Polymer Clay Nanocomposite

Polymer Clay Nanocomposite

Bhupendra Singh
Department of Chemical Technology
University of Mumbai
Matunga, Mumbai – 400 019

Introduction
Nanocomposites have changed the perception towards the concept of polymer composite.
They are the emerging polymer composites of the 21st century. The importance of these
products is growing from industrial and research point of view. Nanocomposite show
drastic improvement in the properties derived from the addition of few percent of the
clays in the polymer matrix. These composites exhibit new and improved properties as
compared to their micro and macro-composite counterparts. This improvement in the
properties is the result of the ultra fine phase dimension of the filler. A nanocomposite is
defined as “a material having two phases, one of the phases is uniformly dispersed into
the second phase on nanoscale level (10-9 m)”. The dimension of the first phase is in the
nanometer range of 1 to 100 nm.1 Nanocomposites typically contain 1-5 wt. % of filler
loading on weight basis depending on the final properties to be achieved. 2
Nanocomposite promise to be the wave of future by having major implications in
industry and technology.3

The purpose of this paper is to present an overview on polymer clay nanocomposite, their
synthesis, properties, characterization and application.

By – Bhupendra Singh
Polymer Clay Nanocomposite

Raw Materials

Polymer

Polymer clay composites have been classified into three categories namely, conventional
composite, intercalated nanocomposite and exfoliated nanocomposite depending on the
type of dispersion. In conventional composites the filler loading is on the higher side (30-
60 vol. %)1 as compared to the nanocomposites (1-5 wt. %). In intercalated
nanocomposites regular insertion of the polymer in between the silicate layers at the
molecular level is observed while in exfoliated nanocomposites individual layers of the
silicate layers are randomly dispersed into the polymer phase.3, 4

Different polymers have been used for the synthesis of the polymer clay nanocomposites
in the last decade. These polymers are divided into two different classes3

 Thermoplastics
 Thermosets

Thermoplastics

The first polymer clay nanocomposite synthesis was reported by Toyota Central R & D a
dozen year ago. Researchers have gone a long way since then in this arena and had
developed various nanocomposites by making use of different polymer and clay
combinations. Out of various thermoplastics used; polyamide-6 is the most studied and
reported nanocomposite. Injection molded polyamide-6 nanocomposite showed excellent
mechanical, barrier, heat distortion property and reduced flammability;5,6 without
sacrificing its impact strength4.Various polyamide-6 nanocomposite products have been
already commercialized.

Thermoplastics such as Poly (ε-Caprolactam ),1,7,8 PET,9 PMMA,10 PP,11,12 PE,12 PS,13
PES,14 PEO,15 Polyimide16 have been used for the synthesis of polymer clay

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Polymer Clay Nanocomposite

nanocomposite. Different methods are employed to synthesize these nanocomposites

such as Melt intercalation process, In-Situ polymerization and Solution process.
Processing of these nanocomposites can be done by conventional methods i.e. Injection
and Extrusion processes.

Thermosets

The most commonly studied thermoset nanocomposites are Epoxy,3,17 Polyurethane9,18

and unsaturated polyesters. Epoxies are the most widely used engineering thermoset
materials as it is easy to process and gives excellent engineering properties on curing.3

For thermoset nanocomposites the complete exfoliation of clay is predicted by

thermodynamic principle. The free energy, ΔG for complete exfoliation of thermoset
nanocomposite is the sum of the terms contributed by the polymer matrix and silicate
clay.

For polymer matrix

ΔGp = ΔHp - TΔSp

For silicate clay

ΔGc = ΔHc – TΔSc

The total free energy change is

ΔGt = (ΔHp + ΔHc) - T (ΔSp + ΔSc) = ΔHt – TΔSt

When monomers or polymers penetrate into the silicate layers the entropy change is
negative while expansion of the gallery shows positive entropy change. The total
enthalpy will determine whether or not exfoliation takes place.

By – Bhupendra Singh
Polymer Clay Nanocomposite

The complete exfoliation condition is that the heat of the intergallery polymerization
released before the gel point requires larger than the van-der Walls attractive energy
between the interlayer. i.e., ΔHp (t ≤ tg) ≥ ΔHc .17

Clay

Clays have been used as fillers in the conventional polymer composites at very high
loading levels for economic reason. The property enhancement is moderate, which is in
contrast with the property improvement in the nanocomposite; where small amount of
filler loading gives higher level of property improvement.1 Clay is a generic name for a
whole family of layered aluminosilicates. Clays are used in wide variety of applications
like ceramic, decorating and industrial products depending upon its form and properties.
Smectite are the fraction of Bentonite ores. Smectite shows its unique property of
swelling in water. There are many species of smectite, of which Montmorillonite and
Hectorite19are of commercial importance. The most commonly used clays in
nanocomposite are organically modified Montmorillonite. Along with montmorillonite
few other types of clay have been reported for the use in the nanocomposite, such as
Saponite,20 Attapulgite 21 and Mica type 16, 19 silicates.

