Science and applications of Tailored Nanostructures 50

4
Polymer nanocomposites – synthesis
techniques, classification and properties

1 2 *1
Waseem. S. Khan , Nawaf. N. Hamadneh , Waqar A. Khan
1
Department of Mechanical & Industrial Engineering, College of Engineering Majmaah University, P.O Box 66, Majmaah
11952, Kingdom of Saudi Arabia.
2
Science Department, College Of Science and Theoretical Studies, Saudi Electronic University, Riyadh 13316, Saudi Arabia.
*
Corresponding author

Outline:
INTRODUCTION…………….…………….…………….…………….…………….…………….…………….……….……………… 51
Nanotechnology ……………………………………………………………………….……………………………………….……..…51
Classification of Nanomaterials ………………….………………………………………………………………………………. 52
Nanoparticles ………….……………………………………………………………………………………………………………….… 52
Nanomaterials …………………………………………….…………………………………………………………………….………. 53
Fullerenes ……………………………………………………………………………………………………………..……………………. 53
Carbon Nanotubes (CNTs) ………………..……………………………………………………………………………………….. 53
Nanowires …………………………………………………………………………………………………………………………….……. 53
Quantum Dots ……………………………………..…………………………………………………………………………………….. 54
Metallic Nanoparticles ……………………………………………………………………………………………………………….. 54
Carbon Black ……………………………………………..……………………………………………………………………………….. 54
Dendrimers ………………………….…………………………………………………………………………………………………….. 54
Nanoclays ………………….……………………………………………………………………………………………………………….. 54
Nanocrystals …………………………………..………………………………………………………………………………………….. 55
NANOCOMPOSITES ……………………………………………………………………………..…………………………………….. 55
Types of Nanocomposites ………………………………………………………………………………………………………….. 56
Polymer Matrix Nanocomposites ……………………………………………………………………………………………….. 56
Ceramic Matrix Nanocomposites ……………………………………………………………………………………………….. 62
Metal Matrix Nanocomposites ……………….………………………………………………………………………………….. 62
POLYMER MATRIX NANOCOMPOSITE PROCESSING TECHNIQUES …………………….……………………….. 63
Intercalation Method ………………..……………………………………………………………………………………………….. 63
Melt Intercalation Method ………………………..……………………………………………………………………………….. 64
In Situ Polymerization Method …………………….…………………………………………………………………………….. 64
Sol Gel Method ………………………………………………………………………………………………………………………….. 64
Direct Mixing of Polymer and Nanofillers …….…………………………………………………………………………….. 64
Melt Compounding …………………………………………………………………………………………………………………….. 65
Solvent Method ………………………………………………………………………………………………………………………….. 65
Conclusions……………………………………………………………………………………………………………………………….. 65
References………………………………………………………………………………………………………………………………….. 66
Science and applications of Tailored Nanostructures 51

Introduction
Nanotechnology

Nanotechnology is the engineering at the atomic or molecular level. It is the collective term for a
wide range of technologies, processing techniques, and measurements that involve the
manipulating of matter at the smallest scale (from 1 to 100 nanometer). The prefix nano has been
driven from the Greek word νᾶνος or Latin word nannus, both meaning dwarf. It was adopted as an
-9
official SI prefix meaning 10 of an SI base unit. Nanotechnology is the study of controlling the
matter on an atomic and molecular level. Generally, nanotechnology deals with structures and
components with size between 1 to 100 nanometer in at least one dimensions, and involves
developing, creating or modifying materials or devices within that length scale. Nanotechnology is
concerned with the creation of particles and materials at nanoscale dimensions. These particles
and materials are referred to as nanoparticles and nanomaterial, respectively, and they exhibit
unusual and exotic properties that are not present in traditional bulk materials. Nanotechnology
can be defined as systems or processes that provide goods and/or services that are obtained from
matter at the nanometer level, i.e., from sizes in the range of one-billionth of a meter [1-2].
According to Drexler, “Nanotechnology is the principle of manipulation of the structure of matter at
the molecular level. It entails the ability to build molecular systems with atom-by-atom precision,
yielding a variety of nanomachines [1-2].” Nanoscience is the study of the fundamental principles of
molecules/atoms and structures with at least one dimension between 1 and 100 nanometers.
These structures are termed as nanostructures. Nanotechnology is the application of these
nanostructures into useful nanoscale devices [3]. The laws of science are not enough to deal with
engineered nanomaterials or nanostructures. Nanomaterials possess a large surface area, a high
aspect ratio, and a high surface-to-mass ratio. The unusual features of nanomaterials can
significantly influence the physical, chemical, biological, mechanical, and electrical properties [1-2].
Nanotechnology is a wide interdisciplinary field of research, innovation, development and industrial
activity that has been growing in a speedy way worldwide for last few years [4-6]. It entails physics,
chemistry, biology, material science, colloidal science engineering and electronic processing,
composites, application and concepts in which the defining characteristic is one of size or
dimension [4]. It involves the fabrication, processing, imaging, measuring and application of
materials that are in the size range of up to 100 nm. The term “nanotechnology” was first
introduced in 1974 by a Japanese Engineer, Norio Taniguchi. The term implied a new technology
which can control materials beyond micrometer scale [4]. In 1959, Richard Feynman gave the ideas
of creating nanoscale machines. In his famous lecture in 1959 “There’s Plenty of Room at the
Bottom”, Feynman presented the idea of creating new materials at nanoscale dimensions, which
began a variety of nanotechnology discussions, many of which still continue today. In the 1980s,
IBM Zurich scientists invented the tunneling microscope, a landmark achievement in
nanotechnology development, which allowed scientists and researchers to analyze materials at the
atomic or molecular level. Recently, the expenditure on nanotechnology research and development
has increased drastically. Research in nanotechnology continues to expand worldwide, and in the
next decade, nanotechnology could have a $1 trillion impact on the global economy.
Nanotechnology is currently in a very infantile stage. However, we can organize matter on the
atomic scale, and there are already numerous products available as a direct result of our rapidly
increasing ability to fabricate and characterize feature sizes less than 100 nm [2]. Nanotechnology
has the capability to change our standard of life. Some of the latest applications of nanotechnology
are energy storage and production, information technology, medical purposes, manufacturing,
Science and applications of Tailored Nanostructures 52

