6.

MODERN MATERIALS
Fundamental principles, Bonding in solids – primary and secondary, Polymers – classification,
Types of polymerization, structure property relationships and molecular weight, Liquid crystals -
Classification with examples and applications, Ceramics-classification and fabrication, Chemical
composition of cement, Manufacture, Classification, glass, superconducting materials,
Composite materials-classification, fabrication and advantages, Biomaterials-classification,
characteristics and application, Nano materials-Introduction, preparation, Nanoscale particles
Learning objectives
Upon completion of the chapter, students will be able to
 Understand the fundamental principles of material science
 Explain how functional needs are related to structure and bonding
 Apply experimental design techniques to material production
 Define liquid crystal phases and give specific examples and properties of various types
 Understand the essential concepts used in nanomaterial synthesis
 Discuss the applications of nanomaterials in different fields
6.0 Fundamental principles
Materials are substances or an ingredient used in the primary production or manufacturing of a
good. Raw materials are often natural resources such as oil, wood and iron. Transportation,
housing, clothing, communication, recreation, and food production-virtually every segment of
our lives is influenced by materials.
Different substances have different properties because,
 They contain different elements and different combinations of elements.
 They contain different types of chemical bonds
 They have different sizes of the units
 The solid state structure may contain different types of assemblies e.g., molecular
packing arrangement may be different or the geometry of linkage in an extended three
dimensional structure may vary.
The elements commonly used in a large number of useful materials include non-metals such as
C, Si, B, N, O, and P, and metals such as Al, Mg, Ti, Sn, Fe, Cu, Cr and Ni. Other elements such
as Cd, Ga, Ge, Pt, Ag and Au are also used in smaller quantities and for specialized applications.
The replacement of carbon by silicon in polymers brings about large changes in the properties of

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the product material. These differences result in the different sizes of the atoms, their electronic
configurations, redox properties, and the types and lengths of the bonds they form with
neighboring atoms. For example, silicon has the same outer shell electronic configuration as
carbon, but it is larger and forms double bonds to O, N or other Si atoms. Silicon also has the
ability to expand its octet and form bonds to 4, 5 or 6 other atoms, whereas carbon is restricted to
bonds to 2, 3 or 4 other atoms. Several of these differences are responsible for the fact that pure
silicon is a semiconductor whereas diamond is not.
Material science involves the study of the relationship between structure and properties of
materials. The basis of materials science involves relating the desired properties and relative
performance of a material in a certain application, to the structure of the atoms and phases. The
major determinants of the structure of a material and thus its properties are its constituent
chemical elements and the way in which it has been processed into its final form. These
characteristics, taken together and related through the laws of thermodynamics, govern a
material’s microstructure, and thus its macroscopic properties.
Structure: The structure of a material (atomic, crystal, micro and macro structures), usually
relates to the arrangement of its internal components. It may be atomic or subatomic level.
 At the atomic level: arrangement of atoms in different ways, for instance two allotropes
of carbon, graphite and diamond show, different properties.
 At the microscopic level: arrangement of small grains of material provides different
optical properties to transparent vs. frosted glass.
Properties: Properties of materials are grouped into six categories based on the way in which
material responds to the environment. For instance, the mechanical, electrical and magnetic
properties are the responses to mechanical, electrical and magnetic forces, respectively. Other
important properties are thermal (transmission of heat, heat capacity), optical (absorption,
transmission and scattering of light), and the chemical stability in contact with the environment
(like corrosion resistance). In addition to structure and properties two other components are
involved in the material sciences and engineering- namely “Processing” and “Performance.”
Processing: Like structure and properties of the materials, the processing of materials is equally
important for the better performance of the materials. It is the application of heat (annealing and
quenching) and mechanical forces to affect their microstructure and, therefore, their properties.

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Classification of materials
Materials science encompasses various classes of materials, each of which may constitute a
separate field. In the broader sense we can classify the materials into;
1. Solid materials
2. Advanced materials
3. Nanomaterials
1) Solid materials: These materials have been conveniently grouped into three basic
classifications; metals, ceramics, and polymers based on chemical makeup and atomic structure,
and most materials fall into one distinct grouping or another, although there are some
intermediates. In addition, there are the composites, combinations of two or more of the above
three basic materials classes.
Metals and alloys: Metals are elements which can lose their outer electrons. The valence
electrons are detached from atoms, and spread in an 'electron sea' that "glues" the metal ions
together. Atoms in metals and their alloys are arranged in a very orderly manner and in
comparison to the ceramics and polymers are relatively dense. Metals are usually strong,
malleable, ductile, good electrical and thermal conductors and are opaque to light but-exhibit
typical metallic luster. Example: aluminum, steel, brass, gold.
Ceramics: A ceramic is an inorganic, non-metallic solid prepared by the action of heat and
subsequent cooling. They are usually combinations of metals or semiconductors with oxygen,
nitrogen or carbon forming corresponding oxides, nitrides, and carbides. Examples: glass,
porcelain, fire brick. These materials may have a crystalline or amorphous structure.
Polymers: Polymers are substances of high molecular mass formed by the joining together of
monomers with low molecular mass. They are bound by covalent forces and also by weak van
der Waals forces, and usually synthetic polymers have a backbone of C-C bonds. They
decompose at moderate temperatures (100-400 ○C), and are lightweight. Other properties vary
greatly. Examples: plastics (nylon, teflon, polyester), wool, leather and rubber. They are used in
bottles, packaging, insulators, kitchenware and other appliances.
Composites; A composite is composed of two (or more) constituent materials with significantly
different properties. The design goal of a composite is to achieve a combination of properties that
are not displayed by any individual materials, and also to incorporate the best characteristics of
each of the component materials. Further, some naturally occurring materials are combined to

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make composites which are stronger, lighter or less expensive when compared to conventional
materials. Examples; cements, metal composites, ceramic composites, fiber reinforced polymer.
2) Advanced materials
Advanced materials have superior properties such as toughness, hardness, durability and
elasticity when compared to conventional materials. They can have novel properties like the
ability of memorize shape or sense changes in the environment and respond. Materials that are
used in high-technology applications are sometimes termed advanced materials. Advanced
materials include semiconductors, biomaterials, and shape memory alloys.
Semiconductors: A semiconductor is a material which has electrical conductivity between that
of a conductor such as copper and that of an insulator such as glass. Further, the electrical
characteristics of these materials are extremely sensitive to the minute proportions of
contaminants. They are the building blocks of modern electronics including transistors, solar
cells, light emitting diodes and integrated circuits. Examples: Si, Ge, Ga, As.
Biomaterials; They can be any type of material that has a biomedical or biological application.
They might have a therapeutic use or a diagnostic use and the material must have properties that
meet the demands of that applications. For example, a polymer employed to form a disposable
contact lens must be soft and have an easily wetted surface, whereas the polymer used to fill a
dental cavity must be hard and wear resistant. The most important characteristics of that
influence the choice of a biomaterial are biocompatibility, physical requirements and chemical
requirements. It should be readily integrated into the body without inflammatory reactions.
Tubing used to replace a defective blood vessel must be flexible and materials used in joint
replacements must be wear-resistant. Biomaterials must be medical grade, approved for use in
any particular medical application. Certain contaminants like unreacted monomers, traces of
catalyst used to effect the polymerization, fillers or plasticizers may pose threat if the same
plastic material were implanted in the body over a long period
3) Nanomaterials: Nanomaterials are defined as materials with at least one external dimension
in the size range from 1-100 nanometers. Often, the behavior of nanomaterial may depend more
on surface area than particle composition itself. Relative-surface area is one of the principal
factors that enhance its reactivity, strength and electrical properties. These materials are
discussed in a separate section.

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6.1 An overview of bonding in solids
A chemical bond is defined as a force that acts between two or more atoms to hold them together
in a stable arrangement. Solids can be classified according to the nature of the bonding between
their atomic or molecular components. The classification based on the type of bonding
distinguishes four kinds.
i. Ionic solids
ii. Covalent solids
iii. Molecular solids
iv. Metallic solids
Typical members of these classes have distinctive electron distributions, thermodynamic,
electronic, and mechanical properties. In particular, the binding energies of these interactions
vary widely. Bonding in solids can be of mixed or intermediate kinds and not all solids have the
typical properties of a particular class. So bonding in solids can be broadly classified into two
types; primary bonds and secondary bonds. Further, the primary bonds can be classified into the
three types as follows; ionic, covalent and metallic bonds.
6.1.1 Ionic bond
The electrostatic attraction between the cation and the anion produced by electron transfer
constitutes an ionic bond. An ionic bond is typically formed between a metal and a non-metal.
Ionic or electrovalent bonds are formed by transfer of valence electron from one atom to another.
This type of bond units, two atoms one of which has excess electrons than the stable number
(2/8), and the other is short of electrons. Sodium chloride is a typical compound formed in this
way. The sodium atom (2,8,1) transfers its excess electron to a chloride atom (2, 8, 7), and thus
both attain a stable inert gas type electron configuration. Sodium acquires the electron
configuration of neon (2,8) and becomes positively charged. Chlorine acquires the electron
configuration of argon (2, 8, 8), and become negatively charged. These oppositely charged ions
are held together by electrostatic force of attraction. Overall the crystal is electrically neutral and
each unit cell must reflect the stoichiometry of the compound.

A+ + B- → A+ B- + Lattice energy

electrovalent bond e.g. 2 Na(s) + Cl2 (g) → 2NaCl(s)

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The characteristic properties of ionic compounds are the following;
 They are solids at room temperature
 Crystals of ionic solids are hard and brittle.
 They possess high melting points and high boiling points.
 They do not conduct electricity in the solid state. They are good conductors of electricity
when they are in the molten state or in aqueous solution.
 They are soluble in polar solvents but insoluble in nonpolar solvents.
 They do not exhibit isomerism.
More common structures are the Rock salt structure which has a fcc unit cell and the Cesium
chloride structure, which has a bcc unit cell. Less common structures include the Zinc blende,
Wurtzite, Fluorite and Rutile structures. An ionic solid consists of positive and negative ions
arranged in such a way that each ion is surrounded by nearest neighbors of opposite charge. Each
ion is bonded by electrostatic attractions to all the ions of opposite charge immediately
surrounding it.
6.1.2 Covalent bond
Covalent bonds are formed by overlap of atomic orbitals and mutual sharing of electrons. A
covalent bond is typically formed by two non-metals having similar electro-negativities and
hence the atoms must share the electrons. The two atoms contribute one electron each and then
share the resulting pair of electrons. A hydrogen molecule is formed when two atoms combine
together to make H2.
H. + .H → H–H

+ →

Shared electron pair

Covalently bonded compounds usually form molecular structures. Molecular solids are
collections of distinct molecules held in place only by intermolecular forces. A covalent network
solid has atoms at the crystal lattice sites that are linked together by covalent bonds into a three
dimensional array example; diamond.

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The characteristic properties of covalent compounds are the following;
 They are gases, liquids or solids at room temperature
 They are soft and much readily broken
 They have low melting points and boiling points
 They are soluble in organic solvents
 They are rigid and directional; causes stereoisomerism
 They do not conduct electricity in any state
6.1.3 Metallic bond
The bonding which holds the metal atoms firmly together by force of attraction between metal
ions and the mobile electrons is called metallic bond. A metallic solid has metal atoms occupy in
the crystal lattice sites. If many metal atoms are brought together, the outer electrons of each can
merge together and overlap. Then they are in a position to move around and between all the
atoms. These electrons have become delocalized and hence more stable. A block of metal can be
thought of as an array of positive ions immersed in a sea of delocalized electrons. The great
cohesive forces resulting from the delocalization is responsible for the great strength noted in
metals. Band theory of metals is used to describe bonding. In a metal, the outer orbitals of a
very large number of atoms overlap to form a very large number of molecular orbitals that are
delocalized over the metal. A large number of closely spaced energy levels form ‘bands’. The
valance band may be half-filled as in case of alkali metals or there may be overlap of valence
band and conduction band as in case of alkaline earth metals. Hence metals are good conductors
of electricity. The metals crystallize in one of the three main types of metallic space lattices; fcc,
bcc and hcp.

