier properties of the matrix after nanocomposite formation.D. and within 2 months. Reproduced from Wu.

Photo-degradation The degradability of nanocomposites under UV light is a serious problem that may limit their applications. who found no relation between biodegradability and barrier properties in PLA/OMLS nanocomposites. it has been found that nanocomposites exhibit lower stability than the corresponding neat polymers [231]. on the other hand. Obviously. Reproduced from Ray. they did not report on the permeability. As is shown in Fig. Since it is well established that the degradation of hydrocarbon chains leads to the formation of hydroxyl and keto groups. the intensity in the carbonyl region was significantly less. It was observed that the induction period decreased from 8 to 4 h by using PP-g-MA as compatibilizer and a two-phase degradation mechanism was observed.10. This explanation contradicts the results of Ray et al. Mw of PLA and PLACN4 under compost [208]. [261] studied the photooxidative degradation of PE/MMT nanocomposites compared with neat polyethylene. 78 shows FTIR spectra in the carbonyl region upon UV irradiation. which means that the material is undergoing degradation. Yamada.S. 77. whereas in the second stage a dramatic increase in the rate . Morlat [262] and Mailhot et al. [260]. Pavlidou. For example. which implies the absence of degradation on polymer backbone.D. C. Rw and of matrix. Okamoto and Ueda by permission of Elsevier Science Ltd. Huaili et al. From the aforementioned contradictory results. The increase in the absorbance at 3200–3600 and 1600–1800 cm−1 was rapid in nanocomposites in comparison with neat polymer. In the first stage (up to 40 h) there was no evidence for hydroxyl band formation in the IR spectra. (a) Real pictures of biodegradability of neat PLA and PLACN4 recovered from compost with time. 6. UK. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 1189 Fig. In the few studies addressing this issue. Initial shape of the crystallized samples was 3 cm × 10 cm × 0. (b) Time dependence of residual weight. [263] studied the effect of compatibilizers on photo-degradation and its kinetics by comparing PP nanocomposites with neat polymer. Fig. there is a considerable increase in the intensity of the carbonyl region with an increase of irradiation time in PE/o-MMT.. which indicates less degradation.1 cm. they studied the extent of photo-degradation by FTIR observations. it becomes obvious that the increase or the decrease in nanocomposite biodegradation is still under discussion and no conclusion can be driven about mechanisms on the basis of the current literature [231]. 76. the degradation of PE/o-MMT nanocomposite was greater than that of pure PE polymer after 200 h irradiation. In the pure PE.

Moreover.1190 S. (a) FTIR spectra of PE/o-MMT nanocomposites before and after 200 h irradiation. the incorporation of layered silicates in polycarbonate appeared to increase the rate at which chain scission occurs. although no explanation has so far been given for the differences in photo-degradation stability between the nanocomposites and the pure polymers. such as strength.D.5 wt. Shimin. polymer–layered silicate nanocomposites are far lighter in weight than a conventional composite. [264]. when single layers are dispersed in a polymer matrix. The degradation products were the same in the composite and the neat polymer. Furthermore. 77.%. On the other hand. thermal and oxidative stability. The materials were characterized by UV/vis spectroscopy and FTIR spectroscopy and it was concluded that the degradation of the nanocomposite was less than that of the neat polymer [265].11. it has been suggested that the best way to increase the outdoor durability would be to develop nanocomposites by modification of the clay rather than functionalization of thermoplastics [231]. There is no marked decrease in the clarity due to the nanodispersed fillers (e. A UV-accelerated weathering tester programmed to cycle for 8 h of UV radiation and 4 h of dark condensation was selected for the exposure study. Nanocomposites: advantages and applications As described above.. polymer nanocomposite materials often exhibit properties superior to conventional composites. stiffness. the organoclay can be incorporated in the final Fig. In any case. Reproduced from Huaili. Chungui. 6. The silicate content used ranged from 0 to 3. layered silicate platelets. as well as flame retardant behavior [267]. Pavlidou. PP. Guangming and Mingshu by permission of Elsevier Science Ltd.g.. 7. Optical clarity Microsized particles used as reinforcing agents scatter light. FTIR spectra of PE/nanocomposite at carbonyl region during photo-degradation [261]. of photo-oxidation was found. Thus. However. According to Patterson et al.% of C18MMT in 3 mm thick film of PP before there develops haze observable by the eye). albeit their micron lateral size. thus reducing light transmittance and optical clarity [266]. 78. This is a general behavior in UV/vis transmittance for thick films (3–5 mm) of polymer/MMT nanocomposites based on PVA. in another study. the effect of accelerated weathering of polycarbonate nanocomposites was investigated. Chungui. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Fig. are just 1 nm thick. the resulting nanocomposite is optically clear in the visible region. Shimin. which makes them quite competitive for specific applications [55]. one has to load 20 wt. C. barrier properties. for systems with favorable thermodynamics of mixing. Guangming and Mingshu by permission of Elsevier Science Ltd. there is a loss of intensity in the UV region (for < 250 nm) mostly due to scattering by the MMT particles. These improved properties are generally attained at lower filler content in comparison with conventionally filled systems. and several epoxies [31]. which could inhibit its use in applications where optical clarity is important. these carbonate scissions produced a yellowing of the polycarbonate. UK. . (b) FTIR spectra of pure PE before and after 200 h UV irradiation [261]. Reproduced from Huaili. whereas. UK. Therefore.

