/
National Institute of Technology, Durgapur
Department of Metallurgical and Materials Engineering
MME 521: Materials Science
Version vO.O
Mukesh Bhardwaj
August 4, 2009
1 Introduction
Materials play key role in our life. The most important
issue of security has been decided by the availability of
materials. Indian Wootz steel swords is one good exam-
ple. Availability of gun powder and forged steel canons
further provided the edge in warfare. In modern age, it is
decided by the availability of nuclear material, advanced
materials for missiles and satellite and last but not least
semiconductor materials, which has totally transformed
our present existence. Materials are so important that
early civilizations have been designated by the level of
their materials development like stone age, bronze age,
iron age and now it may be called as silicon age. The
earliest humans had access only to a limited naturally
occuring materials like stone, wood, clay, skin etc. With
time they discovered techniques for producing superior
materials like pottery and various metals. Further, it
was realized that the properties can be altered through
alloying, heat treatment and mechanical processing.
In any engineering application, a set of performances
are expected. Performance depends on properties of
materials. Properties are governed by the structure.
The structure depends on processing. Structure can be
described at various dimensions. Subatomic structure
deals with electrons within the individual atoms and in-
teractions with their nuclei. On an atomic level, struc-
ture encompasses the organization of atoms or molecules
relative to one another. The order of the magnitude
of dimensions is Angstrom (10-10 m). The next larger
structural realm, which contains large group of atoms
is termed microscopic and can be observed using a mi-
croscope. The structural elements that may be viewed
with the naked eye are termed macroscopic.
Property is defined as the response of material when
exposed to external stimuli. For example, a specimen
subjected to forces will experience deformation, or a pol-
ished metal surface will reffect light. A property is a
material trait in terms of the kind and magnitude of
response to a specific imposed stimulus. Generally, def-
initions of properties are made independent of material
1
shape and size.
Virtually all important properties of solid materials
may be grouped into six different categories: mechan-
ical, thermal, electrical, magnetic, optic and deteriora-
tive. For each there is a characteristic type of stimu-
lus capable of provoking different responses. Categories,
stimulus and their response and corresponding proper-
ties are shown in Table 1.
Materials can be further classified as metals, ceram-
ics and polymers. This scheme is based on chemical
makeup and atomic structure. In addition, there are
composites, which are combination of two or more of
the above three basic material classes. Another classi-
fication is advanced materials-those used in high tech-
nology applications-viz. semiconductors, biomaterials,
smart materials and nanoengineered materials.
Metals are composed of one or more metallic elements
(such as Fe, AI, Cu, Ti, Au and Ni) and often also non-
metallic elements (like, C, Nand 0) in relatively small
amounts. Metals are characterized by high thermal and
electrical conductivity, relatively high stiffness and duc-
tility. Metals are resistant to fracture, opaque to light
and have lusturous appearance over polished surface.
These properties are attributed to nonlocalised valence
electrons. In addition, some of the metals (Fe, Co, Ni)
have desirable magnetic p,roperties. Pure metals are not
good enough for many applications, especially structural
applications. Thus metals are used in alloy form i.e. a
metal mixed with another metal to improve the desired
qualities. For example, aluminum, steel, brass and gold.
Ceramics are compounds between metallic and non-
metallic elements and are most frequently oxides, ni-
trides and carbides. For example, Al203, Si02, SiC,
Si3N4, porcelain, cement and glass. Ceramic materi-
als are relatively stiff, strong and hard. Unlike metals,
they are extremely brittle and susceptible to fracture.
They are poor conductor of heat and electricity and
are more resistant to high temperatures and harsh envi-
ronments than metals and polymers. Ceramics may be
transparent, translucent or opaque. Some oxide ceram-
ics (Fe304) exhibit magnetic behavior.
 Table 1: Categories, stimulus and their response and corresponding properties.
Category Stimulus Response
Mechanical load deformation
Thermal heat temperature
Electrical Electric field current
Magnetic magnetic field domain orientation
Optical light angle
Deteriorative environment loss of material or property reactivity
Polymers include plastic and rubber materials. Many
of them are organic compounds that are chemically
based on carbon, hydrogen and other nonmetallic el-
ements (0, N, Si). They have very large molecular
structures, often chain-like in nature and have a back-
bone of carbon atoms. For example, polyethylene, ny-
lon, polyvinyl chloride, polycarbonate, polystyrene and
silicone rubber. These materials typically have low den-
sities. On a per mass basis, their strength and stiff-
ness are comparable to metals and ceramics. One major
drawback of polymers is their tendency to soften and/or
decompose at modest temperatures. They have low elec-
trical conductivity and are nonmagnetic.
A composite is composed of two or more individual
materials which come from the categories: metal, ce-
ramics and polymers. The design goal of a composite is
to achieve a combination of properties that is not dis-
played by any single material, and also to incorporate
the best characteristics of each of the component ma-
terials. For example, fibreglass consists of small glass
fibres embedded within epoxy or polyester. The glass fi-
bres are relatively strong and stiff, whereas the polymer
is ductile but also weak and flexible. Thus the resulting
fibreglass is relatively stiff, strong, flexible and ductile.
In addition, it has a low density.
Advanced materials are utilized in high technology
application. By high technology, we mean a device or
product that operates or functions using relatively intri-
cate and sophisticated principles. For example, comput-
ers, fiber-optic systems, spacecraft, aircraft and military
rocketry. These advanced materials are typically tradi-
tional materials, whose properties have been enhanced.
They may also be newly developed materials. Advanced
materials include semiconductors, biomaterials, smart
materials and nanoengineered materials.