.
The electron sea model of bonding in metals

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 Half filled

a) filled

Conduction band (empty)

b)
Valence band (filled)

Schematic diagram of band description of metals

The characteristic properties of metals include the following;
 They have bright metallic luster
 They are malleable and ductile
 They have high electrical and thermal conductivity
 The melting points vary according to the efficiency of metallic bonding
6.1.4 Secondary bonds
These bonds are weak in comparison to the primary bonds. Secondary bonding exists between
virtually all atoms or molecules but its presence may be obscured if any of the three primary
bonding types is present. Secondary bonding is evidenced for the inert gases, which have stable
electron structures, and in addition, between molecules in molecular structures that are
covalently bonded. Secondary bonding forces arise from atomic or molecular dipoles. In essence,
an electric dipole exists whenever there is some separation of positive and negative portions of
an atom or molecule. Dipole interactions occur between induced dipoles, between induced
dipoles and polar molecules. So secondary bonding can be classified as;
 Hydrogen bonds
 Dipole-dipole bonds

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  Dipole-Induced dipole bonds
 London forces
Hydrogen bonds: The electrostatic attraction between an H-atom covalently bonded to a highly
electronegative atom X such as nitrogen, oxygen or fluorine and a lone pair of electrons on X in
another molecule is called hydrogen bonding.
:∂-X-H ∂+ + :∂-X- H∂+→ :∂-X-H ∂+ :∂-X- H∂+
H-bond
The hydrogen-bond attraction can occur between molecules (intermolecular) or within different
parts of a single molecule (intramolecular). The examples of intermolecular hydrogen bonding
include (HF)n, (H2O)n, (NH3)n and (CH3COOH)2. The examples of intramolecular hydrogen
bonding include o-nitrophenol, 2-nitrobenzoic acid and o-flurophenol. Though the H-bonds are
weak forces, they are strong enough to influence physical properties such as boiling points,
solubility, viscosity and crystal structure. Energy associated with hydrogen bonding lies in the
range of 15 - 40 kJ/mole.
Dipole-dipole bonds: The strongest secondary bonding type exists between adjacent polar
molecules. The associated binding energies are significantly greater than for bonds involving
induced dipoles. HCl is an example of polar molecule. The positive end of one dipole attracts the
negative end of the other. There is a net attraction between the polar molecules. Generally such
attractions are about 1 % as strong as a covalent bond.
Dipole-induced dipole bonds: Permanent dipole moments exist in some molecules by virtue of
an asymmetrical arrangement of positively and negatively charged regions; polar molecules
will induce a dipole in adjacent nonpolar molecules, and a bond will form as a result of attractive
forces between the dipole and induced dipole. The magnitude of this interaction depends on the
magnitude of dipole moment of the polar molecule and the polarizability of the non-polar
molecule. Eg. solution of polar solutes in nonpolar solvents.
London forces: A dipole may be created or induced in an atom or molecule that is normally
electrically symmetric; that is, the overall spatial distribution of the electrons is symmetric with
respect to the positively charged nucleus.. All atoms are experiencing constant vibrational
motion that can cause instantaneous and short-lived distortions of this electrical symmetry for
some of the atoms or molecules, and the creation of small electric dipoles. One of these dipoles
can in turn produce a displacement of the electron distribution of an adjacent molecule or atom,

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which induces the second one also to become a dipole that is then weakly attracted or bonded to
the first. The momentary attraction between the molecules of a liquid caused by instant dipole
and induced dipole are called London Forces. These attractive forces may exist between large
numbers of atoms or molecules, which forces are temporary and fluctuate with time.
Liquefaction and, in some cases, the solidification of the inert gases and other electrically neutral
and symmetric molecules such as H2 and Cl2 are realized because of this types of bonding.
Melting and boiling temperatures are extremely low in materials for which induced dipole
bonding predominates; of all possible intermolecular bonds, these are the weakest.

6.2 Polymers
6.2.1. Terms and terminologies
The word polymer is derived from the two greek words, poly and meros, meaning many and
parts or units respectively. Polymers are macro molecules formed by linking smaller structural
units, called monomers interconnected by covalent bonds. Example: Polythene is formed by
linking a large number of ethene (or ethylene) molecules together as shown below.

H H
H H
Polymerisation
n C C C C
H H n
H H
Ethene Polythene

Degree of polymerization: The number of repeating units (n) in the chain. Polymers with high
degree of polymerization are called high polymers and these have very high molecular weights
(104 to 106). Polymers with low degree of polymerization are called oligomers.

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Functionality: The number of reactive sites or bonding sites. The reactive functional groups are
like –OH, -COOH, NH2, -SH and –NCO.
Examples: CH3CH2OH one reactive - OH group is present so
functionality is one (i.e., monofunctional)
HO CH2 CH2 OH two – OH groups are present, so bifunctional
HOOC CH2 CH (COOH) CH2 COOH trifunctional
The presence of double or triple bonds in the molecule bestows polyfunctionality on them.
e.g., ethylene - due to presence of a double bond, it can take on two atoms of hydrogen or
halogens. i.e., when the double bond is broken, two single bonds become available for
combination. So functionality is two. Depending upon the functionality of the monomers used,
we will get linear, branched or three dimensional cross-linked polymers.
6.2.2. Classification of polymers
Polymers can be classified in several ways, based on their origin, structure, methods of
formation, response to heat and crystallinity and applications.
Based on the origin, polymers are broadly classified as (a) Natural polymers (b) synthetic
polymers.
Natural polymers are those which are obtained naturally. Examples: Cellulose, Silk & Starch.
Synthetic polymers are those which are made by man. Examples: polythene, PVC, & polyester.
There are a few semi-synthetic polymers which are chemically modified natural polymers.
Examples: cellulose acetate, cellulose nitrate & halogenated rubbers.
Based on molecular structure, the polymers further can be classified as follows
(a) Linear (b) Branched (c) Cross-linked
If all the monomeric units combine linearly with each other to form a polymer, and all the
monomer units are identical, it is called a linear homopolymer.
e.g., ………..- M – M – M – M – M – M – M - …………
If the monomeric units are not identical and are of different, it is called a linear co-polymer.
e.g., ………..- M – M1 – M – M1 – M – M1 – M - …………
If the linear co-polymers in which the units of each type form fairly long continuous sequences
(blocks) are called block co-polymers.
e.g., ………..- M – M – M – M - M1 – M1 - M1 - M1 - M – M – M – M – …………
If the linear polymer branches out, then it is called a branch polymer.

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On the basis of the method of formation, the polymers can be classified as follows;
(a) Addition polymers (b) Condensation polymers
Addition polymers are formed by a process of self-addition of monomers. The molecular mass
of a polymer is an integral multiple of the molecular mass of a monomer. Examples:
polyethylene & synthetic rubbers.Condensation polymers are formed by condensation reaction
i.e., reaction between two or more monomer molecules with the elimination of simple molecules
like water, ammonia and HCl. Examples: Urea-formaldehyde resins, phenol-formaldehyde resins
& polyesters.
The polymers can be classified on the basis of the response to heat as follows; (a) Thermo
softening (b) Thermosetting
The polymers, which soften on heating and can be converted into any shape, which they can
retain on cooling, are called as thermo softening or thermoplastic polymers. The process of
heating, reshaping and retaining the same on cooling can be repeated several times. Examples:
polyethylene, nylons & sealing wax. The polymers which undergo some chemical change on
heating and convert themselves into an infusible mass are called as thermosetting polymers.
Examples: bakelite, egg yolk.
The polymers can be classified on the basis of their applications as follows;
(a) Plastics (b) Elastomers (c) Fibers (d) Resins
Plastics are the polymers, which are soft enough at some temperature to be molded into a desired
shape and hardened on cooling so that they can retain that shape. Examples: poly styrene, poly
vinyl chloride & poly methyl methacrylate. Elastomers are polymers in which the structural
units are either zig zag or helical chains. They undergo elastic changes when subjected to an
external force, but readily regain their original shape when the force is withdrawn. Examples:
natural rubber & silicone rubbers. Fibers are characterized by their molecular chains arranged
parallel to each other in a spiral or helical pattern which do not undergo stretching or
deformation and the molecular length is at least 100 times its diameter. Examples: nylons &
terylene. Resins are much lower molecular weight polymers either in liquid or solid form used as
adhesives or molding powders. It has a glossy appearance. Resins constitute the major essential
part of the plastics. Examples: polysulfide sealants & epoxy adhesives.

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6.2.3 Polymerization: Polymerization may be defined as the union of two or more smaller and
simpler molecules of similar or different types, with or without elimination of H2O, NH3 etc.,
resulting in the formation of new C - C linkages.
Types of Polymerization: addition (chain growth) polymerization & condensation (step growth)
polymerization
Addition polymerization: The reaction in which self-addition of several olefinic monomers to
each other takes place without elimination of by products is known as addition polymerization.
It is a reaction that gives a product, which is an exact multiple of the original monomeric
molecules. The addition polymerization must be initiated by using heat or light or pressure or
catalyst for the breakage of the double bonds of monomers.

TFE PTFE
Condensation Polymerization: The reaction in which the intermolecular condensation takes
place through functional groups of monomers, having affinity for each other and with continuous
elimination of by products is known as condensation polymerization.

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Distinguishing features of addition and condensation polymerization
ADDITION POLYMERISATION CONDENSATION POLYMERISATION
 Monomers undergo self-addition  Monomers undergo intermolecular
to each other without loss of by condensation with continuous elimination
products of by products such as H2O, NH3& HCl.
 Unsaturated vinyl compounds  Monomers containing the functional
undergo addition polymerization groups (-OH, -COOH, -NH2) undergo
this polymerization
 Monomers are linked together  Covalent linkages are through their
through C-C covalent linkages functional groups
 Eg.:polystryrene, plexiglass, PVC  Eg.: nylons, terylene, PF resins

6.2.4 Structure and properties of polymers

Macromolecules may be elastic or rigid; hard or soft; transparent or opaque; may have strength
of steel but can have very light weight; may be soften on heating or can set to a hard mass on
cooling the melt. These properties may vary from one type of polymer to another and even
among the same type.
Strength: This property is discussed based on forces of attraction and slipping power.
Based on forces of attraction: The strength of the polymer is mainly affected by the magnitude
and distribution of attractive forces between the polymer chain. These attractive forces are of
two different types viz., primary or covalent bond and secondary or intermolecular forces.
In case of straight chain and branched chain polymers, the individual chains are held together by
weak intermolecular force of attraction. But in these polymers, strength increases with increase
in chain length (in turn increase in molecular weight) i.e., attains mechanical strength if the chain
length is greater than 150-200 carbon atoms in the chain. Less than these numbers, the polymers
will be soft and gummy, but brittle at low temperature. Intermolecular forces can be increased
by introducing polar groups like carbonyl & hydroxyl. In cross-linked polymers, monomeric
units are held together only by means of covalent forces. Hence possess greater strength than
straight and branched chain.
Based on slipping power: Slipping power is defined as movement of molecules one over the
other. E.g., polyethylene molecule is simple and uniform, hence movement of molecule one

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over other is possible, i.e., slipping power is high. Hence it has lesser strength. But in case of
poly vinyl chloride (PVC), there is bulky chlorine atoms are present along the chain length hence
movement is restricted, i.e., slipping power is less. Hence higher strength when compared to
polyethylene. But in case of cross-linked polymer, movement is totally restricted because of the
presence of covalent bond. Hence these products are strong, rigid and tough.
Plastic deformation: When a polymer is subjected to some stress in the form of heat or pressure
or both, permanent deformation in shape takes place, which is known as plastic deformation.
This property actually helps in molding of plastics. Slippage is more in case of linear molecules
than branched and cross-linked, because of the presence of weak intermolecular forces and hence
they show greatest degree of plastic deformation. At high pressure, temperature also increases,
the weak van der Waal’s forces acting between molecules become more and more weak. Such
types of materials are called thermoplastic materials. No slippage occurs in case of cross-linked
molecules, because of only primary covalent bonds present throughout the entire structure. Such
types of polymers are known as thermosetting polymers. However, when considerable external
force or temperature exceeding the stability of material is applied, it will result in total
destruction.
Crystallinity: Based on the relative arrangement of polymer chains with respect to each other,
polymer can exhibit amorphous and crystalline nature. An amorphous state is characterized by
completely random arrangement of molecules and crystalline form by regular arrangement of
molecules. The crystallization tendency of a polymer depends on the ease with which the chains
can be aligned in an orderly arrangement. Crystalline regions of a polymer are formed when the
individual chains are linear, contain no bulky substituents and are closely arranged parallel to
each other. The chains of polymer may be held together by Vander walls forces, hydrogen
bonding or polar interactions. A polymer with high degree of crystallinity will have high tensile
strength, impact and wear resistance, high density and high fusion temperature. Polymers with a
long repeating unit or with low degree of symmetry do not crystallize easily, hence forms
amorphous structure e.g., polystyrene. Crystallization imparts denser packing of molecules due
to increase of intermolecular forces of attraction. Such type of polymers will have sharp
softening point, greater strength and rigidity. Polymers are in general amorphous with some
degree of crystallinity.

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Chemical resistance: Chemical resistance of the polymer depends upon the chemical nature of
monomers and their molecular arrangement. As a general rule of dissolution, ‘like materials
attract’ and while unlike materials repel. Thus a polymer is more soluble in structurally similar
solvent. For example, polymers containing polar groups like – OH, - COOH, usually dissolve in
polar solvents like water, ketone & alcohol, but these are chemically resistant to non-polar
solvents. Similarly non-polar groups such as methyl, phenol dissolve only in non-polar solvents
like benzene & toluene. Moreover, polymers of more aliphatic character are more soluble in
aliphatic solvents and aromatic groups dissolve more in aromatic solvents.
As a general rule, the tendency of solubility in a particular solvent decreases with increase in
molecular weight of the polymer, (i) high molecular weight polymer on dissolving yield
solutions of high viscosities (ii) crystalline polymers exhibit higher resistance than less
crystalline polymers of similar chemical character (iii) greater the degree of crystallinity, lesser is
its solubility.
Today several drugs and essential oils are stored in plastic bottles for long shelf life. If they
disintegrate or change in their chemical composition they may render the ineffective or may
cause it to react adversely when used leading to specific disorder or can cause reactions from
minor to quite severe. Therefore, chemical resistance of plastic bottles is important to prevent
drug polymer interactions.
Elasticity: Elasticity of the polymer is mainly because of the uncoiling and recoiling of the
molecular chains on the application of force. In an upstretched elastomer we can observe a
peculiar configuration of irregularly coiled and entangled snarls in a random fashion, indicating
the amorphous state. In a stretched state snarls disentangle and straighten out in a proper chain
orientation, indicating the crystalline state. The crystallinity in a stretched rubber band can be
observed from its opaqueness and warmth it produces when touched by lips. For a polymer to
show elasticity the individual chains should not break on prolonged stretching. To avoid this (i)
introducing cross-linking at suitable molecular positions (ii) allowing bulky side groups such as
aromatic and cyclic on repeating units (iii) introducing non-polar groups on the chains.
6.2.5 Molecular weight of polymers
A simple molecule has a fixed molecular weight. In contrast, a polymer comprises molecules of
different molecular weights and hence, its molecular weight is expressed in terms of an ‘average’
value. E.g., ethylene gas, which is a low molecular weight compound, each of its molecules has

16
the same chemical structure and hence, a fixed molecular weight of 28. But upon
polymerization, it forms polyethylene and we encounter an indefinite chemical structure of -(-
CH2-CH2-)n, where ‘n’ can change its value from one polyethylene molecule to another present
in the same polymer sample.
When ethylene is polymerized to form polyethylene, a number of polymer chains start growing
at any instant, but all of them do not get terminated after growing to the same size. The chain
termination is a random process and hence, each polymer molecule formed can have a different
number of monomer units and thus different molecular weights. So a sample polymer can be
thought of as a mixture of molecules of the same chemical type, but of different molecular
weights. This unequal length is specific to most synthetic polymers while equal chain length is
specific to proteins.
The molecular weight of the synthetic polymer can be taken statistically and expressed as some
average of the molecular weights contributed by the individual molecules that make the sample.
So the molecular weight of a polymer can be expressed by two most and experimentally
verifiable methods of averaging viz., (i) Number average and (ii) weight average.
Number-average molecular weight: Number average molecular mass of a polymer can be
defined as the total mass of all the molecules in a polymer sample divided by the total number of
molecules present.

