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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

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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 mechanical mixing, solution polymerization, bulk
size of the filler particles, and interaction between parti- polymerization, and emulsion polymerization have been
cles and polymer matrix[2]. Clays are the most abundant, used. Among the approaches stated above, emulsion
natural, and inexpensive class of filler materials. They are polymerization is more attractive for ease of handling,
extracted as coarse particles made up of tactoids (layered low cost, and environmental friendliness[9]. PS is a
structure), which can be exfoliated giving high aspect highly commercialized thermoplastic material which is
ratio particles. Polystyrene (PS) is among the most exten- used in a variety of applications including packaging,
sively used polymers. The degree of clay dispersion in construction, appliances, consumer electronics, medical,
polystyrene/clay nanocomposite has been governed by and various other uses. In last two decades, one of the
type of clay, surfactant used in clay modification, and rapidly growing areas for plastics is packaging industry.
the synthesis method. The commonly used clays are This is due to ease, low price, safety, and good aesthetic
montmorillonite (MMT), hectorite, and saponite[3]. The qualities of plastics[10]. Thermoplastics are replacing
clay dispersion in a polymer matrix can give three types metals in several applications. They may offer better
of composite materials, i.e., (i) conventional microcom- corrosion resistance, lightweight per item, lower cost,
posite (no exfoliation); (ii) intercalated polymer/clay and better flexibility in part design[11]. The enhance-
nanocomposites; and (iii) exfoliated polymer/clay ment of thermal stability and flammability performance
nanocomposite[4]. The terms intercalated and exfoliated of widely used thermoplastics is a major concern both in
layered silicate nanocomposites are often used to academic world and in industries[12]. As a result, modi-
describe two extremes of silicate layer organization in fication of polystyrene (one of the most commercialized
composite structure. Intercalation means the insertion thermoplastics) by addition of flame retardants is
(intercalation) of one or several polymer chains in crucial. It has been shown that the nanoparticles, bromi-
galleries of original tactoids, which may lead to some nated flame retardants and Sb2O3, can be used as flame
longitudinal expansion of galleries[5]. The regular layer retardant additives or fillers for polystyrenes[13]. PS also
stacking arrangement is preserved in intercalation, exhibits some disadvantageous properties, i.e., relatively
however exfoliation (delamination) implies complete high flammability. This is the reason why polystyrene
rupture of original layer stacking and uniform disper- composites have been studied for properties
sion. Exfoliated nanocomposite generally has excep- improvement[14]. Polystyrene is a synthetic hydrophobic
tional properties comparative to other composites[6]. polymer that is not biodegradable. Thus, it may cause
Owing to nanometer-sized particle dispersion, nano- environmental pollution[15]. There are different
composite exhibits markedly improved properties rela- alternatives for reducing the dispersion problems and
tive to pure polymers or conventional composites. for converting it into valuable products including
These nanocomposites possess improved strength and polymer modification and functionalization[16]. The
modulus, increased solvent and heat resistance, insertion of polar groups into synthetic polymers
decreased gas permeability, and decreased flammability, causes initiation of hydrophilicity[17]. Functionalized
for example, a doubling of tensile modulus and strength polystyrene has different applications, for example, as
is obtained for polymer/layered silicate nanocomposite a polyelectrolyte for water treatment processes[18].
with as little as 2 vol% of inorganic content. Besides,
the heat distortion temperature of nanocomposite
Clay
increases up to 100°C, extending their use to higher tem-
perature environments such as automotive under the The rapid progress of chemistry in development of
hood parts. In addition, heat release rate in nanocompo- nanoparticles has verified tremendous improvements
site reduces up to 63% at heat flux of 50 kW m 2 without in this field[19]. The concept of using nanoparticles as
an increase in soot formed during combustion[7]. fillers in polymer materials was introduced due to their
exclusive mechanical, optical, electrical, and thermal
properties[20]. Variety of nanoparticles such as alumina,
Polystyrene
micro and nanosized silicon carbide, calcium carbonate,
Polystyrene (PS) is a resourceful polymer with the silica, zinc, and carbon black nanoparticles have been
features of good optical transparency, low price, used as fillers to improve the material properties for
mechanical properties, and excellent electric polymer nanocomposite[21]. Clay is the most widely
insulation[8]. PS is a commercialized and mass pro- studied material as filler in the production of polymer
ductive polymer. Therefore, continuing research efforts nanocomposite. It is relatively much preferred for the
have been devoted to the development of polystyrene– synthesis of polymer nanocomposite as it is economical,
clay nanocomposite. Different methods based on simple 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 studied[45,46]. Hectorite has been used as an adsorbent
negative surfaces of the clay. This occurs because of for color removal of basic dyes and metal ions[47].
