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Priya et al. World Journal of Pharmacy and Pharmaceutical Sciences

SJIF Impact Factor 6.041

Volume 5, Issue 5, 288-301 Review Article ISSN 2278 4357




D. Nagasamy Venkatesh, Veeramachaneni Krishna Priya* and Kosaraju Bhavitha

Department of Pharmaceutics, JSS College of Pharmacy, (A Constituent College of JSS

University, Mysuru), Udhagamandalam - 643 001. Tamil Nadu.

Article Received on
28 Feb 2016, This review is a relative source for polymer nano composite research,
Revised on 22 March 2016,
Accepted on 12 April 2016 which includes the fundamental properties, different manufacturing
DOI: 10.20959/wjpps20165-6618 methods and various applications of polymer nanocomposite materials.
this review article mainly focuses on the various scientific principles
and mechanisms which are related to the methods of formulating and
*Corresponding Author
Veeramachaneni processing with a discussion on various commercial applications and
Krishna Priya also on various health/safety concerns (a major problem for
Department of manufacturing and scale-up). Hence, the relative discussion on
Pharmaceutics, JSS
technology, modeling, characterization, processing, manufacturing,
College of Pharmacy, (A
applications and health/safety concerns for polymer nanocomposites is
Constituent College of
JSS University, Mysuru), over viewed in this article.
Udhagamandalam - 643
001. Tamil Nadu. KEYWORDS: layered silicates, graphite nanoplatelets, carbon nano
tubes, nano particles, nano fiber.

The use of organic or inorganic filler has become very common in the polymeric systems.
Polymer composites are manufactured commercially for many different type of applications
such as sporting goods, aerospace components, automobiles, etc. From past 20 years, there
has been a strong focus on the development of polymeric nanocomposites. In this polymeric
nanocomposite system at least one of the dimensions of the filler material would be of the
order of a nanometer. The final product obtained need not have to be in nanoscale, it can be
micro- macroscopic in size. This sudden development in the field of nanotechnology has been
facilitated by the emergence of scanning tunneling microscopy and scanning probe
microscopy in early 1980s. Scientists are able to see the nature of the surface morphology

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with atomic resolution with the help of these powerful tools. Simultaneously, due to the rapid
growth in various computer technologies it became easier to characterize and predict various
properties at nano scale by various modulations and simulations. The unique combinations of
the nanomaterials characteristics, such as size, mechanical properties and low concentrations
are necessary to effect change in a polymer matrix, which is coupled with the advanced
characterization and simulation techniques which are now available, have generated much
interest in the field of nanocomposites. (Shevtsov, I.Y., Markine, V.L., Esveld, C. Optimal
design of wheel profile for railway vehicles. Wear, Volume 258, Issue 7-8, p. 1022-1030).

Polymer nanocomposites can be fabricated and can be processed in many ways which are
similar to that of conventional polymer composites. Chemistry in Britain in 1998 published
an article titled Nano sandwiches which stated that the, Nature is a master chemist with
incredible talent. Using various natural reagents and different polymers such as
carbohydrates, lipids and proteins, nature creates various strong composites such as bones,
shells and wood. These are the few examples of nanocomposites, which are made by mixing
two or more phases such as particles, layers or fibers, where at least one of the phases is in
the nanometer size range. Nanoscale science and technology research is progressing with use
of a combination of atomic scale characterization and detailed modeling. The properties of
nanocomposite materials depend not only on the morphology and interfacial characteristics,
but also on the properties of their individual parents (nano filler and nylon, in this case), says

Conventional Composite Manufacturing Techniques using Nanocomposites
There will be an improvement in a property which arises when the length scale of the
morphology (i.e., nano) and fundamental physics associated with a property coincide. Two
principal factors which cause the properties of nanomaterials to differ significantly from other
material sare increase in the relative surface area and also the quantum effects. Some of the
nanocomposites may show properties which are predominately affected by various interfacial
interactions and others may exhibit the quantum effects associated with nanodimensional
structures. In few areas, fundamental studies of mechanical, electrical, thermal, optical and
chemical properties are required along with related research for real applications. Fabrication
method is the method of choice for manufacturing of nano-phased structural polymer
composite material. There are few methods which are predominantly used for the

