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Review on Polymer Nanocomposites by Using Various Resins and

Nanoclays and Their Applications
Deep Chandra Prajapati1, Praveen Gaurav Singh2, Madhuri Girdhar3 and Anupam
Kumar*

ABSTRACT: This review paper focuses on recent development and current research investigated that techniques were used for
enhancing the properties of nanocomposites and their potential applications. Major application of nanocomposites are in the field of
aerospace, automotive, marine, infrastructure, military, food industry, food packaging, biomedical like bone replacement /repair,
dental, and controlled drug delivery. In this review we are focused on the distinct type of resins and nanoclays using for enhanced the
properties such as mechanical, thermal, durability, flame retardant, barrier, modulus, strength, toughness, resistance to chemical, gas
impermeability, electrical instruments etc. The biodegradable nanocomposites including materials, Polymer layer silicate (PLS), Poly
(L-lactide) PLA / OMLS (organo-modified layered silicate), Poly (- caprolactone) (PCL), Nylon-6 based nanocomposites,
Polyethylene (PE), Polycarbonate (PC) Poly (vinyl chloride) (PVC), Polystyrene (PS), Styrene butadiene rubber (SBR), Polyaniline
(PA), Starch, Cellulose, Oil based nanocomposites.
KEYWORDS: Nanofiller, nanoparticles, carbon nanotubes CNT, Montmorillonite MMT, hectorite, and saponite,
Polymethylmethacrylate (PMMA), organoclays (OCs bentonite), TPS-clay, cellulose acetate propionate (CAP), and cellulose acetate
butyrate (CAB).

Introduction
Nanocomposites are an advance field plastics that contain very
small amount of (>10) nanometre sized clay nanoparticles;
those clays particles enhanced the thermal, mechanical, flame
retardant, barrier properties of base polymer (Karabulut M.,
2003). When small amount of (<5 wt %) nanoparticles filler
used, it can increase the modulus, strength, toughness,
resistance to chemical attack, gas impermeability, resistance to
thermal degradation and stability of polymeric material
(Timmerman et al., 2002). The production of biodegradable
nanocomposites is used for making sustainable bio- reinforced
composite applied in automotive, construction materials,
agriculture, packaging, medical devices (Sunday A et al.,
2012). The improvement of the mechanical properties of
nanocomposites such as tensile strength and elastic modulus
of reinforced polymers depends on several factors ie. filler

particles size and concentration, aspect ratio,

dispersion and Morphology. The addition of
nanoparticles
enhances
the
mechanical
properties,
thermochemical properties, and permeability (Sunday A et al.,
2012).
Deep Chandra Prajapati1
Anupam Kumar*
RESEARCH SCHOLAR1 AND ASSISTANT PROF*
Department of Biotechnology
LPU, Phagwara, Punjab (India)
Email: deep.06bt@gmail.com

Improvement of nanocomposite properties are obtained with a

small amount of clay mixed with polymer because the layered
structure of clay provide the exceptionally good barrier
properties that cannot be found in the composites filled with
glass fiber (Choi et al., 2003).The combination of
biodegradable PHB/HB organocaly Nanocomposite
enhances the mechanical properties (Choi et al., 2003). The
nanocomposites are produced from recycled thermoplastics as
the matrix and montmorillonite as the filler with the help of co
rotating twin screw extruder (Karabulut. 2003). The two
approaches widely used for nanoscale particles production are
achieved by introducing nanoparticles into polymer matrix to
create a polymer /nanoparticles composites and by another
fabricating material themselves on the nanoscale .Utilization
of nanoparticles in the fabricated nanocomposites include
inorganic, organic and metal particles such as clays,
nanotubes, magnetite, Au, Ag, hydroxyapatite, cellulose,
chitin whiskers and lignin (Yang et al., 2007).
The polymer nanocomposites (PNC) are the alternative
of polymer (thermoplastic, thermosets and elestomers) of
conventional filled polymers or polymer blends. The
development of the PNC, two types nanoparticles used is
layered silicates and carbon nanotubes. Three main
constituents of the nanocomposites the matrix, the
reinforcement fiber, and the so called interfacial region (E
Gacitua et al.,2005).The enhancement of the thermal stability
of composites from the blending of PHB with other polymer
or filling PHB with nanofiller such as montmorillonite or
carbon nanotubes. The metal nanoparticles may increase or
suppress the thermal stability of nanocomposites. Pd and Ag