much larger adsorption capacity of the clay for these Hectorite-supported metal catalyst and pillared hectorite
cations. This reaction increases the basal spacing of have been prepared[48]. These modified hectorites have
MMT clays after treatment with organic cations. The been used as catalyst for hydrogenation reactions.
obtained compounds are known as organophilic Hectorite has been modified by two cationic surfactants
bentonites[37]. Bentonites are extensively used as (cetyldimethyl benzylammonium chloride and cetylpyr-
catalysts, as geoenvironmental barriers and liners (for idinium chloride). These organically modified hectorites
landfills), for dye removal from water-based waste may be used as adsorbent for the removal of anionic
streams as oil-spill cleanup and remediation agents. dyes, pesticides, and organic compounds. At present,
Acid-activated bentonites have been a valuable product no studies are available on organically modified hectorite
for several decades. The manufactured materials are for the removal of anionic dyes[49].
broadly available and comparatively economical solid
sources of protons. They have been used to manufacture
Kaolinite
industrially important products such as catalysts,
catalyst supports, and adsorbents. Acid activation Kaolinite is the most abundant mineral of kaolin group,
creates the so-called bleaching earths, which are clays which also includes nacrite, dickite, halloysite, and their
suitable for a variety of decolorizing applications[38]. 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
Hectorite
aluminum cations coordinated by hydroxyl groups, with
The chemical formula for hectorite is Na0.3(Mg,Li)3 some hydroxyl substituted by the oxygens of Si–O sheet.
Si4O10(OH)2. A specimen of hectorite; obtained from The layers are held together through hydrogen bonds,
the mine and has a soft and greasy texture. It is one of dipolar interaction, and van der Waals forces, which
the more expensive clays due to its exceptional result in low-intrinsic inner surface reactivity. Its
thixotropic properties. The major uses of hectorite are chemical structure, Al2Si2O5(OH)4, has a molecular
in chemical, industrial material production, and in weight of 258.10 g/mol with an ideal composition of
cosmetics[39]. Hectorite, along with MMT, is one of the 46.55% SiO2, 39.49% Al2 O3, and 13.96% H2O[50]. The
most frequently used smectite-type layered silicates for basal spacing of kaolinite is 0.72 nm[51]. Since it is made
the preparation of polymer nanocomposites because of up of two types of interlayer surfaces, i.e., (SiO)6 macror-
its high ion-exchange capacity and surface area[40]. The ings on one side and alumina groups on the other side,
difficulty of dispersing hectorite in highly viscous and kaolinite is, thus, notable by its noncentrosymmetric
hydrophobic polyolefin matrix such as polyethylene structure. This asymmetry creates large superposed
can be overcome by replacing the hectorite interlayer dipoles in lamellar structure, which results in large
cations with long-chain alkyl ammonium or phos- cohesive energy. Therefore, the intercalation chemistry
phonium cations[41]. The synthetic hectorite clay, of kaolinite is less developed than that of swelling
laponite, can be exfoliated in water to monodisperse smectites[52]. The kaolinite grains are found in the form
nanoplatelets of 30 nm diameter and 1 nm thickness[42]. of plates throughout the sedimentary rocks of volcanic
A laponite suspension will change into an isotropic soft source[53]. With hydrogen bonding between the layers,
solid after aged over time due to electrostatic interaction kaolinite has often been classified as a nonexpandable
of negative charge on the surface and positive charge mineral. There are a limited number of organic
at the edge[43]. The hectorite clay is mostly used as a compounds which can be intercalated between kaolinite
rheology modifier in surface coatings, paints, adhesives, layers. The compounds mostly used are dimethylsulfox-
and personal care products. Due to charged nature of ide (DMSO), N-methylformamide, formamide,
clay particles, product property is sensitive to a slight hydrazine, n-dodecylamine, urea, deuterated DMSO,
change in pH and ionic strength, which considerably potassium acetate, and methanol, which can be directly
limits application of the materials. Thus it is a common intercalated between kaolinite layers[54]. Kaolinite is
technique to add polymers to suspensions, which stabi- used in several industrial applications, usually in paper
lizes the suspension by steric hindrance after adsorption. industry as filler and in ceramic industry where its main
Moreover, polymers prolong the shelf life under a variety function is to offer whiteness to ceramic body[55]. It is
of pH and ionic strength[44]. The effect of adsorbed also used as filler in paints, rubber, cosmetics, and
polymer on linear viscoelastic rheology, i.e., behaviors pharmaceutical applications[56]. Kaolinite has a potential
at the small deformation limit, has been intensively to be an ideal precursor for the preparation of new
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 921