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manufacture of conventional composite parts are wet lay-up, pultrusion, resin transfer
molding (RTM), vacuum assisted resin transfer molding (VARTM), autoclave processing,
resin film infusion (RFI), prepreg method, filament winding, fiber placement technology, etc.
When compared with other methods Wet lay-up is a simple method; it would allow the resin
to be applied only in the mold, but due to voids mechanical properties of the product are poor
and the final product obtained is nonuniform. Pultrusion is a continuous process with a high
production rate and is of low cost. The materials which accumulate near the die assembly can
create a jam. Voids can be formed if the dies run with too much opening for the fiber volume
input. Constant cross section is a limitation of this process, but the fibers in pultruded
material are generally well aligned; it will help to reduce fiber misalignment in the various
composite through optimization of manufacturing process variables, such as pull-speed,
preformer temperature, nanoparticle alignment and/or dispersion. The RTM is a closed mold
operation. Resin flow and fiber wet-out are the major issues in this process; resin flows both
in the plane and in the transverse directions of the preform. Fiber wet-out would mainly
depend on the fiber architecture and the permeability of the preform. Recent developments in
textile and resin technology helped the designer and manufacturer to use RTM for the
fabrication of parts for the primary and secondary structures. Various approaches in textile
technology helped to improve the wetability of the preforms. A fiber volume fraction will be
of 5560%. Higher unit of toughness can be achieved by various technologies like
three-dimensional weaving and stitching technology.

Autoclave processing is a favorable technique to process and manufacture various complex

shapes which are having high-quality composite structures. It has the capacity to process both
the thermoset and thermoplastic composites which are having uniform thickness and
minimum porosity. However, the major problem in this process is higher capitalization
cost.with the increase in the requirement for high-performance composite materials for
further generation aircrafts, these autoclave applications remains one of the most widely used
techniques in the aerospace industry.

Characterization Techniques for Nanocomposites

Characterization tools are critical to understand the basic physical and chemical properties of
PNCs. For various structural applications, it helps in the study of emerging materials by
giving information on some intrinsic properties. Various techniques for characterization have
been used in polymer nanocomposite research. Wide-angle X-ray diffraction (WAXD),

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small-angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and transmission
electron microscopy (TEM) are the most commonly used methods.

The SEM gives images of surface features related with a sample. scanning probe microscopy
(SPM) and scanning tunneling microscopy (STM), which are essential in nanotube research.
The SPM utilizes various interactions between the sharp tip and a surface to acquire an image.
A sharp conducting tip is held (typically about 0.5nm), such that electrons present can
tunnel across the gap. The surface structure and electronic information at atomic level can
be known by this method. The formulation of the STM inspired the evolution of other
scanning probe microscopes, such as the atomic force microscope (AFM). The AFM utilizes
the sharp tip to scan across the sample. Raman spectroscopy also proved a useful probe of
carbon-based material properties. (Bruno Faria, Jose N).

Nanoplatelet-reinforced Systems
Two different types of nanoplatelet particle composites are reviewed in this article: silicate
clay minerals and graphite.

Historically, the word clay has been defined to be made of small inorganic particles (part of
soil fraction less than 2mm), without any definite composition or crystallinity. The clay
mineral (also called a phyllosilicate) is mainly made of a layered type and it is a fraction of
hydrous, magnesium, or aluminum silicates. All the clay minerals contain two types of sheets,
tetrahedral (T) and octahedral (O). The most commonly used smectite type layered silicates
for the preparation of nanocomposites are Hectorite, saponite and montmorillonite.
Montmorillonite (MMT) has the broad acceptability for use in polymers due to their largeer
surface area, and surface reactivity. It is a hydrous alumino silicate clay mineral which has a
2:1 expanding layered crystal structure, with aluminum octahedron sandwiched in between
the two layers of silicon tetrahedron. Each and every layered sheet is approximately of 1nm
thickness (10A), the lateral dimensions of these layers may be varied from 30nm to several
microns or larger, based on the specific layered silicate. The particular ratio is around
101000 and the surface area is in the range of 750m2/g. When one of the octahedral sheet is
bonded to other tetrahedral sheet, a 1:1 clay mineral results. The 2:1 clays are comprised
when two tetrahedral sheets bond with one octahedral sheet. The particular ratio of 1000 is
feasible when the clay platelet is well-dispersed into the polymeric matrix without breaking.
Basically, breaking up of clay platelets while mixing at high shear and large shear stress
condition will result in a particular ratio of 30300.

