Importance of the Material Science & Engineering

• Appropriate knowledge of materials required for Micro-electronic ircuits such as

LSI (Large scale Integrated Circuits)

• In the field of Manufacture of MOSFETS (Metal Oxide semiconductor Field Effect

Transistors) with n-p-n junctions and FET (Field Effect Transistors) for current

distribution.

• Developments of ALLOYS with excellent mechanical properties suitable for Air-

craft, Space craft, FBTR operations

• Development of materials useful in electrical insulations, magnetic devices,

superconducting materials, high sensitivity and high fidelity communication

equipment,

• Artificial body implants such as teeth, arteries, heart valves, heart, bones in the

human body.

• Knowledge used in the development of low cost housing materials such as plastics,

polymers and composite materials.

• Development of Glasses and ceramics for high temperature and other Engineering

applications.

Knowledge in materials will help to choose the appropriate materials with specific

direction in the construction to avoid maximum loss and get more live to the structure.

(Longevity of the structure can be improved).

Other important parameter must be acquainted, while we are learning about the

materials is “MEASUREMENT” to quantify the things.

1
 Measurement can be defined as Comparison of unknown things with standard things is

known as measurement

Classification of Engineering Materials

This is a study of some basic materials used by the engineers working in various

activities. It is an important issue to engineers to select the suitable materials for their day-

to-day use. There SIX categories

1. Ferrous and non-ferrous metals: about different properties and uses of different types

of steels, cast iron and their alloys. And also gives information about Al, Cu, Pb, Zn, Ni,

Mg, Cd, Vanadium, antimony and their alloys. ( to select an alloy for a component)

2. Organic Materials: deals with various characteristics of polymers,plastics, rubber,

wood etc. Includes the study of mechanical and electrical behaviour of polymers. (also

essential for engineers)

3. Composite Materials and Ceramics: deals with agglomerated and laminated materials.

This will also give information regarding reinforced materials. Ceramics are also very

essential for engineers to design the layout of the factory and also artificial implants etc.

4. Semiconductors: a study of semiconductors and transistors. It is useful in the

preparation of integrated circuits and semiconductors materials. This is very essential

for an electronic or telecommunication engineer to prepare for his components.

5. Insulating materials: materials with dielectric properties of insulation materials. These

are very important in the electronic and space research activities.

6. Magnetic Materials: gives information about the various properties of Magnetic

materials. It also explains about the types of magnetism and different magnetic materials.

It has got more applications in the field of electrical and electronic engineers

2
Introduction to Atomic Structure

Atom consists of a few fundamental particles, Among important fundamental

particles are so many theories existed to explain the structure of Atom. Some of the well

explained theories are:

1. Thomson’s atomic model (watermelon model)

2. Rutherford’s atomic model (planetary theory)

3. Bohr’s atomic model (modifies the previous theories)

4. Sommerfield’s atomic model

5. Modern atomic model

• all these theories are well explained about the internal structure of the atoms

(electrons, protons and neutrons and their arrangement)

• Bohr’s suggested the following

1. Electrons revolve around nucleus without loosing energy, as long as they are in the

same orbit (with definite energy).

2. Smallest orbit (first) has least energy, farthest orbit (last from nucleus) has maximum

energy.

3. Energy is emitted by an electron, when it moves from a higher level to lower energy or

vice –versa. E2-E1 = hf. (Frequency of radiation)

4. Angular momentum of an electron revolving around the nucleus is given

by the relation mvr = n. h/2π (h= plank’s constant).

3
Energy of an electron in Bohr’s atomic model

Let us assume an atom which a single electron is revolving in some orbit around

the nucleus

Let e= Charge of the electron

m = Mass of the electron

Z = No. of protons in the nucleus of the atom

N = an integer representing the orbit in which electron is revolving

rn = radius of the orbit in which the electron is revolving

Vn = Tangential velocity of the electron

h = Planck’s constant

Ԑo = absolute permittivity (F/m)o = absolute permittivity (F/m)

The force between the nuclear proton and the electron in circular orbit in the Bohr

model is given by Coulomb’s equation

Z e2
F= ---------- (1)
4 π ∈0 r 2n

Centrifugal force acting on the electron due to its motion along the circular path

m v 2n
Fe = ----------- (2)
rn

4
The force supplies the necessary centripetal force for uniform circular motion then F = Fe
2
Z e2 m vn
• 2
=
r n 4 π ∈0 rn

Z e2 2
• =mv n −−−−−(3)
r n 4 π ∈0

Total Energy of revolving election T.E = KE + PE

Kinetic energy of the revolving electron

m v 2n
K . E=
2

Substituting the value of m v 2n from equation (3)

1 Z e2 Z e2
K E= =
2 r n 4 π ∈0 r n 8 π ∈0

Potential energy of electron due to its position in the electric field of the nucleus is

obtained when it is moved from a radius r n to the infinity. It is done by integrating the

work done against the force of attraction between the nucleus and the electron between the

limits rn and infinity. Therefore potential energy of the electron

∞

• P . E .=−∫ F e. dr n
rn

Minus sign indicate that the energy spent in moving the electron from r n to identify

is against the force of attraction between the nucleus and electron, i.e Fe, substituting of Fe

in the above equation from equation (1)

∞ ∞
Z e2 −Z e2 1
P E=−∫ 2 dr n = ∫ dr
r r n 4 π ∈0
n
4 π ∈0 r r 2n n
n

∞
Z e2 −1 −Z e 2 1 −Z e 2
¿−
[ ] = =
[ ]
4 π ∈0 r n r 4 π ∈0 r n r n 4 π ∈0
n

Total energy of the electron T E = KE + PE

5
 Z e2 Z e2 −Z e2
T E= − = ---------------- (6)
r n 8 π ∈0 r n 4 π ∈0 r n 8 π ∈0

Bohr’s Angular momentum of an electron moving in the radius rn with a tangential

velocity vn,

nh
• m v n r n= −−−(7)
2π

• Dividing the equation (7) by equation (3)

nh
m vn rn 2π nh2 ∈0 r n
• 2
= 2
=
m vn Ze Z e2
r n 4 π ∈0

Z e2
• v n= −−−−(8)
nh2 ∈0

• Now substituting this value Vn in equation (7)

Z e2 nh
• m r=
nh 2 ∈0 n 2 π

n 2 h2 ∈0
• rn =
πmZ e 2

Substituting rn in equation (6)

Z e2 −m Z 2 e 4
Total Energy of the electron= =
• n2 h 2 ∈0 8 ∈02 n2 h2
∗8 π ∈0
πmZ e 2

If you substitute all the numerical values of m,e,,h, ∈0

−13.6 Z 2
• T E= eV (n = 1,2,3 ……….) 1eV = 1.6*10-19 Joules
n2

6
Chemical Bonds

Most of the elements are found in the form of clusters or aggregate of atoms. In

which (cluster) atoms are held together and is essentially neutral, is known as a molecule.