nanocomposite materials, since it is cost effective as was performed by treating with octadecylammonium
compared to MMT clays[57]. Kaolin is readily available cation[61]. The polymer nanocomposite was character-
and cost-effective mineral to reinforce polymers. ized using different techniques such as XRD, infrared
Although when particle fillers are integrated into (IR) spectrophotometry, thermal gravimetric analysis
polymers, strength, elongation, and impact properties (TGA), differential scanning calorimetry (DSC),
are not usually sacrificed, owing to strong tendency to rheology, and tensile measurements. The results showed
self-agglomerate[58]. The best way to avoid aggregation that the basal space of silicate layer increased from 12.6 to
is to graft polymer chains onto the particles 32.3 Å, as determined by XRD. The microstructure was
covalently[59]. 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
Polystyrene/montmorillonite nanocomposite greatest enhancement in thermal stability. The rheologi-
Polystyrene–MMT nanocomposite has been synthesized cal properties of PS–OMMT composites were studied
using suspension polymerization by Xie et al.[60]. The using advanced rheometric expansion system-rheometer
reaction system of PS–MMT nanocomposite during operated in dynamic mode with parallel plate geometry.
suspension polymerization is shown in Figure 2. X-ray The storage and loss moduli were increased with an
diffraction (XRD) and transmission electron microscopy increasing clay content. The stress-at-break was also
(TEM) results showed that the silicate layers were improved as compared to virgin polystyrene. Poly-
exfoliated and having fine dispersion in polystyrene styrene–organoclay nanocomposite has been synthesized
matrix. Further results demonstrated that the PS– by graft polymerization of styrene on vinyl monomer-
MMT nanocomposite has better mechanical properties MMT[62]. The preparation was performed by modifi-
and thermal stability compared with pure polystyrene. cation of MMT with different vinyl monomers such
The optimum organo-MMT content to give property as N,N-dimethyl-n-octadecyl-4-vinylbenzyl-ammonium
improvement is 5 wt% for thermal stability of nanocom- chloride, n-octadecyl-4-vinylbenzyl-ammonium chlor-
posite and 7.5 wt.% for mechanical property. The alkyl ide, triphenyl-4-vinylbenzylphosphonium chloride, and
chain length of the surfactant used in fabricating of tri-n-butyl-4-vinylbenzylphosphonium chloride. In situ
organo-MMT affects the synthesized PS nanocomposite. polymerization of styrene monomer with different
The organoclay in nanocomposite seems to have dual ratios of vinyl monomer-MMT was then performed.
role: (i) as nanofiller leading to an increase in the storage The distinctive properties of the prepared materials were
modulus and (ii) as plasticizer leading to the decrease inspected by different physical and chemical methods.
instorage modulus. This results in lower storage Verification of vinyl monomer-cation intercalation in
modulus of polystyrene–trimethyl octadecyl ammonium clay interlayers was obtained by IR spectra. The thermal
chloride MMT and polystyrene–trimethyl tallow properties were determined using TGA, which revealed
ammonium chloride MMT nanocomposite than that of higher thermal stability for PS/MMT nanocomposite
polystyrene–trimethyl dodecyl ammonium chloride than neat polystyrene. X-ray diffraction analysis
MMT and polystyrene–trimethyl coco ammonium demonstrated that the nanocomposite was exfoliated at
chloride MMT nanocomposite[60]. Polymer nanocom- � 25 wt% of organoclay content. Scanning electron
posite based on organically modified MMT (OMMT) microscopy (SEM) showed a complete dispersion of PS
and polystyrene has been prepared with different into the clay galleries. Moreover, TEM showed the
compositions using melt processing. The pristine MMT formation of spherical particles within a nanosize of
was obtained from Algerian plant with a cation-exchange 150–400 nm. A series of polymer/clay nanocomposite
capacity of 119 meq/100 g. The modification of MMT (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
Figure 2. Reaction system of PS/MMT nanocomposite in resistance of PS was effectively improved by the inclusion
suspension polymerization. of low loading organophilic clay platelets. Moreover,
922 S. HAIDER ET AL.

the effect of organoclay on mechanical properties for as- and the particle forming efficiency of the nanocomposite
prepared PCN materials, e.g., impact tests, flexural tests, were found better in sc-CO2 medium than in aqueous
and micro and nanoindentation tests were measured and medium. Bentonite clay was used as compatibilizing
compared. PCN materials exhibited an evident improve- and reinforcing filler for natural rubber/polystyrene
ment in mechanical properties of PS by incorporating (NR/PS) blend prepared through latex blending
low loading organophilic clay platelets[63]. The fire per- process[66]. The reinforcing and compatibilizing perfor-
formance of polystyrene/OMMT nanocomposite was mance of bentonite clay in NR/PS blends were evaluated.