Semiconductors have electrical properties that are in-
termediate between electrical conductors and insulators.
Furthermore, the electrical characteristics of these ma-
terials are extremely sensitive to the minute concentra-
tions of impurity atoms.
Biomaterials are employed in components implanted
into the human body for replacement of diseased or dam-
aged body parts. These materials must not produce
toxic substances and must be compatible with body tis-
sues. Metals, ceramics, polymers, composites and semi-
"
Properties
elastic modulus, ultimate tensile strength
thermal conductivity, heat capacity
electrical conductivity, dielectric constant
coercivity, magnetic saturation
index of refraction, reflectivity
conductors may be used as biomaterials.
Smart (or intelligent) materials are a group of new and
state of the art materials. These materials are able to
sense changes in their environments and then respond to
these changes in predetermined manners. They consist
of sensors and actuators. Actuators may be called upon
to change shape, position, natural frequency or mechan-
ical characteristics in response to changes in tempera-
ture, electric field or magnetic field. Four types of mate-
rials are commonly used for actuators: shape memory al-
loys, piezoelectric ceramics, magnetostrictive materials
and electrorheological/magnetorheological fluids. Shape
memory alloys, after deformation revert back to their
original shape when temperature is changed. Piezoelec-
tric ceramic expand and contract in response to electric
field and vice versa. Similarly magnetostrictive materi-
als are responsive to magnetic fields. Electrorheological
and magnetorheological fluids are liquids that experi-
ence dramatic changes in viscosity upon the application
of electric and mangetic fields, respectively. Materials
employed as sensors include optical fibres, piezoelectric
materials and microelectromechanical devices.
Nanoengineered materials are made by manipulating
and moving atoms and molecules to form new structures
of a few atomic dimensions. This ability to carefully ar-
range atoms provide opportunities to develop mechan-
ical, electrical, magnetic and other properties that are
not otherwise possible. The examples are carbon nan-
otube and fulerene.
There are technological challenges for the develop-
ment of even more sophisticated and specialized mate-
rials. For nuclear energy, fuel, containment structure
and facilities for the disposal of radioactive waste are to
be developed. In case of automobile sector, new high
strength, low density structural materials are required
to be developed. For engine components, materials with
high temperature performance are needed. New materi-
als are required for economical sources of energy produc-
tion. Solar cells are costly. Hydrogen fuel cell materials
development is very attractive and feasible nonpolluting
energy conversion technology. Recycling of these mate-
rials is also another major issue.
 Table 1: Categories, stimulus and their response and corresponding properties.
Category Stimulus Response
Mechanical load deformation
Thermal heat temperature
Electrical Electric field current
Magnetic magnetic field domain orientation
Optical light angle
Deteriorative environment loss of material or property reactivity
Polymers include plastic and rubber materials. Many
of them are organic compounds that are chemically
based on carbon, hydrogen and other nonmetallic el-
ements (0, N, Si). They have very large molecular
structures, often chain-like in nature and have a back-
bone of carbon atoms. For example, polyethylene, ny-
lon, polyvinyl chloride, polycarbonate, polystyrene and
silicone rubber. These materials typically have low den-
sities. On a per mass basis, their strength and stiff-
ness are comparable to metals and ceramics. One major
drawback of polymers is their tendency to soften and/or
decompose at modest temperatures. They have low elec-
trical conductivity and are nonmagnetic.
A composite is composed of two or more individual
materials which come from the categories: metal, ce-
ramics and polymers. The design goal of a composite is
to achieve a combination of properties that is not dis-
played by any single material, and also to incorporate
the best characteristics of each of the component ma-
terials. For example, fibreglass consists of small glass
fibres embedded within epoxy or polyester. The glass fi-
bres are relatively strong and stiff, whereas the polymer
is ductile but also weak and flexible. Thus the resulting
fibreglass is relatively stiff, strong, flexible and ductile.
In addition, it has a low density.
Advanced materials are utilized in high technology
application. By high technology, we mean a device or
product that operates or functions using relatively intri-
cate and sophisticated principles. For example, comput-
ers, fiber-optic systems, spacecraft, aircraft and military
rocketry. These advanced materials are typically tradi-
tional materials, whose properties have been enhanced.
They may also be newly developed materials. Advanced
materials include semiconductors, biomaterials, smart
materials and nanoengineered materials.
Semiconductors have electrical properties that are in-
termediate between electrical conductors and insulators.
Furthermore, the electrical characteristics of these ma-
terials are extremely sensitive to the minute concentra-
tions of impurity atoms.
Biomaterials are employed in components implanted
into the human body for replacement of diseased or dam-
aged body parts. These materials must not produce
toxic substances and must be compatible with body tis-
sues. Metals, ceramics, polymers, composites and semi-
2
Properties
elastic modulus, ultimate tensile strength
thermal conductivity, heat capacity
electrical conductivity, dielectric constant
coercivity, magnetic saturation
index of refraction, reflectivity
conductors may be used as biomaterials.
Smart (or intelligent) materials are a group of new and
state of the art materials. These materials are able to
sense changes in their environments and then respond to
these changes in predetermined manners. They consist
of sensors and actuators. Actuators may be called upon
to change shape, position, natural frequency or mechan-
ical characteristics in response to changes in tempera-
ture, electric field or magnetic field. Four types of mate-
rials are commonly used for actuators: shape memory al-
loys, piezoelectric ceramics, magnetostrictive materials
and electrorheological/magnetorheological fluids. Shape
memory alloys, after deformation revert back to their
original shape when temperature is changed. Piezoelec-
tric ceramic expand and contract in response to electric