When the atoms of the elements combine to form molecule, a force of attraction is

developed between the atoms, which hold them together, this force is known as BOND.

Ex. O2 molecule, O—O

Oxygen molecule has less energy than its two oxygen atoms. It is also stable

than the two individual oxygen atoms. (To be discussed about octet rule and inert

gases).

Cause of bonding: to achieve stability (configuration)

1. By loosing one or more electrons to another atom

2. By gaining one or more electrons from another atom

3. By sharing one or more electrons with other atom

TYPES BONDING

Interatomic Bonds Intermolecular Bonds

Strong bonds weak bonds

Primary Bonds100-1000 KJ
Secondary Bonds 1-50KJ

ionic covalent metallic Dispersion Dipole

Hydrogen
1−2 A 2-5 A

7
Ionic Bond: is formed when one or more electrons, from the outermost shell of one atom,

are transferred to the outermost shell of another atom.

– The atom which loses electron, should have low ionization energy (donor)

– The atom which gains electron should have high electron affinity

(acceptor).

– Ex. NaCl, (alkali metals low values, halogen high affinity)

Properties of Ionic Bonds

1. They are very rigid, atoms tightly packed, unidirectional and crystalline nature

2. Ionic solids are bad conductors of electricity in their solid state

3. Ionic solids are good conductors of electricity in their molten state

4. Ionic solids have high melting and boiling temperatures (high energy needs to

dissociate bonds

5. Ionic solids are freely soluble in water but slightly soluble in organic solvents

(high dielectric constant)

Covalent bond

Covalent bond is formed when two or more electrons of an atom, in its outermost

energy level, are shared by electrons of other atoms. (pair of electrons sharing by two

atoms).

Properties of covalent bond:

1. Covalent compounds are bad conductors of electricity

2. Covalent compounds have low melting and boiling temperatures (high energy

needs to dissociate bonds)

3. Covalent compounds are not soluble in water but are soluble in organic solvents

8
Metallic Bond:

Properties of metallic bond

1. Metallic solids have high electrical and thermal conductivities

(electrostatic forces of attraction and electrons are free to move)

2. Metallic solids have bright lustre (absorb light and get excited and

electron start oscillating and emit light radiation)

3. metallic solids are malleable and ductile

4. metallic solids have low melting and boiling temperature (electrostatic

forces are weak and less energy is required)

9
Secondary bonds:

Dispersion bond

Dipole bond

Hydrogen bond

10
The factors responsible for these bonding in materials are

1. Ionization potential (I.P)

2. Electron Affinity

Ionization potential can be defined as the energy in eV or joules to remove an electron

from a neutral gaseous atom

Na + I Na+ + e- ∆H = I =5.1 eV (I = Ionization energy)

Electron affinity can be defined as the energy released or absorbed when an electron is

added to a neutral gaseous atom

Cl + e- Cl- + ∆H affinity

These two factors are playing a vital role in the formation of any kind of a bond that is

existed between two atoms. The resultant energy of these two factors will decide the

strength of the bond.

∆H crystal may be defined as “the energy accompanied by the process of bringing a

positive and a negative gaseous atoms or ions from an infinite distance of separation to a

distance of closest approach or to a distance equal to equilibrium spacing where a stable

lattice is formed (i.e. one mole).

∆H lattice may be defined as “ the energy associated with the dissociation of a bond and to

keep the atoms away from each other from the equilibrium spacing”

The equilibrium spacing (closest approach of atoms) is referred to “Bond Length”

∆H crystal = - ∆H lattice

Bond energy = Bond dissociation energy

Co-ordination Number (CN):

The number of respective ions in the nearest (around or first neighbourhood) is called as

coordination number.

11
This can be calculated through the ionic ratio of cation to that of anion. This also decides

the ligancy binding characteristics of the ionic solids.

CN value = radius of the Cation (r)/ radius of Anion(R)

The structure of the ionic solids can be predicted through this ratio

Crystal Geometry
Crystal definition: Crystals are solids bounded by smooth surfaces, more or less

plane surfaces arranged in a regular pattern and are formed due to operation of interatomic

forces at the time of consolidation of the mass from the fluid state, under suitable

conditions. [OR]

Crystals are bodies bounded by surface, usually flat, arranged on a definite plane which

is an expression of internal arrangement of the atoms

a regular geometric forms

Crystal must have

a characteristic internal atomic strength

12
Lattice:

A lattice is an ordered array of points describing the arrangement of particles that form a

CRYSTAL.

Fundamental grouping of atoms in space is called Motif.

Space Lattice: is an infinite array of points in three dimensions in which every point has

surroundings identical to that of every other point in the array.

A lattice point is known as a motif or basis. We can obtain a crystal structure by

combining the lattice with the motif (i.e., crystal structure = lattice + motif). Figure shows

a periodic pattern consisting of a two-dimensional (2-D) net and a motif. The motif is

arranged symmetrically and is repeated at each point of the 2-D net to create the periodic

pattern, and thus the lattice structure is also symmetric.

13
Unit Cell :

May be defined as “Smallest repeating unit volume in three dimensions (x,y,z

directions), which on translation completely fills the space and has all the characteristics of

a crystal. Hence, it is the smallest volume that carries a full description of the entire lattice.

The volume of the unit cell can be represented with the help of three imaginary axes,

which are said to be crystallographic axes.

Crystallographic axis is an imaginary indefinite axis which is passing through the centres

of the opposite faces as well as the centre of the crystal. Each crystal possesses three

crystallographic axes which perpendicular to each other and intersecting each other at one

14
point, that intersecting pointing generally coincidence with the centre of gravity of the

crystal. All the crystallographic axes are perpendicular to each other.

To describe the unit cell as well as entire cell, one has to take the help of some

parameters; those are called as lattice parameters.

Lattice parameters:

The intercepts a, b and c (translational vectors) define the dimensions of the unit cell

and are known as primitives or axial lengths. The angles ‘γ ' represents the angle

between ‘a’ and ‘b’ axes, the angle ‘α’ represents the angle between ‘b’ and ‘c’ axes, and

the ‘β’ represents the angle between ‘c’ and ‘a’ axes, all these three known as inter-axial

angles (α, β, γ ¿ .