food and water purification, instrumentation, biomedical and environmental uses. Several
nanotechnology-based products already available on the market such as electronic components,
nanopaints, storage devices, stain-free fabrics, and medical components [2]. The basic attribute of
this technology is the size that makes it so feasible to be used in many different fields. The nano
size of the materials provides certain advantages like high surface area and low surface defects in
the material, thereby improving the material properties. One of the fundamental aspect of
nanotechnology is the creation of new materials having one of the dimension at nanoscale. These
materials, known as nanomaterials, are engineered at nanoscale have entirely different properties
than their “bulk” counterpart. Nanomaterials are being used in almost everyday objects such as
window coatings, sunscreens and other cosmetics, textiles, paint, cutting boards, socks, etc. Na-
nomaterials may also be found in human hip joints, Organic Light Emitting Diodes (OLEDs) for
displays and ear implants, pacemaker and water splitting. The commonly used engineered
nanomaterials in consumer products are nanosilver, carbon nanotubes, metal oxides at nanosized
(ferrous oxides, titanium dioxide and zinc oxide), silica and gold. Other engineered nanomaterials
used in consumer, medical and industrial products are nanocarbon, cerium oxide, nickel, aluminum
oxide and the nanoclays copper oxide, iron oxide and quantum dots.

Classification of Nanomaterials

The classification of nanomaterials is based on the number of dimensions, which are in nano range
(≤ 100 nm).

 0D nanomaterials have all the dimension within nanoscale, i.e. no dimension is larger than
100 nm. The most common example of 0D-dimensional nanomaterials is the nanoparticle.
These nanoparticles can be crystalline or amorphous, metallic, ceramic, or polymeric.
 1D nanomaterials have at least one dimension in nano range. This leads to needle like –
shaped materials having one dimension at nanoscale. 1D nanomaterials include
nanoplatelets, nanorods, nanoclays and nanosheets.
 2D nanomaterials have two dimensions in nano range. 2D nanomaterials include
nanofibers, nanotubes, nanorods and whiskers. Carbon nanotubes are good example of 2D
nanomaterials.
 3D nanomaterials have all three dimension in nano range. 3D nanomaterials include
nanogranules, nanoclays and equiaxed nanoparticles.

The nanomaterials can be crystalline or amorphous or polycrystalline. They can composed of a

single or multi-phase chemical elements. They could be in various forms and shapes, metallic,
ceramic or polymeric.

Nanoparticles

A nanoparticle is a fundamental component in the fabrication of a nanostructure having

dimensions between 1 to 100 nm. Nanoparticles are generally the final products of a series of
chemical, physical and biological processes [7]. Metallic nanoparticles have different chemical and
physical properties than their bulk counterparts (e.g., lower melting temperatures, specific
properties, high surface area, mechanical strength etc.). These properties are very attractive for
various industrial applications. A nanomaterial (dimension <100 nm) can take many forms such as
particle, wire, tubes, rod and sphere. Nanoparticle products generally include metal oxides,
Science and applications of Tailored Nanostructures 53

quantum dots, silicon dioxide, dendrimers, and some layered structures. In recent years, the
development of new nanoparticles has been growing rapidly. The categories of nanoparticles are as
below:

Nanomaterials

Materials built with structural components whose size is less than 1 µm in at least one dimension
are defined as nanomaterials.

Fullerenes

They are naturally occurring molecules of carbon, in the form of hollow sphere, ellipsoid, or tube.
Fullerenes are similar in structure to graphite, which is composed of a sheet of linked hexagonal
rings, but they contain pentagonal (or sometimes heptagonal) rings that prevent the sheet from
being planar. Fullerences are a pure form of carbon molecules in the form of a hollow sphere, tube,
ellipsoid, and various other shapes. Spherical Fullerences are termed as buckyballs. Cylindrical
Fullerences are called carbon nanotubes. Fullerences are similar to graphite in structure, which is
composed of a hexagonal ring that form a three dimensional structure. Fullerences were first
synthesized by laser ablation of graphite target in helium gas. However, laser vaporization is also
used in fullerence synthesis. The other techniques used in fullerence production are thermal
decomposition of hydrocarbon, combustion of hydrocarbon and thermal plasma pyrolysis of
hydrocarbon [8].