field and vice versa. Similarly magnetostrictive materi-
als are responsive to magnetic fields. Electrorheological
and magnetorheological fluids are liquids that experi-
ence dramatic changes in viscosity upon the application
of electric and mangetic fields, respectively. Materials
employed as sensors include optical fibres, piezoelectric
materials and microelectromechanical devices.
Nanoengineered materials are made by manipulating
and moving atoms and molecules to form new structures
of a few atomic dimensions. This ability to carefully ar-
range atoms provide opportunities to develop mechan-
ical, electrical, magnetic and other properties that are
not otherwise possible. The examples are carbon nan-
otube and fulerene.
There are technological challenges for the develop-
ment of even more sophisticated and specialized mate-
rials. For nuclear energy, fuel, containment structure
and facilities for the disposal of radioactive waste are to
be developed. In case of automobile sector, new high
strength, low density structural materials are required
to be developed. For engine components, materials with
high temperature performance are needed. New materi-
als are required for economical sources of energy produc-
tion. Solar cells are costly. Hydrogen fuel cell materials
development is very attractive and feasible nonpolluting
energy conversion technology. Recycling of these mate-
rials is also another major issue.
 Table 1: Categories, stimulus and their response and corresponding properties.
Category Stimulus Response
Mechanical load deformation
Thermal heat temperature
Electrical Electric field current
Magnetic magnetic field domain orientation
Optical light angle
Deteriorative environment loss of material or property reactivity
Polymers include plastic and rubber materials. Many
of them are organic compounds that are chemically
based on carbon, hydrogen and other nonmetallic el-
ements (0, N, Si). They have very large molecular
structures, often chain-like in nature and have a back-
bone of carbon atoms. For example, polyethylene, ny-
lon, polyvinyl chloride, polycarbonate, polystyrene and
silicone rubber. These materials typically have low den-
sities. On a per mass basis, their strength and stiff-
ness are comparable to metals and ceramics. One major
drawback of polymers is their tendency to soften and/or
decompose at modest temperatures. They have low elec-
trical conductivity and are nonmagnetic.
A composite is composed of two or more individual
materials which come from the categories: metal, ce-
ramics and polymers. The design goal of a composite is
to achieve a combination of properties that is not dis-
played by any single material, and also to incorporate
the best characteristics of each of the component ma-
terials. For example, fibreglass consists of small glass
fibres embedded within epoxy or polyester. The glass fi-
bres are relatively strong and stiff, whereas the polymer
is ductile but also weak and flexible. Thus the resulting
fibreglass is relatively stiff, strong, flexible and ductile.
In addition, it has a low density.
Advanced materials are utilized in high technology
application. By high technology, we mean a device or
product that operates or functions using relatively intri-
cate and sophisticated principles. For example, comput-
ers, fiber-optic systems, spacecraft, aircraft and military
rocketry. These advanced materials are typically tradi-
tional materials, whose properties have been enhanced.
They may also be newly developed materials. Advanced
materials include semiconductors, biomaterials, smart
materials and nanoengineered materials.
Semiconductors have electrical properties that are in-
termediate between electrical conductors and insulators.
Furthermore, the electrical characteristics of these ma-
terials are extremely sensitive to the minute concentra-
tions of impurity atoms.
Biomaterials are employed in components implanted
into the human body for replacement of diseased or dam-
aged body parts. These materials must not produce
toxic substances and must be compatible with body tis-
sues. Metals, ceramics, polymers, composites and semi-
[ ~--
Properties
elastic modulus, ultimate tensile strength
thermal conductivity, heat capacity
electrical conductivity, dielectric constant
coercivity, magnetic saturation
index of refraction, reflectivity
conductors may be used as biomaterials.
Smart (or intelligent) materials are a group of new and
state of the art materials. These materials are able to
sense changes in their environments and then respond to
these changes in predetermined manners. They consist
of sensors and actuators. Actuators may be called upon
to change shape, position, natural frequency or mechan-
ical characteristics in response to changes in tempera-
ture, electric field or magnetic field. Four types of mate-
rials are commonly used for actuators: shape memory al-
loys, piezoelectric ceramics, magnetostrictive materials
and electrorheological/magnetorheological fluids. Shape
memory alloys, after deformation revert back to their
original shape when temperature is changed. Piezoelec-
tric ceramic expand and contract in response to electric
field and vice versa. Similarly magnetostrictive materi-
als are responsive to magnetic fields. Electrorheological
and magnetorheological fluids are liquids that experi-
ence dramatic changes in viscosity upon the application
of electric and mangetic fields, respectively. Materials
employed as sensors include optical fibres, piezoelectric
materials and microelectromechanical devices.
Nanoengineered materials are made by manipulating
and moving atoms and molecules to form new structures
of a few atomic dimensions. This ability to carefully ar-
range atoms provide opportunities to develop mechan-
ical, electrical, magnetic and other properties that are
not otherwise possible. The examples are carbon nan-
otube and fulerene.
There are technological challenges for the develop-
ment of even more sophisticated and specialized mate-
rials. For nuclear energy, fuel, containment structure
and facilities for the disposal of radioactive waste are to
be developed. In case of automobile sector, new high
strength, low density structural materials are required
to be developed. For engine components, materials with
high temperature performance are needed. New materi-
als are required for economical sources of energy produc-
tion. Solar cells are costly. Hydrogen fuel cell materials
development is very attractive and feasible nonpolluting
energy conversion technology. Recycling of these mate-
rials is also another major issue.
2 Interatomic bonding 2.1 Primary interatomic bonds