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As discussed above, graphite contains a similar geometry (layered structure) with nanoclay
and so a clay polymer reinforcement concept is applicable. Graphite flakes are known as host
materials for intercalated compounds. By rapid heating few graphite-intercalated compounds
(GICs) are expanded and a have a drastic increase in volume will takes place. Many
literatures quoted that expansion is by graphite flakes with polymer systems for lightweight
and conductive polymer composites.


Organically Modified Clay Platelets
In polymer layered silicate (PLS) nanocomposites, arrangement of the layers leads to van der
Waals gap in between the layers called the interlayer or gallery. Isomeric substitution (for
example tetrahedral Si4 by Al3 or octahedral Al3 by Mg2 or Fe2) inside the layers
creates negative charges which are neutralized by alkali and alkaline earth cations (typically
Na or Ca2) present inside the galleries. This type of layered silicate is identified by a
common surface charge known as the cation exchange capacity (CEC).

Generally, the organically remodelled silicate nanolayers were referred as nanoclays or

organosilicates. It is necessary to know whether the physical mixture of a polymer and
layered silicate may form nanocomposites or not. Hydrated Na or K ions are present in
Pristine-layered silicates. To provide layered silicates compatible with other polymer matrices,
there is a need to convert the normal hydrophilic silicate surface to an organophilic one and it
can be done by ion exchange reactions with cationic surfactants. Sodium montmorillonite
(Nax(Al2-xMgx)(Si4O10)(OH)2 mH2O) type layered silicate clays are available as micron
size tactoids, which contains hundreds of individual plate-like structures with various
dimensions of 1mm 1mm 1nm. These are held by electrostatic forces (gap in between two
adjacent particles 0.3nm). The MMT particles, which are not separated, are generally referred
as tactoids. The most troublesome task is to break down the tactoids to the scale of each
individual particles in the dispersion process to form fine nanocomposites, which has been a
serious issue in present research in various literatures. In immiscible systems, which
commonly correspond to the more traditionally filled polymers, the poor physical interaction
between organic and inorganic components may lead to poor mechanical and thermal
properties. In contrast, the dispersion of the independent nanosheets of the layered silicates in
the polymer matrix forms a large contact area. More likely, uniform dispersion would lead to
interfacial coupling between the individual sheets and the polymer matrix which facilitates

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the stress transfer to the reinforcement phase. This would reduce the weak points present in
conventional polymer composites.

Graphite Nanoplatelet
Natural flake graphite (NFG) is also comprised of layered nanosheets, in which carbon atoms
are placed on the NFG layer and are screued up by covalent bonds, while those positioned in
adjacent planes are bound by weaker van der Waals forces. The weak interplanar forces
allows certain atoms, molecules and ions to insert into the interplanar spaces of the graphite.
The interplanar spacing is increased. As it does not contain any net charge, inserting of
graphite cannot be done by ion exchange reactions into the galleries like layered silicates.The
original graphite flakes with a thickness of 0.460mm may be expanded up to 220,000mm
in length. These layers are separated down to 1nm thickness, by forming a high aspect ratio
(2001500) and high modulus ( 1TPa) graphite nanosheets. Furthermore, when dissolved in
the matrix, the nanosheet shows a broad interface surface area (2630m2/g) and plays a key
role in the development of both the physical and mechanical properties of the resultant
nanocomposite. Expanded graphite (EG) can be prepared by continous heating of
intercalation compound (GIC), which is initially prepared from an NFG. generally, the
structure of EG has parallel boards, which disintegrate and deform automatically and forms
many pores of different sizes ranging from 10nm to 10mm. As it has a high expansion ratio,
the galleries of EG can be easily passed through physical adsorption. Frank Mcklich.

Nano-clay-reinforced Composites
In situ intercalative polymerization
By this technique, formation of polymers occur in between the intercalated sheets. In situ
polymerization is depended on the following procedure: swelling of the layered silicate
within the liquid monomer and the polymerization can be initiated either by heat or radiation,
by the diffusion of a suitable initiator, or by an organic initiator. This approach was applied in
manufacturing of nylonmontmorrillonite nanocomposite, and later it was extended to other
thermoplastics. This is a convenient method for thermoset clay nanocomposites.