Weight-average molecular weight: The sum of the fractional masses that each molecule
contributes to the average according to the ratio of its mass to that of the whole sample.

White foam cups, clear plastic cups and ultrathin fishing line are made of polystyrene with
different average molar masses while Styrofoam cups are made from beads of polystyrene with

17
an average mass of approximately 15000 g/mol. Clear plastic cups are made by melting
polystyrene with average mass of approximately 250000 g/mol. Ultrathin fishing lines are
composed of polystyrene with an average mass of 1000000 g/mol.
Application of AMM: It is used to characterize a polymer. Samples of the polymer prepared
under different conditions may have different AMM. It affects the mechanical, solution & melt
properties of the polymer. Chain length is related to the ease of processing of the polymer. The
longer the chain, the more difficult the melt is to process. The polymer chain becomes more
entangled as the molecules get larger and offer more resistance to flow at the molecular level. In
most applications, the polymer must be able to flow so that it can be flattened into sheets,
molded into bottles and so on.
Numerical Problems:
1) A protein sample consists of an equimolar mixture of Haemoglobin (M=15.5 Kg mol-1),
Ribonuclease (M=13.7 Kg mol-1) & Myoglobin (M=17.2 Kg mol-1). Calculate Mn & Mw
2) A polypropylene [-CH2–CH(CH3)-] sample contains the following composition.
Degree of polymerization 400 800 600
% of composition 25 35 40
Calculate Mn & Mw of polypropylene sample by neglecting the end groups.
6.3 Liquid crystals
Liquid Crystals (LC) have properties both of those of conventional liquids and those of
solids. They find application in the areas of science and engineering, particularly in display
systems of modern electronic gadgets. Devices using liquid crystal displays have the advantage
of low power consumption and hence are widely used in display devices of mobile
communication appliances, aircraft cockpit, laptops and other electronic equipment.
In a crystalline state, the molecules (or atoms) are positioned and oriented in space in a regular
repeated manner in a rigid arrangement and are immobile. They tend to orient in a preferred
direction i.e., the molecules in solids have a positional and orientational order. In liquid state,
the molecules neither occupy specific positions nor remain oriented in a particular manner. The
molecules are somewhat free to move at random and collide with one another, abruptly change
their positions. The liquids have neither positional order nor orientational order. A liquid crystal
(LC) is a state of matter exists between solids and liquids with both the properties. Normally
when a low molar mass solid melts, it forms an ordinary liquid and is isotropic. Organic

18
substances which are geometrically anisotropic i.e., long and relatively narrow molecular shape
exhibits this intermediate state of order between solid crystals and isotropic liquids. They
undergo more than a single transition in passing from solid to liquid through different
intermediate states on heating. These intermediate states with different molecular ordering are
also known as mesophases, derived from a Greek word, mesos for middle. All molecules in a
mesophase orient with respect to each other and in certain types of mesophases, further exhibit
some regular position with respect to each other. The molecular arrangement in solids, liquid
crystals and liquids can be represented as below.

In a liquid crystal, the molecules possess orientational order, i.e., the molecules tend to remain
oriented in a particular direction. The direction of preferred orientation in a liquid crystal is
called the director ( n ) and may be imagined to be directed towards the top or bottom of the
page. Since the molecules are in constant motion, in liquid crystal phase they spend more time
pointing along the director than along any other direction. The extent of orientational order can
be described by taking an average. An average of 0° indicates perfect orientation and can be
expected in solids. An average of greater than 45° indicates no orientational order and found in
liquids. However, in liquid crystals a smaller average angle with the director is observed which
indicates orientational order.
The quality of any device using LCs depends mainly upon the physical properties of the LC
molecules. To achieve a high performance of the LC device, it is essential to select the most
appropriate LC material according to the specific requirements of the desired device. In general,
the LCs must satisfy the following characteristic properties
a. Liquid crystalline nature should be at room temperature and the entire
temperature range of the device operation
b. Chemically, electrochemically, photochemically and thermally stable
c. Should have high electrical resistance

19
 d. Permanent electric dipole, hence either a positive or negative dielectric
anisotropy.
e. Should possess easily polarizable substituents
6.3.1 Classification of Liquid Crystals
Based on the response to temperature or concentration, Liquid Crystals are broadly
classified as
 Thermotropic LCs
 Lyotropic LCs
The liquid crystalline substances which undergo transitions by variation in temperature
are called thermotropic LCs. Eg. P-azoxyanisole. The liquid crystalline substances which
undergo transitions by the influence of solvents are called Lyotropic LCs. Eg. Sodium stearate.
Both these systems can be characterized by anisotropic viscous, electrical, optical and
mechanical properties. Organic molecules, which are able to form thermotropic as well as
Lyotropic mesophases, are termed as Amphotropic LCs.
Thermotropic Liquid Crystals: Based on the phase structures, the TLCs are further classified as
a. Nematics
b. smectics
c. columnar
d. cubic
Nematic: The most liquid like structure in which, one or two molecular axes are oriented parallel
to one another, resulting in an orientational long-range order.
Smectic: Layer structures with many possibilities of the state of order inside the layers and
different possibilities of mutual arrangement of the layers, showing long range
orientational and more or less positional order
Columnar: Structures with columns consisting of parallel arranged disc-like molecules.
Cubic: Structures with micellar lattice units or complicated interwoven networks.
Based on the shape of the constituting molecules, the thermotropic LCs can be further classified
as
(i) Calamitic LCs
(ii) Discotic LCs
(iii) Polycatenar LCs

20
 (iv) Bent (Banana ) LCs
Calamitic Liquid Crystals: The LC compounds possessing rod-like molecular shape belong to
this category. The general molecular structure of a calamitic LC is as given below.

Rʹ A L B L C L D Rʺ
Where A, B, C and D are called the rigid cores (containing a phenyl, biphenyl, naphthyl,
cyclohexyl or five/six membered heterocycles) of the molecule. In a Liquid crystal, there should
be atleast one rigid core.
‘L’ is the linking group (an imine, azo, azoxy, ester, thioester, C=C and C≡C)
Rʹ or Rʺ is the end group/chain (a halo group, cyano, nitro, alkyl or alkoxy groups)
Some examples of the calamitic LCs are given below.

p-sexiphenyl

C10F21

(perfluorodecyl)-decane
Discotic Liquid Crystals: Discotic compounds consist of flat and disc-like rigid cores which
surrounded by flexible chains such as alkyl, alkyloxy or alkanoyloxy. These molecules (with flat
and disc-like shape) are able to pack with different structures. In most of the cases, the disc-
shaped molecules are packed one upon another to form columns. Within the columns, the
molecules can have certain order or disorder. The columns themselves are arranged in a two-
dimensional network leading to Columnar Phases with hexagonal, rectangular or oblique
symmetry. The general structure of discotic LCs can be represented with the following cartoon
picture.

21
In discotic liquid crystals, the molecular diameter (d) is much greater than the disc thickness (t)
to form anisotropy. A typical molecular structure of a discotic molecule is shown below.
R R

R R

R R

where R=alkyl chain

Polycatenar Liquid crystals: Polycatenar mesogens represent a hybrid class of thermotropic

LCs, which can be described with intermediate molecular features between classical rod-like and
disc-like mesogens. Schematically the central core of polycatenar LCs comprises a calamitic
region, with half-discs on the extremities. This hybrid molecular structure allows them to exhibit
both calamitic (nematics/smectic) and discotic (columnar) phases, depending on the specific
molecular structure of the components. E.g., the tetracatenar mesogens (shown below), at
shorter chain lengths exhibit nematic and/or smectic-C phases, while at longer chain lengths
exhibit columnar phases. Thus, by varying the chain length of the molecules, the mesomorphism
can be changed from a typical calamitic phases (layered structures) to discotic phases (columns).
The numbers of the flexible end chains of the core can be indicated by using the term, m,n–
polycatenary mesogen. The different polycatenar LCs can be represented with the following
schematic diagrams.

2,2-polycatenary mesogen (Hemiphasmidic) 3,1-polycatenarymesogen (Hemiphasmidic)

22
3,2-polycatenary mesogen (Forked hemiphasmidic) 3,3-polycatenarymesogen (Phasmidic)
Polycatenar molecules possess a number of flexible alkyl chain substituents, which varies
from two to six (bi- to hexa-catenar compounds). Bi-catenar LCs (in most of the cases) exhibits
classical calamitic LCs phases (nematics or smectic). Some examples of bi-, tri-, tetra-and hexa-
catenar LCs are given below.

Bicatenar mesogen
Bent Liquid Crystals: They consist of two mesogenic groups linked through a rigid core in such
a way that the molecule is not a linear (as shown in the following figure). The central rigid core
(Z) may be a phenyl or biphenyl or naphthyl group. The mesogenic groups attached to the
central core are mostly the calamitic molecules consisting of two (or more) aromatic rings with
different linking groups (A, B, X, Aʹ, Bʹ, Xʹ) and a terminal chain/a substituent in para position to
the linking group of the aromatic rings. The angle between the two calamitic wings (bending
angle) is around 120°. In case of a benzene central core, the mesogens are connected in 1 and 3
positions (i.e., meta position to each other). If the central core is a naphthyl, the two calamitic
wings are connected in 2 and 7 positions.

Z
X
X'

A
A'

B
H3 C
n B'
CH3
m

23
Lyotropic Liquid Crystals: They form anisotropic aggregates when combined with a solvent,
like water. The phase behavior is dependent on the concentration and polarity of solvent and
also on the temperature. Molecules which form Lyotropic phases are usually amphiphilic, having
non-polar, hydrophobic "tails" at one end with a polar, hydrophilic "head" at the other end. Some
examples are sodium sterate (soap) and phospholipids. The concentration of material in the
solvent and the response of the amphiphile to the solvent environment dictate the type of
Lyotropic phase formed. For example, in a polar solvent like water, micelles are formed in which
the hydrophobic tails assemble together and the hydrophilic heads groups are presented to the
solvent. When combined with a non-polar solvent such as hexane, an inverse micelle is formed
where the hydrophobic tails shield the hydrophilic head groups from the non-polar environment.
Under certain conditions, these micelles further aggregate to form more complicated assemblies,
such as lamellar and hexagonal Phases, which generate lyotropic liquid crystal phases. Lamellar
phases are particularly significant as they form the structural basis for biological membranes
Examples of Lyotropic liquid crystals and their phase structures

Sodium Sterate Phospholipid

Micellar aggregates and phase structures formed by Lyotropic liquid crystals are shown below.

24
6.3.2 Applications of liquid crystals:
Liquid crystal displays operate at low voltages (a few volts) and consume less power as
compared to other displays and hence are used in:
1. Liquid crystal displays: Used in display devices such as watches, calculators, mobile
telephones, laptop computers and clocks.
2. Liquid crystal thermometers: Chiral nematic LCs reflect light and the color reflected is
dependent upon temperature.
3. In medicine: The heat evolved in radiation testing devices where radiation energy is
converted into heat energy. LCs can be used to detect subcutaneous tumors. As tumor
cells are warmer than normal cells, which show a different color than normal cells on
LCs.
4. Optical Imaging and recording: LC cell is placed between two layers of photoconductor.
When light is applied to photoconductor, it increases the conductivity of material. This
causes an electric field to develop in the LC corresponding to the intensity of light. The
electric pattern can be transmitted by an electrode, which enables the image to be
recorded.
5. Non-destructive mechanical testing: LCs have tendency to change color when stretched
or stressed. Thus, LC sheets are often used in industry to look for hot spots, map heat
flow, measure stress distribution patterns and so on.
6.3.3 Liquid Crystals in Display systems
The electro-optic effect of liquid crystals controls brightness/darkness of the light emerging from
its elements and this is used in information displays. Information is passed on to the user using
LCs which control the brightness/darkness of the parts of a display. Numeric display has seven
segments whereas alphabets are displayed using fourteen segments. More complex graphic
images are formed using pixels (picture elements) which are closely packed array of dots in two
dimensions.
Light from the area of each of the seven segments or pixels is controlled independently and is
used to create any one of the ten digits. When an electric field is applied to a segment, the liquid
crystal in that segment undergoes deformation (is activated) and when polarized light is incident,
the light is modulated depending on the deformation in that segment. In twisted nematic displays
(TND), the nematic LC is sandwiched between two ITO coated glass plates with parallel

25
(homogeneous) alignment of its molecular director with the glass walls. However, the two glass
plates are twisted by 90° relative to each other (as shown in the following figures).

