Polymer-Plastics Technology and Engineering

ISSN: 0360-2559 (Print) 1525-6111 (Online) Journal homepage: http://www.tandfonline.com/loi/lpte20

Overview on Polystyrene/Nanoclay Composite:

Physical Properties and Application

Safia Haider, Ayesha Kausar & Bakhtiar Muhammad

To cite this article: Safia Haider, Ayesha Kausar & Bakhtiar Muhammad (2017) Overview
on Polystyrene/Nanoclay Composite: Physical Properties and Application, Polymer-Plastics
Technology and Engineering, 56:9, 917-931, DOI: 10.1080/03602559.2016.1233563

To link to this article: https://doi.org/10.1080/03602559.2016.1233563

Accepted author version posted online: 20

Oct 2016.
Published online: 20 Oct 2016.

Submit your article to this journal

Article views: 212

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=lpte20
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING
2017, VOL. 56, NO. 9, 917–931
http://dx.doi.org/10.1080/03602559.2016.1233563

Overview on Polystyrene/Nanoclay Composite: Physical Properties and

Application
Safia Haidera, Ayesha Kausara, and Bakhtiar Muhammadb
a
Nanosciences Division, National Center for Physics, Quaid-i-Azam University Campus, Islamabad, Pakistan; bDepartment of Chemistry,
Hazara University, Mansehra, Pakistan

ABSTRACT KEYWORDS
This article reviews the research and progress on polystyrene and nanoclay-based nanocomposite. Fuel cell; kaolinite;
Polystyrene is one of the most extensively used commercial polymers in the world. This review is montmorillonite;
designed to be an expansive source for polystyrene–clay nanocomposite research, including nonflammability;
polystyrene
synthesis, characterization, structure/property relationship, manufacturing techniques, and
applications considering thermal, mechanical, barrier, electrical conductivity, non-flammability,
and biodegradability. The frequently used clays with polystyrene are montmorillonite, bentonite,
hectorite, and kaolinite. The polystyrene–clay nanocomposite has several interesting commercial
significances in packaging, automotive, fuel cell, construction, and electrical materials. Finally, future
challenges toward the technical applications of these advance materials have been discussed.

GRAPHICAL ABSTRACT

Introduction Usually one property is gained at the cost of other. Sim-

ultaneous improvement in mechanical and flammability
Polymer nanocomposite is of great interest due to
properties has major impact on the materials’ demand
enhancement in significant material properties relative
in industry[1]. Inorganic fillers were initially incorpor-
to virgin polymer or conventional composite materials.
ated into polymers to produce cheaper materials. The
A nanocomposite is two-phase material in which one
use of such fillers may result in enhancements in
phase is dispersed and the second phase is in nanometer
stiffness, barrier properties, chemical resistance, and
scale. It is rare that a technology can improve both
thermal stability. Such changes in properties depend
mechanical properties and flammability of a polymer.

CONTACT Ayesha Kausar asheesgreat@yahoo.com Nanosciences Division, National Center for Physics, Quaid-i-Azam University, 44000, Islamabad,
Pakistan.
Color versions of one or more of the figures in this article can be found online at www.tandfonline.com/lpte.
© 2017 Taylor & Francis
918 S. HAIDER ET AL.
on nature and properties of the filler and also shape and
size of the filler particles, and interaction between parti-
cles and polymer matrix[2]. Clays are the most abundant,
natural, and inexpensive class of filler materials. They are
extracted as coarse particles made up of tactoids (layered
structure), which can be exfoliated giving high aspect
ratio particles. Polystyrene (PS) is among the most exten-
sively used polymers. The degree of clay dispersion in
polystyrene/clay nanocomposite has been governed by
type of clay, surfactant used in clay modification, and
the synthesis method. The commonly used clays are
montmorillonite (MMT), hectorite, and saponite[3]. The
clay dispersion in a polymer matrix can give three types
of composite materials, i.e., (i) conventional microcom-
posite (no exfoliation); (ii) intercalated polymer/clay
nanocomposites; and (iii) exfoliated polymer/clay
nanocomposite[4]. The terms intercalated and exfoliated
layered silicate nanocomposites are often used to
describe two extremes of silicate layer organization in
composite structure. Intercalation means the insertion
(intercalation) of one or several polymer chains in
galleries of original tactoids, which may lead to some
longitudinal expansion of galleries[5]. The regular layer
stacking arrangement is preserved in intercalation,
however exfoliation (delamination) implies complete
rupture of original layer stacking and uniform disper-
sion. Exfoliated nanocomposite generally has excep-
tional properties comparative to other composites[6].
Owing to nanometer-sized particle dispersion, nano-
composite exhibits markedly improved properties rela-
tive to pure polymers or conventional composites.
These nanocomposites possess improved strength and
modulus, increased solvent and heat resistance,
decreased gas permeability, and decreased flammability,
for example, a doubling of tensile modulus and strength
is obtained for polymer/layered silicate nanocomposite
with as little as 2 vol% of inorganic content. Besides,
the heat distortion temperature of nanocomposite
increases up to 100°C, extending their use to higher tem-
perature environments such as automotive under the
hood parts. In addition, heat release rate in nanocompo-
site reduces up to 63% at heat flux of 50 kW m 2 without
an increase in soot formed during combustion[7].
Polystyrene
Polystyrene (PS) is a resourceful polymer with the
features of good optical transparency, low price,
mechanical properties, and excellent electric
insulation[8]. PS is a commercialized and mass pro-
ductive polymer. Therefore, continuing research efforts
have been devoted to the development of polystyrene–
clay nanocomposite. Different methods based on simple
mechanical mixing, solution polymerization, bulk
polymerization, and emulsion polymerization have been
used. Among the approaches stated above, emulsion
polymerization is more attractive for ease of handling,
low cost, and environmental friendliness[9]. PS is a
highly commercialized thermoplastic material which is
used in a variety of applications including packaging,
construction, appliances, consumer electronics, medical,
and various other uses. In last two decades, one of the
rapidly growing areas for plastics is packaging industry.
This is due to ease, low price, safety, and good aesthetic
qualities of plastics[10]. Thermoplastics are replacing
metals in several applications. They may offer better
corrosion resistance, lightweight per item, lower cost,
and better flexibility in part design[11]. The enhance-
ment of thermal stability and flammability performance
of widely used thermoplastics is a major concern both in
academic world and in industries[12]. As a result, modi-
fication of polystyrene (one of the most commercialized
thermoplastics) by addition of flame retardants is
crucial. It has been shown that the nanoparticles, bromi-
nated flame retardants and Sb2O3, can be used as flame
retardant additives or fillers for polystyrenes[13]. PS also
exhibits some disadvantageous properties, i.e., relatively
high flammability. This is the reason why polystyrene
composites have been studied for properties
improvement[14]. Polystyrene is a synthetic hydrophobic
polymer that is not biodegradable. Thus, it may cause
environmental pollution[15]. There are different
alternatives for reducing the dispersion problems and
for converting it into valuable products including
polymer modification and functionalization[16]. The
insertion of polar groups into synthetic polymers
causes initiation of hydrophilicity[17]. Functionalized
polystyrene has different applications, for example, as
a polyelectrolyte for water treatment processes[18].
Clay
The rapid progress of chemistry in development of
nanoparticles has verified tremendous improvements
in this field[19]. The concept of using nanoparticles as
fillers in polymer materials was introduced due to their
exclusive mechanical, optical, electrical, and thermal
properties[20]. Variety of nanoparticles such as alumina,
micro and nanosized silicon carbide, calcium carbonate,
silica, zinc, and carbon black nanoparticles have been
used as fillers to improve the material properties for
polymer nanocomposite[21]. Clay is the most widely
studied material as filler in the production of polymer
nanocomposite. It is relatively much preferred for the
synthesis of polymer nanocomposite as it is economical,
easily available, and environment-friendly material.
 POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 919