studied by limiting oxygen index (LOI) and cone The enhancement in mechanical properties of NR/PS
calorimetr[64]. SEM, electron-dispersive spectroscopy, blends with weight ratios of 90/10, 80/20, and 70/30
and attenuated total reflection Fourier transform infra- was observed with the addition of 3 and 5 parts per
red (FTIR) spectroscopy were used to study the charring 100 rubber (phr) clay. The characterization using FTIR
process of nanocomposites. The residue collected upon spectroscopy and XRD indicated that the silicate layer
thermal degradation was analyzed by various methods was intercalated by NR and PS molecular chains. The
to find out its composition and to understand the compatibilization action of bentonite clay was also
flame-retardant mechanism of the nanocomposite. reflected by shift of glass transition temperature (Tg) of
Introduction of OMMT had no influence on LOI of NR to higher temperature than the blends. These results
the nanocomposite; however, it significantly decreased suggested that the tensile and tear properties of the
heat release rate (HRR) and mass loss rate (MLR) of blends were controlled by compatibility between NR
the material. The flame-retardant mechanism is due to and PS. The mainly improved properties of blends were
charring in the condensed phase. The porous structure found with the addition of 3 phr bentonite clay. The flow
of the charred residue reduced the HRR, MLR, and so properties of bentonite were studied with a combination
retarded the burning of material. 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-
Polystyrene–bentonite nanocomposite
nation had a major effect on clay suspension depending
Polystyrene–bentonite clay nanocomposite has been on the order of the polymer addition. The addition of
prepared by emulsion polymerization in both aqueous 50 mg/L anionic polystyrene sulfonate followed by
and supercritical carbon dioxide (sc-CO2) media[65]. 200 mg/L nonionic poly(vinyl alcohol) improved the
The scheme for processing of nanoclay in sc-CO2 rheological properties. The composites of surfactant-free
medium is shown in Figure 3. The particle size of the PS nanoparticles and modified Na-activated bentonite
nanocomposite decreased with an increase in clay load- (MLB) have been studied by Uğur et al.[68] using
ing in both the media. The distinct- and uniform-sized steady-state fluorescence (SSF) technique. The com-
particles were observed in sc-CO2 medium, while posite films were prepared from a mixture of pyrene
agglomerated particles were obtained in aqueous (P)-labeled PS particles and MLB at various composi-
medium. TEM and XRD results indicated exfoliated tions at room temperature. These films were annealed
nature of clay layers in nanocomposite synthesized in at elevated temperature exceeding Tg of polystyrene.
sc-CO2 medium, whereas intercalation and low exfoli- Scattered light (Is) and fluorescence intensities (IP) from
ation were observed for nanocomposite synthesized in P were measured after each annealing step to observe
aqueous medium. The interlayer distance of the clay the stages of film formation. The progression of trans-
was increased from 2.36 to 4.9 nm in sc-CO2 medium, parency of the composite films was also monitored.
while it increased from 2.36 to 3.67 nm in aqueous Atomic force microscopy (AFM) was used to identify
medium. The mechanical properties of the nanocompo- the variation in physical structure of annealed composite
site synthesized in sc-CO2 medium were found higher films. The nanocomposite films showed a percolation
than in aqueous medium. Similarly, thermal properties 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.
Figure 3. Scheme for processing of nanoclay in sc-CO2 medium. 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].