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nanoparticles act as the catalyst for the thermal degradation of
PHB. Addition of metal nanoparticles such as metal oxides or
metal chalcoginides has effect on the nanocomposites (Yeo et
al., 2010). The development of the recent method is to
fabricate PHB/ Polyaniline (PANE) nanocomposites. PANI is
an intrinsically conductivity polymers (ICP) used as
radiostabilizing agent in nanocomposites of Poly methyl
methacrylate (PMMA) and PANI nanofiber (Araujo et al.,
2011). Organically modified layered silicate (OMLS) clays
used in nanocomposites for the improvement of physical
properties such as strength gas barrier flammability and
thermal and environmental stability. Montmorillonite MMT,
hectorite, and saponite are clays commonly used in polymer
composites (Joshi S., 2008).
The production of polymer nanocomposites with single
walled carbon nanotubes enhances the mechanical properties
and nanotubes alignment. Solvent evaporation method and
efficient fabrication method for the multiwall carbon
nanotube-polystyrene composites and SWNT polymer
composites improves mechanical properties of amorphous and
samicrystalline polymer (Hggenmueller et al., 2003). The
fabrication of biopolymer with carbon nanotube (CNT)
composites for nanocomposites improves the thermal,
mechanical and electrical conductive properties. The better
solubility in the PHB/chloroform solution and casted films
which is mixed with PHB and Multiwall carbon nanotube
MWNTs are functionalized with alkyl group (Jung et al.,
2001). latex PHO (polyhydroxyoctonate) are prepared by the
chemical treatment of sodium hypochloride .The natural
nanocomposites material made by PHO latex as matrix and
polysaccharides as fillers of cellulose whiskers and starch
microcrystal
(Dubief
et
al.,
1999).The
scaffold
naoncomposites are formed by the salt leaching processing of
poly 3 hydroxybutyrate with 10% bioglass nanoparticles.
Biomaterials play the important role for the manufacturing of
the scaffold where pertinent cell attach, grow, proliferate and
differentiate (Hajiali et al., 2010). Some of physical processes
that determine the linear and non linear optical properties of
nanocomposites, such as structures properties of composites
are shown in, Maxwell Garnett geometry composites, Layered
geometry composites, Bruggeman geometry composites
(Boyd et al,. 1996).
Use of nanocomposites for the food industry like food
and beverage packaging sector and food products are cooking
oil including nanoparticles material such as micelles,
liposomes, nanoemulsion, cubosomes, nutraceutical improve
the safety and quality of products (Sozer and Jozef., 2008).

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Sizes of range of nanomaterials

Another use of bionanocomposites in the field of Biomedical

includes biopolymer polysaccharides, aliphatic, polyesters,
proteins, polypeptides and polynueclic acids filler including
clays. Nanocomposite polymers are commonly used in tissue
engineering, bone replacement /repair, dental, and controlled
drug delivery (Hule and Pochan., 2007). Certain polymeric
nanoparticles such as micelle based used in chemotherapies of
ovarian cancer. There are different types of micelle such as
PLGA, polymerosmes are acid cleavable (Yallapu et al.,
2010). The characterization of nanoclay nanocomposites
determines the level of exflotation and dispersion. Analyzing
the resin contain nanoclays and determination of different
methods including X ray diffraction, Transmission electron
microscopy (TEM), Scanning electron microscopy (SEM),
Environmental scanning electron microscopy (ESEM),
Electron dispersive X ray spectroscopy (EDS/EDAX),
Thermogravimetric analysis (TGA), (Synder R., 2007).
Polymer layer silicate nanocomposites
The layer silicate is commonly used in the formation of
nanocomposites because of starting clay materials are easily
available and general family of 2:1 layered or phyllosilicate
(Alexander and Dubois., 2010). Their crystal structure contain
a layers made by the fusion of two external silica tetrahedron
atoms and central octahedral sheet of alumina or magnesium
hydroxide (Ray and Okamoto., 2003). The thickness of layer
is around 1 nm and lateral dimensions vary from 3 nm of
micron or layers depending on the particular layer silicate. The
isomorphic substitution within layer example (Al3+ replaced
by Mg2+ or Fe2+, or Mg2+ replaced by Li1+) and generate a
negative charge exchange capacity inside the galleries
(Lagashetty and Venkataraman., 2005). Montmorillonite
(MMT), saponite, and hectorite are the most commonly used
layered silicates.