Carbon Nanotubes (CNTs)

Carbon nanotubes are long, thin cylinders of carbon, and were first discovered by lijima in 1991 in
Japan using an arc-discharge method. These are large macromolecules having unique size, shape
and possess remarkable physical and mechanical properties. CNTs are a special form of fullerenes,
consisting of concentric layers of graphite (multi-walled CNTs) separated by Van der Wall forces.
However, CNTs composed of a single layer (Single-walled CNTs, or SWCNTs) were also discovered.
CNTs are similar in structure to C60 (buckyballs), but they are elongated to form a tubular structure
[8]. A single-walled CNT has a diameter of 0.6–5 nm, whereas a multi-walled CNT has an inner
diameter of 1.5–15 nm and an outer diameter of 2.5–50 nm. CNTs can be produced in various
aspect ratios, and their lengths also vary, depending on the processing technique [8]. Nanotubes
have a wide range of electronic, thermal, and structural properties that change depending on the
different kinds of nanotube (defined by its diameter, length, and chirality, or twist). CNTs are a very
good example of true nanotechnology, since they are less than 100 nanometer in diameter and can
be thinner than 5 nanometer.

Nanowires

Nanowires are extremely thin wires having diameters on the order of few nanometer or less. There
are two processes that are generally used to manufacture nanowires: deposition and suspension.
Nanowire are composed of either conducting or semiconducting nanoparticles with diameters
between 1 to 100 nanometer and high aspect ratios. These wires are also termed as “quantum
wires” since quantum effect becomes more dominant at nanoscale. They possess least dimension
for efficient transport of electrons and therefore can be used as interconnects in nanoelectronics.
Science and applications of Tailored Nanostructures 54

Various types of nanowires are being fabricated including metallic, semiconductor and insulating
nanowires.

Quantum Dots

Quantum dots are tiny semiconductor nanostructure that confine the motion of electrons in
conduction band, holes in valence band or excitations of bound pairs of conduction band electrons
and valence band holes in all three spatial directions. Quantum dots have diameter in the range of
2-10 nanometer (10- 50 atoms) having novel optical, electronic, magnetic and catalyst properties.
Quantum dots have discrete quantized energy spectrum and the corresponding wave functions are
spatially localized within the quantum dots, but extend over many periods of the crystal lattice.
Researchers have found their applications in many areas such as solar cells, transistors and LEDs.

Metallic Nanoparticles

The term metal nanoparticle is used to describe nanosized metals with dimensions (length, width
or thickness) within the size range 1‐100 nanometers. A nanoparticle is a basic component of a
nanostructured material. Generally, the size of a nanoparticle is in the range of 1–100 nm. Metallic
nanoparticles exhibit different physical and chemical properties than their bulk counterparts and
some of these properties might prove attractive in industrial applications. Nanoparticles possess
some unique features, such as high surface area-to-volume ratio, large surface energy, quantum
confinement, short-range ordering, etc. The commercially available metallic nanoparticles are silver
(Ag), Au, Pt, ZnO, and metal oxides such as copper oxide (CuO), SiO 2, TiO2, aluminum
oxide(alumina) (Al2O3), and iron oxides (Fe3O4, and Fe2O3).

Carbon Black

Carbon black is virtually pure elemental carbon in the form of colloidal particles that are produced
by incomplete combustion or thermal decomposition of fossil fuels. It is black in color, finely
divided pellet or powder. It is generally used in tires, rubber, many plastic products and printing
ink. Generally, anthropogenic combustion of fossil fuel produces a wide variety of particles,
including some ultra-fine particles that are compatible with nanoparticle definitions, and therefore
referred to as carbon black, having particle size in the range of 10-300 nm [9].

Dendrimers

Dendrimers are a family of nanoscale three dimensional macromolecules with a star-like

appearance having highly branched architecture. Dendrimers have three main components: an
inner core, an interior structure (branches), and surface group at the exterior surface. By varying
these three components, dendrimers of different shapes and sizes can be produced. Their structure
greatly impacts their physical and chemical properties. Dendrimers are an ideal candidate for
applications in biology, engineering and material science.

Nanoclays

Nanoclays are nanoparticles of layered mineral silicates, have become a class of organic-inorganic
hybrid materials. Depending on chemical composition and morphology of particles, nanoclays are
Science and applications of Tailored Nanostructures 55

organized into several classes such as montmorillonite, bentonite, kaolinite, hectorite, and
halloysite. Nanoclays are a class of hybrid organic-inorganic nanomaterials with potential uses in
polymer nanocomposites, as rheological modifiers, gas absorbents and drug delivery carriers.
Layered silicate is a generic term referring to synthesized layered silicates (montmorillonite,
laponite, and hectorite) as well as natural clays. Montmorillonite is the most common nanoclay
used in many materials applications. The plate-like montmorillonite consists of a one-nanometer-
thick aluminum silicate layer surface modified with cations having dimensions in length and width
that are measured in hundreds of nanometers [10].

Nanocrystals

Nanocrystals are crystalline particles with at least one dimension in nanometers. Nanocrystals have
wide range of applications. The properties of nanocrystals can be changed depending on the
techniques in their synthesis. They have been used in the manufacture of filters that refine crude
oil into diesel fuel. Nanocrystals can also be layered and applied to flexible substrates to produce
solar panels. They can be incorporated into electronic devices such as light emitting diodes (LEDs)
for energy-efficient lighting, and they are being used in filtration to refine crude oil into diesel fuel.
They are also finding application in many other areas such as solar cells, catalysts, and sensors.