The axial lengths (a,b,c) and three inter-axial angles (α, β, γ ¿ are together known

as Lattice parameters

Primitive Unit Cell: The volume of unit cell is a*b*c. if this volume in space contains

only one lattice point, then it is said to be ‘Primitive unit cell’. Sometimes

unit cell contains more than two or more lattice points, then it is called

as a non-primitive unit cell. Unit cell has one lattice point.

15
 Lattice point is defined as the effective number of points in an unit cell under

consideration.

To explain the geometry of the crystal which will reflect the internal arrangement of

atoms, one has to take the help of the term “SYMMETRY”.

Symmetry reflects the regularity of the form or arrangement around an axis of the

crystals.

There are three types of symmetries to explain the perfect crystal structure.

1. Planes of symmetry

2. Axis of symmetry

3. Centre of symmetry.

(Together called as elements of symmetry)

1. Planes of symmetry: A plane which divides the crystal not just into two equal halves

but also into two equal halves which are mirror images of each other

2. An axis of symmetry: is defined as a line through the crystal such that after rotation through 360

degrees the crystal assumes a congruent position; an identical view being seen again.

There are four axes of symmetry; (on rotation)

i. The same view occurs every 180 – axis of 2-fold symmetry

ii. The same view occurs every 120 – axis of 3-fold symmetry

16
 iii. The same view occurs every 90 – axis of 4-fold symmetry

iv. The same view occurs every 60 – axis of 6-fold symmetry

3 A centre of symmetry:

When similar faces occur in parallel pairs on opposite sides of a crystal, is said to

possess ‘a centre of symmetry’.

17
BRAVAIS LATTICES

Many scientists are expecting that many lattices can be generated in three

dimensions with different primitive and non-primitive cells. Bravais introduced the

concept of space lattice in the study of crystal structures. Bravais showed that there are

only fourteen different ways of arranging identical points in three-dimensional space,

satisfying the condition of periodicity, so that they are in every way equivalent in their

surroundings. These fourteen types of arrangements are called the space lattices or

Bravais lattices. There are 7 primitive and 7 non-primitive cells.

On the basis of primitive cell, crystals are grouped into 7 systems. They are cubic,

tetragonal, orthorhombic, monoclinic, triclinic, hexagonal and rhombhohedral (trigonal).

Crystal systems and corresponding Bravais lattices with their features are described below.

18
Simple cubic (SC) cell:

A unit cell is said to be primitive when he cell has lattice points only at its

corners. The primitive cubic unit cell is also called a simple cubic (SC) cell.

Unit cell Volume, V: If all the edges of the cube are of equal length ‘a’. Then, the volume

is given by V = a3. Effective number of atoms per unit cell (Z):

19
 A unit cell is a part of an infinite scheme, and is not an isolated entity. Therefore,

several adjacent cells share each lattice point. As a result, the basis attached to a lattice site

contributes only a fraction of its mass and volume to one unit cell. Let only one atom,

having a radius ‘r’, be attached to one lattice point

20
 Each corner atom is linked to eight surrounding cells in the three-dimensional array as

shown in the figure. Hence, in effect, each atom contributes 1/8 th of its content to a unit

cell as shown in the previous figure.

SC cell being a primitive cell does not contain lattice points with the body volume or

in the Centre of faces. The total contribution comes from the corner atoms of the unit

cell and is given by

Z = 8 x 1/8 = 1 atom/cell

If the radius of the atom is ‘r’ then

Lattice parameter ‘a’ = 2r

Then ‘r’ = a/2

Packing fraction (atomic packing fraction, APF)

The fraction of space occupied by atoms in a unit cell is known as atomic packing

fraction. It is defined as the ratio of volume of effective number of atoms in the

unit cell to the total volume of the unit cell.

( Number of atoms /unit cell) x ( volume of each atom)

– APF=
( volume of theunit cell)

4
Volume of the atom in the spherical shape v= π r 3
3

where ‘a’ = 2r

4 3
1X πr
3 4 π r3 π
APF= = = =0.52
3∗(2r ) 6
3 3
a

Percentage void space: The void space in the unit cell is the vacant space left utilized in

the cell. It is expressed as percentage

21
 %void space = (1-APF) * 100

(1-0.52) *100 = 48

Density of SC crystal, ρ:

As a unit cell possesses all the structural properties of a bulk crystal, the density of

Mass ZW
a unit cell must be the same as that of the bulk crystal, thus, Density, ρ = =
Volume V

M
where ‘W’ is the mass of each atom, which is given by W=
NA

M is the molecular weight of the material and NA is the Avogadro Number

Therefore, the density of a cubic crystal is given by

ZM ZM M
ρ= = =
N A N A a N A a3
3

FACE CENTRE CUBIC (FCC) CELL:

It is a non-primitive cell having six lattice points at the centres of its six faces and

eight atoms at the eight corners of the cube, as shown in the figure.

Volume of the unit cell is given by V = a3.

Effective number of atoms per unit cell, Z

A unit cell is surrounded by other unit cells, while each corner of the cell is

shared by eight adjacent cells, and each face is shared by two adjacent cells, as shown in

the figure. Therefore, each face-centred atom contributes half of its mass and volume to

one cell, while each corner atom contributes 1/8th

22
 There are 6 faces and 8 corners in a cubic cell. The number of atoms effectively

contributing to the FCC cell is = 6 x1/2 + 8x1/8 = 3 + 1 = 4 atoms/cell.

Atomic Radius (r):

In FCC cell, atoms are in contact along the face diagonal of the cube, as shown in

the figure

CB 2=CD 2+ BD 2

CB=4r,CD=BD=a ( 4 r )2=a 2+ a2=2 a2

a
4r = 2a r=
2√ 2

23
Atomic packing fraction, APF:

( Number of atoms /unit cell) x ( volume of each atom)

• APF=
( volume of theunit cell)

4 3
4X πr a
3 16 π r 3 where r =
APF= = 2√ 2
a3 3∗(2 r)3

π
APF = =0.74
3 √2

Percentage void space = 1-0.74 = 0.26

Density of cubic crystal of FCC is given by

ZM ZM M
ρ= = = FCC , Z= 4
N A N A a 3 N A a3

ZM ZM 4M
ρ= = =
N A N A a N A a3 for FCC
3

24
BODY CENTRED CUBIC (BCC) CELL

The body centred cubic has a lattice point within the cell in addition to the eight

corner lattice points, as son in figure.

4 3
Volume of the atom in the spherical shape v= π r
3

Volume of the unit cell, V = a^3

Effective number of atoms per unit cell, Z.