Montmorillonite

Approximate formula for montmorillonite is

[R+0.33(Al, Mg)2Si4O10(OH)2.nH20 ]

Where R+ in natural mineral can be one or more of the Na+,K+,Ca+2,cations.22

Montmorillonite have a dimension below the visible light wavelength; properly oriented
and transparent, this is a critical requirement in barrier packaging. Na-montmorillonite is
the major mineral constituent of Bentonites and has high swelling capacity as compared
to Bentonites having Ca–montmorillonite as major mineral. Na-montmorillonite is a
smectite in which Na and water molecules are the interlayer material. The largest and

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 Polymer Clay Nanocomposite

highest quality Na – Bentonite deposits in the world are situated in South Dakota,
Wyoming and Montana. 23

Montmorillonite are the preferred materials in nanocomposite because of

• Low levels of loading

• High aspect ratio ( as high as 1000 )
• Good transparency
• Safe handling
• Natural abundance
• Economic and
• Good chemical resistance 1,7

Montmorillonite shows hydrophilic nature; hence it can not be homogeneously dispersed

into the organic polymeric phase. The higher aspect ratio of silicate particles can be
maximized by dispersing individual silicate layers into the polymer matrix.1 Therefore to
incorporate montmorillonite into the polymer phase it is organically modified by a cation
exchange reaction.7 This improves the compatibility of montmorillonite with the polymer.
Owing to its cation exchange properties the clay gallery ions can be replaced by organic
cationic species such as alkyl ammonium ions. As the gallery cation changes from
inorganic to organic, the surface property changes from hydrophilic to organophilic.3

Compatibilizing Agents

Clays do not disperse well in the organic polymer matrix. The differences in the surface
tension force between the clay and polymer matrix; produces an obstacle in the
dispersion of clay particles in the polymer. The direct blending results in clustering
tendency of the silicate layers, thus posing limitation on its use as nanoclays. Hence
chemical modification is essential for the clay before using it in nanocomposite.9The
inorganic cations present in the clay intergallery provide the site for the water molecules
to form monolayer or multilayer structure. The layered spacing is governed by the
amount of water present. This makes clay hydrophilic in nature. To mix the clay with the

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Polymer Clay Nanocomposite

polymer matrix its hydrophilicity has to be decreased and organophilicity has to be

improved. As smectite clays exhibit cation exchange properties, the clay gallery ions can
be replaced by organic cationic species, such as alkyl ammonium ions. 3 Compatibilizing
agents are typically a molecule having one hydrophilic and one organophilic functional
group. Non polar nature of the alkyl chain reduces the electro static interactions between
the silicate layers to facilitate the diffusion of the polymer into the galleries of layered
silicate.

Organically modified montmorillonite is synthesized by a cation exchange reaction

between montmorillonite and alkyl ammonium ion or amino acids. The presence of this
cation in the galleries provides hydrophobicity to the Na- montmorillonite. 4 Na
-montmorillonite has composition of sodium ion and negatively charged montmorillonite.
It forms homogeneous dispersion in water but does not disperse in the organic polymer
matrix. To reduce the hydrophilicity and improve the organophilic nature of Na-
montmorillonite it has to be treated with compatibilizing agent.16 Various compatibilizing
agents have been used for the synthesis of the polymer clay nanocomposite.

Compatibilizing agents such as 11-amino acid,24 octadecylammonium salt,4 12-

aminolauric acid,2,19 dimethyl dehydrogenated tallow quaternary ammonium chloride,5
have been employed for the nylon-6 clay nanocomposite synthesis.
Disteryldimethlyammonium chloride,7 cetyltrimethyl ammonium bromide (CTMA),25
26
dimethylpropanediamine 12-aminododecanoic acid1 were used in the preparation of
poly(ε-caprolactone) clay nanocomposite.

Dimethyl dehydrogenated tallow quaternary ammonium chloride is reported to be used in

the synthesis of SAN-MMT nanocomposite by solution polymerization method.10
Ammonium salt of dodecylamine was incorporated as compatibilizing agent for the
synthesis of polyimide nanocomposite.16 n-Hexadecylammonium chromide17 and alkyl
ammonium chloride3 was used in the Epoxy/clay nanocomposite as compatibilizing
agent.

By – Bhupendra Singh
 Polymer Clay Nanocomposite

Nanocomposite Synthesis

Nanocomposites can be synthesized by different routes. Most commonly used routes are

 Melt-intercalation process
 In-situ polymerization process
 Solution process
 Emulsion polymerization

Melt intercalation process (Compounding process)

This method involves mechanically blending organically modified clays with polymer
matrix. The nanocomposite is formed by addition of swollen and pretreated layered
silicate to the polymer melt. The swollen clay permits easy exfoliation of clay in the
polymer matrix.27 The nanocomposite is then annealed.28 Annealing of the polymer clay
nanocomposite sample at the extrusion temperature leads to coarsening of the clay
(silicate) superstructure and further improvement of exfoliation. This resulted in unique
rheological properties and stable morphology.29 The quality of dispersion depends on

1. Organic modifier
2. Processing and
3. Mixing conditions5

This is a promising new approach to fabricate polymer clay nanocomposite by using

conventional polymer processes like extrusion and injection molding. The formation of
nanocomposites by above processes is governed by the thermodynamic interaction
between the polymer chains and the silicate layers; and the transport of the polymer
chains from the bulk melt into the silicate layers. 4 The polymer and nanofillers are
preconditioned to remove moisture. The polymer is then fed into the compounder along
with nanoclay with calibrated volumetric feeders.