Nanocomposites
Nanocomposites are composite materials having one of the phases with dimension in the
nanometer range. Nanocomposites are possible alternatives to microcomposites and monolithic
due to their outstanding properties. However, the preparation techniques of nanocomposites
present challenges due to the control of elemental composition and stoichiometry in the
nanophase. Additionally, the discovery of carbon nanotubes in 1991 and their use in the fabricating
nanocomposites, added a new interesting feature to this area.
Nanocomposites are materials to which nanosized filler components are added in order to improve
the properties of the resulting materials [11]. Nanocomposites are composed of two or more
distinct constituents or phases having different physical and chemical properties and are separated
by a distinct interface. Their unique properties are not depicted by any of the constituents. The
constituent that is generally present in greater quantity is called the matrix. The constituent that is
embedded into the matrix material in order to improve the mechanical properties of
nanocomposites is called reinforcement (or nanomaterials). Reinforcement is generally in the form
of nanosized filler materials. Generally, nanocomposites show anisotropy (properties are
directionally dependent) because of the distinct properties of constituents and inhomogeneous
distribution of the reinforcement.
The term nanocomposite is extensively used to describe an extremely broad range of materials,
where one of the dimension is in nano range. Nanocomposites are generally more advantageous
than conventional composites in many aspects. The advantages of nanocomposites are as below
[12]:
1. The improvement in properties of the matrix material in nanocomposites can be achieved
by the addition of small amount of nanofiller materials compared to conventional
composites that require high concentration of micro particle in order to improve
properties.
Science and applications of Tailored Nanostructures 56

2. Due to the addition of small percentage of nanofiller materials, nanocomposites are much
lighter in weight compared to conventional composites.
3. Nanomaterials having size dependent properties enhances thermal, chemical, mechanical,
optical, magnetic and electrical properties to a much greater extent than conventional
composites.

Nanocomposites are extremely good alternative to conventional composite materials due to their
outstanding properties and are finding a wide range of applications in various fields.
Nanocomposite systems with carbon nanotubes have been a topic of recent research and
development since their discovery in 1991 and there has been a steady and continuous increase in
number of publications on this topic, including reviews and patents from time to time.
Nanocomposites are also found in nature, for example in the structure of the abalone shell and
bone. Nanocomposites differ from conventional composites due to high surface area to volume
ratio of the reinforcing nanoparticles and their exceptionally high aspect ratio. The reinforcing
material can be made up of particles (e.g. minerals, metallic nanoparticles, Carbon nanotubes),
sheets (e.g. exfoliated clay stacks, graphene) or fibers (e.g. Electrospun nanofibers). The area of the
interface between the matrix and nano-reinforcement is typically an order of magnitude higher
than the conventional composites. Clays are a group of nanofiller materials which have been
extensively used for the preparation of polymer matrix nanocomposites. Polymer/clay
nanocomposites have been receiving tremendous attention recently in academia and in industries
due to their improved properties compared to conventional composites. Clay minerals are
belonging to a main group of silicates with layered structure known as layered silicates. The layered
silicates are natural or synthetic mineral materials composed of regular stacks of aluminosilicate
layers having high aspect ratio and high surface area. Clay is a soil fraction having particle size of
around 2 micrometer and thickness in nanorange generally around 1nm. There are many types of
clays with differences in their formula, properties and structures. Polymer/clay nanocomposites
can be fabricated in a number of ways including in situ polymerization, melt blending, solution
mixing and latex methods.

Types of Nanocomposites

Nanocomposites are classified according to the types of reinforcement materials and matrix
materials used in their construction. According to the type of matrix material, nanocomposites are
generally classified into following three classes [13]:

1. Polymer Matrix Nanocomposites

2. Ceramic Matrix Nanocomposites
3. Metal Matrix Nanocomposites

Polymer Matrix Nanocomposites:

Polymer nanocomposites are materials that have polymer as a matrix material and nanoadditives
are used as reinforcement material. The additives can be one-dimensional (nanotubes and fibers),
two-dimensional (layered materials like clay) or three-dimensional (spherical particles). Polymer
nanocomposites have been gaining considerably attention both in academia and in industries, due
to their outstanding mechanical properties such as high elastic stiffness and strength with a small
Science and applications of Tailored Nanostructures 57

concentration of nanoadditives. The other excellent properties of polymer nanocomposites are