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
Figure 4. TGA of PA and PA–organobentonite composite[69]. (TSP). The improved performance may be directly
related to the thermal stability and redox properties of
and dispersed into polyamide and polystyrene. Addition [Fe(bpy)3]2þ, while [Fe(bpy)3]2þ-Hec showed good fire
of 2 wt% organobentonite (optimal concentration) to performance, char forming properties, and thermal
polyamide increased tensile strength by 53% and stability (Figure 6)[70]. The PS-[Fe(bpy)3]2þ-Hec nano-
Charpy impact by 140%. With an inclusion of 2 wt% composite showed a residue amount of 3.0 � 0.2 g
organobentonites (optimal concentration) into poly- which fairly equates the inorganic content of the nano-
styrene, the tensile strength was increased to 28% and composites and indicated little to no char formation.
the Charpy impact increased to 25%. The polyamide PS-C18-Hec nanocomposite showed slightly high
(PA) and PS-organobentonite nanocomposite showed residue amount of 3.8 � 1.0 g (Table 2). An organically
better mechanical properties and Charpy impact than 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 analysis showed the development of fibrillar morphology
emulsifying action of organoclay was also revealed by due to the inclusion of clay. Elbokl et al.[77] formed
the presence of only one Tg in DSC thermograms. intercalated nanocomposite by free radical-initiated
The performance of the obtained PS nanocomposite polymerization reaction of styrene and a kaolinite
was improved as compared to natural clay PS DMSO intercalate. The DMSO molecules were com-
nanocomposite[72]. Porter et al.[73] prepared Cuþ2- pletely replaced by one layer of polystyrene chains in
exchanged hectorite clay films by in situ polymerization the interlamellar spaces of kaolinite. The nanohybrid
of many organic monomers. In the case of styrene, decomposed at temperature above 300°C (air), with a
surface polymerization occurred in conjunction with maximum exotherm at 370°C. The results of the XRD
partial intercrystallite intercalation and polymerization. proved the intercalation of polystyrene in the interlamel-
Polystyrene on the clay surface exhibited a possible lar spaces of kaolinite (Figure 7). Abdallah et al.[78]
brush-like structure. Intercrystallite polystyrene may concluded that the overall electrical behavior was
exist in two faraway phases, one of which is similar to influenced by some processes such as ion diffusion,
surface bulk polymer, while the other has high degree electron hopping, and space charge polarization during
of material stiffness owing to higher degree of polymer composite microstructure formation[78]. The optical
ordering. Polystyrene hectorite clay nanocomposites and electrical characteristics of kaolinite/polystyrene
were also prepared by melt blending of polystyrene with composites containing 20 wt% kaolinite with grain sizes
an oligomerically modified clay[74]. 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-
Polystyrene/kaolinite nanocomposite ometer. The optical band gap and energy tail widths of
Botan et al.[75] synthesized PS/kaolinite (Kao) nanocom- localized states were determined for the prepared
posite by in situ emulsion polymerization. First kaolin composites. It was found that the optical energy gap
was modified using DMSO by displacement method and the energy tail width changed with the kaolinite
(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 Figure 7. XRD powder patterns (2θ ¼ 2–18°) for (a) kaolinite,
neat matrix. DSC records showed an increase in melting (b) kao–polystyrene, and (c) kao–DMSO[77].
POLYMER-PLASTICS TECHNOLOGY AND ENGINEERING 925

grain size. The electrical properties were studied using membranes in fuel cells and seat textiles, fuel systems,
AC impedance measurements performed at different mirror housings on various vehicle types, engine covers,
temperatures and frequency of 100 kHz–1 MHz. door handles, intake manifolds, and timing belt
covers[84]. For example, a thermoplastic nanocomposite
containing nanoflake reinforcement (trade name Basell
Application of polymer–clay nanocomposite
TPO-Nano) is being employed for the development of
Polystyrene–clay nanocomposites have found applica- stiff and light exterior parts. Furthermore, porous
tions in a range of technical fields; few of them are polymer nanocomposite can be used for the develop-
described in this section. Polymer–clay nanocomposites ment of pollution filters[85]. Other technological
have gained significant recognition in materials industry application in the horizon is in air bag sensors, where
due to improved performance and applicability in nano-optical platelets are kept inside the polymer outer
polymer and metal replacement. For example, PNC layer for conveying signals at speed of light[86].