At large distances, the interatomic interations are neg- 2.1.1 Ionic bonding
ligible. However, when atoms are close, the equilibrium
distance between two atoms is decided by the sum of two
kind of forces: attractive and repulsive. The magnitude
of each of these forces is a function of interatomic dis-
tance. The origin of an attractive force FA depends on
the particular type of bonding that exists between the
two atoms. When the two atoms are brought closer, the //
cation
outer electron shells of the two atoms begin to overlap /- .
and a strong repulsive force FR comes into play. The o ,: - -=-~.~
! ",,,....-.,
net force FN between the two atoms is given by: "Bond

(1)
" ~ he=
I
'"
'" /' =stt<' =-
E"'>'4 ':rE,;:f

E~y" Eo ~ ; -''''-
/

The distance at which FN becomes zero, that is the dis- H 0, I --

E!Q\Jitibriumdistance of separation (roi
I at E/"I'ergyminimum{Bondenergy}
tance between centre of the two atoms 1'0, is the equi- I
librium interatomic distance. Once in this position, the I
two atoms will counteract any attempt to separate them
by attractive force, or to push them together by a repul-
sive action. Figure 1: Energetics of ionic bonding.
Sometimes, it is more convenient to work with the
potential energies between two atoms instead of forces. Ionic bonding is found in compounds that are com-
Mathematically, energy, E and force F are related as posed of both metallic and nonmetallic elements. Metal-
lic elements exist at extreme left in the periodic table
(2) whereas nonmetallic one are located at extreme right
EN = J F.'Vdr
of the periodic table. Atoms of metallic elements easily
(3) give up their valence electrons to the nonmetallic atoms.
J FA d1'+ J FR dr In the process all the atoms acquire stable or inert gas
EA + ER (4) configurations and in addition, an electrical charge; that
is, they become ions. Sodium chloride (Na+Cl-) is the
FN = 0 corresponds to minimum in EN vs l' curve Classic ionic material. A sodium atom can assume the
and is denoted as Eo at interatomic distance 1'0. Eo is
electron structure of neon by a transfer of its one valence
called as bonding energy. 3s electron to chlorine atom. After such a transfer, the
Although the preceding. treatment has dealt with an
chlorine ion has a net negative charge and an electron
ideal situation involving only two atoms, a similar yet
configuration identical to that of argon.
more complex condition exists for solid materials be-
The attractive bonding forces are coulombic by virtue
cause force and energy interactions among many atoms
of their net electrical charge. For two isolated ions, the
must be considered. The magnitude of the bonding en-
attractive energy EA and repulsive energy ER are re-
ergy and the shape of the energy versus interatomic sep-
spectively given by following equations.
aration curve vary from material to material and they
both depend on the type of atomic bonding. A num-
(5)
ber of material properties depend on Eo curve shape
and bonding type. For example, materials having large
(6)
bonding energies have high melting and boiling points.
Materials with steep energy curve with interatomic dis-
In these equations, A, Band n are constants whose value
tances have high stiffness and low coefficient of thermal
depend on the particular ionic system. The value of n
expansion.
is approximately 8.
Three different types of primary or chemical bond are
Ionic bond is termed nondirectional as the magnitude
found in solids: ionic, covalent and metallic. For each
of the bond is equal in all directions around an ion. For
type, the bonding necessarily involves the valence elec-
ionic materials to be stable, all positive ions must have
trons. The nature of bonds depends on the electron
as nearest neighbors negatively charged ions in a three
structures of the constituent atoms. Secondary or pqys-
dimensional scheme and vice versa. Bonding energies
ical forces and energies are also found in all materials.
are relatively large and lies in the range between 600 and
They are weaker than the primary ones. They influence
1500 KJjmol (6 and 16 eVjatom). This is reflected in
the physical properties of some materials.