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Polymer Clay Nanocomposite

The layered silicates are dispersed in the melt phase by shearing action. High shearing
mixers or internal mixers are used for the synthesis of the nanocomposite. Twin screw
compounder is ideal equipment. Screw parameters and compounding parameters are
modified to achieve the optimum properties. Nylon-66 films are casted by using high
shearing single screw or twin screw compounder. A schematic representation of the flow
diagram for melt-intercalation process is as shown below in fig. 1

Clay

Nanocomposite
Blending Annealing

Thermoplastic

Fig. (1) Flow chart for the synthesis of nanocomposite by melt-intercalation process

The particle size of the layered silicates in the nylon 6 matrix is reduced through the melt
intercalation process. Most of the silicate layers are exfoliated into nanometer layers and
randomly dispersed in the nylon 6 matrixes via melt intercalation process.4 TEM results
showed that the intercalated silicate layers through the melt extrusion process are
exfoliated into nanoscale layers and randomly dispersed in the nylon-6 matrixes.

In situ polymerization process (In reactor polymerization)

In-situ polymerization method is very useful method for the preparation of high
performance polymer nanocomposites.17 In this method nanocomposite is synthesized by
introducing the monomer, into the organically modified clay and then polymerizing it in-
situ. Kojima Etal.30 has reported the preparation of Nylon-6 nanocomposite at normal
pressure. In his experiments montmorillonite was dispersed in water, to which ε-
carolactam and hydrochloric acid was added. It was then stirred and filtered to get
montmorillonite intercalated with ε-carolactam. This intercalated ε-carolactam is then
charged into a reaction vessel along with 6-Aminocaproic acid. The mixture was heated

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Polymer Clay Nanocomposite

at 2600C for 6 hours in nitrogen atmosphere under normal pressure. After reaction
completion the product was cooled and subjected to milling operation to obtain pellets.

Kurachi and co-workers at Toyota R&D have reported following procedure for the
synthesis of nanocomposite. A 2 L Parr reactor is charged with ε-carolactam and
montmorillonite that had been reacted with 12- aminolauric acid. The vessel was then
purged with nitrogen for 25 minutes and sealed. The temperature is raised to 110 0C and
again purged with nitrogen for 30 seconds. Temperature is then raised to 250 0C under
nitrogen atmosphere. The reaction proceeds for two days with slow stirring. Pour the
molten polymer into cold water, filter it and dry it for 24 hours at 0.1 mm Hg pressure.2 In
most cases the synthesis involves either intercalation of a suitable monomer and then
exfoliating the layered host by subsequent polymerization.4

Flow diagram for In-Situ Polymerization process is as shown fig. (2)

Monomer

Swelling Polymerization Nanocomposite

Clay

Fig. (2) Flow diagram for In- Situ polymerization process

Swelling of clay

Silicate layers swell in the monomer and exfoliate during the polymerization. Swelling
occurs because of monomers entering into the gallery between the silicate layers; which
increase the intergallery height. As the silicate layers move apart from each other the
mutual attraction between them decreases resulting in the drop of shear rate required to
disperse the silicate layers into monomers. The two important factors affecting swelling is
swell time and temperature during swelling.

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Polymer Clay Nanocomposite

Dispersion Procedure

Dry silicate layers are added to the monomer under stirring condition. The stirring should
be enough to create a homogeneous mixture. Temperature is increased to ease the
monomer intrusion into the gallery between the silicate layers. Further stirring is
continued and the mixture is then charged into the reactor. The polymerization of the
mixture is carried out under agitation and blanket of nitrogen. After the completion of the
reaction the nanocomposite is washed, palletized and dried. This dried nanocomposite is
then used for making the final product.31

Viscosity Control

Viscosity of the mixture tends to increase while mixing. To control the viscosity water
can be added to the mixture without affecting the dispersibility of the clay. Also as
silicate clay and polymer mixtures are thixotropic in nature hence viscosity can be
controlled just by increasing the shear rate. The ε-caprolactam containing nanoclays have
a tendency to develop increased viscosity while polymerizing.

In-situ formed polymer clay nanocomposite outperformed melt compounding by a

significant margin. The resulted nanocomposite has a “tethered” system where polymer
molecules terminate at the clay surface. Tethered systems show enhanced thermal
stability with improved fire retardancy property.31

Solution polymerization

Organically modified clay is suspended in suitable solvent under vigorous stirring

condition. Organoclay swells in the solvent. To this mixture monomer and initiator is
added. The mixture is allowed to react while vigorous stirring condition is maintained.
Reaction is then terminated. The product is separated and washed several times. It is then
dried under reduced pressure to remove the washing solvent.

Preparation of SAN- MMT nanocomposite is reported by using this method.10 A

modified method is used to prepare Rubber-Clay nanocomposite. In this method instead

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Polymer Clay Nanocomposite

of monomer as used above; polymer dissolved in solvent is added to the mixture of

preswollen organoclay. The last step consists of removing the solvent by evaporation
under vacuum.32 Figure (3) represents the steps involved in the solution polymerization
process.

Solvent

Swelling Solvent
Evaporation
Clay

Intercalation & Nanocomposite

Monomer Polymerization

Fig. (3) Flow diagram representing the steps involved in the solution polymerization
process.

Emulsion Polymerization

A new approach to the polymer nanocomposite synthesis; based upon one step emulsion
polymerization is reported by M. H. Noh Etal. Various properties such as polymer
loading into the inter layer of silicates, molecular masses of intercalated polymer, gallery
expansion, thermal stability, mechanical properties and dispersibility of silicate layers in
polymer matrix was found to exceed to those of products made by solution
polymerization method. Emulsion polymerization can play an important role in synthesis
of polymer clay nanocomposite; it also eliminates the environmental problems associated
with the solution polymerization process.