BCC cell has eight lattice points at the eight corners of the cube and one lattice point at

centre within the cell, it is not shared by any nearby atoms. It is totally belonged to the

unit cell only. Lattice points are = 1+ 8*1/8 = 1+ 1 = 2 atoms/cell.

25
 Percentage void space = (1-0.68) = 0.32*100 = 32

Density of the BCC crystal, here Z = 2

ZM ZM 2M
ρ= = =
N A N A a N A a3
3

2M
ρ=
N A a3

HCP STRUCTURE:

Hexagonal closed packed (HCP) structure is one of the most common metallic

structures. About 25 metals exhibit this structure. Metals do not crystallize into the simple

hexagonal crystal structure. The atoms attain lower energy and a more stable condition

only by forming HCP structure.

Effective no of atoms per unit cell:

The isolated HCP unit cell is shown in the figure. Each corner of the Hexagonal face

is shared by six unit cells. Its contribution is 1/6 th of its volume and mass to one unit cell.

There are six corner atoms in the base. Further, there is an atom at the centre of the each

26
hexagonal face, which is shared by two adjacent unit cells. Three atoms forming a triangle

in the Middle layer are within the body of the cell and cannot be shared by adjacent cells.

The total contributions to the effective number of atoms in the cell is as follows

Z= 6* 1/6 portion of top plane atoms + Half contribution of centre atom of the top plane +

3 atoms at centre (no sharing) + 6 * 1/6 portion of the bottom plane atoms + Half

contribution of centre atoms of the bottom plane

Z = [6*1/6] + ½[top centre atom] + 3 + [6*1/6] + ½[bottom centre atom]

= 1+1/2+3+1+1/2= 6

Atomic radius of the HCP atom 2r=a r = a/2

Volume of the unit cell:

The volume of the unit cell may be determined by computing the area of the base of

the unit cell and then by multiplying it by the cell height. The area of the base of the unit

cell is the area of the hexagon ABDEFG.

27
Area of the hexagon ABDEFG = 6(area of ∆ABC)

6(1/2a)(a sin 60) = ¿ ¿

Volume of the unit cell = (area of hexagon)*(height of unit cell)

3 2 √ 3 a 2C
=3 [√ ]
2
a ∗C=3
2[ ]
if ‘c/a’ ratio is equal to 1.63

3 2 √ 3 a2 8 a=3 3
Then Volume of the hexagonal cell, V = 3 [√ ]
2
a c=3
2[ ]√ 3
√2 a

6∗4 3
Zv πr π
Atomic packing fraction, APF = = 3 = =0.74
V 3 3 √2
3 √2 ( 2 r )

Void space % = (1-APF) *100 = (1-0.74)*100= 26%

6M 6M
Density of the HCP cell = ρ= =
N A V N A 3 √ 2 a3

Calculation of c/a ratio

Referring to the HCP unit cell in the figure, it is seen that a=b and the angle θ=120.

The axis is normal to the plane containing ‘a’ and ‘b’. Therefore α=β=90. Let P, Q and R

be the centres of the adjacent atoms in the middle plane and N and M be the centres of the

28
adjacent atoms in the plane immediately above and below the plane PQR, as shown in the

figure. Now let us join M to N and M and N to P, Q and R. It forms two tetrahedrons

MPQR and NPQR with PQR as the common base. The line MN passes through the point

T, which is the intersection of the three medians of the triangle PQR. RS is one of the

medians ad therefore TR = 2TS MN= c and PQ=QR= a

As the median of an equilateral triangle is also perpendicular to the opposite side,

angle QSR = 90

RS2 = RQ2- QS2

a 2 √3
√
RS= a2− () 2
= a
2

2 2 a
RT = 2TS = ( TS+TR) = (RS) = 2 √3 a =
3 3 3 2 √3

a2 2
2 2
3 3√ 2

√
NT =√ NR −RT = a − = a (NR=NQ=NP=a)

2 8
c=2 NT =2
√ √
3
a= a
3

c 8
a √
= =1.63
3

29
Difference between Crystalline and Non-crystalline materials

X-Ray diffraction method

This method is very useful to find the system of the crystallization of the material.

Bragg Law of X-ray diffraction:

A beam of x-rays directed at crystal interacts with the electrons of the atoms in the

crystal present in different planes. The electrons oscillate under the impact and become a

new source of electromagnetic radiation. The wave emitted by the electrons has the same

frequency as the incident x-rays. The emissions in particular direction is the combined

effect of the oscillations of all atoms and x-rays. This will depend on the incident x-rays,

their wavelength as well as the spacing between atoms in the crystal. This effect can be

explained and visualized through the “Bragg Law”.

30
 A set of parallel planes in a crystal is shown in the figure. A beam of x-rays of

wavelength ‘^’ is directed towards the crystal at an angle ‘θ’ to the atomic planes.

Consider a set of planes consisting of plane-1, plane-2 and plane-3 which are rich in

atoms. Let the incident rays AB and DE be reflected at B and E and E from the atoms,

along BC and EF respectively as shown in the figure.

‘d’ is the distance between the same set of planes. Now draw perpendiculars BP and

BQ on the X-ray DEF. From the geometry of the figure, we find that the path difference

(i.e. extra distance travelled by the x-ray DEF as compared to the x-ray ABC)

PE+EQ=d sinθ+d sinθ= 2d sinθ

We know that if this path difference is equal to an integral multiple of wavelength of

x-ray, the two rays are in phase with each other. And if it is equal to an odd multiple of ^/2,

the two rays are out of phase each other.

Thus the condition for maxima may be written as

n ^ = 2 d sin θ where n=1,2,3,4 .. . . ..

Condition: The reflected rays will reinforce each other only when this path difference

is equal to an integral multiple of the wave length.

31
 ‘n’ is call the order of reflection n= 1,2,3…….n

If (hkl) is (100) then such a plane is called first order Plane.

(200) is the second order plane so on.

a
d hkl =
√ h +k 2+l2
2

^=2 d hkl sinθ

a
^=2 sinθ
√h + k 2+l2
2

4 a2 2 2
2 2 2
sin θ=^ and let Q2= √h2 + k 2+l 2
√ h + k +l
^2 sin 2 θ 2sin 2 θ 4 a2
= 2 -------------Q = 2
4 a2 Q ^

Q2 α sin2 θ since ^ and 'a’ are constant

The reflections (h2 + k 2+ l2 ) are proportional to sin2 θ .There are extension rules to

identify the structure of the crystals of cubic system.

Simple cube -- 1:2:3:4:………….