There are two types of clays found in nature, i.e., Montmorillonite

expanding and nonexpanding clays. The expanding
Montmorillonite is the most extensively known and
clays are phyllosilicates, smectite, and MMT, and the
useful mineral from smectite group. Layered silicates,
nonexpanding clays are talc, kaolin, and mica. For the
such as sodium-MMT (Na-MMT), are usually used as
preparation of nanocomposite, clay choice is usually
inorganic filler. Their crystal lattice consists of two-
made on the basis of cation-exchange capacity and layer
dimensional layers, where a central octahedral sheet of
morphology. The most frequently used clays for the
alumina or magnesia is fused with two external silica
formation of polymer nanocomposite are MMT,
tetrahedra at the tip[30]. The layer thickness of sheets
hectorite, and saponite[22]. The frequently used in-
is around 1 nm. These layers may arrange into stacks
organic filler particles are platelet clay mineral particles
with a regular van der Waals gap called the interlayer
consisting of layered silicates, e.g., MMT, bentonite,
having a spacing of 0.96 nm. Isomorphous substitution
hectorite, cloisite, and kaolinite. Their crystal structure
of Alþ3 by Mgþ2 or Siþ4 by Alþ3 within the silicate layer
consists of layers made up of two silica tetrahedra fused
generates a net negative charge on the layer, which is
to an edge-shared octahedral sheet of either alumina or
counter balanced by alkali or alkaline earth metal
magnesia. The layer stacking leads to regular van der
cations in galleries. The interlamellar cations have one
Waals gap between the layers called interlayer or gallery.
or two shells of water of hydration surrounding
Isomorphic substitution inside the layers generates
them. For example, MMT has chemical formula [Mx
negative charges that are usually counter balanced by
(Al4 xMgx)Si8O20(OH)4], where “M” is a monovalent
cations existing in the interlayer. The amount of layered
cation which exists in the intergallery spaces, and “x”
silicates is usually less than 5% in polymer matrix and
is the degree of isomorphous substitution. There are
they are capable to go through cation-exchange
several layers of organization inside the clay minerals.
reactions[23]. The surface of layered silicates generally
The typical particle size is 8–10 mm which contains
is hydrophilic and this limits their dispersion in organic
the tactoids. The smallest primary particles are stacks
phases, such as in polymer matrices[24]. To make
of parallel lamellae with an average of 15–20 sheets
organophilic layered silicates, it is possible to replace
per particle and of the order of 0.1–1 µm[31]. The most
inorganic cations with organic cations, preferably
frequently used clay mineral for the preparation of
R NHþ 3 groups where R is generally a long aliphatic composites is MMT[32]. The dispersion of MMT parti-
residue[25]. The long organic chains with positively
cles in polymers may form (i) conventional composite:
charged ends are tethered to the surface of negatively
the filler particles are agglomerated, causing stress
charged silicate layers, therefore resulting in increase
concentration and hence reducing the mechanical
in gallery height[26]. The use of organoclays as precur-
performance; (ii) intercalated nanocomposite: polymer
sors to nanocomposite formation has been extended into
molecules are inserted between individual silicate layers;
various polymer systems, including epoxy, polyimide,
and (iii) delaminated (exfoliated nanocomposite): the
polyurethane, nitrile rubber, polypropylene, polyesters,
silicate layers are no longer in close contact to interact
polystyrene, and polysiloxanes[27]. For nanocomposite,
with each other and are fully dispersed in matrix[33].
clay nanolayers must be evenly dispersed (exfoliated)
The last two types of composites show much better
in polymer matrix to avoid aggregated tactoid formation
mechanical, thermal, and barrier properties[34].
(Figure 1)[28]. Once nanolayer exfoliation has been
obtained, the enhancement in tensile properties, barrier
properties, solvent uptake, flame retardance, and
Bentonite
thermal stability may be observed[29].
Bentonite is a type of clay primarily composed of
montmorillonite, i.e, a 2:1 type aluminosilicate. It has
a crystalline structure with an octahedral layer of
aluminum hydroxide between two tetrahedral layers of
silica. The isomorphous substitutions require cations,
denominated exchange cations, to balance the negative
charges in their laminar edges[35]. These clays
interact with organic compounds such as quaternary
ammonium cations to form complexes of varying
stabilities and properties[36]. When natural bentonite
Figure 1. Different types of nanocomposites arising from is in contact with aqueous solution of quaternary
interaction of layered silicate and polymer. ammonium salts, the exchange cations of clay are
920 S. HAIDER ET AL.
replaced by organic cations, which are adsorbed on the
negative surfaces of the clay. This occurs because of
much larger adsorption capacity of the clay for these
cations. This reaction increases the basal spacing of
MMT clays after treatment with organic cations. The
obtained compounds are known as organophilic
bentonites[37]. Bentonites are extensively used as
catalysts, as geoenvironmental barriers and liners (for
landfills), for dye removal from water-based waste
streams as oil-spill cleanup and remediation agents.
Acid-activated bentonites have been a valuable product
for several decades. The manufactured materials are
broadly available and comparatively economical solid
sources of protons. They have been used to manufacture
industrially important products such as catalysts,
catalyst supports, and adsorbents. Acid activation
creates the so-called bleaching earths, which are clays
suitable for a variety of decolorizing applications[38].
Hectorite
The chemical formula for hectorite is Na0.3(Mg,Li)3
Si4O10(OH)2. A specimen of hectorite; obtained from
the mine and has a soft and greasy texture. It is one of
the more expensive clays due to its exceptional
thixotropic properties. The major uses of hectorite are
in chemical, industrial material production, and in
cosmetics[39]. Hectorite, along with MMT, is one of the
most frequently used smectite-type layered silicates for
the preparation of polymer nanocomposites because of
its high ion-exchange capacity and surface area[40]. The
difficulty of dispersing hectorite in highly viscous and
hydrophobic polyolefin matrix such as polyethylene
can be overcome by replacing the hectorite interlayer
cations with long-chain alkyl ammonium or phos-
phonium cations[41]. The synthetic hectorite clay,
laponite, can be exfoliated in water to monodisperse
nanoplatelets of 30 nm diameter and 1 nm thickness[42].
A laponite suspension will change into an isotropic soft
solid after aged over time due to electrostatic interaction
of negative charge on the surface and positive charge
at the edge[43]. The hectorite clay is mostly used as a
rheology modifier in surface coatings, paints, adhesives,
and personal care products. Due to charged nature of
clay particles, product property is sensitive to a slight
change in pH and ionic strength, which considerably
limits application of the materials. Thus it is a common
technique to add polymers to suspensions, which stabi-
lizes the suspension by steric hindrance after adsorption.
Moreover, polymers prolong the shelf life under a variety
of pH and ionic strength[44]. The effect of adsorbed
polymer on linear viscoelastic rheology, i.e., behaviors
at the small deformation limit, has been intensively
studied[45,46]. Hectorite has been used as an adsorbent
for color removal of basic dyes and metal ions[47].
Hectorite-supported metal catalyst and pillared hectorite
have been prepared[48]. These modified hectorites have
been used as catalyst for hydrogenation reactions.
Hectorite has been modified by two cationic surfactants
(cetyldimethyl benzylammonium chloride and cetylpyr-
idinium chloride). These organically modified hectorites
may be used as adsorbent for the removal of anionic
dyes, pesticides, and organic compounds. At present,
no studies are available on organically modified hectorite
for the removal of anionic dyes[49].
Kaolinite
Kaolinite is the most abundant mineral of kaolin group,
which also includes nacrite, dickite, halloysite, and their
hydrated analogs. The kaolinite structure consists of a
Si2O5 sheet bound on one side to dioctahedral
gibbsite-type layer. The gibbsite-type layer consists of
aluminum cations coordinated by hydroxyl groups, with
some hydroxyl substituted by the oxygens of Si–O sheet.
The layers are held together through hydrogen bonds,
dipolar interaction, and van der Waals forces, which
result in low-intrinsic inner surface reactivity. Its
chemical structure, Al2Si2O5(OH)4, has a molecular
weight of 258.10 g/mol with an ideal composition of
46.55% SiO2, 39.49% Al2 O3, and 13.96% H2O[50]. The
basal spacing of kaolinite is 0.72 nm[51]. Since it is made
up of two types of interlayer surfaces, i.e., (SiO)6 macror-
ings on one side and alumina groups on the other side,
kaolinite is, thus, notable by its noncentrosymmetric
structure. This asymmetry creates large superposed
dipoles in lamellar structure, which results in large
cohesive energy. Therefore, the intercalation chemistry
of kaolinite is less developed than that of swelling
smectites[52]. The kaolinite grains are found in the form
of plates throughout the sedimentary rocks of volcanic
source[53]. With hydrogen bonding between the layers,
kaolinite has often been classified as a nonexpandable
mineral. There are a limited number of organic
compounds which can be intercalated between kaolinite
layers. The compounds mostly used are dimethylsulfox-
ide (DMSO), N-methylformamide, formamide,
hydrazine, n-dodecylamine, urea, deuterated DMSO,
potassium acetate, and methanol, which can be directly
intercalated between kaolinite layers[54]. Kaolinite is
used in several industrial applications, usually in paper
industry as filler and in ceramic industry where its main
function is to offer whiteness to ceramic body[55]. It is
also used as filler in paints, rubber, cosmetics, and
pharmaceutical applications[56]. Kaolinite has a potential
to be an ideal precursor for the preparation of new