The method is based on a solvent system in which the polymer or pre polymer is soluble and
the silicate layers are swellable. The layered silicates, owing to the weak forces that stack the
layers together, can be easily dispersed in an adequate solvent such as water, acetone,
chloroform, or toluene. The polymer then adsorbs onto the delaminated sheets and when the

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solvent is evaporated, the sheets reassemble, sandwiching the polymer to form. This strategy
can be used to synthesize epoxyclay nanocomposites, but removal of solvent is a critical
issue here. Moreover, there is a disadvantage in using a large amount of solvent in the resin
system. This process also includes the emulsion polymerization where the layered silicate is
dispersed in the aqueous solution. Melt Intercalation: In this technique, no solvent is required
and the layered silicate is mixed within the polymer matrix in the molten state. A
thermoplastic polymer is mechanically mixed by conventional methods such as extrusion and
injection molding with organophillic clay at an elevated temperature. The polymer chains are
then intercalated or exfoliated to form nanocomposites.

This is a popular method for preparing thermoplastic nanocomposites. The polymers, which
are not suitable for adsorption or in situ polymerization, can be processed using this
technique. (Sebastian Suarez, Federico Lasserre,).


In the early 1990s, Toyota researchers reported work based on true nylon-6clay
thermoplastic nanocomposites technology and now it has a broad-based proprietary patent
technology that is licensed to companies in Japan and the USA.

In their work, mechanical properties showed significant improvement at a loading of only

4.2wt% clay, the modulus doubled and the increase in strength was more than 50%. Also an
improvement in thermal properties was observed with the increase of heat distortion
temperature (HDT) by 80 C compared to the pristine polymer. In recent years, for
nanocomposite formation, organoclay has been used in various polymer systems including
epoxy, polyurethanes, vinyl ester, etc. Ballistic performance is an important issue for the
survivability and damage tolerance studies for aerospace and automotive structures. The US
Army research laboratory investigated the ballistic impact strength of polycarbonate-layered
silicate nanocomposites. According to their description, nanocomposites can play an
important role in longer-range missiles and a greater payload for aircraft. Ablatives are
required to protect aerospace launching systems against solid rocket exhaust plumes
(3600 C) at very high velocity. They demonstrated that nanoclay plays a key role in
reducing the flammability on coating systems. (Frank Mcklich).

Flammability is another important issue for many applications. Other studies show that
nanocomposites prepared from he nylon family, epoxy, polystyrene or vinyl ester, exhibit

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reduced flammability compared to pure polymers.

Fiber-reinforced nanocomposites are manufactured through affordable RTM and VARTM

processes described in different literatures. Hussain et al. achieved an almost (by dispersing
only 1% by weight nanosilicates) 18 and 24% improvement in flexural strength and fracture
toughness respectively in S2 glass/ vinylesterclay nanocomposites compared to
conventional composites. They achieved improvements in compressive strength and modulus
using this technique. Fielding et al. achieved uniform dispersion of the nanoclay of carbon
fiber reinforced epoxy nanocomposites using RFI in the autoclave. Nanocomposites formed
by melt blending have been described in different literatures. Dennis et al. described how the
type of extruder and screw design affects the degree of dispersion of nanoclay in a polyamide

Graphite Nanoplatelet Polymer Composites

Improvement in electrical conductivity is achieved by adding a graphite platelet in a
polystyrene. It basically represents the sharp transition of the polymer from an electrical
insulator to an electrical semiconductor with the addition of a graphite nanoplatelet. The
percolation threshold value of the conducting composite (with 1.8wt% of expanded graphite)
was much lower than that of conventional composites. A graphite platelet is used as
reinforcement in both epoxy and PP systems to investigate the mechanical, thermal, and
electrical properties of the nanocomposites. Fukushima and Drazal showed better flexural and
tensile properties of chemically functionalized graphite nanoplatelet in the epoxy matrix. In
addition they achieved lower CTE and electrical resistivity compared to other carbon
materials like carbon fiber, carbon black, etc. These properties of graphite nanoplatelet
combined with low cost make it useful in electromagnetic interference (EMI) shields, thermal
conductors, etc. Graphite is well known for its stiffness and excellent thermal and electrical
conductivity, which are absent in clay materials. Yasmin used both graphite/epoxy and
clay/epoxy nanocomposites to investigate the performance of reinforcement and they found
that graphite/epoxy has a higher (16% for 2wt% particle content) elastic modulus compared
to the clay/epoxy for the same particle content.