3
their high melting points. Ionic materials are character-
istically hard and brittle and electrically and thermally
insulative.
2.1.2 Covalent bonding
In covalent bonding, stable electron configurations are
assumed by the sharing of electrons between adjacent
atoms. Two atoms that are covalently bonded will each
contribute atleast one electron to the bond and the
shared electrons may be considered to belong to both
atoms. The covalent bond is directional. Many non-
metallic elemental molecules (H2, C12, F2 etc) as well
as molecules containing dissimilar atoms, such as CR1,
H20, HN03, and HF, are covalently bonded. Further-
more, this type of bonding is found in elemental solids
such as diamond, silicon and germanium and other solid
compounds composed of elements that are located on
the right hand side of the periodic table, such as GaAs,
InSb and SiC.
For N' valence electrons, an atom can covalently bond
with at most 8 - N' other atoms. For example, chlo-
rine atom can bond to only one chlorine atom, whereas
in diamond, each carbon atom covalently bonds with
four other carbon atoms, thus forming three-dimensional
interconnecting structure. Covalent bond may be vey
strong, as in diamond, which is very hard and has very
high melting temperature greater than 35500C, or they
may be very weak as with bismuth which melts at about
270°C. Polymeric materials are a long chain of carbon
atoms that are covalently bonded together.
It is possible to have interatomic bonds that are par-
tially ionic and partially covalent. For a compound, the
degree of either bond type depends on the relative po-
sitions of the constituent atoms in the periodic table or
the difference in their electronegativities. The percent-
age ionic character of a bond between elements A and
B (A being the most electronegative) may be approxi-
mated by the expression
%ionic character = {1-exp[-(0.25)(XA -XB)2]} x 100
2.1.3 Metallic bonding
Metallic materials have one, two or atmost three valence
electrons. These valence electrons are not bound to any
particular atom in the solid and are free to drift through-
out the entire crystal. The remaining nonvalence elec-
trons and atomic nuclei form ion cores. The free elec-
trons shield the positively charged ion cores from mu-
tually repulsive electrostatic forces. Consequently, the
metallic bond is nondirectional. Bonding may be weak
or srong; energies range from 0.7 eV/atom for mercury
to 8.8 eV/atom for tungsten. Their respective melting
temperatures are -39 and 34100C. Metals are good con-
ductor of heat and electricity as a consequence of their
4
free electrons. Furthermore, at room temperature, met-
als and their alloys fail in a ductile manner.
2.2 Secondary bonding or van der Waals
bonding or physical bonding
Secondary bonds are weak in comparison to the primary
chemical ones. Bonding energies are typically of the or-
der of 0.1 eV / atom. 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 forces arise from atomic
or molecular dipoles. An electric dipole exists when-
ever there is some separation of positive and negative
portions of an atom or molecule. The bonding results
from the coulombic attraction between the positive end
of one dipole and the negative region of an adjacent one.
Dipole interactions occur between (a) polar molecules,
(b) polar molecule and induced dipole in a nonpolar
molecule or an atom and (c) induced dipoles between
two nonpolar molecules or atoms. Hydrogen bonding, a
special type of secondary bonding (category a), is found
to exist between molecules having hydrogen and higly
electronegative elements such as fluorine, oxygen and
nitrogen as one of the constituents. These are discussed
below.
In case of hydrogen bond between molecules of H-F,
H-O or H-N, the electron associated with hydrogen is
pulled so close to anions due to their high electroneg-
ative character that the hydrogen end of the bond is
essentially a positively charged bare proton that is un-
screened by any electron. This highly positively charged
end of the molecule is capable of a strong attractive force
with the negative end of an adjacent molecule. Among
the secondary bonds, hydrogen bond is strongest and
the bond energy may be as high as 0.52 eV/molecule.
The permanenet dipole bond exist between molecules
having permanent dipoles by virtue of the difference in
electronegativity of its constituent elements. For exam-
ple, in case of HCl molecule, the hydrogen end is slightly
positive and Cl is slightly negative. Thus there exist per-
manent dipole moment and negative end of one molecule
is bonded to the positive end of the other.
In case of polar molecule induced dipole bonds, there
exist polar molecules which induce dipoles in adjacent
nonpolar molecules or atoms by distorting their electron
cloud.
In case of nonpolar molecules or atoms, there exist no
dipole moment. However, at any instant of time, the
electron cloud may be slightly distorted, thus resulting
in temporary dipole moment. This induces dipole mo-
ment in the neighbouring molecule/atom. It is therefore
named as fluctuating induced diploe bond and is weakest
in the category of secondary bonds.
 3 Crystalline and noncrystalline ma-
I terials
In case of crystalline solids, both short range and long
range order exists. In case of noncrystalline solids, only
short range order exist. The structure is close to that of
liquid and are called as amorphous (or glassy) solids.
Crystalline solids may exist as either single crystals or
polycrystals. When the periodic arrangement of atoms
extends throughout the entirety of the specimen with-
out interruption, the result is a single crystal. In case of
polycrystalline solids, which is more generally the case,
a collection of many small crystals separated by grain
boundaries exist. These grains have random crystal-
lographic orientations. There exists some atomic mis-
match within the region where two grains meet. This
region is called grain boundary.
In general, the properties of a crystal in different di-
rections are different. In a polycrystalline material, if
there exist random orientation between various grains,
the result is isotropic material, Le., with uniform prop-
erty in all directions. However, if there exist preferen-
tial orientation, Le., more number of grains are oriented
in a praticular directions. The property of the mate-
rial are no more same in all directions. The material is
anisotropic and is said to have a texture.
4 Structure of crystalline solids
4.1 Unit cell, crystal systems and Bravais
Lattices
A crystalline material is one in which the atoms are sit-
uated in a repeating or periodic array over large atomic
distances, such that upon solidification, the atoms will
position themselves in a repeatitive three dimensional
pattern, in which each atom is bonded to its nearest
neighbor atoms. All metals, many ceramic materials
and certain polymers form crystalline structures under
normal solidification conditions.
When describing crystalline structures, atoms are
thought of as being solid spheres having well defined
diameter. This is termed as atomic hard sphere model.
If the atoms positions are represented by points in three-
dimensional space, it is called as lattice.
The atomic order in crystalline solids indicates that
small groups of atoms form a repeatitive pattern. The
smallest repeatitive unit is called as unit cell. Thus, the
unit cell is the basic building block of the crystal struc-
ture and defines the crystal structure by virtue of its
geometry and the atom positions within. The unit cell
is chosen such that it possess highest fold of symmetry
and then is of minimum size.
Based on unit cell geometry, that is, the shape of the
unit cell parallelopiped without regard to the atomic po-
sitions in the cell, there can exist maximum seven crystal
systems. In these crystal systems, if lattice points are
defined, there can exist maximum 14 Bravais lattices
and are shown in Figure 2. At a lattice point, there can
exist an atom (AI, Cu, Au, Pt), a molecule (methane),
ion pair (NaCI), atom pair (diamond, Si, Ge). A unit
cell is defined using six parameters, Le., three axes (a, b
and c) passing through the unit cell corner and are de-
fined along the unit cell edges and three interaxial angles
(a, {3and ')').
4.2 Crystallographic points, directions and
planes
Six parameters of a unit cells were defined. In the unit
cell, conventions have been developed to designate point
locations, directions and planes. Three indices are used
for such purposes. The basis for determining index val-
ues is the unit cell, with a right-handed coordinate sys-
tem consisting of three axes situated at one of the cor-
ners and coinciding with the unit cell edges. For some
crystal systems- namely, hexagonal, rhombohedral (trig-
onal), monoclinic and triclinic- the three axes are not
mutually perpendicular, as in the cartesian coordinate
scheme.
The position of any point located within a unit cell
may be specified in terms of its coordinates as fractional
multiples of the unit cell edge lengths (i.e., in terms of
a, b and c). For example index of a point given as lq
is equivalent to coordinate (la, 1b, !c).
A crystallographic direction is defined as a line be-
tween two points, or a vector. Any vector can be trans-
lated throughout the crystal lattice without alteration,
if parallelism is maintained. Therefore, a vector of con-
venient length is positioned such that it passes through
the origin of the coordinate system. The length of the
vector projection on each of the three axes is determined.
These are measured in terms of the unit cell dimensions
a, band c. These three numbers are multiplied or di-
vided by a common factor to reduce them to the small-
est integer values. The three indices, not separated by
commas, are enclosed in square Drackets. Any negative
index is denoted by placing bar above it. For example,
cube diagonals can be expressed as [111], [III], [Ill]
and [111]. This entire family of directions is denoted as
< 111 >. Directions in cubic crystals having the same
indices without regard to order or sign, for example,
[123] and [213], are equivalent. This is in general, not
true for other crystal systems. For example, for crystals
of tetragonal symmetry, [100] and [010] directions are
equivalent, whereas [100] and [001] are not.
A problem arises for crystals having hexagonal sym-
metry in that some crystallographic equivalent direc-
tions will not have the same set of indices. This is cir-
cumvented by utilizing a four-axis coordinate system.
The three ai, a2 and a3 axes are contained within a sin-
5
 7 Crystal systems 14 Bravais Lattices