nanocomposite materials, since it is cost effective as
compared to MMT clays[57]. Kaolin is readily available
and cost-effective mineral to reinforce polymers.
Although when particle fillers are integrated into
polymers, strength, elongation, and impact properties
are not usually sacrificed, owing to strong tendency to
self-agglomerate[58]. The best way to avoid aggregation
is to graft polymer chains onto the particles
covalently[59].
Polystyrene/montmorillonite nanocomposite
Polystyrene–MMT nanocomposite has been synthesized
using suspension polymerization by Xie et al.[60]. The
reaction system of PS–MMT nanocomposite during
suspension polymerization is shown in Figure 2. X-ray
diffraction (XRD) and transmission electron microscopy
(TEM) results showed that the silicate layers were
exfoliated and having fine dispersion in polystyrene
matrix. Further results demonstrated that the PS–
MMT nanocomposite has better mechanical properties
and thermal stability compared with pure polystyrene.
The optimum organo-MMT content to give property
improvement is 5 wt% for thermal stability of nanocom-
posite and 7.5 wt.% for mechanical property. The alkyl
chain length of the surfactant used in fabricating of
organo-MMT affects the synthesized PS nanocomposite.
The organoclay in nanocomposite seems to have dual
role: (i) as nanofiller leading to an increase in the storage
modulus and (ii) as plasticizer leading to the decrease
instorage modulus. This results in lower storage
modulus of polystyrene–trimethyl octadecyl ammonium
chloride MMT and polystyrene–trimethyl tallow
ammonium chloride MMT nanocomposite than that of
polystyrene–trimethyl dodecyl ammonium chloride
MMT and polystyrene–trimethyl coco ammonium
chloride MMT nanocomposite[60]. Polymer nanocom-
posite based on organically modified MMT (OMMT)
and polystyrene has been prepared with different
compositions using melt processing. The pristine MMT
was obtained from Algerian plant with a cation-exchange
capacity of 119 meq/100 g. The modification of MMT
Figure 2. Reaction system of PS/MMT nanocomposite in
suspension polymerization.
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 921
was performed by treating with octadecylammonium
cation[61]. The polymer nanocomposite was character-
ized using different techniques such as XRD, infrared
(IR) spectrophotometry, thermal gravimetric analysis
(TGA), differential scanning calorimetry (DSC),
rheology, and tensile measurements. The results showed
that the basal space of silicate layer increased from 12.6 to
32.3 Å, as determined by XRD. The microstructure was
identified by the X-ray patterns and TEM. At 2 wt%
OMMT, the nanocomposite showed partial intercalation
structure. The nanocomposite with 5 wt% clay indicated
greatest enhancement in thermal stability. The rheologi-
cal properties of PS–OMMT composites were studied
using advanced rheometric expansion system-rheometer
operated in dynamic mode with parallel plate geometry.
The storage and loss moduli were increased with an
increasing clay content. The stress-at-break was also
improved as compared to virgin polystyrene. Poly-
styrene–organoclay nanocomposite has been synthesized
by graft polymerization of styrene on vinyl monomer-
MMT[62]. The preparation was performed by modifi-
cation of MMT with different vinyl monomers such
as N,N-dimethyl-n-octadecyl-4-vinylbenzyl-ammonium
chloride, n-octadecyl-4-vinylbenzyl-ammonium chlor-
ide, triphenyl-4-vinylbenzylphosphonium chloride, and
tri-n-butyl-4-vinylbenzylphosphonium chloride. In situ
polymerization of styrene monomer with different
ratios of vinyl monomer-MMT was then performed.
The distinctive properties of the prepared materials were
inspected by different physical and chemical methods.
Verification of vinyl monomer-cation intercalation in
clay interlayers was obtained by IR spectra. The thermal
properties were determined using TGA, which revealed
higher thermal stability for PS/MMT nanocomposite
than neat polystyrene. X-ray diffraction analysis
demonstrated that the nanocomposite was exfoliated at
� 25 wt% of organoclay content. Scanning electron
microscopy (SEM) showed a complete dispersion of PS
into the clay galleries. Moreover, TEM showed the
formation of spherical particles within a nanosize of
150–400 nm. A series of polymer/clay nanocomposite
(PCN) materials, consisting of thermoplastic polystyrene
sample and dispersing inorganic organoclay platelets,
were effectively prepared[63]. First, organoclay was pre-
pared by performing cation-exchange reactions between
sodium ions existing in interlayer region of clay mineral
and intercalation agent. This is followed by dispersing
organophilic clay in polystyrene matrix through melt
intercalation using twin-screw mixing method. The
as-prepared PCN materials were characterized using
powder XRD and TEM. It was found that the wear
resistance of PS was effectively improved by the inclusion
of low loading organophilic clay platelets. Moreover,
922 S. HAIDER ET AL.
the effect of organoclay on mechanical properties for as-
prepared PCN materials, e.g., impact tests, flexural tests,
and micro and nanoindentation tests were measured and
compared. PCN materials exhibited an evident improve-
ment in mechanical properties of PS by incorporating
low loading organophilic clay platelets[63]. The fire per-
formance of polystyrene/OMMT nanocomposite was
studied by limiting oxygen index (LOI) and cone
calorimetr[64]. SEM, electron-dispersive spectroscopy,
and attenuated total reflection Fourier transform infra-
red (FTIR) spectroscopy were used to study the charring
process of nanocomposites. The residue collected upon
thermal degradation was analyzed by various methods
to find out its composition and to understand the
flame-retardant mechanism of the nanocomposite.
Introduction of OMMT had no influence on LOI of
the nanocomposite; however, it significantly decreased
heat release rate (HRR) and mass loss rate (MLR) of
the material. The flame-retardant mechanism is due to
charring in the condensed phase. The porous structure
of the charred residue reduced the HRR, MLR, and so
retarded the burning of material.
Polystyrene–bentonite nanocomposite
Polystyrene–bentonite clay nanocomposite has been
prepared by emulsion polymerization in both aqueous
and supercritical carbon dioxide (sc-CO2) media[65].
The scheme for processing of nanoclay in sc-CO2
medium is shown in Figure 3. The particle size of the
nanocomposite decreased with an increase in clay load-
ing in both the media. The distinct- and uniform-sized
particles were observed in sc-CO2 medium, while
agglomerated particles were obtained in aqueous
medium. TEM and XRD results indicated exfoliated
nature of clay layers in nanocomposite synthesized in
sc-CO2 medium, whereas intercalation and low exfoli-
ation were observed for nanocomposite synthesized in
aqueous medium. The interlayer distance of the clay
was increased from 2.36 to 4.9 nm in sc-CO2 medium,
while it increased from 2.36 to 3.67 nm in aqueous
medium. The mechanical properties of the nanocompo-
site synthesized in sc-CO2 medium were found higher
than in aqueous medium. Similarly, thermal properties
Figure 3. Scheme for processing of nanoclay in sc-CO2 medium.
and the particle forming efficiency of the nanocomposite
were found better in sc-CO2 medium than in aqueous
medium. Bentonite clay was used as compatibilizing
and reinforcing filler for natural rubber/polystyrene
(NR/PS) blend prepared through latex blending
process[66]. The reinforcing and compatibilizing perfor-
mance of bentonite clay in NR/PS blends were evaluated.
The enhancement in mechanical properties of NR/PS
blends with weight ratios of 90/10, 80/20, and 70/30
was observed with the addition of 3 and 5 parts per
100 rubber (phr) clay. The characterization using FTIR
spectroscopy and XRD indicated that the silicate layer
was intercalated by NR and PS molecular chains. The
compatibilization action of bentonite clay was also
reflected by shift of glass transition temperature (Tg) of
NR to higher temperature than the blends. These results
suggested that the tensile and tear properties of the
blends were controlled by compatibility between NR
and PS. The mainly improved properties of blends were
found with the addition of 3 phr bentonite clay. The flow
properties of bentonite were studied with a combination
of anionic polystyrene sulfonate (molecular weight ¼
70,000 g/mol) and nonionic poly(vinyl alcohol)
(molecular weight ¼ 50,000 g/mol)[67]. This combi-
nation had a major effect on clay suspension depending
on the order of the polymer addition. The addition of
50 mg/L anionic polystyrene sulfonate followed by
200 mg/L nonionic poly(vinyl alcohol) improved the
rheological properties. The composites of surfactant-free
PS nanoparticles and modified Na-activated bentonite
(MLB) have been studied by Uğur et al.[68] using
steady-state fluorescence (SSF) technique. The com-
posite films were prepared from a mixture of pyrene
(P)-labeled PS particles and MLB at various composi-
tions at room temperature. These films were annealed
at elevated temperature exceeding Tg of polystyrene.
Scattered light (Is) and fluorescence intensities (IP) from
P were measured after each annealing step to observe
the stages of film formation. The progression of trans-
parency of the composite films was also monitored.
Atomic force microscopy (AFM) was used to identify
the variation in physical structure of annealed composite
films. The nanocomposite films showed a percolation
threshold at 20 wt% MLB content. Void closure
activation energies decreased as the percent of MLB
increased, no variation was observed in backbone
activation energies. Burmistr et al.[69] have prepared
polymer/clay composites using melt blending of organo-
bentonite with linear polymers (polyamide, polysterene
and polypropylene) in a disk-screw extruder. The orga-
noclay was prepared by surface treatment of Na-form
bentonite with polymeric quaternary ammonium salts.
XRD showed that organobentonite layers were exfoliated
 POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 923

Table 1. Physical–mechanical properties of nanocomposites[69].