automotive body components bring scratch and rust
resistance along with weight savings. The embedded
Civil engineering
nanoparticles in cloth induce stain and water resistance
to clothing. Tennis balls with an interior nanoplatelet Polymer–clay nanocomposite is emergent area of
coating provide enhanced air retention for extensive nanotechnology, which have the potential to offer many
performance. The infrastructure is falling into place at wide-ranging benefits to current matrix polymers. Their
the governmental, investment, commercial, and aca- ability to increase the service life of materials subjected
demic levels to support continuing growth of the nano- to aggressive environments could be utilized to increase
technology industry including chemicals, electronics, the durability of glass and carbon fiber composites. This
medicines, photonics, and energy in addition to materi- advantage could permit the use of composite materials in
als. Nanocomposites can bring enhancement in perfor- situations where their performance under aggressive
mance and properties along with savings in processing environments is insufficient for the in-service con-
and fuel usage due to weight reduction of more than ditions. The increase in service life would allow the com-
50% in selected parts[80]. 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
Flame retardancy
nanocomposite have also resulted in several industrial
The use of polymer/clay nanocomposite for flame- applications. These include impellers and blades for vac-
retardant applications is becoming widespread. The clay uum cleaners, power tool housings, mower hoods, and
nanocomposite can substitute part of the flame- covers for portable electronic equipment such as mobile
retardant package while maintaining fire safety ratings phones and pagers[88]. Another example is the use of
at a lower flame-retardant loading[81]. The use of polymer nanocomposites in glues for the manufacturing
nanocomposite in vehicle parts and systems is expected of pressure molds in the ceramic industry. Moreover,
to improve flammability, manufacturing speed; enhance unsaturated polyester (UPE) nanocomposite can be
thermal and environmental stability; reduce weight; and used in fiber-reinforced products used in marine,
promote recycling. Nanocomposite-based parts give construction, and transportation industries[89].
strength, stiffness, and reliability better than metals. Currently, UPE–fiberglass nanocomposite, whose
They offer corrosion resistance, enhanced modulus, formulations are offered from Polymeric Supply, Inc.,
noise dampening, thermal stability, and dimensional is being used in boat accessories that are stronger and
stability[82]. The heat-resistant polymer nanocomposite less prone to color vanishing[90].
is used to make firefighter’s protective clothing and
lightweight components appropriate to work in situa-
Barrier application
tions of high stress and temperature. This comprises
skins of jet aircrafts and hoods of automobiles, as When food will not be consumed instantly after pro-
opposed to heavier and costlier metal alloys. They can duction, it must be contained in a package that serves
also replace corrosion-prone metals in building of various functions. Packaging is used to protect food
bridges and other large structures with potentially from dirt or dust, light, oxygen, pathogenic micro-
stronger and lighter capabilities[83]. Regarding the organisms, moisture, and a variety of other harmful
variety of applications of polymer nanocomposite, major substances. The packaging must be safe under intended
impacts over the automotive industry can be high- conditions of use, inert, cheap to produce, lightweight,
lighted, including their use in tires, gas separation 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.
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
Figure 11. Differences between a diesel engine and a fuel cell
were used to prepare PEMs by dispersion in an organic
engine. solvent, followed by the addition of ionomer solution
(Figure 12)[107].
composites with excellent transport and mechanical
properties. The ionic/electronic conductivity and biode- Future relevance
gradability of these nanocomposites were enhanced by
The development of nanocomposites represents a very
the addition of small amount of clay. Clay often behaves
attractive way to improve and diversify properties of
as a nucleating agent for crystallization of semicrystalline
conventional polymers without changing polymer
polymers, though intercalating polymers become
compositions and processing. In contrast to conven-
amorphous with clay loading[103]. Layered nanoporous
tional filled polymers, nanocomposite is composed of
materials consist of an intermediate structure between
nanometer-sized fillers, nanofiller, which is homoge-
typical layered materials (smectite clays) and crystalline
neously dispersed inside the polymer matrix. The
nanoporous frameworks (zeolites). Each layer includes
addition of just a few wt% of nanofillers has intense
a porous network, while the gallery between layers pro-
impact on the physical, chemical, electrical, and mechan-
vides the ability for intercalation, pillaring, and
ical properties of polymers. Such change is frequently
exfoliation[104]. Layered silicate with three-dimensional
favorable for engineering purpose. This nanocomposite
microporosity allows adsorption, catalysis, and ion-
technology has emerged from the field of engineering
exchange applications. Amherst-3 (AMH-3) is a layered
plastics and potentially expanded its applications to
silicate, with available internal porosity from all direc-
structural materials, coatings, packaging to medical,
tions through eight-member rings, with a pore structure
electronic and photonic devices. Recently these high-
made up of eight SiO4 tetrahedra[105]. Layered oxide–
tech materials with excellent properties have begun to
polymer nanocomposite membranes control the meth-
attract researchers in the field of dielectrics and electrical
anol crossover, and proton conductivity has been
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
Figure 12. Different routes for the preparation of organic- fragile system while keeping other properties intact.
inorganic hybrid materials and polymer electrolyte membranes. The field of polymer/clay nanocomposite and broader
928 S. HAIDER ET AL.

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