bumpers.. extrusion. interior and exterior panels). It also saved weight by up to 25% [270]. polymer nanocomposite technology provides a route around these traditional limitations. yellow.268]. red. less brittle. This timing-belt cover exhibited good rigidity. Later. Thus. thermal and barrier properties Additive. Traditionally. construction (building sections and structural panels). heavy metal free coloring Transparent packaging materials. barrier film Step-assist for GMC Safari and chevrolet Astro vans. The aforementioned attractive characteristics of polymer–layered silicate nanocomposites already suggest a variety of possible industrial applications: automoTable 42 Selected commercial polymer nanocomposites. barrier properties and flame retardancy of thermoplastics Nylon. transparency and recycling Improved temperature resistance and stiffness.. General Motors. thermal stability and flame resistance Nanopigments. Blackhawk Automotive Plastics. green.g. blend or composite formulations require trade-offs between desired performance. flame retardancy and barrier properties of thermosets and thermoplastics Thermoplastics and thermosets Electric and electronic.. Honeywell Polymer. excellent thermal stability and no wrap. Clariant Corporation. Product Nylon nanocomposites Characteristics Improved modulus. Ube. and offers. timing-belt cover.D. General Motors and partners Basell. excellent transparency and improved barrier properties Sud-Chemie TNO TNO TNO stages of polymer processing (e. tubing. enhance mechanical barrier properties. for the first time. reduced oxygen transmission rate. barrier properties tive (gas tanks. improved clarity Improved stiffness. ethylene vinyl acetate Additives to enhance mechanical. cost and processibility. unsaturated polyester. Southern Clay Products and Blackhawk Automotive Plastics announced external automotive body parts (step-assist) made from thermoplastic. stronger. high UV-stability Additive. appliance Honeywell Polymer Honeywell Polymer Foster Corporation Noble Polymer . aerospace (flame retardant panels and high performance components). Gitto Global Corporation. the first commercial product of clay-based polymer nanocomposites was the timing-belt cover made from PA6 nanocomposites by Toyota Motors in the early 1990s. flexible devices Automotive. A TPO nanocomposite with as little as 2. epoxy. However. fire retardancy.g. adhesive.g. containers Barrier films. injection or compression molding) to obtain nanocomposite materials. e. food. very good impact properties Basell. mechanical properties. Southern Clay Products Mitsubishi Gas Chemical Company Bayer Medium barrier bottles and films High barrier beer bottles Catheter shafts and balloons. electronics). strength. cosmetics. barrier fuel line). blue. improved barrier properties Doubling of stiffness. heavy-duty electrical enclosure Juice or beer bottles. film and barriers. building and construction materials Decorative coloring. RTP Company Elementis Specialties Bentone With a broad range of polarity Nanofil Planomers PlanoColors PlanoCoatings Improve the mechanical. Toyota Motors. medical and health care.g. styrene-ethylene butylene-styrene. polymer nanocomposites are amenable to most of the common processing techniques in today’s industrial practice—which will lower the barriers to their commercialization [31]. It is for this reason that many companies have taken a strong interest and have invested in developing nanoclays (Table 41) and polymer nanocomposites (Table 42) [270]. etc. protective coatings. Another unique aspect of nanocomposites is the lack of property trade-offs. engineering resins Thermoplastic olefin and urethane. food packaging. Among these. medical. high gloss and clarity.S. the opportunity to design materials without the compromises typically found in conventionally filled polymers [267. paper coating Producer Bayer. UV-stable coloring. transparent barrier coatings Producer Southern Clay Products 1191 Nanomers Masterbatches Microfine powder Pellet Nanocor PolyOne Corporation. textiles.5% layered silicate is as stiff and much lighter than parts with 10 times Applications Automotive parts (e. heat distort temperature. packaging (e. multi-layer films. improved flame retardancy High barrier properties Doubling of stiffness. olefin layered silicate nanocomposites. higher heat distort temperature. Product Cloisite Characteristics Organophilic Applications Additives to enhance flexural and tensile modulus. furniture. [269]. permeability. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 Table 41 Selected commercial nanoclays. more easily recycled. C. Unitika Polyolefin nanocomposites M9TM Durethan KU2-2601 (nylon 6) AegisTM NC (nylon 6/barrier nylon) AegisTM OX SETTM nanocomposite nylon 12 ForteTM nanocomposite Stiffer. RTP Company. Pavlidou. engine cover. improved clarity Highly reduced oxygen transmission rate. lighter.