Fig. LCD system with ‘ON’ state

Fig. LCD system with ‘OFF’ state

In such geometry the LC is forced to perform a 90° twist of the director from plate to plate,
resulting in a helical structure. The distance between the plates, hence the thickness of the LC
film, is typically 6–10 µm, which corresponds to half of the helical pitch. To complete the TND
unit, a pair of crossed polarizers is placed on the outer side of the glass plates. In the absence of
an external electric field, when linearly polarized light enters the device, the LC film acts as an
optical wave guide rotating the polarization of the light by 90°. Thus, the light reaches the
second polarizer (analyzer/reflector) with its polarization plane parallel to the polarizer axis and
is transmitted. In this configuration the display appears bright (off-state). In case of reflective
mode displays, the light will pass through the analyzer and be reflected back through the cell.
The observer will see the background of the display, which in this case is the silver gray of the

26
reflector. However, when an electric field is applied (on-state), the LC molecules reorient in
order to align the molecular director with the external electric field, causing the helical
arrangement to be unwound. As a consequence, the light passing through the LC film, is not
guided through 90°, and is not able to pass through the second polarizer. The observer sees a
black character on a sliver gray background. When the electric field is turned off, the molecules
relax back to their 90° twist structure. This is referred to as a positive image, reflective viewing
mode. Carrying this basic technology further, an LCD having multiple selectable electrodes and
selectively applying voltage to the electrodes, a variety of patterns can be achieved.
6.4 Ceramics
The term “ceramic” comes from (Gk. Keramos- burnt matter) indicating that desirable properties
of these materials are normally achieved through a high-temperature heat treatment process
called firing.Ceramics consist of a combination of non –metallic substances mostly silicates and
metal oxides. It is used to indicate refractories, glass, enamels, porcelain, bricks and abrasive
materials. For example, some of the common ceramic materials include aluminum oxide, silicon
dioxide, silicon carbide, silicon nitride and,in addition,the traditional ceramics are those
composed of clay minerals as well as cement and glass. The chemical combination of different
metallic and non-metallic elements gives rise to ceramic materials with a variety of properties.
They could withstand a temperature of 1500 to 2000 0 C, but special application may require the
metals to withstand the temperature upto 5000 0 C.
With regard to mechanical behavior, ceramic materials are relatively stiff and strong,very
hard, brittle, highly susceptible to fracture, higher stability and higher melting points. Most of
these are insulators like other covalent materials. Some of the refractory materials are quite
stable and are thus used as structural materials in structures where resistance to high temperature
and oxidation are important,as in furnaces for steel making and glass making. With regard to
optical characteristics, Ceramics may be transparent,translucent, or opaque, and some of the
oxide ceramics (e.g.,Fe3O4) exhibit magnetic behavior. These new materials have a effect on our
lives;electronic, computer,communication,aerospace and a host of other industries rely on their
use.
6.4.1 Classification of ceramic materials on the basis of application
1. Glasses - products of fusion rapidly cooled to a rigid condition without crystallization.

27
They are non crystalline silicates that contain other oxides. Optical transparency is the most
desirable properties of these materials. The most common uses for these materials are as
ovenware,tableware,ovenwindows because of their strength and excellent resistence to thermal
shock. They also serve as elctrical insulators and as substrates for printed circuit boards and for
heat exchangers and regenerators.
2. Clay products- structural clay products, whitewares
Clay is the principal component of the whitewares and structural clay products. Stuctural clay
products include building bricks, tiles-applications in which structural integrity is important. In
the whiteware ceramics group are porcelain,pottery,china and sanitary ware. Feldspar and quartz
may be added which influence the changes that occur during firing. Fire clays are hydrated
aluminosilicates of composition Al2O3.2SiO2.2H2O.
3. Refractories – fire clay, silica, basic special meterials :
The materials that are employed at elevated temperatures and often in reactive environments . On
the basis of composition and application, the four main subdivisions are fireclay, silica, basic and
special.Typical applications include furnace linings for metal refining, glass manufacturing,
metallurgical heat treatment and power generation.
Acid refractories:They consist of mostly acidic materials like alumina (Al2O3) and silica (SiO2).
They are not attacked or affected by acidic materials, but easily affected by basic materials. They
include substances such as silica, alumina, and fire clay brick refractories. Fireclay bricks are
used in furnace construction to confine hot atmosphere and to thermally insulate structures from
excessive temperatures.
Neutral refractories: These are used in areas where slags and atmosphere are either acidic or
basic and are chemically stable to both acids and bases. The main raw materials belong to, but
are not confined to, the M2O3 group. The common examples of these materials are alumina
(Al2O3), chromia (Cr2O3) and carbon.
Basic refractories:The refractories that are rich in periclase or magnesia (MgO) are termed
basic; they may also contain calcium, chromium, and iron compounds. These are used on areas
where slags and atmosphere are basic; they are stable to alkaline materials but could react with
acids. The steel making process used artificial periclase (roasted magnesite) as a lining material
for the furnace.

28
4. Abrasive meterials – metal oxides and nitrides, being hard and tough are used to cut, grind and
polish other softer materials. Diamond, SiC, Tungsten carbide are common examples. The
abrasives may be employed in the form of loose grains,bonded to an abrasive wheel or coated on
paper or a fabric, used for shorpening kniefs and polishing wodden surfaces.
5. Cements – portland cement:
When mixed with water, inorganic cements form a paste that is capable of assuming just about
any desired shape. Subsequent setting is a result of chemical reactions involving the cement
particles and occurs at the ambient temperature. For portland cement is the most common
hydrulic cement, the chemical reaction is one of hydration. The produced mixture hardens into a
solid mass on reacting with water and provides water resistant product.
6. Advanced ceramics - composite materials, engine rotors: Many of our modern technologies
use advanced ceramics because of their unique mechanical, chemical, electrical magnetic and
optical properties and property combinations. Examples: ceramic ball bearings, piezoelectric
ceramics.
Properties:
1. Glass ceramic materials have relatively high mechanical strength; low coefficient of thermal
expansion (to avoid thermal shock) and high temperature capabilities, good dielectric properties
and good biological compatibility, ease of fabrication. They serve as electrical insulators and as
substrate for printed circuit boards.
2. In refractories porosity must be controlled .Strength, load bearing capacity and resistance to
attack by corrosive materials all increase with porosity reduction. Any residual porosity will have
deleterious influence on both elastic properties and strength.
6.4.2 Ceramic fabrication methods
The general method in fabrication and production of ceramic products involves the following
steps.
i) Fabrication: The ceramic product is formed by throwing the soft mud on a potter’s wheel or
by a mechanical jiggering process. Other methods such as stiff mud process , slip casting, dry
pressing and hot pressing are also used for forming the ceramic body. In the stiff mud process the
mix containing aout 10-20 % water is forced throgh a steel die of the desired shape in a pug mull.
In “slip casting” the slip an aq. suspension of the mix having a proper consistency is poured into
a mould of plaster of Paris. The mould absorbs the water and allows a uniform deposit of the mix

29
on the inner syrface of the mould. Dry pressing is mostly used for making floor and wall tiles
and involves hydrulic pressing of the relativelydry mix (water content is 5-15%). Hot presing is
used for making dense refractory oxides and carbides by using a die and plunger set to press and
simultaneously heat the mix to a sintered article.
ii) Drying: In the second step of manufacture, the shaped ceramic ware is dried in kilns at
controlled humidity and rates of drying to prevent cracking of the product. Drying too fast causes
sample to crack due to non-uniform shrinkage. In the last step the dried ceramic ware is fired at
high temperatures in kilns over a range of temperatures of 800 – 2000oC depending on the
composition of the mix and the properties desired to form a hard and strong finished ceramic
ware.
iii) Firing: Glazed ceramic ware requires a second firing after applying the glaze to the fired
unglazed ceramic ware. Glazes contain a mixture of glass forming materials (example quartz,
feldspar, boric oxide). Glaze is applied to a ceramic ware to give a smooth durable glossy and
decorative surface which is impervious to liquids. Glazes of different compositions are used
depending on the requirement. Glaze mixtures free from iron salts and pigments produce a
colourless glaze which may be transparent or opaque with glossy or mat finish. Metal oxides
and salts such as iron oxide (red or brown), copper oxide (blue) are mixed with the glaze to
impart colour.Salt glazing is mostly used for providing a glossy and impervious finish. Vapour
reacts with the silica on the article forming glossy film of sodium silicate on the surface.
Application of ceramics:
1. Die blanks- Wear resistance properties
2. Cutting tools – for cutting Si wafers, grinding glsses
3. Sensors – ZrO2 as oxygen sensor ( rapid response of the sensor to change in oxygen
concentration)
4.Matts for automobile engines – advanced ceramics
6.4.3 Cement
Cement is a binder material with characteristic properties of setting and hardening when
mixed to a paste with water. Cements can be divided into hydraulic and non-hydraulic types
according to the way in which they set and harden. The hydraulic cement is capable of setting
and hardening under water. Ex: Portland cement, whereas non hydraulic cement hardened in air
and hence cannot be used under water. Ex: ordinary lime.

30
Cement is the main component of concrete. It's an economical, high-quality construction
material used in construction projects worldwide. It may be described as “a material possessing
adhesive and cohesive properties, and capable of bonding materials like stones, bricks and
building blocks. The cements have property of setting and hardening under water by virtue of
certain chemical reactions and hence it is type of hydraulic cement. It is also defined as a fine
mineral powder, which mixed with water, this powder transforms into a paste that binds and
hardens when submerged in water. Cement is made by grinding together a mixture of limestone
and clay, which is then heated at a temperature of 1500-1700°C. What results is a granular
substance called "clinker," a combination of calcium, silicate, alumina and iron oxide.
Functions of the ingredients of cement
Variation in the proportion of these elements affects the properties of cement.
 Lime: Controls strength and soundness. It is the major constituent of cement. Its exact
proportion is important. The excess makes the cement reduces the strength of the cement
because it makes the cement to expand and disintegrate. In case of deficiency, the
strength of cement is decreased and cement sets quickly. The right proportion makes
cement sound and strong.
 Silica: Gives strength, excess quantity causes slow setting. The presence of silica imparts
strength to the cement due to formation of di-calcium silicate (2CaO SiO2 or C2S) and tri-
calcium silicate (3CaO SiO2 or C3S). Silica in excess provides greater strength to the
cement but at the same time it prolongs its setting time.
 Alumina: Quick setting, excess lowers strength. It acts as a flux (rate of flow of energy)
and lowers the clinkering temperature. Alumina in excess reduces strength of cement.
 Calcium sulfate (Gypsum-hydrated calcium sulfate): It helps to retard the setting
action of cement.
 Iron Oxide: Imparts color, helps in fusion of ingredients. It provides color, hardness and
strength. It also helps the fusion of raw materials during manufacture of cement. It
enhances the initial setting time of the cement.
 Sulfur trioxide: Makes cement sound. The presence of small amount of SO3 imparts
strength to the cement.
 Harmful ingredients in cement

31
 Alkali oxides (K2O and Na2O): Controls residues, excess causes cracking. If the amount
of alkali oxides exceeds 1%, it leads to the failure of concrete made from that cement.
Magnesium oxide (MgO): if the content of MgO exceeds 5 %, it causes cracks after
mortar or concrete hardness.
Portland cement: A hydraulic cement capable of setting, hardening and remaining stable under
water. It consists essentially of hydraulic calcium silicates, usually containing calcium sulphate.
A finely ground product obtained by calcining a proportionated mixture of clay containing and
lime containing raw material. It is the most important and reliable cementing material used for
constructional works.
Composition of Portland cement
Name Chemical formula Setting time
Tricalcium Silicate 3CaOSiO2 7 days
Dicalcium Silicate 2CaOSiO2 28 days
Tricalcium Aluminate 3CaOAl2O3 1 day
Tetracalcium Aluminoferrite 4CaOAl2O3Fe2O3 1day
Calsium sulphate CaSO4 -
Calcium oxide CaO -
Magnesium oxide MgO -
Reactions occurring during setting and hardening of cement
The setting of cement-paste is due to the hydration of tricalcium aluminate, dicalsium silicate
CaO.Al2O3[OR C3A] + 6H2O 3CaO.Al2O3.6H2O + 880 kJ/kg
Tricalcium aluminate hydrated tricalcium aluminate (crystalline)

2[2CaOSiO2][ORC2S] + 4H2O 3CaO.2SiO2.6H2O + Ca(OH)2 + 250kJ/kg

Dicalcium silicates gel formation calcium hydroxide

3CaOSiO2 + 6H2O 3CaO.2SiO2.3H2O + 3Ca(OH)2 + 500 kJ/kg

Tricalcium silicate hydrated tricalcium silicate (gel formation)
Sequence of chemical reactions during setting and hydration of cement
When water is added to cement, its various constituents undergo hydration and crystallization at
different rates. At first hydration of tricalcium aluminate takes place, and then the hydration of

32
tricalcium silicate begins within 24 hours and gets completed in 7 days. The gel of aluminate
begins to crystalize and at the same time dicalcium silicate begins to hydrate in 7 to 28 days.
Thus the initial setting of cement is due to the hydration of aluminate. The development of early
strength between 1 to 7 days is due to the hydration of tricalcium silicate and further hydration of
aluminate. The increase of strength between 7 to 28 days is due to the hydration of dicalcium
silicate and continued hydration of tricalcium silicate.

gel gel
cement + hydration formation of
1day 7 day formation 28 day
water paste of C3A
of C3S C2S and C3S

Function of gypsum (hydrated calcium sulfate) in cement:

When portland cement clinker is ground without the addition of retarder (gypsum), the reactions
with water are very rapid and quick setting will occur. The alumina containing phases present in
portland cement reacts rapidly to give rise to undesirable quick set. Therefore some retarders like
gypsum is added to portland cemmet during its setting and hardening proces. Gypsum is a
mineral and is hydrated calcium sulfate in chemical form. Gypsum plays a very important role in
controlling the rate of hardening of the cement. During the cement manufacturing process, upon
the cooling of clinker, a small amount of gypsum is introduced during the final grinding process,
which stop the rapid reaction normally shown by the aluminiunate phase and that causes the
formation of calcium sulphoaluminate in place of hydrated calcium aluminates. The added
gypsum then retards the dissolution of tricalcium aluminate by forming insoluble calcium
sulpho-aluminate (3CaO.Al2O3.xCaSO4.7H2O). This retards the early initial set of the cement.
Gypsum increases setting time of cement, so that it settles slowly and become harder and does
not contain air spaces.
6.4.4 Glass: A hard, brittle, noncrystalline, super cooled liquid of infinite viscosity more or less
transparent substance produced by fusion of many metallic silicates like Na, K and Ca, along
with soda and lime. The main ingredients for making glass are:-

1. Limestone (CaCO3),
2. Soda ash (Na2CO3), and
3. Sand/Silica (SiO2)
4. Cullets (broken glass material)
33
Properties: Amorphous, has no definite melting point, can absorb or transmit light, good
electrical insulator, is affected by alkalis, not affected by air, water or acids or chemical reagents,
softened on heating and has no crystal structure etc.
Manufacture:
a) Batch melting process: raw materials like sand, soda ash and limestone along with the
other ingredient were mixed in proper proportions with cullets and finely powdered. The
batch mixture is poured into reaction tank in which heating is done by burning producer
gas and mixture over the charge. At high temperature (1700-1800ºC) the mixture melts
and fuses to form clear jelly-like substance which is then cooled to form glass. This is
known as soda-lime glass.
The following reactions taking place during the process
CaCO3 + SiO2 CaSiO3 +CO2
Na2CO3 + SiO2 Na2SiO3 +CO2
When all the CO2 escaped out of molten mass, decolorizing substances added to remove to
remove ferrous compounds if present or coloring substances added to impart required color at
this stage. The heating is continued till the molten mass free from bubbles and then it is cooled to
form glass.

b) Forming and shaping: Molten glass is then worked into articles of desired shape either
by blowing or molding or pressing between the rollers.