It involves addition of surfactant along with unmodified silicate clay under stirring
condition. Monomer is feed with the initiator. Emulsion polymerization proceeds under
vigorous agitation condition. The reaction mixture is cooled to room temperature. The
final product is obtained after filtration and washing several times with water. It is then

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Polymer Clay Nanocomposite

dried under reduced pressure. Styrene-Acrylonitryl copolymer montmorillonite

nanocomposite is prepared by the Emulsion Polymerization technique.10 A flow diagram
for emulsion polymerization technique is as shown in the figure (4)

Initiator
Surfactant
Clay

Polymerization

Water Monomer

Nanocomposite

Fig. (4) Flow diagram for the synthesis of nanocomposite by emulsion polymerization
process

Characterization

For the characterization of the polymer clay nanocomposite X-Ray Diffraction (XRD),
Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM),
Differential Scanning Calorimeter (DSC) and NMR were used. Studies of structural and
morphological characteristic were carried out.

TEM images of N-6/clay nanocomposite showed that the silicate layers disperse
uniformly in the polymer matrix. The microstructure in the nanocomposite was found
similar to that of organoclay, but the interlayer distance was observed to become larger to
3.5 nm; which is compatible with XRD results.4

DSC studies showed the presence of clay promoted γ-crystalline form. From DSC scan
curve it was observed that the Nylon-6 matrix has only one peak corresponding to the α-

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Polymer Clay Nanocomposite

form while the nanocomposite system shows two melting peaks; high temperature peak
corresponding to α-form and the lower temperature corresponding to γ-form of
crystallite4.

NMR studies were carried out for the observation of α and γ crystal forms and amorphous
regions in Nylon-6 clay nanocomposites.

Crystallization behavior of Nylon-6 nanocomposite

Nylon-6 is a multicrystalline polymer having more stable α–form as compared to γ-form.4

Clays induce the γ- crystal growth in nylon 6 while the percentage crystallinity remains
almost the same.2 Generally α-phase and amorphous phase is observed in nylon-6; of
these α- phase is the favored one. Annealing of nylon samples at a temperature close to
the glass transition temperature produces only α and amorphous phases. While, when clay
particles are present in nylon-6, it adopts α and γ-crystal phases in somewhat equal
amounts. Since only α form is present in commercial nylons hence it can be suggested
that the presence of γ- phase must be a result of the interactions between the silicate
layers and the polymer matrix. Clay increases the crystallization rate and has a strong
nucleation effect on the nylon 6 matrix.4 The clay stabilizes or /and induces the γ- phase
of nylon-6 in nanocomposite. The results of crystallization study after annealing for
nylon-6 and nylon-6 nanocomposite showed no change in crystalline and amorphous
phase for nylon-6 but at the same time the morphology was changed for the
nanocomposite as it produced only γ-form of crystal and amorphous phase. The clay
surface induces kinetically favored formation of γ-crystal form.2 It is well established that
the presence of clay induces the formation of γ-form of crystal as compared to α form of
crystal.5

Small amount of clay in nanocomposite promotes the crystallization while large clay
content delays it. The isothermal crystallization is affected by diffusion and nucleation.
Diffusion is related to the activation free energy for transporting polymer segment to the
growing crystal surface. Nucleation term is related to the thermodynamic driving force. A

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Polymer Clay Nanocomposite

small amount of clay acts as a nucleating agent while large amount hinders the
transportation of polymer segment.7

Orientation

The nanocomposites exhibit anisotropic properties which are attributed to the orientation
of the clay layers. The preferential orientation of the clay layer in the polymer clay
nanocomposite was found to be related to the injection / extrusion direction. This
orientation of the clay layer plays a major role in the enhancement of the mechanical
properties of the polymer clay nanocomposite.33

Orientation of montmorillonite and nylon-6 crystallites in nylon composite film is

measured by X. R. D. and TEM. For the film it is seen that the pure nylon-6 film showed
no preferred orientation but on the other hand presence of silicate layers contributes
important role in the preferred orientation of nylon-6 crystallites. γ-form of nylon 6
crystallites tends to form planar orientation in the nylon clay nanocomposite film.6

In nylon clay nanocomposite film it was found that the silicate layers had planar
orientation. The chain axes of nylon-6 crystallites (γ- form) were found parallel to the
film surface but were randomly oriented within the film plane. This orientation of nylon-
6 crystallites in nanocomposite was assumed to be promoted by the presence of
anisotropic silicate monolayer dispersed separately. The degree of orientation of an
anisotropic body depends on both the magnitude of the applied shear stress and the aspect
ratio of the body.34.

Properties

Properties of the nanocomposite material is governed to a greater extent by complex

interactions between different phase and the interfaces between them.3

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Polymer Clay Nanocomposite

Mechanical properties

Surface modified silicates used in extrusion melt compounding when properly mixed
with melt enhances the mechanical properties. For Nylon-6 clay nanocomposite the
flexural modulus increases rapidly with increasing clay content from 0-3.5 wt %. Further
increase in the clay content has little effect on the flexural modulus. Flexural strength
approaches to peak at 3 wt % and decreases with further increase of the clay content. The
tensile modulus increases in the range 0-15 wt % but little effect was observed for clay
content higher than 15 wt %.Notch impact strength remains almost constant in the range
0-17 wt %. For low filler content the properties were found to be far superior to those of
conventional counterpart composites. There is a strong interaction between the matrix
and the clay layers which attributes to the nanoscale size and uniform dispersion of the
clay layers in the nylon-6 matrix. 4,30