the weight savings can reach 20%. a long term goal for Dow Plastics is in-reactor compounding of nano-PP by using nano-clays as the catalyst support for in-situ polymerization of PP homopolymer.. Basell’s Global Business Vice President for Advanced Polyolefins. Bayer has developed a new grade of plastic films for food packaging. polymer nanocomposites are expected to find wide applications as barrier materials. A Bayer coating containing nanoparticles is one of several promising approaches being pursued [271]. depending on the part and the material that is being replaced by the TPO nanocomposite [268]. Ube America is developing nanocomposite barriers for automotive fuel systems. considered for the exterior coating needed to achieve weatherability and abrasion resistance without reducing clarity. Next to the automotive industry. It is predicted that widespread use of polymer nanocomposites would save 1. Therefore. In fact. William Windscheif.5-week beer shelf-life. the optical transparency of polymer nanocomposite film is generally similar to their pristine counterparts. Layered silicate nanoparticles. . replacement of metals and engineering thermoplastics will follow. a role for nanocomposites in polycarbonate automotive glazing is being explored by Exatec of Wixon. which are made from PA6 exfoliated nanocomposites [270]. can retard the diffusion of environmental moisture and other chemicals to the fiber–matrix interface where their presence can result in delamination and fiber weakening. with nano-PP mostly cannibilizing existing PP applications. which is impossible with conventional polymer composites. Pavlidou. despite their attractive degradation characteristics and significant demand for such materials. but a giant one for nanocomposites” and added that it heralds a broader shift to nano-PP in automotive technology [271]. using up to 5% nanoclay in PA6 and PA6/66 blends [271].. head of STA Research in Sndiomish. Meanwhile. Imperm reportedly ensured a 28. However. that is dedicated to PC auto-glazing development. the use of nanoparticles helps to preserve the integrity of FRPs and to prolong the service life of composites when these are used Fig. a joint venture of Bayer and GE Plastics. Such polymers have become indispensable in a wide range of applications. Imperm is said to adhere to PET without tie layers. estimated that in the near future the application of PP-based nanocomposites in the automotive industry will expand. Also quite interesting are potential applications of nanocomposites based on biodegradable polymers. the above property advantages would make them widely acceptable in packaging industries as wrapping films and beverage containers.5 billion liters of gasoline over the life of 1 year’s production of vehicles and reduce related CO2 emissions by more than 5 billion kilograms [270]. Wash. It is worth noticing that the weight advantage of polymer nanocomposites could have a significant impact on environmental protection and material recycling. when distributed within the matrix of a fiber-reinforced polymer (FRP). 79. Dow’s effort is focused on highly loaded (up to 10% clay) nano-PPs for semi-structural automotive uses [271]. the lack of structural and functional stability prevents currently available biodegradable polymers from having widespread commercial impact [267]. For example. biodegradable polymer-based nanocomposites appear to have a very bright future for a wide range of applications as high-performance biodegradable materials [55]. Papaspyrides / Progress in Polymer Science 33 (2008) 1119–1198 the amount of conventional talc filler. Meanwhile.1192 S. Meanwhile. Therefore. Possible growth paths for nanocomposites applications. Nanocor’s Imperm compound supplements the inherent gas barrier of amorphous MDX6 nylon from Mitsubishi Gas Chemical with the addition of nanoclay. while sufficient clarity is retained to meet requirements for the amber bottle [271]. Used as the core of a three-layer PET bottle. However. Thus. Mich. Honeywell is also developing nano-PA materials that can beat the cost of high-barrier plastics or even glass.D. called this application “a small step. In this context. Thus. Consultant Kenneth Sinclair. C. the excellent barrier properties of clay-based polymer nanocomposites could result in considerable enhancement of shelf-life for many types of packaged food.

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