Body centred ---- 2:4:6:8:10:12……

Face Centred ---- 3:4:8:11:12:16:……

Diamond cubic --- 3:8:11:16:……

A simple rule if first two reflections are known

sin2 A
=0.5, crystal structure is BCC , Ratio is 0.75belongs ¿ FCC, if it is equal to 0.375,
sin 2 B

belongs to DC

32
 There are many materials for which it is not possible to obtain single crystals of

required size. For such materials powder photography is highly suitable. One of the

powder photography is known as Debye-Scherrer method invented by P.Debye and

Scherrer. Figure shows that the experiment arrangement. (Consider one set of parallel

crystal planes)

It consists of a cylindrical camera called Debye-Scherrer camera, whose width is

smaller as compared to its diameter. The material used for investigation is crushed into fine

grain powder and compressed into a thin rod or packed into a small capillary tube. A strip

33
of photographic film wrapped in opaque paper is mounted around the inside of the

cylindrical drum of the camera. The specimen is positioned vertically at the centre of the

drum. A narrow beam of monochromatic x-rays enter and leave the drum through the

apertures on the opposite sides of the drum. Each crystallite has the same system of the

atomic planes.

Some of the crystallites are bound to lie with their planes at glancing angle ‘Theta’ to

the incident ray such that Braggs’ condition is satisfied. Each such crystal produces a spot

on the photographic place. As the specimen contains a large number of crystallites oriented

on all directions, almost all the possible values of theta and ‘d’ are variable. Also, for a

particular value of the angle of incidence theta, numerous orientations of a particular set of

planes are possible. The diffracted rays corresponding to fixed values of theta and ‘d’ lie

on the surface of a cone with its apex at the sample and the semi-vertical angle 2theta.

Different cones are observed for different sets of Theta and ‘d’ for a particular value of ‘m’

and also for different combinations of theta and ‘m’ for a particular value of ‘d’. Each cone

of the diffracted beam leaves two impressions on the film in the form of arcs on either side

of the exit aperture and their centers coinciding with the aperture.

 If ‘x’ is the distance at which a diffracted beam strikes the film from the centre “O”

1800 x
then 2 θ= where ‘R’ is the radius of the drum
πR

900 x
θ=
πR

let x1, x2, x3 …. Be the distances between symmetrical arcs on the stretched photograph

film, then

34
 90 0 x 1 90 0 x 2
θ1 = ;θ2= ; ---- - - - - - - -
πR πR

 Using the value of theta into Bragg’s equation, the inter-planar spacing ‘d’ can be

calculated.

 The diffraction pattern obtained in this method helps us distinguish amorphous

material from crystalline material. Amorphous materials do not have reflecting planes.

 The cassette film on stretching shows the in-let and out-let points around which the

diffraction patterns can be seen. They appear as arcs and the distance between these

arcs gives us the ‘S’ values. Thus, the radius of camera from which ‘S’ values can be

obtained is related to S as: S=4Rθ.

35
 BASIC THERMODYNAMIC FUNCTIONS

Energy considerations are important in the internal structures of materials. The lowest

energy state of a material is the equilibrium state which is the most stable state.

Sometimes, higher energy state remains for lone periods and the material is said to be in

metastable state. This is the reason most of the metals are stable in the form of oxides at

room temperature.

The concept of equilibrium and kinetics are intimately associated with the basic

thermodynamics potentials such as internal energy (E), enthalpy (H), Gibbs free

energy(G). The potentials depend on thermodynamic properties such as pressure(P) and

Temperature(T). Another important thermodynamic property that plays vital role is

entropy(S).

E, H and Gibbs free energy G=H-TS

T
C pdT
S=∫ (thermal entropy, when there is no phase change
0 T

w^
∆ S= (Thermal entropy when there is a phase change
T

S=K ln (w) this is called configurational entropy

where ‘w’ is distinguishable number of ways by which the atoms having equal potential

energies are removed from or added into lattice of ‘N’ number of sites and ‘k’ is

Boltzman constant.

∆S = Gfinal – G initial

36
Solid solution: A solid is simply a solution in the solid state and consists of two or more

kinds of atoms forming a single phase. The term solvent is used to refer to the more

abundant atomic form in the solid solution and the term solute to the less abundant. The

solute atoms are distributed throughout the lattice of the solvent crystal.

In the solid solutions, solute atoms may occupy two different types of positions in the

lattice of solvent. If they replace and substitute for the solvent atoms from the lattice, the

resulting combination is called as substitutional solid solution. If the solute atoms become

an integral part with the solvent atoms, occupy interstitial positions between lattice atoms

is said to be interstitial solid solution.

Substitutional solid solution: Alloys of this type are often made to increase strength of

the given metal. Hume-Rothery has framed some empirical rules that govern the formation

of substitutional solid solution. They are summarized as for two metals to form solid

solution in all proportions they must have

1. Less than15% difference in their atomic size

2. No appreciable difference in electronegativity

3. The same valence

4. The same crystal structure.

Ex: Copper substituted for nickel.

Interstitial solid solution: small amount of solute atoms are accommodated in the

interstices between larger solvent atoms as shown in the figure.

Ex. Carbon in Iron of steel.

Crystal imperfections: The ideal crystal has an infinite 3D repetition of identical units,

37
which may be atoms or molecules. Therefore, it does not contain lattice imperfections.

However, ideal crystals neither occur in nature nor can be produced by artificial methods.

The real crystals are limited in size and repeated violations of long range order would be

found in them.

Def: A defect or an imperfection is defined as any deviation from the perfect periodic

arrangement of atoms observed in real crystals.

The defects found in real crystals are classified into four main categories. They are

i. Point defects (zero dimensional defects)

ii. Line defects or dislocations (one dimensional defects)

iii. Planar defects (two dimensional defects)

iv. Volume defects (three dimensional defects)

Point defects: These defects are produced in a crystal due to thermal vibrations. At any

given temperature, some of the lattice points normally occupied by metal ions are vacant,

giving rise to vacancies. A point defect is a localised interruption in the regularity of the

crystal lattice. It produces strain in a small volume of the crystal surrounding the defect,

but does not affect the perfection of distant parts of the crystal.

The point defects can be divided into four types:

1. Vacancies defects

2. Interstitials defects

3. Frenkel defects

4. Schottky defects

5. Phonon and

38
 6. Electronic Defects

Vacancies: Vacancies are produced during solidification as result of local disturbances or

from thermal vibrations of atoms at high temperatures. Whenever one or more atoms are

missing from a normally occupied position (lattice points), the defect is known as

Vacancy.