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Table: Chemical structure of 2:1 phyllosilicate

M= monovalent Cation, x =degree of

substitution (Alexander and Dubois,. 2010).

isomorphous

Polymer/ layered composites are mainly classified into three

types. (1) Intercalated nanocomposites, (2) flocculated
nanocomposites, and (3) exfoliated nanocomposites (E
Gacitua et al., 2005).
(a) Intercalated nanocomposites- Polymer chains are
inserted into layered structure such as clays occur in
the regular fashion.
(b) Flocculated nanocomposites- Sometimes silicate
layered are flocculated due to hydroxylated edgeedge interaction of the silicate.
(c) Exfoliated nanocomposites- Separation of the
individual polymer matrix by the average distance
that depending on clay.

(Ray S .Suprakas, 2006)

Structure of polymer layered silicates

(Ray., 2006) Structure of phyllosilicates. Reproduced from

ref. by permission of Elsevier Science Ltd., UK.

Fig .(1)Alkyl chain aggregation models.(a) Short alkyl chain,

lateral monolayer;(b) intermediate chain lengths; quasi
bilayers and (c) longer chain length; increased interlayer order,
liquid crystalline- type (Ray and Okamoto., 2003).

Poly (L-lactide) PLA / OMLS (organo-modified layered

silicate) based nanocomposites
Aliphatic polyesters play an important role in the field of
biodegradable material formation such as layered silicates,
layered titanates, carbon nanotubes, gold silver, maghemit

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nanoparticles, magnetite nanoparticles, and fluorine mica. The
material properties of PLA are modulus (GPa) 4.8, strength
(MPa)
86,
Distortion
at
break
(1.9
%).

Bright field
(Yang et al., 2007)

TEM

images

of

nanocomposites

The formation of PLA blend done by dissolving the polymer

in hot chloroform in the presence of dimethy distearyl
ammonium modified MMT. In presence of clay form tactoids
with several stacked monolayers. The addition of PEG to
blend PLA results in improved tensile strength (28.2) and
elongation (25 %) as compared to pure PLA (Sunday A et al.,
2012). PLA based nanocomposites are used in wide range of
application such as rheological modifier for paints, ink, and
grease, drug delivery vehicle, cosmetics, adsorbent or toxic
gasses, therapeutic product, and nanoclay for industrial
wastewater as well as potable water treatment is referred to
natural clay (Patel et al., 2005).
Polypropylene based nanocomposites
There are two different method used for the preparation of
polypropylene based nanocomposites. First was from pristine
montmorillonite and reactive compatibilizer trimethyl
ammonium bromide (C6), another from organophilic
montmorillonite (OMT). Some of the polar polymer PA6,
PMMA, PS has been used for successful production of
nanocomposites. The OMTs produced by melt intercalation
clay, Polypropylene and maleic acid modified polypropylene
(MAPP) (Tang Y et al,. 2003). Different polypropylene
nanoclay have been used such as Closite 20A, Closite 30A
Bentenite 107. Another aspect of the nanocomposites
nanoclay attracts the dye molecules through van der wall
forces and possibly hydrogen bonding. Major advantages of
polypropylene are its very low price and quick drying,
relatively low static and resistance to staining and some of
major disadvantages lace of dye ability. Mechanical and
thermal nature, crystallinity and dyeability have been analyzed
with the help of WAXRD, FTIR, SEM and spectrometer