Barrier Properties

The barrier properties of the polymer clay nanocomposite were enhanced by the addition
of nanoclays in the polymer matrix. A conceptual figure for the path of a diffusing gas
through the polymer nanocomposite is as given in the figure (5)

d d’ W

Fig (5) Mechanism

of “tortuous path”

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Polymer Clay Nanocomposite

Total path of a diffusing gas

d’ = d + d.L.Vf / 2W

d - thickness of a film

L - length of clay

W- width of clay

If silicate layers are dispersed parallel in the polymer matrix the torturous factor (τ) is
given by

τ = d’ / d

τ = 1 + (L / 2W) Vf

Vf- volume fraction of clay

Therefore relative permeability coefficient is given by

Pc / Pp = 1 / [1 + ( L / 2W ) Vf ]

This equation roughly estimates the mechanism of “tortuous path” in polymer

nanocomposite.16

Sorption properties of nylon 6 clay nanocomposite

Nylon-6 has inferior resistance to water permeation. Hence it is of great importance to

improve the resistance of Nylon-6 to water permeation since rigidity of the polymer is
lowered by water absorption. Nylon-6 nanocomposites exhibit excellent resistance to
water permeation because of the decrease in the diffusion coefficient as compared to
Nylon-6. The diffusion coefficient decreases with increase in the length and content of
the silicate layers.20 Water vapor transmission of nanocomposite film is determined by
ASTM E 96.1

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Polymer Clay Nanocomposite

Thermal properties

The HDT increases rapidly for nylon-6 nanocomposite with an increase in the clay
content from 0-5 wt. %. Nanocomposites offer effective flame retardancy without
affecting the environmental problems.4 Nylon-6/clay nanocomposite prepared by
intercalation compounding shows that peak value of heat releasing rate of the
nanocomposite decreased by 32% and 63% when the clay content was 2% and 5%
respectively. The density of the nanocomposite was found to be 65-75% of that of general
composite.35

Ablative property

A relative tough, inorganic char formed during the ablation of the nylon-6
nanocomposite. An order of magnitude decrease in the mass loss rate was observed as
compared to the pure nylon. This property was observed for as little as 2 wt% exfoliated
mica type silicates. The uniform distribution of the silicate layers at nanoscale leads to the
formation of uniform char layer resulting in enhanced ablative property. The formation of
char depends on specific interaction between the polymer and the clay surface.36

Mechanism of Intercalation and Exfoliation

Intercalation

Regular insertion of polymer in between the silicate layers is observed in intercalated

nanocomposites. The polymer to layered silicate ratio is almost fixed. They show
electronic and charge transportation properties. Intercalation of 2 vol. % silicate into
Nylon-6 on a nanoscale improved the tensile strength and modulus by more than twice as
compared to the pristine polymer.3

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Polymer Clay Nanocomposite

Exfoliation

In exfoliated nanocomposite the number of polymer chains between the layered silicates
(clay) is variable. These nanocomposites show superior mechanical properties. In
exfoliated nanocomposite 1 nm thick layers are dispersed forming a monolithic structure
at the micro scale. The ability of the silicate layers to exfoliate is affected by factors such
as ion exchange capacity of the silicate, the polarity of the matrix, and the chemical
nature of the interlayer cations. Matching the polarity of the organic cation with the
monomer is very critical for getting good dispersion.1

As the polymer layer enters into the silicate layers, the interlayer spacing of the clay
increases and the interaction between the clay layer decreases. If the miscibility of the
polymer is good enough then it achieves the exfoliated homogeneous dispersion of the
clay.37 Figure 6 represents the mechanism of intercalation and exfoliation.

2000Ao
10Ao
Intercalation
Polymer chain
Compatibilizer

Silicate layer

Exfoliation

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Polymer Clay Nanocomposite

Figure (6) Diagram representing the Intercalation and Exfoliation in polymer clay
nanocomposite

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Polymer Clay Nanocomposite

Individual Nanocomposite

Polyamide

Nylons are widely used as plastic materials for specialty purposes. They can be injection
and extrusion molded. Nylons are used in automobiles, electrical goods, packaging
applications; because these materials exhibit good mechanical, thermal and barrier
properties.38 Semi-crystalline polymers crystallize in different phases (e.g. Monoclinic,
Hexagonal) forming chain folded lamellar crystals. The stability of these phases depends
on experimental conditions (e.g. temperature, pressure) and crystal size. The
nanocomposites prepared by In-Situ polymerization and Melt intercalation method
exhibited homogeneous distribution of the silicate layers into the polymer matrix at low
clay contents. These composites show enhanced thermal stability, tensile modulus and an
increased elastic behavior over a broad temperature range. No effect on Tg was observed
at highest clay content.39 TEM studies for Nylon -6/clay nanocomposite showed the clays
to be 1 nm thick, 100 nm wide layered filler.40

Meta-xylene adipamide (MXD6), a specialty aliphatic nylon. Intercalated

nanocomposites of MXD6 with modified phyllosilicate silicate (smectite clay) layer
showed expansion in the intergallery spacing by at least 5Aº.

Poly (ε-caprolactone)

Poly (ε- caprolactone) is biodegradable aliphatic polyesters and their use in degradable
packaging, medical devices and controlled drug release systems is under investigations.
For poly (ε-caprolactone) - silicate nanocomposite the permeability was reduced by an
order of magnitude at only 4.8 % loading by volume. Full delamination of the
nanocomposite leads to the formation of high aspect ratio (100-1000) impermeable layer
having very good barrier property.1

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Polymer Clay Nanocomposite

Polymethylmethacrylate (PMMA)

PMMA is polymerized in presence of sodium lauryl sulfate with potassium persulfate in

the presence of Na- Montmorillonite at 70oC for 12 h. It is then coagulated by adding
aluminum sulfate solution. The product is then filtered and dried to form the
nanocomposite.