barrier resistance, flame retardancy, wear resistance, magnetic, electrical and optical properties.
A typical polymer composite is a combination of polymer (matrix) and a filler (reinforcement).
Polyamide is a thermoplastic polymer, and carbon and glass fiber are generally used as
reinforcement materials. In aerospace industry, carbon fibers are extensively used as
reinforcement materials. The choice of reinforcement material depends on the applications. The
polymer matrix and fillers are generally bonded by weak intermolecular forces, however, in some
cases chemical bonding is employed, as well. If the filler material in composite is dispersed on an
atomic or molecular level (nanometer level) and chemical bonding with the matrix material is
created, then remarkably improvements in the mechanical properties of the composite material
and some new and unexpected or exotic properties can be achieved. To achieve high strength, clay
minerals (montmorillonite, saponite, hectorite etc) are being used as filler materials. A layer of
silicate clay mineral is around 1nm thickness and composed of platelets of approximately 100 nm in
width, therefore, it displays a high aspect ratio [14]. In comparison, a glass fiber is approximately 4
9
x 10 times the size of a typical silicate layer having 13 micrometer diameter and 0.3 millimeter
length.
Polymers have outstanding properties such as lightweight, high durability, easy processing,
corrosion resistance, ductility and low cost. Compared to ceramics and metals, polymers have
relatively poor mechanical, thermal and electrical properties. Polymers also have poor gas barrier
properties, heat resistance and fire performance properties. Polymers are less dense than ceramics
and metals, they have a low coordination number and lightweight atoms of carbon and hydrogen
as a backbone, which makes them find applications as structural components and construction
materials in lightweight applications such as automobile, defense, aerospace and electronics [15].
Sometimes, unprecedented combinations of properties have been observed in some polymer
matrix nanocomposites such as addition of a very small amount of mica-type silicates (0.03- 0.04 %)
in epoxy increases modulus in rubbery region by approximately 450%. Nanocomposites
development led to the significant progress in the chemical processing of nanoparticles. Recent
interest in polymer nanocomposite has begun initially with fascinating observations involving
exfoliated clay and carbon nanotubes, exfoliated graphite and nanocrystalline metals. In polymer
nanocomposites, the synergistic advantage of “nano-effect” relative to large scale modification is
an important factor affecting the properties of nanocomposites [16]. Experimental investigations
have shown that nanoscale additives bring new phenomena, which changes of the material
properties. The inclusion of nanoparticles with high surface area, high surface energy and often
with anisotropic geometry in the polymer matrix decreases the interparticle distance and increases
polymer matrix interaction strength. Therefore, polymer nanocomposites with completely new set
of properties suitable for new applications and also expand the performance space of traditionally
filled polymers [17]. The micromechanics theories depend on the idea that the properties of
composites are functions of properties of constituents such as volume fraction of components,
shape and arrangement of inclusions and matrix-fiber interface. These theories predict that the
properties of composites are independent of the size of inclusions. This could be true with micro
size reinforcements, but may not be true with nano size reinforcement. Fabricating good polymer
matrix nanocomposites is a challenging issue. Researchers have tried many techniques to fabricate
polymer matrix nanocomposites such as melt mixing, in situ polymerization, mixing filler materials
during electrospinning, and many other approaches. Vollenberg and Heikens produced
nanocomposites samples by thoroughly mixing filler particles with polymer matrix. They used
polystyrene (PS), styrene–acrylonitrilecopolymer (SAN), polycarbonate (PC) and polypropylene (PP)
with alumina beads having 35nm and 400nm dimension as filler materials [18]. The average volume
Science and applications of Tailored Nanostructures 58

fraction of filler particles was maintained at 25%. Sample preparation consisted of dissolving
polymers in a polar solvent and mixing in the beads for several hours on a magnetic stir. The
mixture was then poured over a large surface container to allow the solvent to evaporate and then
it was subsequently dried under a vacuum at 100◦C. Pure polymer was then added to samples to
achieve the desired particle volume fractions. In literature, many processes have been described
for the preparation of polymer nanocomposites including layered materials and those that contain
carbon nanotubes. The common ones are 1) In situ polymerization; 2) Intercalation of polymer
from solution; 3) Direct mixing of polymer and fillers; 4) Melt intercalation; 5) Template synthesis;
and 6) Sol-gel process. The melt blending is a relatively new process of nanocomposite fabrications.
This process involves the melting of polymer to form a viscous liquid. The nanoparticles are
dispersed into polymer matrix by means of high shear rate along with diffusion at high
temperature. The nanocomposites are then fabricated by either compression molding or injection
molding.

Properties of Polymer Matrix Nanocomposites

The properties of nanocomposites do not depend on the properties of individual components but
also depends on the following parameters [18-19]:

 Process used in nanocomposite fabrication

 Types of filler materials and their orientations
 Degree of mixing of two phases
 Type of adhesion at the matrix interface
 Volume fraction of nanoparticles
 Nanoparticle characteristics
 Nature of the interphase developed at the matrix interface
 Size and shape of nanofiller materials and
 Morphology of the system

In order to achieve enhanced properties of nanocomposites, the nanosized particles should be

dispersed and distributed in the matrix material properly, otherwise there will be agglomeration of
particles and the properties of nanocomposites will deteriorate. These aggregates will act as
defects and limits the property enhancement of nanocomposite, therefore to achieve maximum
property enhancement, the nanoparticles should be homogeneously dispersed in the matrix. Figure
4.1 shows different types of nanoparticles in the matrix material, (a) good distribution but poor
dispersion (b) poor distribution and poor dispersion, (c) poor distribution but good dispersion, and
(d) good distribution and good dispersion [20].
The other important factor that affect the nanocomposite property enhancement is the nature of
interface between matrix and filler material. The most common feature of polymer matrix
nanocomposites is the existence of phase border between matrix and filler material and the
development of interface layer between the two. The properties, composition and microstructure
at the interface vary across the interface region and are different from both matrix and filler. If the
interface region has good bond between matrix and filler material the overall properties of the
nanocomposite will be much profound. Most of the interphase properties depend on the bound
surface and therefore the nanocomposite properties can be tailored by optimizing the interfacial
bond between the nanofiller and polymer matrix. The interaction between the interconnecting
phases depends on the ratio of surface energy of filler and matrix. Nanosized particles have high
Science and applications of Tailored Nanostructures 59

surface area and the total surface area of a nanoparticle determines the extent of interface
phenomenon contributing to the properties of nanocomposites [21-22].