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(Bahrami and Mirzaie. 2011). Polymethylmethacrylate
(PMMA) was studied using blend melting techniques,
mixtures of aromatic and aliphatic epoxy- nanoclay and
PMMAepoxy composites system (Park and Sahan, 2003).
PMMA/expanded graphite (EG) composites filler composites
are greatest superior mechanical, thermal and barrio
performance
in
comparison
with
conventional
microcomposites (Zheng and Shing, 2003). Polypropylene
based nanocomposites are one of the most non polar polymer
and has no polar groups in its backbone. The melt intercalating
methods use of compatibilizer, such as maleic anhydride
grafted PP (PP-g- MA) clay (Nguyen and Baird, 2007). The
mixing of clay propylene stearyl ammonium-exchanged
montmorillonite, maleated polypropylene (MAPP), and the PP
homopolypropylene using extraction compounds (Chen et al,.
2002). The potential of using exfoliated graphite
nanoplateletes xGnP polypropylene (PP) composites and
addition of graphite sheet to a polymer matrix improve its,
thermal and mechanical properties. Major applications of
polymeric thermally conductive material are in light ballasts
transformer housing, microchip cooling, fuses, space heater
etc (Kalaitzidou et al., 2007), packaging, fibers, automotive
industry, non durable goods and in building material. The
degradation behaviour is PP nanocomposites compatibilizer
effect on photo-degradation and its kinetics by comparison of
nanocomposites with neat polymer (Panday et al., 2005).
Economic and environmental application of nanocomposites
in the field of automobiles, steel or aluminium of light- duty
vehicle body panel (Lloyd and Lava., 2003).
Poly (- caprolactone) (PCL) based nanocomposites
Poly (- caprolactone) (PCL) is another types of aliphatic
polyester. PCL Based nanocomposites are commonly
synthesized through ring opening polymerization of caprolactone under mild condition. These are polymers
prepared by the different composition of PCL with organomodified montmorillonite by melt blending (Yang et al., 2007)
.PCL based nanocomposites for rigidity, heat resistance of
inorganic materials may become the most important (Avella et
al., 2006). In the latest study of sufficiently exfoliated PCL
based nanocomposites, made of PCL and organoclays (OCs)
with polar and nonpolar modifiers are done by the melt mixing
and heat treatment methods (Chung et al., 2007). Another type
of PCL can be improved in ductility and stiffness by the
addition of montmorillonite clay and electrospun fibers to
PCL (Causin et al., 2009). It can be fabricated using two
techniques: in the melt blending the polymer matrix (PCL)
mixed with CNTs using a DSMs microextruder and in the
coprecipitation method PCL is solubilised in an organic
solvent like tetrahydrofurane (THF). The PCL based
nanocomposites have highest conductivity and highest
dielectric constant (Molenberg et al., 2010). The main
limitation of PCL based nanocomposites is low melting
temperature (650 C), which can be overcome by blending with

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other polymer/ nanocomposites mixed with synthetic BAP and

OMS (Pandey et al,. 2005).

(Ray and Okamoto, 2003)

Multiwall carbon nanotubes (MWNTs)/nylon (PA6)
nanocomposites has been improves the dispersion and
strengthen the interaction between the nanotubes (Lui et al.,
2004). The Multiwall carbon nanotube is used because of
single wall carbon nanotubes (Lai et al., 2004). Polyamide
Nylon 12 is family of polyamide, comparison of the nylon (PA
12) with longer aliphatic chain and lower melting point and
strength than nylon 6 and nylon 66 (Phang et al,. 2005). The
nylon 6 clay nanocomposites reduced the flammability and
form rentation after burn compared with pure nylon 6,
polyamide-clay nanocomposites with improved thermal
stability and flammability (Zhang et al,. 2005).
Polyethylene (PE) based nanocomposites
The polyethylene based nanocomposites is synthesized by in
situ polymerization, solution blending and melt intercalation.
Comparing of the PP and intercalated PEOMMT by using of
twin extruder. These are composites more is pure PE polymers
(Pandey et al,. 2005). Especially nanoclay has been increases
in modulus, strength, barrio properties, and flammability
resistance but PE is hydrophobic in nature because PE/clay is
not easily prepared (Lei et al.2007).

SEM micrographs of 15% PCL + 3% MWNT

SEM micrographs of 13,5% PCL + 3% MWNT

Polycarbonate (PC) based nanocomposites

Nylon-6 based nanocomposites

Nylon is made by anionic ring opening polymerization of
caprolactam and it is used in filaments of toothbrushes, ropes
raincoats and automobiles industry for self-lubricating gears
and bearing. During production of composites the presence of
clay transforms the -phase of nylon-6 into the -phase of
nylon (Pandey et al., 2005). The -phase crystal is
thermodynamically more stable with anti parallel chain linked
by the hydrogen bonds to adjacent chain where the -phase
crystal consists of parallel chain (Phang et al., 2006). The
effect of the particles size on nylone-6 nanocomposites is
more as the addition of smaller particles gives better
reinforcement (Yun Fu et al., 2008). Mostly nylon-6 matrix is
used in the in situ intercalative polymerization (Alexander
and Dubois. 2000). Successful reinforcement of Nylon- 6
nanocomposites with CNT within the matrix of Nylon-6 is
found to increase the mechanical properties. Nylon -6 show
good affinity for the silicate surface because of hydrogen
bonding achieved by high level of exfoliation (Paul and
Robeson,. 2008).