Content of pure bentonite (wt%) Content of organobentonite (wt%)
Polymer Property 0 1 2 5 1 2 5
Polyamide 6 Tensile strength (MPa) 30.86 39.84 36.76 32.71 46.17 47.12 34.61
Charpy impact (kJ/m2) 31.78 28.15 24.12 21.71 68.13 76.12 51.20
Elongation at break (%) 28.75 22.15 18.31 10.81 35.00 34.61 17.22
Polystyrene Tensile strength (MPa) 17.50 18.80 18.41 16.50 21.15 22.34 17.72
Charpy impact (kJ/m2) 15.50 10.42 12.50 9.12 17.31 19.62 11.98
Elongation at break (%) 13.53 25.00 19.75 8.17 39.51 42.15 12.34
Polypropylene Tensile strength (MPa) 14.78 12.77 15.50 6.73 19.36 21.08 20.27
Charpy impact (kJ/m2) 53.35 25.40 21.55 21.82 43.37 47.73 36.65
Elongation at break (%) 61.33 80.00 90.67 40.00 133.00 157.21 26.67

the pure polymer (Table 1). The PA- and PS-organoben-

tonite nanocomposites have also higher thermal stability
as compared to pure polymer matrix. The PA- and
PS-organobentonite nanocomposite showed the finest
balance in properties at 2 wt% of clay loading (Figures 4
and 5)[69].

Figure 4. TGA of PA and PA–organobentonite composite[69].
and dispersed into polyamide and polystyrene. Addition
of 2 wt% organobentonite (optimal concentration) to
polyamide increased tensile strength by 53% and
Charpy impact by 140%. With an inclusion of 2 wt%
organobentonites (optimal concentration) into poly-
styrene, the tensile strength was increased to 28% and
the Charpy impact increased to 25%. The polyamide
(PA) and PS-organobentonite nanocomposite showed
better mechanical properties and Charpy impact than
Polystyrene/hectorite nanocomposite
A synthetic Na-fluorohectorite was organically modified
([Fe(bpy)3]2þ and C18) and then used to synthesize PS
clay nanocomposites by Hausner et al.[70]. The nano-
composite showed improved thermal, gas barrier, and
fire properties, however, PS-[Fe(bpy)3]2þ-Hec nano-
composite showed reduced total smoke produced
(TSP). The improved performance may be directly
related to the thermal stability and redox properties of
[Fe(bpy)3]2þ, while [Fe(bpy)3]2þ-Hec showed good fire
performance, char forming properties, and thermal
stability (Figure 6)[70]. The PS-[Fe(bpy)3]2þ-Hec nano-
composite showed a residue amount of 3.0 � 0.2 g
which fairly equates the inorganic content of the nano-
composites and indicated little to no char formation.
PS-C18-Hec nanocomposite showed slightly high
residue amount of 3.8 � 1.0 g (Table 2). An organically
modified clay, dimethyldioctadecylammomium-
hectorite(DMDO-Hect), was used as emulsifier for
immiscible polystyrene/poly(ethyl methacrylate)
[71]
(PS/PEMA) pair of polymers . The organoclay in this
blend adsorbs selectively PEMA chains and produces

Figure 6. TGA data measured under air (left) and under

Figure 5. TGA of PS and PS–organobentonite composite[69]. nitrogen (right) of [Fe(bpy)3]2þ-Hec (line) and C18-Hec[70].
924 S. HAIDER ET AL.

Table 2. Cone calorimeter data for PS and the PS–clay nanocomposites[70].

PHRRa ΔPHRR THR TSP AMLR Residue tig tPHRR MARHE FIGRA LOI (%)
Sample (kW/m2) (%) (MJ/m2) (m2/m2) (g/sm2) (g) (s) (s) (kW/m2) (kW/m2s) � 0.2 (%)
PS 944 � 26 — 134.8 � 0 5,017 � 114 26.1 � 0.8 0 76 � 3 205 � 0 461 � 9 12.5 � 0.5 18.7
PS[Fe(bpy)3]þ2-Hec 460 � 13 51 132.4 � 1.4 4,415 � 25 11.1 � 0.8 3.0 � 0.2 84 � 1 213 � 25 301 � 3 5.5 � 0.2 19.8
PS-C18-Hec 437 � 5 54 125.1 � 4.9 5,127 � 504 7.1 � 0.2 3.8 � 1.1 66 � 1 123 � 11 239 � 1 6.7 � 0 19.7
PHRR, peak of heat release rate; THR, total heat release; TSP, total smoke produced; AMLR, average mass loss rate; tig, time of ignition; tPHRR, time of PHRR;
MARHE, maximum average rate of heat emission; FIGRA, fire growth rate index; LOI, limiting oxygen index.
a
heat flux 35 kW/m2.

PEMA/DMDO-Hec intercalated structures in which temperature of the compatibilized nanocomposite. SEM

PS chains were shaped into separate domains. The
emulsifying action of organoclay was also revealed by
the presence of only one Tg in DSC thermograms.
The performance of the obtained PS nanocomposite
was improved as compared to natural clay PS
nanocomposite[72]. Porter et al.[73] prepared Cuþ2-
exchanged hectorite clay films by in situ polymerization
of many organic monomers. In the case of styrene,
surface polymerization occurred in conjunction with
partial intercrystallite intercalation and polymerization.
Polystyrene on the clay surface exhibited a possible
brush-like structure. Intercrystallite polystyrene may
exist in two faraway phases, one of which is similar to
surface bulk polymer, while the other has high degree
of material stiffness owing to higher degree of polymer
ordering. Polystyrene hectorite clay nanocomposites
were also prepared by melt blending of polystyrene with
an oligomerically modified clay[74].
Polystyrene/kaolinite nanocomposite
Botan et al.[75] synthesized PS/kaolinite (Kao) nanocom-
posite by in situ emulsion polymerization. First kaolin
was modified using DMSO by displacement method
(Kao–DMSO). After that styrene monomer was interca-
lated into kaolinite. Two types of nanocomposites were
synthesized using 1 and 3 wt% of Kao–DMSO. The
comparison between TGA analyses of nanocomposite
with 3% Kao–DMSO and virgin PS showed that the
thermal decomposition of the nanocomposites with clay
initiated 20°C above the temperature of the initial
thermal decomposition of virgin PS. The influence of
3% Kao–DMSO clay on nanocomposites was also
observed during flame retarding test, in which the burn-
ing rate was reduced by 50% compared to virgin PS.
According to George et al.[76], nanokaolin clay acted as
a proficient reinforcing agent for the polystyrene/
high-density polyethylene blends. Mechanical properties
improved with an optimum of 2 wt% clay. The improve-
ment becomes noteworthy in the presence of a compati-
bilizing agent at 10–15 wt%. The storage modulus of
compatibilized blends was higher than the modulus of
neat matrix. DSC records showed an increase in melting
analysis showed the development of fibrillar morphology
due to the inclusion of clay. Elbokl et al.[77] formed
intercalated nanocomposite by free radical-initiated
polymerization reaction of styrene and a kaolinite
DMSO intercalate. The DMSO molecules were com-
pletely replaced by one layer of polystyrene chains in
the interlamellar spaces of kaolinite. The nanohybrid
decomposed at temperature above 300°C (air), with a
maximum exotherm at 370°C. The results of the XRD
proved the intercalation of polystyrene in the interlamel-
lar spaces of kaolinite (Figure 7). Abdallah et al.[78]
concluded that the overall electrical behavior was
influenced by some processes such as ion diffusion,
electron hopping, and space charge polarization during
composite microstructure formation[78]. The optical
and electrical characteristics of kaolinite/polystyrene
composites containing 20 wt% kaolinite with grain sizes
of 63, 106, 212, and 300 µm and neat polystyrene were
studied[79]. The optical absorption spectra were obtained
in the wavelength 300–800 nm using a spectrophot-
ometer. The optical band gap and energy tail widths of
localized states were determined for the prepared
composites. It was found that the optical energy gap
and the energy tail width changed with the kaolinite
Figure 7. XRD powder patterns (2θ ¼ 2–18°) for (a) kaolinite,
(b) kao–polystyrene, and (c) kao–DMSO[77].