FIGURE 4.1
Distribution and dispersion of nanoparticles in the matrix

FIGURE 4.2
Interphase region between filler and polymer matrix
Science and applications of Tailored Nanostructures 60

As can be seen in Figure 4.2, the structure of the region between filler and polymer matrix consists
of flexible polymer chains, typically in sequences of adsorbed segments and unadsorbed segments.
Adsorbed segments have point contact with nanoparticle surface in the form of anchors/ trains and
unabsorbed segments have no surface contact and exist as loops and tails entangles with other
polymer chains in their vicinity. The thickness of the interphase region depends on many factors
such as flexibility, energy of adsorption, and the extent of polymer chain entanglement. The
interface structure determines the stress or load transfer from matrix to filler [22]. The host
polymer needs to have very good interaction with the nanofiller material surface either chemically
or physically in order to have good polymer properties. Good adhesion at the interface improves
interlaminar shear strength, corrosion resistance, fatigue, dielectric properties, thermal stability,
and flame retardancy at low filler-volume fraction [21, 23, 24, 25].

FIGURE 4.3
Different types of polymer matrix adhesion with the nanoparticle surface

Figure 4.3 shows two different types of polymer matrix adhesion with the surface of nanofiller
material, (a) strong adhesion of polymer chains with nanoparticle surface, and (b) weak adhesion of
polymer matrix with the surface of nanofiller material.
Strong interaction of polymer chain with nanoparticles surface makes flat dense layer residing on
the nanoparticle surface. However, poor interaction results in a lower density region with polymer
loops and tails extending into the matrix. It has been reported in the literature that drastic changes
in the particle properties can be observed when the particle size is in the nanorange. Moreover, as
the dimension reaches the nanorange, the interaction at the phase boundary improved to a great
extent resulting in the enhancement of materials property. The extent to which the host polymer
properties alter also depends on the aspect ratio, shape and orientation of nanoparticles. High
aspect ratio nanoparticles have high surface area compared to low aspect ratio nanoparticles and
high aspect ratio plays an important role in enhancing the properties of nanocomposites.
Asymmetric nanoparticles such as layered silicates or carbon nanotubes enhance polymer
properties (viscosity, shear modulus, tensile strength) to a great extent than symmetrical
nanoparticles with spherical shape etc. Compared with elongated rod like nanoparticles and highly
symmetric nanoparticles, sheet like nanoparticles enhances polymer properties such as gas
permeability and mechanical properties to a great extent [26, 27].
Science and applications of Tailored Nanostructures 61

The properties of nanocomposites depend on their microstructure. The morphological

characteristic nature of the composite system describes the structure property relationship of
polymer nanoplatelets type of nanocomposites. A good dispersion of nanomaterial is hard to
achieve, especially in non-polar polymer, however, uniform dispersion of nanoplatelets ensure
good quality of composites. In the case of nanocomposites containing layered reinforcements,
depending on processing techniques, nature of the components (layered silicate, organic cation
and polymer matrix), dispersion techniques,and the interaction between polymer matrix and
layered nanomaterial, the microstructure of nanocomposites can be classified as exfoliated,
intercalated and phase separated (aggregated) [28]. When the polymer cannot be intercalated
between the silicate layers, a phase separated (aggregated) composite is formed, whose properties
are almost the same as that of conventional microcomposites (Figure 4.4(a)) [28]. In intercalated
nanocomposites, the polymer chains intercalate into the silicate layers in a crystallographically
regular order, regardless of the clay to polymer ratio (Figure 4.4(b)) [28]. A well-ordered multilayer
microstructure is formed with alternating polymeric and clay layers. In an exfoliated
nanocomposites, the clay layers are completely and uniformly dispersed in the polymer matrix. The
clay layers are separated in polymer matrix by an average distance that generally depends on clay
loading. Generally, the clay layers content in an exfoliated nanocomposite is lower than that of an
intercalated nanocomposites. Figure 4.4 shows different types of dispersion of clay layers in
polymer matrix.

FIGURE 4.4
Different types of dispersion of clay layers in polymer matrix

Types of Polymer Matrix Nanocomposites

The major component in polymer matrix nanocomposite is polymer itself. There are many varieties
Science and applications of Tailored Nanostructures 62

of polymers used in the preparation of polymer matrix nanocomposites. These polymers are listed
below [29]:

1. Thermoplastics
2. Thermosets
3. Elastomers
4. Natural and Biodegradable polymers

The choice of polymer matrix material for preparing polymer matrix nanocomposites for a specific
application is generally guided by their mechanical, electrical, magnetic, optical, biocompatibility,
chemical stability and functionalization. Thermoset based nanocomposites are generally most
common nanocomposites and are used in many applications, but recently thermoplastic-based
nanocomposites have attracted much of the research interest both in industry and academia. The
properties of polymers mainly depend on the polymer structure, which in turn depends on the
chemical composition, surface morphology and processing parameters. The difference between
thermoplastic and thermosets polymer is that they respond entirely in a different way to heat and
this is mainly due to the difference in their molecular structure [30-31].