34
 c) Annealing: Glass article then allowed to cool gradually to room temperature by passing
through different chambers with descending temperature. The longer the annealing
period, better the quality of the glass.
d) Finishing: After the annealing process glass articles are subjected to finishing processes
such as cleaning, polishing, cutting etc.,
Types of glass and their uses
There are different types of glass according to the minor additions and variations in the
ingredients used and according to the methods of manufacturing. The different types of glasses
are different in their properties and uses. The important ones are listed below along with their
applications.
1. Soda glass or soda-lime glass: It is the most common variety of glass. It is prepared by
heating sodium carbonate, soda ash and silica. It is used for making windowpanes, tableware,
bottles and bulbs.
2. Borosilicate glass or pyrex glass: It contains silica, boron and small amount of alumina and
some alkali oxides. It is extensively used in industry for pipelines or corrosive liquids, laboratory
apparatus and kitchen wares.
3. Aluminosilicate glass: It contains silica, alumina, boric oxide, magnesium oxide, calcium
oxide and small amounts of sodium oxide and potassium oxide. It is used in high pressure
mercury discharge tubes and chemical combustion tubes.
4. Safety glass: It can also be called shatterproof glass. It is made by placing a sheet of plastic
such as celluloid between sheets of glass and the whole is subjected to slight pressure. It is then
heated till the glass layers and plastic layers merge into one another. On cooling the glass
becomes quite tough. The special quality of this glass is that in case of breakage the broken
pieces stick to the plastic and do not fly off. It is also used for making bulletproof screens.
5. Glass wool: It is fibrous wool like material composed of intermingled fine threads or filaments
of glass. It is used for heat and electrical insulation purposes.
6.5 Composite materials
A composite material is a material system composed of two or more macro-constituents that
differ in shape and chemical composition. Many of our modern technologies require materials
with proper combinations of properties that cannot be met by the conventional metal alloys,
ceramics and polymeric materials. This is especially true for structural materials that have low

35
densities are strong, stiff and abrasion resistant and are needed for aerospace, under water and
transport applications. Other applications of these materials involve automotive, home appliance
and sporting goods, industries.
Material property combinations and ranges have been extended by the development of composite
materials. A composite is composed of two (or more) individual materials which come from the
categories namely metals, ceramics and polymers. Thus, composites are artificially produced
multiphase materials having a desirable combination of the best properties of the constituent
phases. Usually one phase (the matrix) is continuous and completely surrounds the other (the
dispersed phase). The properties of composites are a function of the properties of the constituent
phases, their relative amounts and the geometry of the dispersed phase.
There are a number of composites that occur in nature. For example wood consists of strong and
flexible cellulose fibers surrounded and held together by a stiffer material called lignin.
However, most are synthetic composites. One of the most common and familiar composites is
fiberglass, in which small glass fibers are embedded within a polymeric material (epoxy or
polyester). The glass fibers are relatively strong and stiff (but also brittle), whereas the polymer
is ductile. The plastic matrix holds the glass fibers together and also protects them from damage
by sharing out the forces acting on them. It is still widely used today for boat hulls, sports
equipment, building panels and many car bodies.
An optimum combination of properties is usually sought rather than one particular property, in
selecting a composite material. Eg. wings of an aircraft must be light weight and be strong, stiff
and tough. Several fiber-reinforced polymers possess this combination of properties. Adding
significant amounts of carbon black to natural rubber increases its strength drastically properties
of composite materials are determined by properties of composite materials are determined by
three factors.
i) The materials used as component phases in the composite
ii) The geometric shapes of the constituents and the resulting strength of the composite system
iii) The manner in which the phases interact with one another.
6.5.1 Classification of composites
Composites are classified according to the matrix material and the reinforcement geometry
(particles, fibers, layers). One simple scheme for the classification of composite materials is
shown below which consists of three main divisions.

36
I. Particle reinforced Properties are isotropic
 Large particle
 Dispersion strengthened
II. Fiber reinforced Properties can be isotropic or anisotropic
 Continuous (aligned)
 Discontinuous(short)-Aligned and Randomly oriented
III. Structural Based on build-up of sandwiches in layered form
 Laminates
 Sandwich panels
I. Particle reinforced :The dispersed phase for particle reinforced composites is equiaxed (i.e.
particle dimensions are approximately the same in all directions). Large particle and dispersion –
strengthened composites fall within this category. The distinction between these is based upon
reinforcement or strengthening mechanism. For most of the large particle reinforced composites,
the particulate phase is harder and stiffer than the matrix. In essence, the matrix transfers some of
the applied stress to the particles,which bear the friction of the load. For dispersion-strengthened
composites,particles are normally much smaller. In this the matrix bears the major portion of an
applied load,the small dispersed particles hinder the motion of dislocatins. Thus plastic
deformation is restricted such that yield and tensile strengths,as well as hardness improve.

37
II. Fiber reinforced : The most important composites are those in which the dispersed phase is
in the form of a fiber.The dispersed phase has the geometry of a fiber (large length to diameter
ratio). Design goals of fiber reinforced composites often include high strength and /or stiffness
on a weight basis.With these composites an applied load is transmitted to and distributed among
the fibres via the matrix phse. On the basis of diameter, fiber reinforcements are classified as
whiskers,fibres,or wires.Fiber orientation and concentration have a significant influence on the
strength and other properties of fiber reinforced composites.With respect to orientation, two
extremes are possible;i) a parallel allignment of the longiudinal axis of the fibres in a single
direction and ii) a totally random allignment.Continuous fibres are normally alligned whereas
discontinuous fibres may be alligned randomly oriented or partially oriented. Better overall
omposite properties are realized when the fiber distribution is uniform.

III. Structural : Structural composites are combinations of composites and homogeneous

materials, the properties of which depend not only on the properties of the constituent materials
but also on the geometrical design of the various structural elements. Laminar composites and
sandwich panels are two of the most common structural composites. The properties of laminar
composites are virtually isotropic in a 2-D plane. This is made possible with several sheets of a
highly anisotropic composite,which are cemented onto one another such that the high strength
direction is vareied with each successive layer. Sandwich panels consist of two strong and stiff
faces that are seperated by a core material or structure. These structures combine relatively high
strengths and stiffnesses with low densities.

38
6.5.2 Fabrication techniques for composite materials
There are numerous methods for fabrication of composite materials. Some methods include hand
lay-up,injection moulding,lamination,filament winding,or pultrusion techniques. Selection of a
method for a particular art will depend on the materials,the part designand end use or application.
The oldest method of composite manufacture is’ hand lay up. In it the resin is poured into a
mould or applied to the surface and then the fabric is rolled into the resin or applied to the
surface. This technique is used in boat building, auto repair and home projects because it
requires minimal equipment and the result cures at room temperature. Pultrusion is used for the
manufacture of components having continuous lengths and a constsnt cross sectional shape (i.e.
rods, tubes,beams). With this technique, a continuous fibre rovings or tows (a loose and
untwisted bundle of continuous fibres that are drawn together as parallel strands) are first
impregnated with a thermosetting resin. These are then pulled throgh a stel die that performs to
the desired shape and also establishes the resin/fibre ratio. Then the stock passes through a curing
die that is precision machined so as to impart the final shape. This die is also heated to initiate
curing of the resin matrix. A pulling device draws the stock through the dies and also
determines the production speed. By using centre mandrels or inserted hollow cores,tubes and
hollow sections are made possible. Pultrusion (RTM) is a continuous process that is easily
automated. Production rates are realatively high which makes it very cost effective. Moreover, a
wide variety of shapes are possible. Glass carbon and aramid fibres are principal reinforcement

39
sand normally added in concentrations between 40 and 70 volume percent. Polyesters, vinyl
esters and epoxy resins are commonly used matrix materials.
Resin tranfer moulding (RTM): This is a two piece matching cavity-mould system used for
moulding composites. The reinforcement material is placed in the mould cavity. A chopped mat
is often draped along the inside of the mould. The mould halves are clamped together and the
resin is introduced into the cavity. RTM offers fast curing times and is labour intensive than
other methods.

6.5.3 Advantages and disadvantages of composites

Advantages;
 They can be very strong and stiff, yet very light in weight. So ratios of strength to
weight and stiffness to weight are several times greater than steel or aluminum.
 Fatigue properties are generally better than for common engineering metals.
 Toughness is often greater
 They can be designed such that they do not corrode like steel
 Possible to achieve combinations of properties not attainable with metals,
ceramics, polymers alone.
Drawbacks;
 They are often more expensive than conventional materials and the manufacturing
methods for shaping composite materials are often slow.
 Many of the polymer based composites are subject to attack by chemicals or
solvents.
 Properties of many important composites are anisotropic.
6.5.4 Polymer composites
Composite is any material that is made out of any two materials being put together with a
defined interface. Generally polymer composites are combinations of two polymers in which one

40
of the materials called reinforcing filler phase is in the form of fibres, sheets or particles and is
embedded in the other materials called the matrix phase. The reinforcing material and matrix
material can be metal, ceramic or polymer. Typically reinforcing materials are strong with low
densities while the matrix is usually a ductile or tough material. A polymer composite is a
material made of two or more types of polymers, but they are not chemically joined the way that
as in copolymers are, instead polymer composites have a defined interface between the
polymers.
Materials used in polymer composites: Composites are made of two components, a fibre and
matrix. The fibre is most often glass, carbon fibre, or polyethylene. The matrix is usually a
thermoset polymer like epoxy resin, polydicyclopentadiene or a polyimide. The fibre is
embedded in the matrix in order to make the matrix stronger. Fibre reinforced composites impart
two important properties. They are often stronger than steel, but weight much less. This means
that composites can be used to make automobiles lighter, and thus much more fuel efficient.
The materials generally used are:
Fibers - Glass fibres, carbon fibres or aromatic polymides (or aramids).
Resins: (a) thermosetting: polyesters and epoxides.
(b) thermoplastics: polyolefins, polyimides, vinylic polymers, polyacetals,
polycarbonates and polyphenylenes.
Additives: For structural applications it is mandatory to achieve some degree of flame retardancy.
FR additives are incorporated in the resin itself. Fillers and pigments are also used in the process.
Advantages of polymer composites:
-Light weight.
-High strength to weight ratio.
-More durable than conventional materials like steel and aluminium.
-Good corrosion resistance.
-High fatigue strength.
-High temperature resistance.
Applications:
-Composites of phenolic resins and nylon are used in heat shields for space crafts.
-Which are used in automotive and railway applications.
-As structural material in construction industries.

41
Examples of polymer composites:
(i)Fibre glass or glass-reinforced plastic (GRP):
A common fibre reinforced composite is fibreglass. It’s matrix is made by reacting a polyester
with carbon-carbon double bonds in its backbone and styrene- a mix of the styrene and polyester
over a mass of glass fibres.
O
CH2

O +
O Cross linked resin
O n

The styrene and double bonds in the polyester react by free radical polymerization to form a
cross linked resin. The glass fibre are trapped inside, where they act as a reinforcement. The
matrix adds toughness to the composite, while fibres have good tensile strength. The matrix
gives compressional strength to the composite. Fibre reinforced composites are used in
applications like car engine components, aeroplane parts to boat hulls.
(ii) Kevlar composites:
Kevlar is an aromatic polyimide (or aramid). The chemical composition of Kevlar is poly(para
phenyleneterephthalamide). They belong to the family of nylons. Common nylons, such as
nylon-6,6 do not have very good structural properties, so the incorporation of para-aramids
improve the properties. The aramid ring gives Kevlar its thermal stability, while the para
structure gives it high strength and modulus. Kevlar is used as matrix material where as many
fibres like carbon fibre or glass fibre is used as reinforcing agent.
O

NH
NH

n
O

Advantages:
-Light weight, high strength, thermally stable
-Resistant to impact and abrasion damage. It can be used as protective layer on graphite
laminates.
-Can be mixed with graphite to provide damage resistance and to prevent failure.
Disadvantages:

42
-Fibres themselves absorb moisture, so Kevlar composites are more sensitive to the environment
than glass or graphite composites.
-Poor compression resistance.
(iii) Carbon fibre composites: They are new class of high strength composite materials. Carbon
fibre is a fibre containing at least 90 % carbon obtained by controlled pyrolysis of appropriate
fibres. A large variety of fibres called precursors are used to produce carbon fibres of different
morphologies and characteristics. The important precursors used are polyacrylonitrile, cellulosic
fibres or phenolic fibres. The matrix material can be epoxy resin, phenolics, polyester or
polyvinyls.
6.5.5 Superconductors
Superconductivity is the property of complete disappearance of electrical resistance in solids
when they are cooled below a characteristic temperature. This temperature is called transition
temperature or critical temperature.
Property of superconductor: The important property of the superconductor is Meissner effect.
Superconductors above its critical temperature, Tc. is in a normal conducting state and have
electrical resistance. When magnetic field (B) is applied, it penetrates through the material. But
when superconductor is cooled below its critical temperature the superconductor expels the
magnetic field from inside it. This effect is known as Meissner effect. The energy needed by the
superconductor to expel the magnetic field comes from the exothermic superconducting
transition. The superconductor returns to its initial state when the field is removed.