grain size. The electrical properties were studied using
AC impedance measurements performed at different
temperatures and frequency of 100 kHz–1 MHz.
Application of polymer–clay nanocomposite
Polystyrene–clay nanocomposites have found applica-
tions in a range of technical fields; few of them are
described in this section. Polymer–clay nanocomposites
have gained significant recognition in materials industry
due to improved performance and applicability in
polymer and metal replacement. For example, PNC
automotive body components bring scratch and rust
resistance along with weight savings. The embedded
nanoparticles in cloth induce stain and water resistance
to clothing. Tennis balls with an interior nanoplatelet
coating provide enhanced air retention for extensive
performance. The infrastructure is falling into place at
the governmental, investment, commercial, and aca-
demic levels to support continuing growth of the nano-
technology industry including chemicals, electronics,
medicines, photonics, and energy in addition to materi-
als. Nanocomposites can bring enhancement in perfor-
mance and properties along with savings in processing
and fuel usage due to weight reduction of more than
50% in selected parts[80].
Flame retardancy
The use of polymer/clay nanocomposite for flame-
retardant applications is becoming widespread. The clay
nanocomposite can substitute part of the flame-
retardant package while maintaining fire safety ratings
at a lower flame-retardant loading[81]. The use of
nanocomposite in vehicle parts and systems is expected
to improve flammability, manufacturing speed; enhance
thermal and environmental stability; reduce weight; and
promote recycling. Nanocomposite-based parts give
strength, stiffness, and reliability better than metals.
They offer corrosion resistance, enhanced modulus,
noise dampening, thermal stability, and dimensional
stability[82]. The heat-resistant polymer nanocomposite
is used to make firefighter’s protective clothing and
lightweight components appropriate to work in situa-
tions of high stress and temperature. This comprises
skins of jet aircrafts and hoods of automobiles, as
opposed to heavier and costlier metal alloys. They can
also replace corrosion-prone metals in building of
bridges and other large structures with potentially
stronger and lighter capabilities[83]. Regarding the
variety of applications of polymer nanocomposite, major
impacts over the automotive industry can be high-
lighted, including their use in tires, gas separation
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 925
membranes in fuel cells and seat textiles, fuel systems,
mirror housings on various vehicle types, engine covers,
door handles, intake manifolds, and timing belt
covers[84]. For example, a thermoplastic nanocomposite
containing nanoflake reinforcement (trade name Basell
TPO-Nano) is being employed for the development of
stiff and light exterior parts. Furthermore, porous
polymer nanocomposite can be used for the develop-
ment of pollution filters[85]. Other technological
application in the horizon is in air bag sensors, where
nano-optical platelets are kept inside the polymer outer
layer for conveying signals at speed of light[86].
Civil engineering
Polymer–clay nanocomposite is emergent area of
nanotechnology, which have the potential to offer many
wide-ranging benefits to current matrix polymers. Their
ability to increase the service life of materials subjected
to aggressive environments could be utilized to increase
the durability of glass and carbon fiber composites. This
advantage could permit the use of composite materials in
situations where their performance under aggressive
environments is insufficient for the in-service con-
ditions. The increase in service life would allow the com-
posite materials to be used with more confidence in their
long-term durability in a wider range of conditions[87].
Developments in mechanical properties of polymer
nanocomposite have also resulted in several industrial
applications. These include impellers and blades for vac-
uum cleaners, power tool housings, mower hoods, and
covers for portable electronic equipment such as mobile
phones and pagers[88]. Another example is the use of
polymer nanocomposites in glues for the manufacturing
of pressure molds in the ceramic industry. Moreover,
unsaturated polyester (UPE) nanocomposite can be
used in fiber-reinforced products used in marine,
construction, and transportation industries[89].
Currently, UPE–fiberglass nanocomposite, whose
formulations are offered from Polymeric Supply, Inc.,
is being used in boat accessories that are stronger and
less prone to color vanishing[90].
Barrier application
When food will not be consumed instantly after pro-
duction, it must be contained in a package that serves
various functions. Packaging is used to protect food
from dirt or dust, light, oxygen, pathogenic micro-
organisms, moisture, and a variety of other harmful
substances. The packaging must be safe under intended
conditions of use, inert, cheap to produce, lightweight,
easy to dispose of, and able to withstand intense
926 S. HAIDER ET AL.

conditions during processing or filling. A critical matter

in food packaging is migration and permeability, as no
material is completely impermeable to water vapor,
atmospheric gasses, or natural substances contained in
the food being packaged[91]. Polymer–clay nano-
composite is the material that aimed at solving the
above-mentioned problems[92]. The bionanocomposite
has been synthesized for food packaging films with
improved barrier, mechanical, rheological, and thermal Figure 9. Tortuous path around clay platelet in polymer film
properties (Figure 8). Polymer–clay nanocomposites (a) diffusing gas molecules via pathway perpendicular to film
made from nylon 6 or 6,6 are used for packaging film orientation and (b) diffusing molecules navigate around
impenetrable platelet.
applications, where toughness, higher tensile strength,
and improved barrier properties are important. Two to
sixfold reduction is possible in food packages through membrane fuel cells (PEMFCs) are one of the most
the integration of layered silicate nanoplatelets, which promising clean energy technologies. PEMFCs have
increase the path tortuosity for permeating small certain potential advantages such as portable applica-
molecules (Figure 9)[93], although enhancing polymer tions, high efficiency, and power generation[99]. The
barrier properties is the most noticeable application of key component of a PEMFC is a dense proton-exchange
nanocomposite in the food industry. These materials membrane, which is responsible for proton movement
are stronger, more flame resistant, and have better from anode to the cathode. Hydrogen is catalytically
thermal properties, e.g., melting points, degradation, oxidized at anode to produce protons. The membrane
and glass transition temperatures[94–96]. Polymer–clay is usually placed between two electrodes, i.e., between
nanocomposite offers fine down gauging opportunities the anode and cathode. The protons thus produced
to food packaging industry, in addition to waste reduc- can move from anode to cathode where the protons react
tions and cost savings. Nanocomposite may even offer with oxygen to produce water and heat[100]. The liquid
environmental advantages over conventional plastics[97]. electrolyte systems can be overpowered by solid
proton-exchange membranes due to the exceptional
Fuel cell application features of solid proton-exchange membrane such as
easy handling, amenable to mass production, compact,
Fuel cells are gaining attention as a clean and promising and excellent resistance to the permeation of gaseous
technology for energy conversion. One of the key bene- reactant[101]. The schematic of proton-exchange mem-
fits of fuel cells, compared to other methods, is the direct brane fuel cells is shown in Figure 10[102]. Polymer/clay
energy conversion that enables the achievement of high nanocomposites provide a group of polymeric
efficiency. The polymer electrolyte membrane is the
most vital part of a fuel cell unit and therefore has been
the subject of significant research and development.
Among the various types of proton-conducting
electrolytes inspected for fuel cell applications, polymer
electrolyte membranes (PEMs) are considered as feas-
ible. PEMs enable operation of the cells at desirably
low temperatures[98]. Moreover, the proton-exchange

Figure 8. General properties required for food packaging Figure 10. Schematic representation of proton-exchange
materials. membrane fuel cell.