Particles of Interest Nanoparticles are often defined as particles of less than 100nm in
diameter. Nanometer-sized particles have been made from different organicinorganic
particles and impart composite materials improved properties. Different particles have been

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used to prepare polymer/inorganic particle nanocomposites, including: Metal (Al,Fe,Au,Ag,

etc.). Metal oxide (ZnO,Al2O3,CaCO3,TiO2 etc.). Nonmetal oxide (SiO2).Other
(SiC)Il-(Young Kim, Jung-Hee Lee,).

The selection of nanoparticles depends on the desired thermal, mechanical, and electrical
properties of the nanocomposites. For example, Al nanoparticles are often selected due to
their high conductivity; calcium carbonate particles are chosen because of the relative low
cost of the material and silicon carbide (SiC) nanoparticles are used because of their high
hardness, corrosion resistance, and strength.

Preparation and Processing In the case of organicinorganic nanocomposites, the strength or

level of interaction between the organic and inorganic phases is an important issue. Physical
or simple mechanical mixing causes a weak phase interaction, e.g., hydrogen bonding, vander
Waals forces. On the other hand, a strong chemical covalent or ioniccovalent bond between
the organic and inorganic phases or sol gel technique is the typical preparation method for the
organicinorganic nanocomposites.

Surface chemistry has been studied for understanding the effect of nanoparticles on a polymer
matrix, particlematrix adhesion etc. in different studies. Yong and Hahn used a dispersant
and coupling agent in an SiC/vinylester nanocomposite system to improve the dispersion
quality and strength. Different methods have been used to prepare polymer/inorganic particle
nanocomposites, including: in situ polymerization, melt compounding by twin-screw
extrusion, solution blending, high shear mixing with three roll milling, etc. Tang et al. used
two traditional polymer-processing techniques (free cast and spinning) to prepare
polyacrylonitrile matrix and nano-ZnO composites. (Il-Young Kim, Jung-Hee Lee,).

Properties, Manufacturing, and Application:

Polymer/inorganic particle-based nanocomposites have shown significant improvement in
mechanical, thermal and electrical properties. For example, in nylon-6 filled with 5wt%
50nm silica nanoparticles, an increase in tensile strength by 15%, strain-to-failure by 150%,
Youngs modulus by 23% and impact strength by 78% were reported. Jiang and coworkers
investigated ABS (acrylonitrile butadiene styrene) reinforced with both microsized and nano
sized calcium carbonate particles through melt compounding. It was found that the
ABS/micron-sized particle composites had higher modulus but lower tensile and impact
strength than neat ABS. However, the ABS/nano-sized particle composites increased the

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modulus as well as impact strength. Chen et al. found that different particle sizes influence
the glass transition temperature (Tg) of the nanocomposites. It showed an improvement in
electrical properties of polyethylene nanocomposites by introducing functional groups at
TiO2 nanoparticles. (Nuno Silvestre, Bruno Faria, Jos N.).

Challenges in Processing and Manufacturing of Nanocomposites
Nanocomposite materials hold the potential to redefine the field of traditional composite
materials both in terms of performance and potential applications. There is little doubt that
polymer nanocomposites have tremendous market potential both as replacements for current
composites and in the creation of new markets through their outstanding properties. But
developing the processingmanufacturing technologies in terms of quantity and value for
commercialization will be one of the biggest challenges.

For example: dispersion of nanoparticles or chemical compatibility with matrix materials is

the important issue. A homogeneous dispersion of nanoparticles in a polymer by using
existing/traditional compounding techniques is very difficult due to the strong tendency of
fine particles to agglomerate. At the same time if it is subjected to force, there is a possibility
of splitting of agglomerate nanoparticle. Therefore, premature failure takes place in the final
product. Degassing is another critical problem while processing a nanocomposite. The air
trapped while pouring the highly viscous material in the mold (5 10wt% of clay in the
matrix), initiates crack and failure of specimen can take place under low strains. The
alignment of nanoparticles in the composite matrix can be critical to maximize unidirectional
properties such as strength, modulus and toughness. As in the case for traditional composites,
it is even more challenging to determine the strength, composition and functionality of the
interfacial region.