 Thermoplastics:
Thermoplastics soften when heated and become more fluid as heating continued. The curing
process of thermoplastics is completely reversible as no cross linking takes place. Thermoplastics
soften on heating and solidify and harden on cooling. This property allows thermoplastics to be
remolded and recycled without affecting the properties.

 Thermosets:
Thermosets contain polymer that cross-link together during curing process and form an irreversible
chemical bond. These polymers do not soft or melt on heating but breakdown chemically at high
temperature. Thermosets have improved mechanical properties, high chemical and heat resistance
properties. Thermoset are generally rigid and brittle compared to thermoplastics.

Ceramic Matrix Nanocomposites

Ceramic matrix nanocomposites with at least one phase having nano dimension are a new
generation of engineering materials, having a wide range of applications in industrial sector. The
microstructure of nanoceramic composites results in outstanding electrical and mechanical
properties. Many methods have been reported in literature for the preparation of ceramic matrix
nanocomposites. Generally, the common methods used in microcomposites fabrications are
conventional powder method, polymer precursor route, spray pyrolysis, and chemical methods
such as sol-gel process, colloidal and precipitation approaches and template synthesis [28]. Some
common ceramic matrix nanocomposites include AL2O3/SiO2, SiO2/Ni, Al2O3/TiO2 and Al2O3/SiC
[29]. After the discovery of carbon nanotubes (CNT), they have been widely used in nanocomposite
fabrications. Some common examples of CNT based ceramic matrix nanocomposite include
Al2O3/CNT, MgAl2O4/ CNT and MgO/CNT.

Metal Matrix Nanocomposites

Metal matrix nanocomposites are materials reinforced by nanoparticles consisting of ductile metal
Science and applications of Tailored Nanostructures 63

or alloy matrix in which nanoparticles reinforcement is implanted. These composites consist of

metal/alloy matrix filled with nanoparticles, display physical, chemical and mechanical properties
entirely different from those of matrix material. The nanoparticles are generally used to improve
wear resistance, mechanical properties and damping characteristics. Metal matrix nanocomposites
are being investigated by researchers recently, owing to their superior properties due to
nanoparticle embedment, are finding wide range of applications in structural components [28]. At
nano-level the interaction of particles with dislocations becomes important and results in
remarkable improvement in mechanical properties. The nanoparticles act as a barrier in dislocation
movement and thereby improve the mechanical properties. The common techniques used for the
processing of metal matrix nanocomposites are spray pyrolysis, liquid metal infiltration, vapor
techniques, rapid solidification, electrode position and chemical methods, which include colloidal
and sol-gel methods [28]. Some common metal matrix nanocomposites include Fe-Cr/Al2O3,
Ni/Al2O3, Fe/MgO, Al/CNT and Mg/CNT.

Polymer Matrix Nanocomposite Processing Techniques

Polymer matrix nanocomposites can be fabricated either by chemical or mechanical process.
Uniform and homogeneous dispersion of nanoparticles in the polymer matrix is one of the major
problem encountered in polymer nanocomposite fabrication. The Nanofillers have a tendency to
aggregate and form micron size filler cluster, which limit the dispersion of nanoparticles in the
polymer matrix thereby deteriorating the properties of nanocomposites. Researchers have made
many attempts to disperse nanofillers uniformly and homogeneously in the polymer matrix by
chemical reactions, complicated polymerization reactions or surface modification of filler materials
[32]. Mostly polymer nanocomposites are fabricated by the following four methods.

1. Intercalation method
2. In situ Polymerization
3. Sol Gel method
4. Direct Mixing of polymer and Nanofillers

Intercalation Method

Intercalation method generally involves the dispersion of nanoplatelets types of nanomaterials into
the polymer matrix. It is well-known that incorporation of clays (nanomaterial) into polymer
matrices improves the bulk properties such as stiffness, shrinkage and flammability. Intercalation is
a top down approach and requires surface modification of nanoplatelets for homogeneous
dispersion of plate-like nanofillers in the polymer matrix. Intercalated morphology occurs when
polymer chains diffuse into the gallery spacing of layered structure. The nanoplatelets can be
homogeneously dispersed by the following two techniques [33-35].

 Chemical Technique: This technique involves the in-situ polymerization method in which
nanoparticles are dispersed in monomer and then polymerization reaction takes place. In
this method, nanoplatelets are dispersed into polymer followed by additional
polymerization process. The nanoplatelets are swollen in monomer solution and the
polymer formation occurs between the intercalated sheets by polymerization method.
Science and applications of Tailored Nanostructures 64

 Mechanical Technique: In this method, direct intercalation of polymer with nanoplatelets

takes place through solution mixing. The polymer is dissolved in a co-solvent and
nanoplatelets sheets are swollen in the solvent and these two solutions are mixed
together, the polymer chains in the solution intercalate into the nanoplatelets layers and
displace the solvent.