Major properties of the bisphenol-A based polyester (PC)

because of greater transparency, toughness, thermal and
dimensional stability. PC based nanocomposites is major
application for the making of compact disc, riot shield, vandal
proof glazing, baby feeding bottles, electric component,
helmets etc (Pandey at al., 2005).
Poly (vinyl chloride) (PVC) based nanocomposites
It is widely used in the formation of pipes, house siding,
window profiles, wire cable insulation and flooring because of
PVC is high chemical and abrasion resistance. Thermal
dehydrochlorination of the PVC contains internal allylic
chloride and tertiary chain (Pandey at al., 2005). Hectorite and
bentonite clay is use for the making of poly (vinyl chloride).
In the recent work on PVC LDH (layered double hydroxide)
composites is better properties than PVC because of hydroxide
can be absorbed the HCL. PVC-montmorillonite
nanocomposites are made by melt blending, solution blending,
and polymerization for the use pristine sodium clay and
organically modified clay (Awad et al., 2009).

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Polystyrene based nanocomposites
It can be prepared by different method, such as in situ
polymerization, bulk polymerization, melt blending and
solution blending, by the mixing of clay because of strong
plastic. Clay used in situ polymerization VB-16 (virgin
polymer) and nanocomposites (Pandey et al,. 2005).
Styrene butadiene rubber based nanocomposites
SRB is a hybrid Nanocomposite containing compounds carbon
black and organo modified nanoclay (NC). Carbon black is
mostly used in rubber industry. It is important reinforcement
filler for improving tear strength, modulus (Praveen at al,.
2008).
Polyaniline based nanocomposites (PANI)
PANI-inorganic nanocomposites, it is wide range of properties
such as electrical mechanical structural properties because of
mixing with organic components in low level. The physical
mixture of Na-MMT and PANI is more thermally stable
(Pandey et al,. 2005). PANI is an intrinsically conductive
polymer (IPC), like metal type characteristics, and good
biocompatibility. PANI represents four types oxidation state,
leucoemeraldine, emeraldine, nigraniline and pernigraniline.
PHB/PANI nanofiber composites are formed by the aniline
polymerization reaction in the presence of emulsion of PHB in
water/chloroform/SDS (Araujo et al., 2011).

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acetate propionate (CAP), and cellulose acetate butyrate
(CAB) are thermoplastic. Some of modified nanoclay with
mixing CA/organocaly nanocomposites, trimethyl citrate
(TEC) combined with Cloisite 30B organoclays, and maleic
anhydride-grafted cellulose acetate butyrate (CAB-g-MA)
(Yang et al,. 2007). The production of nanocomposites,
cellulosic plastic with 80% wt% pure cellulose acetate and
20% wt % trimethyl citrate plasticizer was used as polymer
matrix (Sunday et al,. 2012). Another type of reinforce
materials cellulose nanocrystal, it is very low cost, high
availability, renewability, nanoscale dimensions, high surface
area, easy to modification, and good mechanical response to
strees (Lucia and Cao., 2007)
Oil based nanocomposites
The production of oil based nanocomposites from natural oil
such as, soya oil that has been used in the production of resins.
Vegetable oil have contain long fatty acid chain, causes by
desirable flexibility and toughness, to otherwise brittle resin
system such as epoxy, urethane and polyester resins (Pandey
et al., 2005). Plant oil/silica nanocomposites are produced
from the acid-catalyzed curing of epoxidized plant oils with 3glycidoxypropyltrimetoxysilane (Yang et al,. 2007). In the oil
based composites soy-based epoxy resin was mixed with
montmorillonite clay in different concentration then resulting
tensile strength increased (Sunday et al., 2012).
References:

Starch based nanocomposites

Starch based nanocomposites is a low cost and readily
available in market and become to growing interest as
promising option toward enhancing the mechanical and barrier
properties (Yang et al,. 2007). Starch based nanocomposites is
formed by mixing between polymers in the matrix of
thermoplastic. The first nanocomposites were thermoplastic
starch and kaolin clay interaction (Pandey et al,. 2005). In the
resent studies TPS-clay with nanocomposites formed by
natural smectite clays, montmorillonite and hectorite. Advance
studies on the both biodegradable polymer such as, PLA/
starch based nanocomposites, one was cheap and another is
good mechanical properties (Yu Long et al,. 2006).
Cellulose based nanocomposites
The most important advantages of nanofiber reinforcement has
been obtained high strength, random-oriented, biobased, easily
degradable and recycled (Yang et al,. 2007). It has been used
in the polymer reinforcement. The fibers of cellulose of
nanocomposites are called cellulose whiskers. For the
improvement of the cellulose based nanocomposites use of
clay such as, cellulose acetate, TEC, plasticiser and OMS clay
(Pandey et al,. 2005). Raw cellulose is not useful because poor
solubility and thermoplastic character so use for some
modified cellulose, such as cellulose acetate (CA), cellulose

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