The goal of improving the carbon nanofiber matrix interfacial adhesion issue and complete
dispersion must be solved before achieving the full potential of CNF nanocomposites.
McMorrow and Chartoff used a two-roll mill for dispersing carbon nanofibers in vinyl ester
resin via continuous shearing. They found a dry and brittle mixture after 6min of milling and
incomplete dispersion because of the viscosity limitations. However, they mentioned that the
technique holds promise for lower viscosity resins if the temperature and/or added diluents
help to reduce the viscosity of the mixture. They did not achieve a good trend in the
mechanical and thermo mechanical results as a function of CNF loading, which were

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opposite to what was expected for a well-dispersed nanocomposite with good fibermatrix
adhesion. In addition to the composite integrity, the nature of the nanoparticle is also critical
for property improvement. few looked at the defective structures and properties of carbon
nanotubes. They generated model configurations of nanotubes. They found SWNTs to be
relatively defect-free whereas, MWNTs typically had more defects, such as topological
defects (pentagon, heptagon) and structural defects (discontinuous, cone shaped walls, or
bamboo structure). To improve dispersion and compatibility in polymer matrices, nanotube is
being functionalized. There are still some concerns remaining like whether functionalization
of a nanotube will affect the properties to improve the final product. (Cheng, Y., Liu, X., Li,
Z., Liu, L.).

Future Outlook
The potential of nanocomposites in various sectors of research and application is promising
and attracting increasing investment from Governments and business in many parts of the
world. While there are some niche applications where nanotechnology has penetrated the
market, the major impact will be at least a decade away. Currently, there are a few cosmetic
products made by incorporating nanoparticles on the market. To create such macroscale
materials, many issues surrounding the incorporation of nanotubes into a matrix, strategies
for property improvement, and the mechanisms responsible for those property improvements
still remain critical. (Il-Young Kim, Jung-Hee Lee,).

Since only a moderate success has been made over the last 20 years, researchers must
continue to investigate strategies to optimize the fabrication of nanotube-enabled materials to
achieve both improved mechanical and transport properties. Biodegradable polymer-based
nanocomposites have a great deal of future promise for potential applications as
high-performance biodegradable materials. These are entirely new types of materials based
on plant and nature materials (organoclay). When disposed of in compost, these are safely
decomposed into CO2, water and humus through the activity of microorganisms. The CO2
and water will become corn or sugarcane again through plant photosynthesis. Undoubtedly,
their unique properties originating from the controlled nanostructure paves the way for a
much broader range of applications (already commercially available through Unitika Ltd.,
Japan) and opens a new dimension for plastics and composites. (Fox-Rabinovich, G.S.,
Endrino, J.L., Agguire).

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According to several sources, a significant increase in turnover of about 100%/year, leading

to a value of about 1500 million Euro (ca. 500,000 ton/year of polymer nanocomposites) in
2009 is expected. Even if these numbers are overly optimistic, they highlight the tremendous
technological and economical potential associated with polymeric nanocomposites including
not only clay but also other inorganic nanofillers, such as carbon nanotubes, SiO2, SiC and
Si3N4. At present it is difficult to predict which, if any, market sector would not be able to
benefit from this technology. Thus, it may well be that polymeric nanocomposites in the mid
and longer-term will pervade all aspects of life, similar to the way plastics did in the last
century. Clearly a diverse range of sectors such as aerospace, automotive, packaging
(particularly food but also solar cells), electrical and electronic goods, household goods etc.
will profit substantially from a new range of materials which would be offered by this
technology. In the short term (<5 years), the commercial impact may include inkjet markets,
nanoparticles in cosmetics, and automotive applications such as body moldings, engine
covers and catalytic converts, batteries, computer chips. (Vereschaka A.S.).

In the mid-term (10 years), memory devices, biosensors for diagnostics, advances in lighting
are all possible. The time-scale for automotive, aerospace, bio-nanotechnology is a long-term
prospect (>15 years) as these are risk-averse sectors and thereby for large-scale production it
is necessary to carry out strict testing and validation procedures. (Vereschaka A.S. ).

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