Figure 11. Differences between a diesel engine and a fuel cell
engine.
composites with excellent transport and mechanical
properties. The ionic/electronic conductivity and biode-
gradability of these nanocomposites were enhanced by
the addition of small amount of clay. Clay often behaves
as a nucleating agent for crystallization of semicrystalline
polymers, though intercalating polymers become
amorphous with clay loading[103]. Layered nanoporous
materials consist of an intermediate structure between
typical layered materials (smectite clays) and crystalline
nanoporous frameworks (zeolites). Each layer includes
a porous network, while the gallery between layers pro-
vides the ability for intercalation, pillaring, and
exfoliation[104]. Layered silicate with three-dimensional
microporosity allows adsorption, catalysis, and ion-
exchange applications. Amherst-3 (AMH-3) is a layered
silicate, with available internal porosity from all direc-
tions through eight-member rings, with a pore structure
made up of eight SiO4 tetrahedra[105]. Layered oxide–
polymer nanocomposite membranes control the meth-
anol crossover, and proton conductivity has been
Figure 12. Different routes for the preparation of organic-
inorganic hybrid materials and polymer electrolyte membranes.
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 927
developed for fuel cell applications[106]. The difference
between a diesel engine and a fuel cell engine is shown
in Figure 11[102]. A porous-layered silicate or alumino-
phosphate materials exfoliated/intercalated/dispersed in
Nafion1, and other polymeric ionomers acted as a selec-
tive permeable barrier, which blocks methanol per-
meation and maintain proton conductivity. The small
pore size (suitable for proton transport) and highly tor-
tuous paths for methanol diffusion are responsible for
these dual properties. Layered aluminophosphate
triethylamine, aluminophosphateisopropanolamine,
aluminophosphate-imidazole, and the swollen AMH-3
were used to prepare PEMs by dispersion in an organic
solvent, followed by the addition of ionomer solution
(Figure 12)[107].
Future relevance
The development of nanocomposites represents a very
attractive way to improve and diversify properties of
conventional polymers without changing polymer
compositions and processing. In contrast to conven-
tional filled polymers, nanocomposite is composed of
nanometer-sized fillers, nanofiller, which is homoge-
neously dispersed inside the polymer matrix. The
addition of just a few wt% of nanofillers has intense
impact on the physical, chemical, electrical, and mechan-
ical properties of polymers. Such change is frequently
favorable for engineering purpose. This nanocomposite
technology has emerged from the field of engineering
plastics and potentially expanded its applications to
structural materials, coatings, packaging to medical,
electronic and photonic devices. Recently these high-
tech materials with excellent properties have begun to
attract researchers in the field of dielectrics and electrical
insulation. Since such properties are brought about from
the interaction of nanofillers with polymer matrices,
mesoscopic properties are expected to emerge, which
would be interesting to both scientists and engineers[108].
Certainly, clay nanocomposite will continue to be used
for enhanced mechanical, flammability, and barrier
properties, but fundamental limits in clay chemistry
prevent them from being used easily in applications
requiring electrical conductivity or optical applications.
Beside, combination of organoclays with other nano-
fillers to obtain a true multifunctional material will likely
to occur in future. Combining an organoclay with
carbon nanotube or quantum dots may yield interesting
nanocomposite with enhanced mechanical, flamm-
ability, thermal, and electrical properties. The clay can
enhance the properties of some existing mechanically
fragile system while keeping other properties intact.
The field of polymer/clay nanocomposite and broader
928 S. HAIDER ET AL.
field of polymer nanocomposite continue to develop.
These materials have been and will be used in designing
new systems through fundamentals[109].
Conclusion
The advancement of nanoclay–polystyrene matrix
nanocomposite surely represents one of the most
dynamic research areas in polymer science and tech-
nology. The clay minerals are cost-effective and resource-
ful raw materials for polymer nanocomposites due to
their exceptional layered structure, high aspect ratio,
high in-plane strength and stiffness, rich intercalation
chemistry as well as abundant in nature. Different types
of nanoclays such as montmorillonite, bentonite, hector-
ite, and kaolinite and their composites with polystyrene
have been discussed considering their preparation and
characterization techniques. Nanoclays offer low-cost
additives to improve the properties of nanostructured
polymeric materials for wide range of applications. The
enhancement in mechanical properties, solvent resist-
ance, barrier properties, thermal stability, flame retar-
dance, and many other properties has been reported.
Consequently, clay-based polystyrene nanocomposite
has been produced as energy-saving and environment-
friendly materials, packaging, automotive parts, and
building and construction materials. They have been
considered for future use of electrical insulation in power
cables, power apparatus, outdoor insulators, and
insulated wires for electric power technologies. All these
justify the growing interest of both academia and indus-
try in the advancement of PS–clay hybrid materials.
References
[1] Haider, S.; Kausar, A.; Muhammad, B. An overview of
various sorts of polymer nanocomposite reinforced
with layered silicate. Polym.-Plast. Technol. Eng. 2016,
55, 723–743.
[2] Alexandre, M.; Dubois, P. Polymer-layered silicate
nanocomposites: preparation, properties and uses of a
new class of materials. Mater. Sci. Eng. R. 2000, 28, 1–63.
[3] Samakande, A.; Hartmann, P.C.; Cloete, V.; Sanderson,
R.D. Use of acrylic based surfmers for the preparation
of exfoliated polystyrene–clay nanocomposites.
Polymer 2007, 48, 1490–1499.
[4] Gul, S.; Kausar, A.; Muhammad, B.; Jabeen, S.
Technical relevance of epoxy/clay nanocomposite with
organically modified montmorillonite: a review.
Polym.-Plast. Technol. Eng. 2016. doi:10.1080/03602559.
2016.1163593
[5] LeBaron, P.C.; Wang, Z.; Pinnavaia, T.J. Polymer-
layered silicate nanocomposites: an overview. Appl.
Clay Sci. 1999, 15, 11–29.
[6] Sadhu, S.; Bhowmick, A.K. Preparation and properties
of styrene–butadiene rubber based nanocomposites:
the influence of the structural and processing
parameters. Appl. Polym. Sci. 2004, 92, 698–709.
[7] Giannelis, E.P. Polymer-layered silicate nano-
composites: synthesis, properties and applications.
Appl. Organomet. Chem. 1998, 12, 675–680.
[8] Amr, I.T.; Al-Amer, A.; Al-Harthi, M.; Girei, S.A.;
Sougrat, R.; Atieh, M.A. Effect of acid treated carbon
nanotubes on mechanical, rheological and thermal
properties of polystyrene nanocomposites. Compos. B
Eng. 2011, 42, 1554–1561.
[9] Li, H.; Yu, Y.; Yang, Y. Synthesis of exfoliated
polystyrene/montmorillonite nanocomposite by
emulsion polymerization using a zwitterion as the clay
modifier. Eur. Polym. J. 2005, 41, 2016–2022.
[10] Koralege, R.S.H.; Jayasuriya, C.K. Synthesis and
characterization of polystyrene–clay composites. J.
Emerg. Trends Eng. Appl. Sci. 2015, 6, 248–252.
[11] Maldas, D.; Kokta, B.V.; Daneault, C. Influence of
coupling agents and treatments on the mechanical
properties of cellulose fiber–polystyrene composites. J.
Appl. Polym. Sci. 1989, 37, 751–775.
[12] Sánchez-Jiménez, P.E.; Pérez-Maqueda, L.A.; Perejón,
A.; Criado, J.M. Nanoclay nucleation effect in the
thermal stabilization of a polymer nanocomposite: a
kinetic mechanism change. J. Phys. Chem. C. 2012,
116, 11797–11807.
[13] Heeb, N.V.; Graf, H.; Schweizer, W.B.; Lienemann, P.
Thermally-induced transformation of hexabromocyclo
dodecanes and isobutoxypenta bromocyclododecanes
in flame-proofed polystyrene materials. Chemosphere
2010, 80, 701–708.
[14] Su, S.; Jiang, D.D.; Wilkie, C.A. Novel polymerically-
modified clays permit the preparation of intercalated
and exfoliated nanocomposites of styrene and its
copolymers by melt blending. Polym. Degrad. Stab.
2004, 83, 333–346.
[15] Yang, H.S.; Yoon, J.S.; Kim, M.N. Dependence of
biodegradability of plastics in compost on the shape
of specimens. Polym. Degrad. Stab. 2005, 87, 131–135.
[16] Gao, Y.; Li, H.; Wang, X. Synthesis and characterization
of syndiotactic polystyrene-graft-poly(glycidyl
methacrylate) copolymer by atom transfer radical
polymerization. Eur. Polym. J. 2007, 43, 1258–1266.
[17] Bergbreiter, D.E.; Zhong, Z. Anionic grafting onto
divinylbenzene-cross-linked polystyrene. Ind. Eng.
Chem. Res. 2005, 44, 8616–8620.
[18] Bajdur, W.; Pajączkowska, J.; Makarucha, B.;
Sułkowska, A.; Sułkowski, W.W. Effective poly-
electrolytes synthesised from expanded polystyrene
wastes. Eur. Polym. J. 2002, 38, 299–304.
[19] Wilson, O.; Wilson, G.J.; Mulvaney, P. Laser writing in
polarized silver nanorod films. Adv. Mater. 2002, 14,
1000–1004.
[20] Yoon, P.J.; Fornes, T.D.; Paul, D.R. Thermal expansion
behavior of nylon 6 nanocomposites. Polymer 2002, 43,
6727–6741.
[21] Kumar, M.S.; Raju, N.M.S.; Sampath, P.S.; Jayakumari,
L.S. Effects of nanomaterials on polymer composites—
an expatiate view. Rev. Adv. Mater. Sci. 2014, 38, 40–54.
[22] Panwar, A.; Choudhary, V.; Sharma, D.K. Review: a
review: polystyrene/clay nanocomposites. J. Reinf.
Plast. Compos. 2011, 30, 446–459.