Meissner effect

43
Types of superconductors: High magnetic fields destroy superconductivity and restore the
normal conducting state. Depending on the character of this transition, superconductors are
classified into type I and II superconductors.
Type 1 Superconductors: In some superconductors internal field is zero (as expected from the
Meissner effect) until a critical magnetic field, Bc, is reached where a sudden transition to the
normal state occurs. This results in the penetration of the applied field into the interior as shown
in figure 4. Superconductors that undergo this abrupt transition to the normal state above a
critical magnetic field are known as type I superconductors.

Type 1 superconductor
Examples: Hg, Al
Type II Superconductors: They respond differently to an applied magnetic field. (shown in
Figure 4). An increasing field from zero results in two critical fields, Bc1 and Bc2. At Bc1 the
applied field begins to partially penetrate the interior of the superconductor. However, the
superconductivity is maintained at this point. The superconductivity vanishes above the second,
much higher, critical field, Bc2. For applied fields between Bc1 and Bc2, the applied field is able
to partially penetrate the superconductor, so the Meissner effect is incomplete, allowing the
superconductor to tolerate very high magnetic fields.

Type 11 superconductor
44
Example:-YBa2Cu3O7
High temperature superconductor: High temperature superconductors which were discovered
in 1980 will exhibit superconducting properties at much higher temperatures than that of liquid
nitrogen. One of the most popular high temperature superconductor is Yttrium Barium Copper
Oxide (YBCO). Yttrium Barium oxide commonly termed as 123. The oxide is prepared by
heating compacted powder mixtures of Y2O3, BaCO3and CuO in the right proportion to
temperatures between 900 to 1100 °C as shown in reaction below.

BaCO3 decomposes at this temperature to BaO and CO2. This is often followed by another
annealing treatment at 800 °C in the atmosphere of oxygen. The crystal structure of the powder
product obtained is related to the cubic perovskite is shown in figure 5. Three body centred cubic
unit cells are stacked one above another and the lattice type is either tetragonal or orthorhombic,
depending on the oxygen content. The central perovskite cell contains an Y atom, sandwiched
between CuO2 planes. Adjacent to the CuO2 planes are layers of BaO2 and at the top and bottom
of the cell there are Cu-O chains which have variable oxygen content, dependent upon the
overall oxygenation level of the material. The atom distributions in the unit cells are as follows.
Cu at the body corners 8×1/8×3 = 3
Ba at two body centers 1×2 = 2
Y at one body center 1×1 = 1
O at mid points of edges 12×1/4×3 = 9
Some oxygen positions are vacant such that their number is between 6.5 and 7. The
superconducting properties appear to be a function of the oxygen content and therefore of the
partial pressure of oxygen during heat treatment. The superconducting properties of
YBa2Cu3O7−x are sensitive to the value of x, its oxygen content. Only those materials with 0 ≤ x ≤
0.65 are superconducting below Tc, and when x ~ 0.07 the material conducts at the highest
temperature of 95 K.

45
Crystal structure of Yttrium Barium Copper Oxide.

Applications of superconductors
1) In magnetic resonance imaging (MRI)
2) In superconducting quantum interference devices (SQUID).
3) Involving high magnetic field electromagnets
6.6 Biomaterials
A biomaterial is any material, natural or man-made, that comprises whole or part of a living
structure or biomedical device which performs, augments, or replaces a natural function. Bio
materials can have a benign function, or may be bioactive and used for a more interactive
purpose, dental applications, surgery, and drug delivery. It is a synthetic material which can be
used to replace part of a living system or to function in intimate contact with living tissue. The
material might have a therapeutic use, for example, in the treatment of an injury or disease or it
might have a diagnostic use, as art of a system for identifying a disease or for monitoring a
quantity such as the glucose level in blood. Biomaterials are rarely used on their own but are
more commonly integrated into devices or implants. Thus, the subject cannot be explored
without also considering biomedical devices and the biological response to them. Biomaterials
can be metals, ceramics, polymers, glasses, carbons, and composite materials. Such materials are
used as molded or machined parts, coatings, fibers, films, foams and fabrics. The biomaterial is
in contact with biological fluids and this material must have properties that meet the demands of
a particular application. For example, a polymer employed to form a disposable contact lens

46
must be soft and have an easily wetted surface, whereas polymer used to fill a dental cavity must
be hard and wear resistant.
6.6.1 Classification of Biomaterials:
(a) Based on materials used
(i) Polymers: Nylon , Silicones, Teflon, Dacron
(ii) Metals: Titanium, Stainless steels, Co-Cr alloys , Gold
(iii) Ceramics: Aluminum oxide, Carbon, Hydroxyapatite
(iv) Composites: Carbon-carbon
(b) Based on the interaction with biological system
(i) Inert biomaterials: resistance to chemical or biological degradation
(ii) Bioactive materials: slight interaction (positive response)
(iii) Biodegradable biomaterials: intended to dissolve or to be absorbed in vivo
Polymeric Biomaterials: The major requirements of polymeric biomaterials are
biocompatibility, sterilisability, adequate mechanical and physical properties, and
manufacturability. The main advantages of the polymeric biomaterials compared to metal or
ceramic materials are ease of manufacture to produce various shapes (latex, film, sheet and
fibers), ease of secondary processability, reasonable cost, and availability with desired
mechanical and physical properties. Important biomedical applications of synthetic polymeric
biomaterials are:
(i) Polyvinylchloride: Blood and solution bag, surgical packaging, dialysis devices,
catheters and connectors.
(ii) Polyethylene: Pharmaceutical bottle, nonwoven fabric, catheter, pouch, flexible
container, and orthopedic implants.
(iii) Polypropylene: Disposable syringes, blood oxygenator membrane, suture, nonwoven
fabric, and artificial vascular grafts.
(iv) Polymethylmetacrylate: Blood pump and reservoirs, membrane for blood dialyzer,
implantable ocular lens, and bone cement.
Metallic Biomaterials: The first metal alloy developed specifically for human use was the
“vanadium steel” It was used to manufacture bone fracture plates and screws. Most metals Fe,
Cr, Co, Ni, Ti, Ta, Nb, Mo & W are used to make alloys for manufacturing implants. However,
they can be tolerated by the body only in minute amounts. The biocompatibility of the metallic

47
implant is of considerable concern because these implants can corrode in an in vivo environment.
The consequences of corrosion are the disintegration of the implant material per se, which will
weaken the implant, and the harmful effect of corrosion products on the surrounding tissues and
organs.
Ceramic Biomaterials: Ceramic biomaterials are generally hard. They should be non-toxic, non-
carcinogenic, non-allergic, non-inflammatory and biocompatible, Ceramics used in fabricating
implants can be classified as non-absorbable (relatively inert), bioactive or surface reactive
(semi-inert) and biodegradable or resorbable (non-inert). Alumina, zirconia, silicone nitrides, and
carbons are inert bio-ceramics. Certain glass ceramics and dense hydroxyapatites are semi-inert
(bio-reactive), and calcium phosphates and calcium aluminates are resorbable ceramics.
Composite Biomaterials: When composite material is used as biomaterials, it is important that
each constituent of the composite be biocompatible. Moreover, the interface between
constituents should not be degraded by the body environment. Major uses of composites in
biomaterial applications are in dental filling composites, reinforced methyl methacrylate bone
cement and ultra-high-molecular-weight polyethylene, and orthopedic implants with porous
surfaces. Moisture absorption by polymer constituents also causes swelling. Such swelling can
be beneficial in dental composites since it offsets some of the shrinkage due to polymerization.
Flexible composite bone plates are effective in promoting healing but particulate debris from
composite bone.
6.6.2 Characteristics of Biomaterials
The most important choice of biomaterial involves the following characteristics:
1. Biocompatibility, 2. Physical requirements and 3. Chemical requirements
1. Biocompatibility: Higher animals have a complex set of protections against invasions of other
organisms. Any substance that is foreign to the body has potential to generate a response from
our immune system. Molecular sized objects are bound by antibodies and rejected whereas larger
objects induce an inflammatory reaction around them. Biocompatible materials are more readily
integrated into the body without inflammatory reactions.
2. Physical requirements: A biomaterial is often required to meet certain physical demands.
Tubing to be used to replace a defective blood vessel must be flexible and must not collapse
under bending or other distortions. Materials used in joint replacements must be wear resistant.

48
An artificial heart valve must open and close 70 to 80 times a minute, day after day, for many
years. Failure of the heart valve may have fatal consequences for its owner.
3. Chemical requirements: They must be “medical grade”. They must be approved for use in
any particular medical application. Polymer biomaterials contain contaminants such as unreacted
monomers, traces of catalyst used to effect polymerization, fillers or plasticizers and anti-
oxidants. The small amounts foreign materials present in a polymer used as a milk carton pose
no threat in that application but, if the same plastic material if implanted in the body over a long
period, there is a risk involved.
6.6.3 Examples of biomaterial applications
Vascular grafting: Tube-shaped synthetic material surgically implanted in the veins and arteries
are known as vascular grafts. It is a replacement for a sequent of diseased arteries. When taking
the vessels from the patient's own body is not feasible, artificial materials must be used. Dacron
is used as replacement for large diameter arteries around the heart. It is fabricated into a crimped,
woven, tubular form. The graft must integrate with surrounding tissue, after it has been put in
place. It should have an open structure with pores of ~10mm diameter. During the healing
process blood capillaries goes into the graft and new tissues form through it. Similarly, PTFE is
used for the smaller diameter vascular grafts in the limits.
Artificial tissue: The treatment of patients who have lost extensive tissue, for example, burn
patients or those with skin ulcers is one of the most difficult problems. Today, lab-grown skin
can be used to replace grafts in such patients. In such cases, steps must be taken to prevent
rejection of the tissue. To organize the cells, suitable scaffolds such as lactic acid-glycolic acid
co-polymers have been provided. The polymer is formed by condensation reaction.
n HOCH2COOH + n HOCH(CHO)COOH -O-CH2-COO-[CH(CHO)-COO-CH2-COO]n
glycolic acid lactic acid co-polymer
The co-polymer has plenty of polar C-O bonds along the chain and thus provides opportunity for
hydrogen bonds interaction. The ester linkages formed in the condensation reaction are
susceptible to hydrolysis, which is just the reverse reaction. When the artificial tissue is placed in
the underlying co-polymer scaffold slowly hydrolyses away as the tissue cells continue to
develop and merge with adjacent tissue.
Hip replacement: A hip joint replacement is designed to provide joint mobility and structural
support. The biomaterial used must be stable under considerable load, have high fatigue

49
resistance, abrasion resistance and biocompatibility. The components of a modern hip joint
replacement include a metal ball, formed from a hard, corrosion resistant metal alloy, usually
cobalt chromium. The highly polished ball is attached to a titanium alloy stem that fits into the
femur, which has been cut and drilled. The cup, which receives the ball is lined with high
molecular weight polyethylene.
Advantages & disadvantages of biomaterials
Materials Advantages Disadvantages Examples
Polymers: Resilient Not strong Sutures, blood
Nylon Easy to fabricate Deform with time vessels, hip socket,
Silicones May degrade ear,
Teflon nose, other
Dacron soft tissues
Metals Strong, May corrode Joint replacement,
Titanium tough Dense bone plates and
Stainless steels Ductile screws, dental
Co-Cr alloys root implants
Gold
Ceramics Biocompatible Brittle Dental; hip socket
Aluminum oxide inert Difficult to make
Carbon Strong in compression Not resilient
Hydroxyapatite
Composites Strong, tailor-made Difficult to make Joint implants;
Carbon-carbon heart valves

6.7 Thin films

A thin film, in general refers to films with thickness ranging from 0.1µm to about 300µm.
Coatings such as paint or varnish are typically much thicker. Thin films coatings have unique
properties and hence make them desirable for a variety of reasons including materials
conservation and design flexibility. A large number of materials which are used for coatings
today range from the naturally occurring oxide layer which protects the surfaces of many metals

50
such as aluminum, titanium, and stainless steel, to those with very deliberate and controlled
alloying additions to the surface to produce specific properties as follows;
 Chemically stable in the environment where it is used
 Adhere well to the substrate
 Uniform thickness
 Chemically pure or of controlled chemical composition
 Low density of imperfections
 Optical or magnetic properties, insulator or semiconductor as required for
particular applications
As the film is inherently fragile, the bonding between the thin film and substrate provides
the structural support. The bonding forces may be primary chemical in nature. Eg. The oxide
lattices of the metal oxide and the glass blend at the interface forming a thin zone of intermediate
composition. The bonding energies are in the range of 250 - 400 kJ/mol. In some cases, the
bonds are based on intermolecular van der Waals and electrostatic forces. The energies are in the
range of 50-100 kJ/mol. Eg. Deposition of polymer film on a metal surface
6.7.1 Uses of thin films
They are used as conductors, resistors and capacitors. They are widely used as optical
coatings on lenses to reduce reflection and to protect the softer glass against scratching. Thin
metallic films have been used as protective coatings on metals. Eg. Silver plating, chrome
plating. Metal tool surfaces are coated with ceramic thin films to increase their hardness. The top
of the drill bit is normally coated with a thin film of tungsten carbide to impart hardness and
wear resistance. The films are applied to the glass to reduce scratching and abrasion and to
increase lubricity.
6.7.2 Formation of thin films
The process of applying a thin film to a surface is known as thin-film deposition or
fabrication. It is the technique for depositing a thin film of material onto a substrate or onto
previously deposited layers. Thin films are formed by different techniques such as physical vapor
deposition (PVD) or chemical vapor deposition (CVD). When the vapor source is a liquid or
solid, the process is called physical vapor deposition (PVD). When the vapor source is a
chemical vapor precursor the process is called chemical vapor deposition (CVD).