cubic
a=b=c
a=~gOo

tetragonal
a=b:;t:C

a=/3=y=900

orth orho 1"'1

bie
a;:tJ:;cC
o:=I3='y=900

rhombohedral
a=b=c
a=(3=)f#9<P

Ijexagonal
a=I);=C
0:=[3=90<)
.
\1=1200

monodinic
a;:t):;cC
/ .1/
' I

<X='p9G<):t=13
/17
triclii"c
~
o:~~IOO

Figure 2: The 7 crystal systems and the 14 Bravais lattices.

6
gle plane called the basal plane and are at 1200 angle to
one another. The z axis is perpendicular to this basal
plane. The direction is then denoted by four indices
as [uvtw]. The first three indices pertain to projections
along the respective aI, a2 and a3 axes in the basal plane.
The orientation of planes for a crystal structure are
represented in a similar manner. Except for hexagonal
system, the planes are specified by three Miller indices
as (hkl). Any two planes parallel to each other are equiv-
alent and have identical indices. Following procedure is
followed to obtain the indices. If the plane passes the se-
lected origin, another parallel plane must be constructed
within the unit cell by an appropriate translation. The
plane either intersects or parallels each of the three axes.
The length of the planar intercept for each axis is de-
terrnined in terms of lattice parameters a, b and c. The
reciprocal of these numbers are taken. Thus for parallel
axis, the value becomes zero. For other intercepts, non-
zero values are obtained. Multiply them with a suitable
common factor to obtain the set of smallest integers.
The integer indices, not separated by commas, are en-
closed within parenthesis as (hkl). An intercept on neg-
ative side of origin is indicated by a bar. The family of
planes are denoted by enclosing indices in curly braces
as {hkl}.
In case of cubic crystals, planes and directions having
the same indices are perpendicular to one another. For
other crystal systems, there are no simple geometrical
relationships between planes and directions having the
same indices. In case of denoting planes in hexagonal
crystals, four indices are used as discussed earlier in case
of directions.
4.3 Metallic crystal structures
The simplest crystal structure exist for metals. The met-
als tend to be densely packed because of the following
reasons.
. Typically, only one element is present, so all atomic
radii are the same.
. Metallic bonding is not directional.
. Nearest neighbor distances tend to be small in order
to lowerbond energy.
. Electron cloud shields cores from each other
Most of the metals either crystallize as face centred
cubic (FCC), body centred cubic (BCe) or hexagonal
closed packed (HCP). Metals having FCC structure are
Cu, AI, Ag, Ni, Pt, Au, Pb and 'Y Fe. Metals having
BCC structure are Cr, W, a and 'Y Fe, Mo and Ta.
Metals having HCP structure are Cd, Co, a Ti and Zn.
The number of atoms per unit cell (n) is calculated as
the summation of the fraction of all atoms within a unit
cell. The total volume of atoms can thus be obtained
by multiplying n by 4/37fR3 where R is the radius of an
atom in a unit cell. The coordination number is defined
as the total number of nearest neighbours or touching
atoms. Atomic packing factor (AP F) is defined as the
ratio of volume of atoms in a unit cell (Vs) and total
unit cell volume (Ve).
AP F = Vs
Ve
Theoretical density p can be calculated as:
nA
p=-
VeNA
where A is atomic weight and NA is Avogadro number
(6.023 x 1023).
In materials science, closest packed planes and closest
packed directioI1s have special significance. Therefore,
quite often, it is necessary to calculate linear and planar
densities. Linear density (LD) is defined as follows.
LD = number of atoms centred on direction vector
length of direction vector
Planar density (PD) is defined as follows.
PD = number of atoms centred on a plane
area of plane
In case of cubic crystals, the interplanar spacing (dhkd
can be calculated as:
d _ a (7)
hkl - yh2 + k2 + [2
FCC and HCP are the closest packed system with
APF=0.74. In case of HCP, basal plane is the clos-
est packed plane. In case of FCC, {Ill} is the closest
packed plane. In closest packed plane, the central atom
is surrounded by 6 atoms. Thus there are six valleys, on
which maximum 3 atoms can be placed. Thus there are
two ways to place the second layer. Similarly third layer
can also be placed in two possible ways. If the atoms
in the third layer are exactly above that of first layer,
we obtain ABAB... arrangement. This result in HCP
lattice. The atom in second layer can not be above first
layer for closest packed structure. If the atom in the
third layer are also not above the atoms in first layer,
we obtain ABCABC... arrangement. This result in FCC
lattice. Thus FCC and HCP differ only in the sequence
atoms are placed in the third layer.
In closed packed lattices, there are two kind of voids:
tetrahedral and octahedral. Tetrahedral void exist just
between three atoms in one layer and one atom placed
above the valley formed by three atoms in the first layer.
A tetrahedral void is defined by joining the atoms cen-
tre. A model of the void can be obtained by joining 4
equilateral triangles. Octahedral void exist in the valley
which was uncovered by the atoms in the second layer.
7