[23] Murray, H.H. Overview-clay mineral applications.
Appl. Clay Sci. 1991, 5, 379–395.
[24] Blumstein, A.; Parikh, K.K.; Malhotra, S.L.; Blumstein,
R. Polymerization of monolayers. VI. Influence of the
nature of the exchangeable ion on the tacticity of
insertion poly(methyl methacrylate). J. Polym. Sci. A-2
Polym. Phys. 1971, 9, 1681–1691.
[25] Laura, R.D.; Cloos, P. Adsorption of ethylenediamine
(Eda) on montmorillonite saturated with different
cations IV: Ai , Ca and Mg montmorillonite:
protonation, ion-exchange, co-ordination and
hydrogen-bonding. Clay Clay Miner. 1975, 23, 343–348.
[26] Hackett, E.; Manias, E.; Giannelis, E.P. Molecular
dynamics simulations of organically modified layered
silicates. J. Chem. Phys. 1998, 108, 7410–7415.
[27] Okada, A.; Usuki, A. The chemistry of polymer–clay
hybrids. Mater. Sci. Eng. C. 1995, 3, 109–115.
[28] Giannelis, E.P. Polymer layered silicate nanocom-
posites. Adv. Mater. 1996, 8, 29–35.
[29] Nguyen, Q.T.; Baird, D.G. Preparation of polymer–clay
nanocomposites and their properties. Adv. Polym.
Technol. 2006, 25, 270–285.
[30] Bhiwankar, N.N.; Weiss, R.A. Melt intercalation/
exfoliation of polystyrene–sodium–montmorillonite
nanocomposites using sulfonated polystyrene ionomer
compatibilizers. Polymer 2006, 47, 6684–6691.
[31] Vaia, R.A.; Jandt, K.D.; Kramer, E.J.; Giannelis, E.P.
Microstructural evolution of melt intercalated polymer-
organically modified layered silicates nanocomposites.
Chem. Mater. 1996, 8, 2628–2635.
[32] Liu, X.; Wu, Q. PP/clay nanocomposites prepared
by grafting-melt intercalation. Polymer 2001, 42,
10013–10019.
[33] Gilman, J.W. Flammability and thermal stability
studies of polymer layered-silicate (clay) nanocompo-
sites. Appl. Clay. Sci. 1999, 15, 31–49.
[34] Ray, S.S.; Okamoto, M. Polymer/layered silicate nano-
composites: a review from preparation to processing.
Progr. Polym. Sci. 2003, 28, 1539–1641.
[35] Rodríguez-Sarmiento, D.C.; Pinzon-Bello, J.A. Adsorp-
tion of sodium dodecylbenzene sulfonate on organophi-
lic bentonites. Appl. Clay. Sci. 2001, 18, 173–181.
[36] Mortland, M.M. Clay–organic complexes and
interactions. Adv. Agron. 1970, 22, 75–117.
[37] Araújo, E.M.; Melo, T.J.A.; Santana, L.N.L.; Neves,
G.A.; Ferreira, H.C.; Lira, H.L.; Carvalho, L.H.; A’vila,
M.M.; Pontes, M.K.G.; Araújo, I.S. The influence of
organo-bentonite clay on the processing and
mechanical properties of nylon 6 and polystyrene
composites. Mater. Sci. Eng. 2004, 112, 175–178.
[38] Carrado, K.A.; Komadel, P. Acid activation of
bentonites and polymer–clay nanocomposites.
Elements 2009, 5, 111–116.
[39] Dubois, P.; Alexandre, M.; Jérôme, R. Polymerization-
filled composites and nanocomposites by coordination
catalysis. In: Macromolecular Symposia, Wiley-VCH
Verlag: Weinheim, 2003, Vol. 194; pp. 13–26.
[40] Gopakumar, T.G.; Lee, J.A.; Kontopoulou, M.; Parent,
J.S. Influence of clay exfoliation on the physical
properties of montmorillonite/polyethylene compo-
sites. Polymer 2002, 43, 5483–5491.
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 929
[41] Morawiec, J.; Pawlak, A.; Slouf, M.; Galeski, A.;
Piorkowska, E.; Krasnikowa, N. Preparation and
properties of compatibilized LDPE/organo-modified
montmorillonite nanocomposites. Eur. Polym. J. 2005,
41, 1115–1122.
[42] Ramsay, J.D.F. Colloidal properties of synthetic
hectorite clay dispersions: I. Rheology. J. Colloid
Interface Sci. 1986, 109, 441–447.
[43] Sun, W.; Yang, Y.; Wang, T.; Liu, X.; Wang, C.; Tong, Z.
Large amplitude oscillatory shear rheology for non-
linear viscoelasticity in hectorite suspensions containing
poly(ethylene glycol). Polym. 2011, 52, 1402–1409.
[44] Crowl, V.T.; Malati, M.A. Adsorption of polymers and
the stability of pigment dispersions. Discuss. Faraday
Soc. 1966, 42, 301–312.
[45] Frith, W.J.; Strivens, T.A.; Mewis, J. Dynamic mechan-
ical properties of polymerically stabilized dispersions.
J. Colloid Interface Sci. 1990, 139, 55–62.
[46] Grover, G.S.; Bike, S.G. Monitoring flocculation in
situ in sterically stabilized silica dispersions using
rheological techniques. Langmuir 1995, 11, 1807–1812.
[47] Neumann, M.G.; Schmitt, C.C.; Gessner, F. Time-
dependent spectrophotometric study of the interaction
of basic dyes with clays II: Thionine on natural and
synthetic montmorillonites and hectorites. J. Colloid
Interface Sci. 1996, 177, 495–501.
[48] Mastalir, A.; Szöllösi, G.; Kiraly, Z.; Rázga, Z.
Preparation and characterization of platinum nanopar-
ticles immobilized in dihydrocinchonidine-modified
montmorillonite and hectorite. Appl. Clay. Sci. 2002,
22, 9–16.
[49] Baskaralingam, P.; Pulikesi, M.; Elango, D.; Rama-
murthi, V.; Sivanesan, S. Adsorption of acid dye onto
organobentonite. J. Hazard. Mater. 2006, 128, 138–144.
[50] Letaief, S.; Detellier, C. Clay-polymer nanocomposite
material from the delamination of kaolinite in the
presence of sodium polyacrylate. Langmuir 2009, 25,
10975–10979.
[51] Murakami, J.; Itagaki, T.; Kuroda, K. Synthesis of
kaolinite-organic nanohybrids with butanediols. Solid
State Ionics 2004, 172, 279–282.
[52] Ruiz-Hitzky, E. Functionalizing inorganic solids:
towards organic–inorganic nanostructured materials
for intelligent and bioinspired systems. Chem. Rec.
2003, 3, 88–100.
[53] Varga, G. The structure of kaolinite and metakaolinite.
Epitoanyag 2007, 59, 6–9.
[54] Komori, Y.; Sugahara, Y.; Kuroda, K. Intercalation of
alkylamines and water into kaolinite with methanol
kaolinite as an intermediate. Appl. Clay. Sci. 1999, 15,
241–252.
[55] Murray, H.H.; Kogel, J.E. Engineered clay products
for the paper industry. Appl. Clay. Sci. 2005, 29,
199–206.
[56] Dueva, O.V.; Uzunian, G.E. Kaolin: A performance
additive for cosmetics and pharmaceuticals. Cosmet
Toiletries 2001, 116, 67–71.
[57] Krishnan, A.K.; George, T.S.; Anjana, R.; George, K.E.
Effect of modified kaolin clays on the mechanical
properties of polypropylene/polystyrene blends. J. Appl.
Polym. Sci. 2013, 127, 1409–1415.
930 S. HAIDER ET AL.
[58] Buggy, M.; Bradley, G.; Sullivan, A. Polymer–filler
interactions in kaolin/nylon 6,6 composites containing
a silane coupling agent. Compos. A Appl. Sci. Manuf.
2005, 36, 437–442.
[59] Ngo, V.G.; Bressy, C.; Leroux, C.; Margaillan, A. Syn-
thesis of hybrid TiO2 nanoparticles with well-defined
poly(methyl methacrylate) and poly(tert-
butyldimethylsilyl methacrylate) via the RAFT process.
Polymer 2009, 50, 3095–3102.
[60] Xie, W.; Hwu, J.M.; Jiang, G.J.; Buthelezi, T.M.; Pan,
W.P. A study of the effect of surfactants on the proper-
ties of polystyrene–montmorillonite nanocomposites.
Polym. Eng. Sci. 2003, 43, 214–222.
[61] Zidelkheir, B.; Boudjemaa, S.; Abdel-Goad, M.; Djellouli,
B. Preparation and characterization of polystyrene/
montmorillonite nanocomposite by melt intercalative
compounding. Iran Polym J. 2006, 15, 645–654.
[62] Akelah, A.; Rehab, A.; Agag, T.; Betiha, M. Polystyrene
nanocomposite materials by in situ polymerization into
montmorillonite–vinyl monomer interlayers. J. Appl.
Polym. Sci. 2007, 103, 3739–3750.
[63] Liu, S.P.; Huang, I.J.; Chang, K.C.; Yeh, J.M.
Mechanical properties of polystyrene–montmorillonite
nanocomposites—prepared by melt intercalation.
J. Appl. Polym. Sci. 2010, 115, 288–296.
[64] Liu, J.; Fu, M.; Jing, M.; Li, Q. Flame retardancy
and charring behavior of polystyrene–organic
montmorillonite nanocomposites. Polym. Adv.
Technol. 2013, 24, 273–281.
[65] Kamrupi, I.R.; Dolui, S.K. Synthesis of polystyrene/
bentonite clay nanocomposites by emulsion polymeri-
zation in aqueous and in supercritical carbon dioxide
medium. J. Compos. Mater. 2011, 45, 2437–2446.
[66] Ruamcharoen, J.; Ratana, T.; Ruamcharoen, P.
Bentonite as a reinforcing and compatibilizing filler
for natural rubber and polystyrene blends in latex stage.
Polym. Eng. Sci. 2014, 54, 1436–1443.
[67] Mostafa, B.A.; Assaad, F.F. Rheological and electrical
properties of bentonite in anionic polystyrene sulfonate
and nonionic poly(vinyl alcohol). J. Appl. Polym. Sci.
2007, 104, 3886–3894.
[68] Uğur, Ş.; Yargı, Ö.; Günister, E.; Pekcan, Ö. Poly
(styrene) latex/modified Na-activated bentonite
nanocomposite films: a fluorescence study. Appl. Clay.
Sci. 2008, 42, 39–49.
[69] Burmistr, M.V.; Sukhyy, K.M.; Shilov, V.V.; Pissis, P.;
Spanoudaki, A.; Sukha, I.V.; Tomilo, V.I.; Gomza, Y.
P. Synthesis, structure, thermal and mechanical
properties of nanocomposites based on linear polymers
and layered silicates modified by polymeric quaternary
ammonium salts (ionenes). Polymer 2005, 46,
12226–12232.
[70] Hausner, J.; Fischer, B.; Stöter, M.; Edenharter, A.;
Schmid, J.; Kunz, R.; Rosenfeldt, S.; Altstädt, V.; Breu,
J.; Increasing time of ignition for PS-clay nano-
composites filled with [Fe(bpy)3]2þ-modified hectorite.
Polym. Degrad. Stab. 2016, 128, 141–148.
[71] Voulgaris, D.; Petridis, D. Emulsifying effect of
dimethyldioctadecylammonium–hectorite in
polystyrene/poly(ethyl methacrylate) blends. Polymer
2002, 43, 2213–2218.
[72] Schütz, M.R.; Kalo, H.; Lunkenbein, T.; Gröschel, A.H.;
Müller, A.H.; Wilkie, C.A.; Breu, J. Shear stiff, surface
modified, mica-like nanoplatelets: a novel filler for
polymer nanocomposites. J. Mater. Chem. 2011, 21,
12110–12116.
[73] Porter, T.L.; Hagerman, M.E.; Reynolds, B.P.; Eastman,
M.P.; Parnell, R.A. Inorganic/organic host–guest mate-
rials: surface and interclay reactions of styrene with
copper (II)-exchanged hectorite. J. Polym. Sci. B Polym.
Phys. 1998, 36, 673–679.
[74] Zheng, X.; Jiang, D.D.; Wilkie, C.A. Polystyrene
nanocomposites based on an oligomerically-modified
clay containing maleic anhydride. Polym. Degrad. Stab.
2006, 91, 108–113.
[75] de Macêdo Neto, J.C.; Botan, R.; Lona, L.M.F.; Neto,
J.E.; Pippo, W.A. Polystyrene/kaolinite nanocomposite
synthesis and characterization via in situ emulsion
polymerization. Polym. Bull. 2015, 72, 387–404.
[76] George, T.S.; Krishnan, A.; Anjana, R.; George, K.E.
Effect of maleic anhydride grafting on nanokaolinclay
reinforced polystyrene/high density polyethylene
blends. Polym. Compos. 2012, 33, 1465–1472.
[77] Elbokl, T.A.; Detellier, C. Aluminosilicate nanohybrid
materials. Intercalation of polystyrene in kaolinite.
J. Phys.Chem. Solids. 2006, 67, 950–955.
[78] Abdallah, L.S.; Zihlif, A.M. Effect of grain size on the
AC electrical properties of kaolinite/polystyrene
composites. J. Thermoplast. Compos. Mater. 2010, 23,
779–792.
[79] Sbeih, S.A.; Zihlif, A.M. Optical and electrical
properties of kaolinite/polystyrene composite. J. Phys.
D: Appl. Phys. 2009, 42, 145405.
[80] Tullo, A.H. Driving efficiency. Chem. Eng. News. 2006,
84, 12–18.
[81] Morgan, A.B. Flame retarded polymer layered silicate
nanocomposites: a review of commercial and open
literature systems. Polym. Adv. Technol. 2006, 17,
206–217.
[82] Garces, J.M.; Moll, D.J.; Bicerano, J.; Fibiger, R.;
McLeod, D.G. Polymeric nanocomposites for automo-
tive applications. Adv. Mater. 2000, 12, 1835–1839.
[83] Bourbigot, S.; Devaux, E.; Flambard, X. Flammability of
polyamide-6/clay hybrid nanocomposite textiles.
Polym. Degrad. Stab. 2002, 75, 397–402.
[84] Edser, C. Auto applications drive commercialization
of nanocomposites. Plast. Addit. Compound. 2002, 4,
30–33.
[85] Fischer, H. Polymer nanocomposites: from fundamen-
tal research to specific applications. Mater. Sci. Eng. C.
2003, 23, 763–772.
[86] Camargo, P.H.C.; Satyanarayana, K.G.; Wypych, F.
Nanocomposites: synthesis, structure, properties and
new application opportunities. Mater. Res. 2009, 12,
1–39.
[87] Hackman, I.; Hollaway, L. Epoxy-layered silicate
nanocomposites in civil engineering. Compos. A Appl.
Sci. Manuf. 2006, 37, 1161–1170.
[88] Avella, M.; de Vlieger, J.J.; Errico, M.E.; Fischer, S.;
Vacca, P.; Volpe, M.G. Biodegradable starch/clay
nanocomposite films for food packaging applications.
Food Chem. 2005, 93, 467–474.