51
Physical vapor deposition
PVD processes are atomistic deposition processes in which material is vaporized to form a solid
or liquid source in the form of atoms or molecules, transported as vapor through a vacuum or low
pressure gaseous (or plasma) environment to the substrate where it condenses. The material to be
deposited is placed in an energetic, entropic environment, so that particles of material escape its
surface. Facing this source is a cooler surface which draws energy from these particles as they
arrive, allowing them to form a solid layer. The whole system is kept in a vacuum deposition
chamber, to allow the particles to travel as freely as possible. Since particles tend to follow a
straight path, films deposited by physical means are commonly directional, rather than
conformal.
Typically, PVD processes are used to deposit films with thicknesses in the range of a few
nanometers to thousands of nanometers. The substrates can range in size from very small to very
large, in shape from flat to complex geometries. The source-substrate geometry influences the
ultimate film uniformity. Two principal methods for optimizing film uniformity over large areas
involve varying the geometric location of the source and interposing static as well as rotating
shutters between evaporation sources and substrates. The chemical purity of evaporated films
depends on the nature and level of impurities that (1) are initially present in the source, (2)
contaminate the source from the heater, crucible, or support materials, and (3) originate from the
residual gases present in the vacuum system. Typical PVD deposition rates are 10-100 A0/s.

Fig. PVD: Process flow diagram

Vacuum evaporation and sputtering are the two most important methods for depositing thin films
using PVD technique. In evaporation, atoms are removed from the source by thermal means,
whereas in sputtering they are dislodged from solid target (source) surfaces through impact of
gaseous ions.

52
Vacuum deposition: This method is used to form thin films of substances that can be vaporized
without destroying their chemical identities. Eg. Optical lenses are coated with inorganic
materials such as MgF2, Al2O3 and SiO2. During evaporation, a target consisting of the material
to be deposited is bombarded by a high energy source such as a beam of electrons or ions in a
high vacuum chamber with a pressure of 10-5 torr or less. This dislodges atoms from the surface
of the target, ‘vaporizing’ them. Vaporized atoms from the target move in a straight path to the
substrate to be coated. Finally the metal atoms get deposited on the substrate surface mounted at
an appreciable distance away from the evaporation source. Uniformity is obtained by rotating the
substrate to be coated.

Fig. Schematic diagram of vacuum deposition

The vacuum environment may serve the following purposes by providing low pressure plasma
environment, a means for controlling gas and vapor composition and a means for mass flow
control into the processing chamber. And reducing the particle density of undesirable atoms and
molecules (contaminants) so that the mean free path for collision is long
Sputter deposition: This method involves the use of a high voltage to remove material from a
source or target. Atoms removed from the target are carried through the ionized gas within the
chamber and deposited on the substrate. The target surface is the negative electrode or cathode in
the circuit and the substrate is attached to the positive electrode or anode. The chamber contains
an inert gas such as argon that is ionized in the high voltage field. The positively charged ions
(Ar+) are accelerated towards the negatively charged target surface. Upon impact they knock
atom (m) of the target material. These atoms travel in all directions with high kinetic energy and
some of them strike the substrate and form a thin film. Sputtering is widely used to form thin
film of elements such as Si, Ti, Nb, W, Al, Au and Ag and refractory materials such as carbides,
borides and nitrides on metal tool surfaces. The manufacturing of all formats of CD, DVD, and

53
BD are done with the help of this technique. It is a fast technique and also it provides a good
thickness control.

Fig.3: Schematic diagram of sputtering apparatus

Advantages:
• PVD coatings are harder and more corrosion resistant than coatings applied by the
electroplating process. Most coatings have high temperature and good impact strength, excellent
abrasion resistance and are so durable that protective topcoats are almost never necessary.
• Ability to utilize several types of inorganic and organic coating materials on diverse group of
substrates using a wide variety of finishes.
• More environmentally friendly than traditional coating processes such as electroplating and
painting.
• It is possible to change the target material from which the sputtered atoms arise without
disturbing the system so that multilayer films can be formed.
Disadvantages:
 It is a line of sight technique meaning that it is extremely difficult to coat undercuts and
similar surface features
 High capital cost
 Some processes operate at high vacuums and temperatures, require skilled operators
 Processes involving large amount of heat requires appropriate cooling systems
 The rate of coating deposition is usually quite slow

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Chemical Vapor Deposition (CVD)
In this method the surface is coated with a volatile, stable chemical compound at a
temperature below the melting point of the surface. It involves the dissociation and /or chemical
reactions of gaseous reactants in an activated (heat, light, plasma) environment, followed by the
formation of a stable solid product. The deposition involves homogenous gas phase reactions,
which occur in the gas phase, and/or heterogeneous chemical reactions which occur on/near the
vicinity of a heated surface leading to the formation of powders or films, respectively. It has
been used to produce ultrafine powders and thin films.
In general, the CVD equipment consists of three main components:
(a) Chemical vapor precursor supply system: to generate vapor and deliver to the reactor.
(b) CVD reactor component: consists of a reaction chamber equipped with a load-lock for
the transport and placement of the substrate into the chamber, a substrate holder, and a
heating system with temperature control. The main function is to heat the substrate to the
deposition temperature.
(c) Effluent gas handling system: This component consists of a neutralizing part for the
downstream gases, and /or a vacuum system to provide the required reduced pressure for
the CVD process.
Process principles and deposition mechanism: CVD process involves the following key steps:
1. Generation of active gaseous reactant species
2. Transport of these gaseous species into the reaction chamber.
3. Gaseous reactants undergo gas phase reactions forming intermediate species.
(a) At a high temperature above the decomposition temperatures of intermediate species
inside the reactor, homogeneous gas phase reaction can occur where the intermediate
species undergo subsequent decomposition and/or chemical reaction, forming
powders and volatile by-products and the by-products are transported away from the
decomposition chamber.
(b) At temperatures below the dissociation of the intermediate phase,
diffusion/convection of the intermediate species across the boundary layer (a thin
layer close to the substrate surface) occur. These intermediate species subsequently
undergo steps (4-7)

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 4. Absorption of gaseous reactants on to the heated substrate, and the heterogeneous
reaction occurs at the gas-solid interface (i.e. heated surface) which produces the deposit
and by-product species.
5. The deposits will diffuse along the heated substrate surface forming the crystallization
center and growth of the film takes place.
6. Gaseous by-products are removed from the boundary layer through diffusion or
convection.
7. The unreacted gaseous precursors and by-products will be transported away from the
deposition chamber.
Examples: Titanium tetrabromide is evaporated and the gaseous TiBr4 is mixed with hydrogen.
The mixture is then passed over a substrate heated to about 1300 °C, such as silica or alumina.
The metal halide undergoes reaction with hydrogen to form a thin film of titanium metal
TiBr4(g) + 2H2(g) Ti(s) + 4HBr(g)
Films of silicon are formed by decomposing SiCl4 in the presence of H2 at 1200 °C.
SiCl4(g) + 2H2(g) Si(s) + 4HCl(g)

Fig. Schematic diagram of simplified CVD setup

Advantages
 Capable of producing highly dense and pure materials devoid of carbon or oxygen
impurities.
 Produces uniform films with good reproducibility and adhesion at reasonably high
deposition rates.
 Has good throwing power and hence can be used to uniformly coat complex shaped
components and deposit films with good conformal coverage.

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  Able to control crystal structure, surface morphology and orientation of the products by
controlling the process parameters.
 Deposition rate can be adjusted readily. Low deposition rate is favoured for the growth of
epitaxial thin films for microelectronic applications. The deposition of thick protective
coatings is favored by a high deposition rate.
 Reasonable processing cost using CVD technique.
 Flexibility of using a wide range of chemical precursors such as nitrides, borides,
organometallics which enable the deposition of a large spectrum of materials including
metal carbides, nitrides, oxides and sulfides.
 Relatively low deposition temperatures and the desired phases can be deposited in-situ at
low energies.
Drawbacks
 Chemical and safety hazards caused by the use of toxic, corrosive, flammable and/or
explosive precursor gases.
 Difficult to deposit multicomponent materials with well controlled stoichiometry using
multisource precursors because different precursors have different vaporization rates.
 The use of more sophisticated reactor and /or vacuum system by CVD variants such as
low pressure or ultrahigh vacuum CVD, plasma assisted CVD and photo-assisted CVD
tends to increase the cost of fabrication.
Applications:
 Production of high quality optical fibers suitable for long distance applications.
 Diamond thin films: They are used as heat sinks for microelectronics and opto-
electronics, sensors, microwave devices, coatings for IR windows in nuclear detectors,
UV imaging, cold cathodes. The potential applications of diamond films involve speaker
diaphragms which are coated with thin films of diamond to provide improved acoustic
properties.

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6.7.3 Comparison between PVD & CVD
Features PVD CVD
Vacuum evaporation sputtering
Mechanism of Thermal energy Momentum transfer Chemical reaction
deposition
Deposition rate High Low except for pure Moderate
metals
Deposited species Atoms & ions Atoms & ions Precursor molecules
dissociate into atoms
Energy of deposited Low (0.1-0.5 eV) Can be high ( 1-100 Low; can be high with
species eV) plasma-assisted CVD
Throwing power Poor Poor Good

6.8 Nano-materials
Nanoscience and nanotechnology deal with objects that have dimensions in the range from 1 nm
to about 100 nm. Nano-materials are materials which have at least one of their dimension in the
nanometer (1 nm= 10−9 m) range. The physical and chemical properties of nano-materials differ
significantly from those of their bulk counterparts. These new properties result because the ratio
of surface area to volume is now so large that surface effects such as those that give rise to
catalysis, adsorption and adhesion and photonic effects enter a new level because electrons are
confined within such a small volume that quantum effects now dominate optical and electronic
behavior. Nano-fibres, nano-wires, nano-scale particles, Nano-channels and nano-tubes are some
of the important nanostructures. The nano-science field is progressing so rapidly that it is
probably hard to find any technical areas that are not useful.
The most important aspects of this field are connected with four issues;
i) Way in which nanoparticles interact with their neighbours in solid arrays or with a
second phase in composite materials.
ii) Miniaturization of electronic circuits below the micro-scale to pack an increasing
number of features into an integrated array.
iii) Development of methods to produce nano-fibers that are of interest in geological
tissue engineering, advanced textiles and filtration technology.

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 iv) Use of micelles with diameters in the nano range for controlled drug delivery.
6.8.1 Classification
(a) Based on origin
(i) Natural nanomaterials (ii) Artificial nanomaterials
Natural nanomaterials are those which are obtained naturally. Examples:- Carbon-nanotubes
and fibers. Artificial nanomaterials are those which are synthesized artificially Examples:-
Au/Ag nanoparticles, Polymeric nano-composites.
(b) Based on dimension
This classification is based on the number of dimensions which are not confined to the nanoscale
range (<100nm). They may be amorphous or crystalline, single crystalline or polycrystalline,
made up of one or more elements, metallic, ceramics or polymers.
(i) Zero dimensional: Materials wherein all the dimensions are within the nanoscale range are
called zero dimensional nano material. Eg : quantum dots.
(ii) 1 dimensional: Here two dimensions are at nanoscale range, other dimension is not. This
leads to needle like shaped nanomaterials. Eg: nanotubes, nanorods, nanowires.
(iii) 2 dimensional: Here one dimension is at nanoscale range, other two dimensions are not.
They exhibit plate like shapes. Eg : nanocoatings, nanofilms
(iv) 3 dimensional: These materials are not confined to the nanoscale in any dimension. These
are characterized by having three arbitrarily dimensions above 100 nm. They are also known as
bulk nanomaterials. 3-D nano materials can contain dispersions of nanoparticles, bundles of nano
wires/ nanotubes as well as multilayers. Eg : Nanocrystalline materials, nanospheres.
There are other types of classifications based on their field of application, shapes, properties,
structures, manufacturing process and morphologies.
6.8.2 Preparation of nano-materials:
Nanomaterials can be synthesised by two different approaches. They are “Bottom up” and “Top
down methods”. Top-down methods start with micro – or macroscale materials, which are then
broken down chemicals or physically to nanoparticles. Methods that are used include ball
milling, chemical etching, electrospinning and the vaporization of metals using plasmas or high
energy because they are not cheap, slow and not suitable for large scale production. Bottom up
methods involve the assembly of very small units (atoms, molecules or small nanoparticles) to
create larger nanomaterials and systems. The fabrication is much less expensive.