The average interlayer distance of the composite was found to be higher than the pristine
polymer. TGA thermogram of the weight loss as a function of temperature showed the
shift in the thermal decomposition temperature towards the higher temperature range as
compared to the pure PMMA.

The tensile modulus of the composite was found to be increased with the increase in the
clay content. The improvement in the tensile modulus is due to the higher resistance
exerted by the clay layer against the plastic deformation and the effect of the oriented
backbone bonds of polymer chain in the gallery.

In DSC studies the nanocomposite does not show any clear transition as compared to the
pure PMMA, which shows endotherm at approximately at 102oC, corresponding to the
Tg of the PMMA.41

Polyimide

Polyimides are used in microelectronics as it has good heat resistance, chemical stability
and superior electric properties. For its use in advanced electronics it is desirable to
reduce coefficient of thermal expansion, moisture absorption and dielectric constant.
Layers of organically modified montmorillonite are dispersed homogeneously into the
polymer matrix. These layers align themselves parallel to the surface. A film of polyimide
nanocomposite containing 2 wt. % of montmorillonite is found to be as transparent as
polyimide itself. This phenomenon occurs because of molecular level dispersion and the
size of montmorillonite (< 200 nm ) being lesser then the wavelength of visible light. As

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Polymer Clay Nanocomposite

the content of montmorillonite increases in the polyimide nanocomposite the thermal

expansion coefficient decreases notably. This will play an important role in matching the
thermal expansion coefficient of nanocomposite to that of silicon substrates in electronic
applications.16

PET nanocomposite

PET is a polymer having low cost and high performance, finds variety of applications in
packaging films, bottle and engineering plastic applications to fiber application. In PET
nanocomposite the exfoliated silicate layers acts as nucleation promoter. With a clay
content of 5%, the modulus of nanocomposite was improved as much as 3 times that of
pristine PET. The average particle size distribution ranges from 10-100 nm. The heat of
fusion decreases with the content of clay; and the HDT increase with the content of clay.
The melting point of the PET nanocomposite decreased slightly with the content of clay.
At the degradation temperature of the nanocomposite, the nanoscale particle showed
strong interaction with the polymer matrix; thus explaining the enhancement in the
degradation temperature.9

PP/clay nanocomposite

PP containing organophilic layered silicate nanocomposite was prepared by melt

extrusion process at 210º C. PP-g-MA used as a compatibilizer, led to strong exfoliation
of silicate layers within the polymer matrix. Annealing of the sample at the processing
temperature led to coarsening of the silicate superstructure and improvement in the
exfoliation. Stable morphology with network like superstructure was obtained by this
process.29

In another process montmorillonite dispersed in water and ethylene glycol was treated
with hexadecyl trimethyl ammonium bromide. The dried dispersion was mixed with PP
melt using an extruder, from which the glycol was evaporated.27

A house of cards structure in PP/clay nanocomposite under elongational flow was

observed in TEM analysis.42

By – Bhupendra Singh
Polymer Clay Nanocomposite

PP-g-MA Nanocomposite

PP-g-MA/Layered silicate nanocomposite was prepared by melt intercalation process

using PP modified with maleic anhydride by solid- phase grafting process.
Montmorillonite was modified with octadecylammonium ion. This nanocomposite
showed higher tensile strength and modulus as compared to PP and PP-g-MA. Dramatic
improvement in the tensile property was observed up to the silicate content of 3% and
remained constant over 5%. The nanocomposite showed the faster crystallization than
PP-g-Ma.43

PES nanocomposite

Low molecular weight reactive fume silica was successfully dispersed to nanoscale in
PES matrix with small amount of low molecular weight epoxy. Viscosity and processing
temperature were reduced significantly. Improvement in the barrier property and heat
deflection temperature was observed over pristine PES.14

PS nanocomposite

A shear induced ordered structure was observed in an exfoliated PS/clay nanocomposite.

A series of sharp XRD peaks was reported for the extruded PS/clay nanocomposite as
compared to the broad peaks of PS. The ordered structure resulted from the planer
orientation and local ordered microstructure of the 1º particles of silicate layers, induced
by shear flow.13

ABS nanocomposite

The mixture of acrylonitrile and butadiene- styrene was subjected to polymerization in

the presence of fluoromica as clay. The fluoromica was ion exchanged with
benzalkonium ion and 4- vinylpyridinium ion. The mixture was then suspension
polymerized in aqueous poly (vinyl alcohol) to form a precursor. This precursor was then

By – Bhupendra Singh
Polymer Clay Nanocomposite

blended with ABS copolymer and butadiene rubber in a twin screw extruder to form the
nanocomposite.44

PEO

PEO-block-PS copolymer was prepared by melt-intercalation technique. Samples having

higher PEO volume fraction were more likely to produce intercalation.28

Epoxy/clay nanocomposite

The organic modified clay is easily intercalated by the epoxy precursor during the
mixing process. Addition of suitable catalyst and coupling agent into the cured system
significantly reduces the maximum reaction temperature thus leads to favorable reaction
in the formation of Epoxy nanocomposite.17

Applications

Nanocomposites have been rapidly commercialized for different applications.