Frenkel Defect: Whenever a missing atom (responsible for vacancy) occupies interstitial

position (responsible for interstitial defect) as shown in figure is known as Frenkel Defect.

It is a combination of vacancy and interstitial defects. These are more common in ionic

crystals. A Frenkel defect does not change the overall electrical neutrality of the crystal.

The concentration of Frenkel defects does not change the density of the crystal.

39
Substitutional Defects: Whenever a foreign atom (other than the parent atoms) occupies a

lattice position, which was initially meant for a parent atom as shown in the figure. The

atom which replaces the parent atom may be of the same size or slightly smaller or larger

than that of parent atom.

Schottky Defects: Whenever a pair of positive and negative ions is missing from a crystal

as shown in the figure. This type of a defect is electrically neutral. The concentration of

Schottky defects decreases the density of the crystal. This type of defects formed in ionic

crystals.

40
Electronic Defects: Errors in charge distribution in solids are called electronic defects.

These defects are produced when the composition of an ionic crystal does not correspond

to the exact stoichiometric formula.

Def: In ionic compounds when exact ratio of cations to anions as predicted by the

chemical formula are not followed, the errors in charge distribution are known as

electronic defects.

When a stoichiometric compound ZnO is heated in the presence of zinc vapour, a

nonstoichiometric compound ZnyO is produced. Some of ionized zinc atoms enter the

lattice of ZnO and stay around as interstitial cations as shown in the figure. The excess of

cations must be balanced by an equal number of electrons. These defects, electrons are free

to move in the crystal under the influence of an electric field and contribute to the electrical

conductivity of the material.

Phonon: Whenever a group of atoms is displaced from its ideal location, the defect caused

is known as phonon. This defect may cause due to thermal vibrations. This defect

affects electrical and magnetic properties to a great extent.

EFFECT OF POINT DEFECTS:

41
 Point defects are sources of distortion and cause residual strains in the lattice. But in

some cases, they give rise to beneficial effects by improving mechanical and electrical

properties of the materials.

1. The addition of carbon atoms in iron increases its tensile strength.

2. Addition of copper atoms in gold increases its ductility so that it can be drawn into
wires.

3. Vacancies help the transport of atoms through the lattice for annealing etc
purposes.

LINE DEFECTS:

Line defects are one dimensional defects and are also called dislocations.

Dislocations are areas were the atoms are out of position in the crystal structure. A

dislocation is a one-dimensional defect around which some of the atoms are misaligned.

They may be defined as disturbed region between two perfect parts of the crystal. It is a

defect in a crystal structure whereby a part-plane of atoms is displaced from its

symmetrically stable position in the array. Dislocations appear in crystal due to growth

accidents, thermal stresses phase transformation etc.

These are divided into two basic types:

1. Edge dislocation

2. Screw dislocation

Edge dislocation:

In a perfect crystal, atoms are arranged in both vertical and horizontal planes. The

atoms are a perfect equilibrium in their positions and all bond lengths are in equilibrium

42
state. If one of the vertical plane does not extend to the full length, but abruptly terminates,

then it may be viewed as an extra half-plane inserted in between a set of parallel planes.

The edge of such a plane constitutes a linear defect. It is a linear defect centred on the line

along the end of the extra half-plane of atoms.

It may be seen that the atoms above the edge are squeezed and are in a state of

compression while the atoms below the edge are pulled apart and are in a state of tension.

The region of distortion spreads a few lattice distances around the edge. This distortion is

known as Edge Dislocation. This edge is in the direction perpendicular to the plane of the

figure and constitutes the dislocation line.

This dislocation is called a line defect because the locus of defective points produced

in the lattice by the dislocation lie along a line. This line runs along the bottom of the extra

half-plane. The inter-atomic bonds are significantly distorted only in the immediate

vicinity of the dislocation line. The plane in which the dislocation line is present is called a

slip plane. The dislocation line forms a boundary between slipped and unslipped portions.

43
 An edge dislocation is said to be positive when the half-plane appears to have been

inserted from the top of the crystal as shown in the figure. It is denoted by ‘┴’. An edge

dislocation is said to be negative if the extra half-plane lies in the lower part of the crystal.

It is denoted by ‘┬’.

Screw Dislocation:

The screw dislocation is also called as Burger’s dislocation. The geometry of screw

dislocation is shown in the figure. Let us visualize a perfect crystal cut by a plane ‘P”.

Then let the crystal on the right side of the cut be shifted (sheared) relative to that on the

left side by an amount ‘b’. From this figure it is seen that the shift has occurred for he

length of one-atomic spacing in the predominant part of the crystal and reached the line

OO’. Away from this line, the crystal structure is undisturbed and shows an ordered atomic

arrangement. Near the line OO’ atoms of atomic planes lying to the and right of the shear

plane P have undergone displacement with respect to each other. This displacement causes

a local distortion called a SCREW DISLOCATION’. The line OO’ is the line of

dislocation. It may be viewed now that the atoms in the dislocation region lie on a surface

which spiral from one end of the crystal to the other with the line of dislocation as the axis

of the spiral. The displacement of the atoms from their original positions in the perfect

crystal is described by the following equation.

b
r= θ r= the displacement along the dislocation line,
2π

θ= the angle measured from a line perpendicular to the dislocation line.

44
Planar defects: Planar defects are two dimensional defects that separate two regions of the

crystal. These defects are the external faces, grain boundaries, twin boundaries and

stacking faults.

External Surfaces: The surface of a crystal itself is a defect. The surface atoms have

formed bonds with neighbors only on one side, whereas the atoms inside the crystal

formed bonds with neighbors on either side of them. Since the surface atoms are not

bonded to the maximum number of nearest neighbors, they are in a higher energy state

than the atoms in the interior of the crystal. This gives rise to a surface energy. The

crystal tends to minimize the total surface area in order to reduce the surface energy, but it

is not possible because solids are mechanically rigid.

Grain boundaries: A grain boundary is a general planar defect that separates regions of

different crystalline orientation (i.e grains) within a polycrystalline solid. Solids are

formed when the melt of materials are cooled. Depending upon the rate of cooling, either

single crystals or polycrystalline solids form. During crystallization, Crystallites are

crystallized in different orientation. Crystallites with particular orientation tend to join

those with the same orientation. All the crystallites that have the same orientation form a

45
bigger block called grain. When the solidification is compiled, the solid consists of a

number of grains attached to each other. The result is a polycrystalline sample. In between

the grains, there exists a boundary called grain boundary. The boundary region is of a few

atomic diameters wide. There occurs some atomic mismatch in the region of transition

from one grain to its adjacent grain. Grain boundaries are therefore more chemically

reactive than the grains themselves.