An octaheral model can be obtained by joining a square 5 X-ray diffraction
with 8 equilateral triangles: 4 above and 4 below.
Some metals and nonmetals may have more than one In order to characterize crystal structure (dimensions ~
crystal structure. This phenomena is known as poly- 1 A), the wavelength of the electromagnetic radiation
morphism. In case of elemental solids, this condition (signal) used for probing the crystal structure must be
is known as allotropy. The prevailing crystal structure of same order of magnitude. X-rays are used for the pur-
depends on both the temperature and the external pres- pose. X-rays are electromagnetic radiation. The wave
sure. length lies approximately in the range 0.01 to 100 A
and centred around 1 A. The energy of the radiation of
4.4 Ceramic crystal structures wavelength1 A is ~ 12400eV/photon using the formula
E = he/A. Comparing this value with the seventh ion-
Ceramics are composed of at least two elements. The ization energy of nitrogen equal to 668 eV / atom, it can
atomic bonding may be ionic or covalent or mixed de- be concluded that x-rays have enormous power to boil
pending on the electronegativities of its constituents. off even the inner shell electrons.
Following are the factors that govern the crystal struc- For characterization, we model atoms as mirrors.
ture of ceramics.
Therefore angle of incidence is equal to angle of reflec-
. In case of ionic bonding, it is necessary to main- tion. Secondly, interference criteria is considered. If the
tain charge electroneutrality. Thus in case of cal- waves are in phase, constructive interference occurs. If
cium fluorite, there must be twice as many F- as they are out of phase, destructive interference occurs.
Ca2+ ions, which is reflected in the chemical for- The signal consists of coherent (in phase) monochro-
mula CaF 2. matic (single wavelength) x-rays. The diffraction phe-
nomena is shown in Fig. 3. The distance betweeen A-A'
. The ionic radius of the cations (rc) is generally less and B-B' is dhkl. For constructive interference, the extra
than that of anions (ra). Each cation prefer to have distance travelled by ray 2 compared to ray 1 must be
as many nearest neighbor anions as possible. Simi- equal to whole number times wavelength. This result in
larly, the anions also desire a maximum number of Bragg's law given as:
cations nearest neighbors.
2dhkl sin () = nA (8)
Stable ceramic crystal structures form when those an-
ions surrounding a cation are all in contact with that Using Bragg's law, interference criteria is obtained. In-
cation. The coordination number is related to the terference criteria and crystal structure together result
cation-anion radius ratio. For rc/ra < 0.155, cation is in a set of expected reflections. An example is shown in
bonded to two anions in a linear manner. If 0.155 < Fig. 4. This result in finger printing of crystal structure.
rc/ra < 0.225, cation is surrounded by three anions For example {001} results in reflection in case of simple
in the form of a planar equilateral triangle, with the cubic but not in case of BCC or FCC, because there ex-
cation located in the center. For 0.225 < rc/ra < 0.414, ist one more plane at the position of body centre or face
the cation is located at the centre of tetrahedron. For centre, which causes destructive interference. The rule
0.414 < rc/ra < 0.732, the cation is located at the centre in nutshell can be described as follows. All the planes
of octahedron. For 0.732 < rc/ra < 1, the coordination causes reflection in case of simple cubic. In case of BCC,
number is 8 and the cation is positioned at the centre of the sum of miller indices must be even. In case of FCC,
the cube. For rc/ra > 1, the coordination number is 12. either all the miller indices must be odd or all must be
Such relations are purely based on geometrical consid- even. No reflection will occur in mixed cases. The value
eration. These relations are only approximate and there of (h2 + k2 + [2) of allowed reflections in case of simple
are exceptions. cubic is 1, 2, 3, 4, 5, 6, 8, 9 In case of BCC, the
values are 2, 4, 6, 8, 10, 12, 14, 16. . .. This is equivalent
4.5 Polymer crystal structures to the values 1, 2, 3, 4, 5, 6, 7, 8 In case of FCC,
the values are 3, 4, 8, 11, 12. . . .
Since molecules are involved at lattice positions, the
Eliminating dhkl between equations 7 and 8, following
atomic arrangement is more complex for polymers.
equation is obtained.
Polymer molecules are often only partially crystalline,
having crystalline regions dispersed within the remain- A2 sin2 ()
ing amorphous material. Any chain disorder or misalign- (9)
4a2 - h2 + k2 + [2
ment will result in an amorphous region, since twisting,
kinking and coiling of the chains prevent the strict or- Therefore for determining crystal structure, first sin2 ()
dering of every segment of every chain. Cross-linking, values are tabulated. Then the values are normalized
higher molecular weight and higher cooling rate are op- with respect to the first reflection. The values are then
posing factors to crystallization of polymers. multiplied with a minimum natural number necessary