Nylon-6 and PP nanocomposites are used for packaging and injection molded articles.
Semi-crystalline nylon nanocomposites have been used for barrier, containers and fuel
tank system applications. Layered silicate promotes rapid crystallization; hence better
clarity is obtained as compared to pristine nylons; which makes them ideal for film
applications. Nanocomposites can be run at higher line speeds as a result of improved
strength. MXD6 nanocomposite is finding its use as a barrier resin in packaging
applications. It is very useful in applications requiring good barrier properties in high
humid conditions. Nylon clay nanocomposite having excellent mechanical and heat
resistance property find its use in automobile parts. Nylon nanocomposite film having
good barrier property finds use in wrapping films for food industry.45

Polyamide nanocomposite prepared by melt intercalation process can be used in all

molded parts which can be produced using polyamide compounds. It find use in the
motor compartment of a vehicle for casing and for connectors.46 Polymer clay

By – Bhupendra Singh
Polymer Clay Nanocomposite

nanocomposites are widely used in electronics, transportation, construction and consumer

products as they exhibit combination of properties like stiffness and toughness which are
not present in individual polymers.4

Polyimides find use in microelectronics because of it superior electric properties.16

Alicyclic copolymer mixed with disteryl dimethylammonium chloride treated
montmorillonite was found to be useful for automobile parts, electrical parts and
packaging applications.47 Polyamide sheets containing 4 % montmorillonite showed
reduced curling and were useful for packaging drug tablets.48 Multilayer fuel tanks with
excellent gasoline barrier properties and fire resistance were manufactured by HDPE/
clay nanocomposite.49

A subclass of nanocomposite by using graphite as nanofiller may be used as conducting

polymer.50

Conclusion

Nanocomposites can be synthesized for both thermoplastic as well as for thermoset.

Conventional processes such as injection and extrusion molding are employed to get the
final product. The drastic enhancement in the nanocomposite properties is attributed to
the ultra fine phase dimensions of the filler and homogeneous dispersion in the polymer
matrix. To get homogeneous dispersion the compatibility of the clay with polymer matrix
has to be improved. The type of clay and chemical treatment governs the dispersion of
the clay. Compatibilizing agent plays an important role in the dispersion. Low levels of
loading, high aspect ratio, cation exchange capability and natural abundance makes the
Montmorillonite the most effective clay for use in the nanocomposite. Various
compositions of polymer and clay nanocomposite have been developed by different
processes. Manipulation in the compositions will result in getting optimum properties.
The enhanced mechanical properties, barrier properties will increase its use in the
automotive and packaging industry.

By – Bhupendra Singh
 Polymer Clay Nanocomposite

Reference:

1. P.B.Messersmith and E. P. Giannelis, J. Polym. Sci., Part A, Polym. Chem.., 33, 1047-
1057 (1995 )
2. L. J. M athias, R. D. Davis and W. L. Jarret, Macromolecules, 32,7958-7960 (1999)
3. A. Lee, J. D. Lichtenhan, J. Appl. Polym. Sci., 73,1993-2001 (1999)
4. L.Liu, Z. Qi, X. Zhu, J. Appl. Polym. Sci., 71, 1133-1138 (1999)
5. D.L.VanderHart and A. Asano, Macromolecules, 34,3819-3822 (2001)
6. Y.Kojima, A.Usuki, M. Kawasumi, A. Okada, T. Kurauchi, O. Kamigato and K. Kaji; J.
Polym. Sci., Part B, Polym. Phys., 32, 625-630 (1994 )
7. G.jimenez, N. Ogata, H. Kawai, T. Ogihara, , J. Appl. Polym. Sci., 64, 2211-2220 (1997)
8. H. Ge, Y. Hu, S. Yang, X. Jiang, C. Yang, J. Appl. Polym. Sci., 75, 874-882 (2000)
9. Y.Ke, C. Long, Z. Qi, J. Appl. Polym. Sci., 71, 1139-1146 (1999)
10. M. H. Noh, D.C. Lee, J. Appl. Polym. Sci., 74, 2811-2819 (1999)
11. Kodgire, Pravin, Kalgaonkar, Rajendra, Hambir, Sangeeta, Bulakh, Neelima, Jog J.P.; J.
Appl. Polym. Sci., 81, 1786-1792 (2001)
12. Guo, Cun-Yue; Liu, Zhong-Yang;Xu, DE- Min; He, DA- Wei; Hu, You-liang. Yingyong
Huaxue, 18 (5), 351- 356, (2001)
13. Chen, Guang- Ming, Ma, Yong- Mei, Qi, Zong-Neng. Goodeng X. H. Xuebao;22(5),872-
874,(2001)
14. Jana S. C, Jain S.; Polymer, 42 (16) 6897-6905,(2001)
15. Choi, Hyoung J., Seong G Hyun Yang H John Myung S; Macromol. Rapid Commun. 22
(5),320-325,(2001)
16. K. Yano, A.Usuki, A. Okada, T. Kurauchi, and O. Kamigato, J. Polym. Sci., Part A,
Polym. Chem.., 31, 2493-2498 (1993 )
17. Y. Ke, J. Lu, X. Yi, J. Zhao, Z. Qi, J. Appl. Polym. Sci., 78, 808-815 (2000)
18. Y. S. Yang and L. J. Lee, Polymer, (29) 1793-1800 (1988)
19. A.Usuki, A. Kaiwai, Y. Kojima, M. Kawasumi, A. Okada, T. Kurauchi, and O. Kamigato
; J. Appl. Polym. Sci., 55, 119-123 (1995)