[89] Schubel, P.J.; Johnson, M.S.; Warrior, N.A.; Rudd, C.D.
Characterisation of thermoset laminates for cosmetic
automotive applications: Part III–Shrinkage control
via nanoscale reinforcement. Compos. A Appl. Sci.
Manuf. 2006, 37, 1757–1772.
[90] Presting, H.; König, U. Future nanotechnology
developments for automotive applications. Mater. Sci.
Eng. C 2003, 23, 737–741.
[91] Arvanitoyannis, I.S.; Bosnea, L. Migration of substances
from food packaging materials to foods. Crit. Rev. Food
Sci. Nutr. 2004, 44, 63–76.
[92] Jia, X.; Li, Y.; Cheng, Q.; Zhang, S.; Zhang, B.
Preparation and properties of poly(vinyl alcohol)/silica
nanocomposites derived from copolymerization of
vinyl silica nanoparticles and vinyl acetate. Eur. Polym.
J. 2007, 43, 1123–1131.
[93] Goettler, L.A.; Lee, K.Y.; Thakkar, H. Layered silicate
reinforced polymer nanocomposites: development and
applications. Polym. Rev. 2007, 47, 291–317.
[94] Zhou, Q.; Pramoda, K.P.; Lee, J.M.; Wang, K.; Loo, L.S.
Role of interface in dispersion and surface energetics
of polymer nanocomposites containing hydrophilic
POSS and layered silicates. J. Colloid Interface Sci.
2011, 355, 222–230.
[95] Podsiadlo, P.; Kaushik, A.K.; Arruda, E.M.; Waas, A.
M.; Shim, B.S.; Xu, J.; Nandivada, H.; Pumplin, B.G.;
Lahann, J.; Ramamoorthy, A.; Kotov, N.A. Ultrastrong
and stiff layered polymer nanocomposites. Science
2007, 318, 80–83.
[96] Li, Y.C.; Schulz, J.; Mannen, S.; Delhom, C.; Condon,
B.; Chang, S.; Zammarano, M.; Grunlan, J.C. Flame
retardant behavior of polyelectrolyte–clay thin film
assemblies on cotton fabric. ACS Nano 2010, 4,
3325–3337.
[97] Sinha Ray, S.; Yamada, K.; Okamoto, M.; Ueda, K.
Polylactide-layered silicate nanocomposite: a novel
biodegradable material. Nano Lett. 2002, 2, 1093–1096.
[98] Çelik, S.Ü.; Bozkurt, A.; Hosseini, S.S. Alternatives
toward proton conductive anhydrous membranes for
fuel cells: heterocyclic protogenic solvents comprising
polymer electrolytes. Progr. Polym. Sci. 2012, 37,
1265–1291.
[99] Devrim, Y.; Erkan, S.; Bac, N.; Eroğlu, I. Preparation
and characterization of sulfonated polysulfone/
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 931
titanium dioxide composite membranes for proton
exchange membrane fuel cells. Int. J. Hydrogen Energy
2009, 34, 3467–3475.
[100] Yang, C.; Costamagna, P.; Srinivasan, S.; Benziger, J.;
Bocarsly, A.B. Approaches and technical challenges
to high temperature operation of proton exchange
membrane fuel cells. J. Power Sources 2001, 103, 1–9.
[101] Bose, S.; Kuila, T.; Nguyen, T.X.H.; Kim, N.H.; Lau, K.
T.; Lee, J.H. Polymer membranes for high temperature
proton exchange membrane fuel cell: recent
advances and challenges. Progr. Polym. Sci. 2011, 36,
813–843.
[102] Mishra, A.K.; Bose, S.; Kuila, T.; Kim, N.H.; Lee, J.H.
Silicate-based polymer-nanocomposite membranes for
polymer electrolyte membrane fuel cells. Progr. Polym.
Sci. 2012, 37, 842–869.
[103] Chen, B.; Evans, J.R.; Greenwell, H.C.; Boulet, P.;
Coveney, P.V.; Bowden, A.A., Whiting, A. A critical
appraisal of polymer–clay nanocomposites. Chem.
Soc. Rev. 2008, 37, 568–594.
[104] Choi, S.; Coronas, J.; Sheffel, J.A.; Jordan, E.; Oh, W.;
Nair, S.; Shantz, D.F.; Tsapatsis, M. Layered silicate
by proton exchange and swelling of AMH-3. Micropor-
ous Mesoporous Mater. 2008, 115, 75–84.
[105] Jeong, H.K.; Nair, S.; Vogt, T.; Dickinson, L.C.;
Tsapatsis, M. A highly crystalline layered silicate with
three-dimensionally microporous layers. Nat. Mater.
2003, 2, 53–58.
[106] Hudiono, Y.; Choi, S.; Shu, S.; Koros, W.J.; Tsapatsis, M.;
Nair, S. Porous layered oxide/Nafion1 nanocomposite
membranes for direct methanol fuel cell applications.
Microporous Mesoporous Mater. 2009, 118, 427–434.
[107] Tripathi, B.P.; Shahi, V.K. Organic–inorganic
nanocomposite polymer electrolyte membranes for
fuel cell applications. Progr. Polym. Sci. 2011, 36,
945–979.
[108] Tanaka, T.; Montanari, G.C.; Mulhaupt, R. Polymer
nanocomposites as dielectrics and electrical insulation-
perspectives for processing technologies, material
characterization and future applications. IEEE Trans.
Dielectr. Electr. Insul. 2004, 11, 763–784.
[109] Morgan, A.B.; Gilman, J.W. Polymer–clay nano-
composites: design and application of multi-functional
materials. Mater. Matters 2007, 2, 20–25.