8
 on introduction of vacancies, the entropy of the system
increases. However, this can not continue endlessly as
work has to be done in order to break bonds and create
a vacancy. There is a trade off and equilibrium number
of vacancies Nv increases with temperature according to
the following relation

Figure 3: Diffraction of x-rays by planes of atoms A-A' where, N is the total number of atomic sites, Qv is the
and B-B'. energy required for the formation of a vacancy, T is the
absolute temperature in Kelvin and k is Boltzmann's
constant.
For specification of composition of an alloy in terms of
<, "its constituent elements, the two most common ways are
ight percent and atom percent. The basis for weight
[) '!. :.~
percent (wt%) is the weight of a particular element rela-
tive to the total alloy weight. For an alloy that contains
Figure 4: Diffraction pattern for powdered lead. two hypothetical atoms denoted by 1 and 2, the concen-
tration of 1 in wt%, CI, is defined as
to clear the fraction. Then miller indices are guessed.
Finally the value of sin2 ()/ (h2+ k2 + [2) is calculated to (10)
check that the values obtained for all the reflections are
same. Then miller indices pattern is studied in order to where mi and m2 represent the weight (or mass) of el-
understand the type of crystal structure. Using equation ements 1 and 2, respectively. The concentration of 2
9, the value of lattice parameter is obtained. would be computed in an analogous manner.
The basis for atom percent (at%) calculations is the
Q. Determine the crystal structure and lattice parame- number of moles of an element in relation to the total
ter, given that >. = 1.5418 A and 2() values are 44.48, moles of the elements in the alloy. The number of moles
51.83, 76.35, 92.90, 98.40, 121.87, 144.54, 155.51. The in some specified mass of a hypothetical element 1, nml,
answer is FCC lattice with lattice parameter equal to may be computed as follows:
3.53 A which is that of Ni.
(11)
6 Imperfections in solids where mi is the mass in grams and Al is the atomic
The lattice is never perfect. There are always various weight of element 1.
kind of defects or imperfections. They are classified as Concentration in terms of atom percent of element 1
point defect (0 dimension), line defect (1 dimension), in an alloy containing 1 and 2 atoms, C~ is defined as
follows.
surface defect (2 dimension) or volume defect (3 dimen-
sion). (12)

Q. Knowing the definition of weight percent and atom

6.1 Point defects
Point defects are the result of change in local order at a
regular lattice position. If the atom is missing from the
regular lattice position, it is called as vacancy. If an ex-
tra atom is located between two regular lattice positions,
it is called as self-intersti tial.
Point defects are equilibrium defects. In a perfect lat-
tice of say pure metal, all the atoms are alike and indis-
tinguishable. Therefore, only one configuration is pos-
sible. However, if some vacancies are introduced then
the number of lattice positions will be greater than the
total number of atoms in the lattice and in such condi-
tion, more than one configuration is possible. Therefore
percent, write the formulae for conversion from one unit
to other.
In case of an alloy, two things may happen. Either
there exist complete solubility between solute and sol-
vent and is called solid solution or there may occur pre-
cipitation of separate phase. If an atom of solute substi-
tute for an atom of solvent, it is called as substitutional
solid solution. If an atom of solute occupies the void
space between solute atoms, it is called as interstitial
solid solution. These are called impurity point defects.
For substitutional solid solution to occur throughout
the composition range (extended solid solubility), fol-
lowing Hume Rothery rules must satisfy.

9
\
'1