By – Bhupendra Singh
 Polymer Clay Nanocomposite

20. Y.Kojima, A.Usuki, M. Kawasumi, A. Okada, T. Kurauchi, and O. Kamigato J. Appl.

Polym. Sci., 49, 1259-1264 (1993)
21. Wang, Yizhong, Dong, Hua, Yu, Dingsheng, H. S. Ji, Suliao; 14(2), 16-18,(1997)
22. The Merck Index, 12th Ed., pg. 6337,N. J. U.S.A. (1996)
23. Ullmann’s Encyclopedia of Industrial Chemistry, fifth ed. Vol. A7 pg. 111-116; Weinheim
New York. (1996)
24. O. Yuchun, Y. Feng, Y. Zhon-Zhen, J. Polym. Sci., Part B, Polym. Phys., 36, (5)789-795
(1998 )
25. Lyu, Sung, Gyu, Park, Dae, Youn, Bae, K. Soo, Sur, G. soo; Polymer, 25(3), 421-426,
(2001)
26. Barber, R. Boyd, Matayabs, J. Christopher, In, Gilmer, J. Walker; PCT Int. Appl.
Wo.0034,393, (2000)
27. W. Udo, K. Bernd, W. Dieter, G. Thomas; German Offen. De. 10,002,997,(CL.
CO8J3/20)(2001)
28. Beyer, Fredrick L, Tan, Nora C, Beck; Mater. Res. Soc. Symp. Proc.; 628, CC4.5.1-
CC4.5.6 (2001)
29. Reichert, Peter, Hoffmann, Botho, Block, Thorsten, Thomann, Ralf, Mulhaupt, Rolf,
Friedrich, Christian; Macromol. Rapid Commun.22(7) 519-523 (2001)
30. Y.Kojima, A.Usuki, M. Kawasumi, A. Okada, T. Kurauchi, and O. Kamigato; J. Polym.
Sci., Part A, Polym. Chem.., 31, 983-986 (1993 )
31. nanocor inc
32. Y. Wang, L. Zhang, C. Tang, D. Yu, J. Appl. Polym. Sci., 78, 1879-1883 (2000)
33. Varlat, K; Reymond, E; Kloppfer, M. H; Vigier, G; Varlet; J; J. Polym. Sci., Part B,
Polym. Phys., 39, (12)1360-1370 (2001 )
34. Y.Kojima, A.Usuki, M. Kawasumi, A. Okada, T. Kurauchi, O. Kamigato and K. Kaji; J.
Polym. Sci., Part B, Polym. Phys., 33, 1039-1045 (1995 )
35. Shu, Zhongjun, Chen, Gungming, Qi, Zongnerg; Sullao Gongye. 28(3), 24-26, (2000)
36. Vaia, Richard A., Price, Gary, Rutu, Patrick N., Nguyen, Hieu T., Lichtenhan, Josheph,
Appl. Clay Sci. 15(1-2),67-92, (1999)
37. M. Kawasumi, N. Hasegawa, M. Kato, A. Usuki and A. Okada,Macromolecule;30,6333-
6338(1997)

By – Bhupendra Singh
 Polymer Clay Nanocomposite

38. M. I. Kohan Etal. Nylon Plastics, Wiley New York.

39. Kucha, F. Dieta, Lemstra, Pict J., Keller, Andrew, Batenburg, Lawrence F., Fischer,
Hartmut R.; Mater. Res. Soc. Symp. Proc. 628, cc11.12.1-cc11.12.7,(2001)
40. Usuki, Arimitsu, Hasegawa, Naoki, Kadoura, Hiroaki, Okamoto, Tokuhiko; Nanolett.
1(5), 271- 272,(2001)
41. D. C. Lee and L. W. Jang; J. Appl. Polym. Sci., 61, 1117-1122 (1996)
42. Okamoto, Masami, Nam, P. Hoai, Maiti, parlay, Kotaka, Tadao, Hasengawa, Naoki,
Usuki, Armitsu; Nanolett. 1(6), 295- 298,(2001)
43. Kim, M. Jung, Choi, M. Ho, Koo, C. Min, K. S. Ouk, Chung, I. Jae; Hwahak Konghak
38(5) 691-697,(2000)
44. K. W. Ta, L. M. Sung, H. H. Ping, W. C. Kuang, C. S. Cheng; Jpn. Kokai Tokyo, Koho,
JP, ,200,135 (2001)
45. Fukusima, Yoshiaki; Nippon Kagaku Kaishi,(9)605-611(2000)
46. Korbe, Roland, Alexander, V. Geenen, A. Arnold; PCI Int. Appl. WO. 29,767,(1999)
47. Murakami, Toshihide, Minami, Koji, Ohara, Teiji, igarashi, Ichiro, Matsumoto, Yuichi;
Jpn. Kokai Tokkyo Koho Jp 181,483,(2001)
48. Nakota, Hiroki, Yanase, Koichi, Kawauchi, Yuji, Furukawa, Sadashi, Takeda, Masaki,
Shimobe, Yasuo; Jpn. Kokai, Tokkyo Koho Jp 181,409,(2001)
49. Michihata, Yoshizo, Takada, Shigeki, ; Jpn. Kokai Tokkyo Koho Jp 179,901,(2001)
50. Guo-Hua C., Da-Jun W., Wen-Gui W., Bin He and Wen-Li Y.; Polymer International,
50,980-925,(2001)

By – Bhupendra Singh