Twin Boundaries: A twin boundary is a special type of grain boundary. Atoms on one

side of a twin boundary are located in mirror-image positions of the atoms on the other

side. The boundary between the twinned crystals will be a single plane of atoms. The

crystals on either side of he plane are mirror images of each other. There is no region of

disorder and the boundary atoms can be viewed as belonging to the crystal structures of

both twins and shown in the figure.

46
Stacking Faults: The stacking faults are usually produced during the growth of crystals.

Stacking faults are observed in FCC metals. An face centred cubic crystals is regarded as

formed by the stacking of hexagonal close packed atomic layers, A,B and in the sequence

–ABCABCABC……… if one of the layers goes missing, then stacking fault occurs in the

crystal. For example, if the A layer in the third set of sequence fails to appear, the

sequence changes to ABCABCBCA….. Then the sequence is interrupted and a stacking is

produced and shown in figure.

Volume Defects: volume defects such as cracks may rise in crystals during the process of

crystal growth. A crack may result during the growth due to a possible small electrostatic

dissimilarity between the stacking layers. Inclusion of foreign particles or non-crystalline

regions of the size of 20 Å also belong to the category of volume defects.

Role of imperfections in plastic deformation:

Plastic deformation is due to the motion of a large number of dislocations.

Dislocations are the elementary carriers of plastic flow thus they define material

mechanical properties. Dislocations can be edge dislocations, screw dislocations and

exist in combination of the two. There is compression near the extra plane, higher

atomic density and tension following the dislocation line.

47
 From an atomic perspective, plastic deformation corresponds to the breaking of bonds

with original atom neighbours and then reforming bonds with new neighbours as large

numbers of atoms or molecules move relative to one another. Slip is the process by

which a dislocation moves and deforms a material.

 Dislocations generate from existing dislocations and from defects, grain boundaries

and surface irregularities. BCC and FCC crystals have more slip systems that is more

ways for dislocation to propagate. Thus, those crystals are more ductile than HCP

crystals and HCP crystals are more brittle. Dislocations are imperfections in the

crystal lattice, which are mobile and can move through the lattice when stress is

applied. They have extremely important effects on the materials properties,

mechanical strength. Metals are strengthened by making it more difficult to move

dislocations.

Dislocation reactions:

1. If the dislocations are so oriented that their stress fields cancel, the dislocations

attract each other

2. If stress fields reinforce, the dislocations repel each other.

3. Two parallel edge dislocations of opposite signs and of the same Burgers vector on

the same or nearby slip planes attract each other.

4. On the slip plane such dislocations come together, they annihilate each and leave a

perfect lattice.

5. Interaction between such dislocations on adjacent planes may cause their

annihilation, leaving however a row of vacancies or interstitials atoms.

48
6. Parallel edge dislocations of the same sign, when on the same slip plane, repel each

other.

7. If such dislocations are on separate planes they attract or repel each other

depending on the angle between the slip direction and the line joining them.

8. Screw dislocations of opposite sign and same Burger vector attract each other. If

they come together they are annihilated, leaving behind a perfect lattice. Screw

dislocations of the same sign and Burger vector however repel each other.

49
 MECHANICAL PROPERTIES OF MATERIALS

This unit deals with the mechanical behaviour of materials and their response to an

applied force. Their mechanical behaviour depends on the type of boding existing in the

micro-structure and the arrangement of atoms in the crystal lattices.

The selection of the material for any equipment is essentially based on its capacity to

resist any failure or fracture due to an applied stress. Heavily stressed material is more

prone to undergo chemical corrosion.

It is essentially to have knowledge in the materials changes or behaviour, when they

are subjected to stresses before recommending them to a particular engineering service.

Stress: The elastic properties of solids are generally discussed in terms of stress and strain.

Stress is a measure of the force causing a deformation. Strain is a relative measure of the

deformation a stress causes. The sum of all the elementary interatomic forces which the

material put forth to neutralize the applied load is called stress.

Stress Definition: When deforming force is applied on a body, the force of reaction,

internal restoring force developed to bring back the body to its original state is called

as stress.

Units of stress are Pascal, N/m2.

restoring force
Stress=
Area of cross section

At equilibrium, restoring force is equal to external deforming force so,

deforming force F
Stress= =
Area of cross section A

 Types of stresses:The basic stresses are normal stress, shear stress and bulk stress.

50
Normal stresses: if deforming force is applied normal to the area, hen the stress is called

normal stress. The normal stresses are generally denoted by a Greek letter (σ). The normal). The normal

stresses can be either tensile or compressive whether the stresses act out of the area or into

the area.

a. Tensile stress: A normal stress is called tensile when the body is subjected to pull

and there is an increase in length. It is also called as longitudinal stress. Under tensile

stress the bar suffers stretching or elongation.

b. Compressive stress: A normal stress is called compressive when the body is

subjected to thrust and there is a decrease in length. Under compressive stress the bar

suffers shortening.

Shear stress: if deforming force is applied tangentially, then the stress is called

tangential stress. Such forces are associated with a shearing of the material, and are

referred to as shear forces. The resulting stress is known as shear stress.

Def: When the stress is tangential to the surface due to the application of force parallel

to the surface then it is called as shearing stress.

force F
Shearing Stress= =
Surface Area A

Volume or bulk stress: if the solid say a rectangular block is immersed in a fluid, it is

compressed uniformly on all sides. The force applied by the field acts in perpendicular

direction at each point of he surface and the block is said to be under compression.

This leads to decrease in its volume without any change of its geometrical shape.

51
Strain: When a single force acts normally on a body, it undergoes some deformation.

Strain is the dimensional response given by material against mechanical loading, that is

deformation produced per unit length.

Def: The ratio of change produced in the dimensions of a body by system of forces to its

original dimensions is called strain. Strain is a dimensionless quantity and as it is a

ratio it has no units.

Elongation
Strain=
Original Length

Types of strain: Strain is classified into three types depending upon the change produced

in the body.

Longitudinal Strain: When the force acts along the length of the body, a change in

length is produced without any change in shape. The ratio of change in length to the

original length without any change in shape is called longitudinal strain.

Shear strain: It is defined as the ratio of relative displacement between two layers,

under the action of tangential force to the distance between them.

Volume strain: ratio between change in volume and original volume.

Hooke’s Law: This law gives the relationship between stress and strain.

According to Hooke’s law strain is proportional to stress producing it within the elastic

limits.

stress
k= . K is coefficient of elasticity and called modulus of elasticity and its
strain

unit is Pascal, N/m2. it depends on nature of the material and conditions of the

manufacturing.