Melt Intercalation Method

Melt intercalation is a promising method extensively used in the industry. This method involves
mixing the nanofillers (clays) into the polymer matrix at molten temperature. In this method,
mixture of polymer and nanofibers are annealed either statically or under shear. This method is
compatible with current industrial processes, such as extrusion and injection molding and it allows
the use of polymers, which are not suitable for in situ polymerization or solution intercalation. Melt
blending is a similar process. It involves the melting of polymer powder or pellets to form a viscus
solution and nanofillers are added into polymer solution by high shear rate combined with high
temperature diffusion. The final shape of components can be fabricated by compression molding,
injection molding or fiber production technique.

In Situ Polymerization Method

In situ polymerization involves the swelling of the nanofillers in monomer solution since the low-
molecular weight monomer solution can easily seeps in between layers causing swelling [35]. The
resulting mixture is polymerized either using radiation, heat, initiator diffusion or by organic
initiator. The monomer is then polymerized between interlayers thereby forming either exfoliated
or intercalated nanocomposites. In Situ template synthesis is a similar method. In this method, the
clay layers are synthesized in the presence of polymer chains. Both polymer matrix and clay layers
are dissolved in an aqueous solution and gel is generally refluxed at high temperature. The polymer
chains are trapped inside the clay layers and nucleation and growth of clay layers take place on the
polymer chains at high temperature. The only drawback of this process is that high temperature
synthesis causes decomposition of polymer.

Sol- gel Method

Sol- gel method is a bottom up approach and it is based on an opposite principle than all the
previous methods. The term sol-gel is associated to two relations steps, sol and gel. Sol is a colloidal
suspension of solid nanoparticles in monomer solution and gel is the 3D interconnecting network
formed between phases [35]. In this method, solid nanoparticles are dispersed in the monomer
solution, forming a colloidal suspension of solid nanopartices (sol), they form interconnecting
network between phases (gel) by polymerization reactions followed by the hydrolysis procedure.
The polymer nanoparticle 3D network extends throughout the liquid [35]. The polymer serves as a
nucleating agent and promotes the growth of layered crystals. As the crystals grow, the polymer is
seeped between layers and thus nanocomposite is formed.

Direct Mixing of Polymer and Nanofillers

Direct mixing of a polymer matrix and nanofillers is a top down approach of nanocomposite
fabrication and it is based on the breakdown the aggregated nanofillers during mixing process [32,
Science and applications of Tailored Nanostructures 65

35]. This method is suitable for fabricating polymer matrix nanocomposites and it involves two
general ways of mixing the polymer and nanofillers. One way is mixing a polymer, in the absence of
any solvents, with nanofillers above the glass transition temperature of the polymer, generally
called melt compounding method [32, 35]. The other way involves mixing of polymer and
nanofillers in solution employing solvents, generally called solvent method/solution mixing [35].

Melt Compounding

This method involves nanofibers addition to the polymer above the glass transition temperature. In
this kind of method, the shear stress (hydrodynamics force) is induced in the polymer melt by
viscus drag, and this shear stress is used to breakdown the nanofiller aggregates and thereby
promotes homogeneous and uniform nanofiller dispersion in the polymer matrix.

Solvent Method

In this method, nanoparticles are dispersed in the solvent and polymer is dissolved in a co-solvent.
The resulting nanocomposites are recovered from solvent through solvent evaporation or by the
solvent coagulation method. In this method, the shear stresses induced in the polymer matrix are
lowered compared to that in melt compounding. The nanofillers are pre-dispersed in the solvent by
sonication in order to breakdown the nanofiller aggregates [35].
The polymer nanocomposites fabricated by one of the above methods are finally processed by
conventional manufacturing methods like injection molding, calendaring, casting, compression
molding, blow molding, rotational molding, extrusion molding, thermoforming, etc [35].

Conclusions
Nanotechnology is the study and control of matter at dimensions of 1 to 100 nanometer. When
materials are reduced to nanosized they display some unusual and exotic properties due to “nano-
effect”. The field of nanotechnology has become one of the most famous area of research and
innovation, recently. Polymer science is an integral part of nanotechnology. Polymer composites
are made by the combination of a polymer and synthetic or natural inorganic filler materials. Filler
materials are employed in order to improve the properties of polymer composites. In recent years,
polymer nanocomposites have attracted great interest, both in industry and in academia, since
they exhibit remarkable improvement in properties, when compared to conventional
microcomposites. Polymer nanocomposites contain nanofiller materials, which cause “nano-effect”
and drastically improve nanocomposite properties. In this chapter, the classification of
nanomaterials has been discussed and all types of nanomaterials have been elaborated. New
technologies require materials that have novel properties and nanomaterials possess novel
properties, which help in improving the properties and performance of components compared to
conventionally processes components. In this context, nanomaterials are the most suitable
materials to meet the emerging demands arising from scientific community. In this chapter, the
classification of nanocomposites based on matrix materials has been discussed along with their
processing techniques. However, some of these techniques pose challenges as far as the dispersion
of nanophase in polymer matrix is concerned. Thus giving opportunities for researchers to
overcome this problem being encountered with nanosized materials. Nanocomposites offer
improved performance compared to conventional composites and monolithic counterpart. Polymer
Science and applications of Tailored Nanostructures 66

nanocomposite have already being used in many industrial sectors and their applications have been
rising drastically.

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