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“Bottom up” Approach:
(i) Vapor deposition: It refers to any process in which materials in the vapour state are
condensed through chemical reactions or conversion to form a solid material. There are two
types of vapor deposition process. They are Physical vapor deposition and chemical vapor
deposition process.
(a) Physical vapor deposition process ( PVD)
This approach is used to make metallic or metal oxide ceramic nanoparticles. It involves
evaporation of solid metal followed by rapid condensation to form nanosized clusters that settle
in the form of a powder. Various approaches to vaporize the metal can be used and variation of
the medium into which the vapor is released affects the nature and size of the particles. Inert
gases are used to prevent oxidation when creating metal nanoparticles, whereas a reactive
oxygen atmosphere is used to produce metal oxide ceramic nanoparticles. The main advantage of
this approach is low contamination levels. Final particle size is controlled by variation of
parameters such as temperature, gas environment and evaporation rate.
Melting cooling nanoparticles
Material Reactive gas
Precursor Evaporation molecular clusters

(b) Chemical vapour deposition (CVD)

In this process, the precursor gases are delivered to the reaction chambers at low temperatures.
Chemical reactions occur on and/or near the heated substrate, resulting in the deposition of a thin
film on the surface. (Refer 6.7.4)

Source gas
Adsorption, diffusion, deposition
Thin films on
substrate

(ii) Chemical synthesis

a) Sol-gel method
The sol-gel process is a wet-chemical technique used primarily for the fabrication of materials
starting from a chemical solution which acts as the precursor for an integrated network (or gel) of
either discrete particles or network polymers. The process usually consists of five steps:

60
 1. Preparation of a precursor solution: The desired colloidal particles are dispersed in a
liquid to form a sol. Typical precursors are metal alkoxides, which undergo various forms
of hydrolysis and poly-condensation reactions. The formation of a metal oxide involves
connecting the metal centres with oxo (M-O-M) or hydroxo (M-OH-M) bridges,
therefore generating metal-oxo or metal-hydroxo polymers in solution. We have to adjust
reaction conditions to control surface area, density, porosity and pore size.
2. Deposition of the sol onto a substrate: The sol solution is coated on a substrate by
spraying, dipping or spinning.
3. Formation of gel: The particles in the solid state are polymerised through the removal of
the stabilizing components. This can be done either by heating the sol at a low
temperature or allowing it to stand for certain duration. This results in the formation of a
three dimensional continuous gel.
4. Drying process: Removal of the remaining liquid (solvent) phase requires a drying
process, which is typically accompanied by a significant amount of shrinkage and
densification. The rate at which the solvent can be evaporated or extracted is ultimately
determined by the distribution of porosity in the gel. The ultimate microstructure of the
final component will clearly be strongly influenced by changes imposed upon the
structural template during this phase of processing.
5. Heat Treatment: After drying, a thermal treatment, or firing process, is often necessary to
favor further poly-condensation and enhance mechanical properties and structural
stability via final sintering, densification and grain growth.
The sol-gel approach is a cheap and low temperature technique that allows for the fine
control of the product’s chemical composition. Even small quantities of dopants, such as organic
dyes and rare earth elements, can be introduced in the sol and end up uniformly dispersed in the
final product. It can use used as a means of producing very thin films of metal oxides for various
purposes. Examples include Gallium based nano-materials, Dye-doped gel Glasses, Glass
dispersed liquid crystals, Synthesis of glass-metal nano-composite, Metal-silica and Metal oxide-
silica nanocomposites.
b) Reduction method
Metallic colloidal particles can be produced by reducing metal salts in solution by reagents such
as formaldehyde. The size of the nanoparticle controls the color of the colloids produced.

61
Semiconductor nanoparticles have been produced by allowing a waste-soluble Cd salt to react
with sodium nitride in a polymer matrix which controls diffusion.
(iii) Electro-deposition
Electro-deposition has been used for a long time to make electroplated materials on a conducting
substrate. Ions in solution are deposited onto the negatively changed cathode. The process in
relatively cheap and fast and allows complex sharps. The layer thickness depends on the current
density and the time for which the current flows. This method is used in the deposition of metal
oxides and chalcogenides. By carefully controlling the number of electrons transferred, the
weight of material transferred can be determined in accordance with Faraday’s law of
electrolysis.

Electro deposition can be carried out by either electroplating or electroless plating or multilayer
plating technique. The fact that electrochemical deposition, also being an atomic deposition
process, can be used to synthesize nanocomposites, has generated a great deal of interest in
recent years.
“Top Down” Approach:
(i) Ball milling
In this process, small balls are allowed to rotate around the inside of a drum and drop with
gravity force on to a solid enclosed in the drum. The significant advantage of this method is that
it can be readily implemented commercially. The grinding of ceramics can reduce them to a fine
powder with each individual particle having nanoscale dimensions. It is difficult to avoid
contamination of the nanoparticles by the materials used in the abrasion process and the particle
sizes are not uniform. Polymers cannot be reduced to nanoparticles by grinding because their

62
molecular structure and their impact resistance. Ball milling can be used to make a variety of
new carbon types, including carbon nanotubes. It is useful for preparing other types of
nanotubes, such as boron nitride nanotubes and a wide range of elemental and oxide powders.
For example, iron with grain sizes of 13-30 nm can be formed. Ball milling is the preferred
method for preparing metal oxides.
To successfully prepare metal oxides, it is important to keep the crystallites from reacting, and to
have an understanding of the kinetic energy transferred during crushing. Much of the commercial
know how is in the nature of the additive. However, a by-product can sometimes be useful. In the
production of naocrystalline Zirconia (ZrO2), zirconium chloride is treated with magnesium
oxide during milling to form zirconia and magnesium chloride:
ZrCl4 + 2MgO ZrO2 + 2MgCl2
The by-product, magnesium chloride, acts to prevent the individual nanocrystallites of zirconia
agglomerating. It is washed out at the end of the process.
(ii) Solution combustion method
In this method, metal nitrates (oxidizer) are mixed with organic compounds such as urea,
hydrazine, glycine (fuel) in water. The water is evaporated by boiling, and when sufficiently dry,
the remaining slurry self-ignites to produce very fine metal oxide powder. The reaction is very
rapid and short reaction time limits the crystal growth.
Metal nitrates (aq) + Fuel (aq) - combustion products (s) + heat + gases
6M(NO3)3 + 10 H2NCH2COOH + 18O2→ 3M2O3 + 20CO2 + 25H2O + 5N2 + 18NO2
Solution combustion is a self-propagating process in which exothermic reaction takes place with
evolution of gases. The advantages of this method include the following –
i) The synthetic temperature (350 0C) used is lower than that used in conventional
methods.
ii) Ability to dope desired amounts of impurities with better homogeneity.
iii) The powders are voluminous, foamy and have larger surface area.
iv) Apparatus required is simple fast and inexpensive method
6.8.3 Nanoscale particles
When particle sizes of solid matter are created with nano-dimensions, quantum effects rule
the behavior and properties of particles and the materials’ properties change significantly from
those at larger scales. Physical properties (melting point, boiling point, resistivity, permittivity),

63
chemical properties (fluorescence, reactivity, reaction rates), mechanical properties (hardness,
stress/strain, abrasion, wear resistance), electrical conductivity, magnetic permeability and
optical (color, optical density, refractive index) properties change as a function of the size of the
particle. The four important ways in which nanoscale materials may differ from bulk are
 Electromagnetic forces begin to dominate at nanoscale.
 Quantum mechanics has to be used to describe motion and energy instead of classical
mechanics.
 Greater surface to volume ratios.
 Random molecular motion becomes predominant.
At the nanoscale, particle-particle interactions are either dominated by weak Van der Waals
forces, stronger electrostatic interactions or covalent interactions. The interaction forces, either
attractive or repulsive, crucially determine the fate of individual and collective nanoparticles.The
particle stabilization vs aggregation is influenced by several factors such as energy of the
particle, particle concentration, magnitude of van der waals interactions, particle charge and
ionic charge.
Fullerenes
Fullerenes are materials with a three dimensional network of carbon atoms in the form of a
hollow sphere, ellipsoid, tube or other shapes. The first fullerene moleculeC60 (buckyball) has a
truncated icosahedron structure with 12 pentagons and 20 hexagons with a carbon atom at the
vertices of each polygon. The bonding pattern of the C60 fullerene is shown here, with yellow
lines representing double bonds and red lines representing single bonds. The pentagonal rings
contain only single bonds; double bonds have a shorter bond length and lead to instability in the
pentagonal ring. The limitations on double bond locations lead to poor delocalization of
electrons, increasing the molecule’s reactivity.

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Fig. The molecular structure of C60
Similar cage –structure molecules of carbon with 20, 26, 70, 76, 82, & 240 also are prepared. C20
is the smallest known fullerene.
Potential applications:
Fullerenes have potential applications in medicine, nanoelectronics, and energy.
 They have potential application for hydrogen storage for fuel-cell powered vehicles
 Fullerene cages with encapsulated molecule have many potential applications. For
example, they will be able to encage a radioactive tracer and inject that safely into the
human body.
Nanofibers
These are highly engineered fibers with diameters in the range of 100-300 nm and they are at the
lower end of the micro fiber ranges. A human hair has a diameter around 80 micrometers and is
about 200 times bigger in diameter than an average nanofiber. The smallest nanofibers made
today are between 1.5 and 1.75 nm. They have enormous specific surface area, excellent
mechanical properties in proportion to weight, high porosity and small pore size. Nanofibers
enable the modification of a nanofibrous layer using various chemical or physical processes
which can significantly improve surface properties which offer immense opportunities for
creating products with new properties.

65
Fig. SEM image of nanofibers
The properties of nanofibers significantly depend upon the material from which they are made.
Electrospinning is the most common method widely employed in industry to produce nanofibers.
A solution of a polymer in a hypodermic syringe is extruded through a needle by the action of a
syringe pump. A direct current potential in the range of 15,000-30,000 V is connected between
the metal needle and a metallic target. As each drop of solution emerges slowly from the beadle
tip, it is attracted to the target by potential difference. This process induces thin fibers of solution
to be spun out on target. The solvent evaporates and the deposited nanofibers form a random
fibermat. The different morphologies are obtained by changes in the concentration of solution,
the gap between needle tip and the target and the rate of extrusion through the needle.

Fig. Electrospinning apparatus

Potential applications
1. Filtration systems, protective clothing against chemical and biological warfare agents because
of higher surface area.
2. They can be used as template for making different structures/coatings, catalysts/enzyme
supports. Eg. Cell growth on nanofibers will permit tissue growth which will be more readily
accepted by the body.

66
3. Used in making reinforced composites by nanofibers, twisted in yarns. Eg. Electrospun nylon
fibers.
4. Application in medicine including drug delivery, scaffolds for growing cells and agriculture.
Eg. EDTA, a chelating compound, has been encapsulated in nanofibers which can remove heavy
metals, particularly lead, cadmium and copper.
5. They will have applications in producing solar sails in space, aircraft wings, bullet-proof vests
because of light weight property.
6. They can be used in fuel cell, Micro/Nano electronic devices. Eg. Nanofibers can be used to
greatly decrease the size of a fuel cell while increasing the electrical output.
7. Carbon nanofibers have excellent mechanical properties, high electrical conductivity, and high
thermal conductivity. They can be incorporated to a wide range of matrices including
thermoplastics, thermosets, elastomers, ceramics, and metals.
Nanowires
Nanowires have a width that ranges from 1-100 nanometers, but their length is not so limited.
Since they can be lengthened by simply attaching more wires end to end or just by growing them
longer, they can be as long as desired. Many different types of nanowires exist, including
metallic (e.g., Ni, Pt, Au), semiconducting (e.g., Si, InP, GaN etc.), and insulating (e.g.,SiO2,
TiO2) and conducting polymer. Silver nanowires have been synthesized by the reduction of
solution of silver salts in the presence of polyvinylpyrrolidine, Silicon nanowires have been
prepared via CVD techniques from SiCl4 gas.

Fig. SEM image of Ag nanowires

Nanowires are expected to exhibit significantly different optical, electrical, and magnetic
properties from their bulk 3-D crystalline counterparts because of their very high density of

67
electronic states, increased surface area, diameter-dependent bandgap, increased surface
scattering for electrons and lesser conductivity (influenced by edge effects).
Potential applications:
1. The nanowires could be used to link tiny components to extremely small circuits in
electronic devices and in the preparation of Schottky and p-n junction diodes.
2. Optoelectronic devices and switches, transistors, LEDs and thermoelectric devices.
3. Chemical & biochemical sensing devices: Nanowire sensors are smaller, more sensitive,
demand less power, and react faster than their macroscopic counterparts.
4. Data storage/transfer: transfer data up to 1,000 times faster, and store data for as long as
100,000 years without degradation.
5. Batteries/generators: tiny, efficient solar panels, turning light into energy, able to hold 10
times the charge of existing batteries.
Nanotubes;
A nanotube is a nanometer-scale tube-like structure. This category includes nanochannels and
clathrate and zeolite nanotubes. Carbon nanotube (CNT) or bucky tube is a tubular allotrope
form of carbon with diameter as small as 1nm or 2D graphene sheet rolled into a tube. They are
cylindrical structures with a network of C-C bonds arranged like acoil in awide variety of
different forms that range from single walled tubes to multi-walled structures with 2-50
concentric shells.

Fig. Structure of CNT

Carbon nanotubes have a high tensile strength and high modulus of elasticity combined with a
very large surface area to volume ratio. The discovery of the electronic conductivity of CNTs
may eventually have major impact on electronic circuits. They may be either electronic
semiconductors or metal level conductors depending on tube diameter and chirality. They are
strong like steel because of C-C covalent bonding and seamless hexagonal network architecture,
light like aluminum, elastic like plastic.

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Potential applications:
1. As reinforcement agents in ceramics and electronically conductive reinforcing agents in
polymer composites.
2. They hold the promise of creating novel devices, such as carbon-based single-electron
transistors, that significantly smaller than conventional transistors.
3. Other possible use as field emission materials which generate electrons when placed in an
electric field and are irradiated with laser light.
Summary
One of the important goals of chemical research has been the discovery and
development of materials with useful properties. The range of materials includes fibers, films,
coatings, adhesives and substances with special electrical, magnetic or optical properties. The
properties and applications of several types of materials that play an important role in modern
society are discussed. Polymeric materials, liquid crystals, glass, cement, and composite
materials are explained. The classification of ceramic materials on the basis of application and
those of biomaterials based on different parameters are described. The most common
superconductor material YBCO described with respect to properties and structure. Thin film
formation techniques and their application in different fields are highlighted. Future advances
certainly depend on the discovery and development of materials with new, valuable properties.
The observable, macroscopic properties are the result of micro-structures and atomic or
molecular level processes.
Review questions:
1. Differentiate between ionic and covalent solids.
2. What are the different types polymerization processes? Give any four differences.
3. Justify the statement: Synthetic polymers do not have exact molecular weight.
4. What structural features make PVC to have higher strength than PE?
5. Explain the different classes of liquid crystals with suitable examples.
6. How are biomaterials classified? Explain three important characteristics that influence their
choice.
7. Describe the methods involved in ceramic fabrication.
8. What are the uses of thin films? How does sputtering differ from vacuum deposition?
9. Explain the principle of working of CVD technique with suitable examples.
10. Write the procedure involved in the sol-gel and solution combustion methods of
nanoparticle preparation.
11. Explain the batch melting process involved in the manufacture of glass.
12. What is the role of gypsum in Portland cement?

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