52
DIFFERENT MODUULI OF ELASTICITY

Elastic modulus is the coefficient that relates a particular type of stress to the strain.

Elastic moduli are properties of materials and are measures of stiffness. Modulus of

elasticity is a conversion of Hooke’s Law to make it dimension-independent by referring

the force to unit area and unit length.

There are three basic types of stress and three associated moduli. Three general types

of elastic moduli are associated with stresses that produce changes in length, shape or

volume. They are known Young’s Modulus shear modulus and bulk modulus respectively.

i. Liner stress –Young’s Modulus or modulus of length

ii. Shearing stress- Shear modulus, modulus of rigidity or shape

iii. Volume stress – Bulk modulus or modulus of volume

Young’s Modulus: when a wire or rod is stretched by a longitudinal force, the ratio of

longitudinal stress to longitudinal strain within elastic limit is called young’s Modulus.

This is denoted by ‘Y’ and unit is as that of pressure, N/m2.

longitudinal stress F / A FL
Y= = =
longitudinal strain ∆ l/ L A ∆l

Shear Modulus: solids also have rigidity that resistance is to shear loads. The resistance

to shear loads in solids is called modulus of rigidity.

Def: the ratio of tangential force per unit area to angular deformation

produced is called rigidity of modulus. It is represented by ‘G’ and units is as

that of pressure, N/m2.

tangential stress F/ A F / A T
G¿ = = =
shearing strain θ θ θ

53
Bulk Modulus: When force is applied normally and uniformly to the whole surface of the

body such that the shape remains the same and change occurs in volume, the body is

compressed.

Def: the Ratio of normal stressto the volume strain is called bulk modulus of

elasticity and represented by ‘K’. Its units are as that of pressure N/m2.

Bulk stress F/ A FV PV
K¿ = = =
Volume strain ∆V /V A ∆ v ∆V

POISSON RATIO:

If a wire or bar is stretched, besides undergoing extension along the direction of the

force it also undergoes contraction in the perpendicular directions. As a result, it becomes

longer but also thinner.

The strain produced along the direction of the force is called longitudinal strain and

that produced in perpendicular direction is called lateral strain.

Def: The ratio of lateral contraction to longitudinal elongation is called ‘Poisson

ratio’. It is denoted by ‘ν’.’.

Lateral strain μ
Poisso n' s rario ' ν’.'= =
Longitudinal strain ^

Stresses-Strain diagram and its uses:

Stress-Strain diagram gives the behaviour of a wire under progressive tension. We can

study the relationship between stress and strain by plotting graph between the two for

various values of stress and accompanying strain.

The figure represents the stress-strain diagram for a wire. In figure, a straight and

sloping part OA of the curve shows that the strain produced is directly proportional to

stress applied. OA obeys Hooke’s law perfectly. In tis region, the wire regains its original

54
length when unloaded and so it is called the range of perfect elasticity. At a wire reaches

elastic limit. After the elastic limit is crossed, the strain increases more rapidly than stress.

In AB region of the curve, the extension of the wire is partly elastic and partly plastic.

At point B even after unloading, it does come back to original condition along OA. It

takes dotted path BC so that there remains residual stress OC in it and permanent set is

acquired by the wire. At point B even the addition of very small load causes enormous

elongation. The points B and D are called supper and lower yield points. After D wire

becomes plastic. DF is called tensile strength of the wire. E is the breaking point. The load

at which the wire breaks is called Breaking weight. The maximum load to which wire can

be subjected divided by the original cross sectional area is called the breaking stress. It is

obvious that work has to be done in stretching the wire destruction under increasing stress.

The work is stored in the wire in the form of potential energy similar to compressed spring.

It is found that even within the elastic limit, practically all substances takes some time

to come back their original length after deforming force is removed. This delay in

55
recovering back is called “elastic after effect”. If a body is continuously subjected to stress

and strain, it gets fatigued. Fatigue can be removed by giving sufficient rest to wire.

RELATION BETWEEN DIFFERENT MODULI OF ELASTICITY:

Consider a cube (fig) of unit length of an isotropic material such that one of its

vertexes coincides with the origin. Let us assume that three stresses P, Q and R, are acting

perpendicular to three faces ABCE, BCGE, EBFA. Each one of these stresses produce

extension in its own direction and compression along other two perpendicular directions. If

‘^’ is the extension per unit stress the elongation along the direction of P= ‘^P.

If ‘f’ is the contraction per unit length per unit stress, the contraction along the

direction of P due to other two stresses will be ‘fQ and ‘fR.

Let us assume that all three stress simultaneously on the cube.

Net elongation along the direction of P = e = ^P –fQ - fR.

Net elongation along the direction of Q = f = ^Q –fP - fR.

Net elongation along the direction of R = g = ^R –fP – fQ.

We can express three elastic constants Y,G and K in terms of ^ and f

Suppose only strain P acts and Q=R= 0, In this case we have simple longitudinal

stress, Linear strain = ^P

56
 Then Young’s modulus

stress P 1
Y= = = −−−−−(1)
strain λpp λp

Suppose stresses R=0 and P= -Q, elongation along the direction of

P = e= ^P –fQ - fR.= ^P –f (-P) – f(0) = (^+f) P

The angle of shear θ = 2e= 2(^+f) P

stress P P 1
Rigidity Modulus G= = = =
angle of shear θ 2(λp+ μ) P 2( λp + μ)

1
2 ( λp+ μ ) = −−−−−−−−−−−(2)
G

Suppose stresses P=Q=R, in this case body is subjected to uniform stress in all

directions. Increase in the volume or bulk strain.

3e = 3(^P –fQ – fR) = 3(^P –fP – fp) = 3(^P –2fP)= 3P(^ –2f)

stress P 1
Bulk Modulus K = = =
bulk strain 3 ( λp−2 μ)P 3( λp−2 μ)

1
( λp−2 μ )= −−−−−−−−−(3)
3K

Relation between Y, G and K

Adding equations 2 and 3

1 1
( λp−2 μ ) +2 ( λp+ μ )= +
G 3K

1 1
λp−2 μ+ 2 λp+2 μ= +
G 3K

1 1 3 K +G
3 λp= + =
G 3K 3 KG

57
 3 K +G
λp=
9 KG

3K G
λp= +
9 KG 9 KG

1 1 1
= +
Y 3G 9 K

TRUE STRESS: It is defined based on the actual area of cross-section which is obtained

by dividing the applied load with the actual area of cross-section, Ai measured at that

instant of failure.

F
σ s=
Ai

TRUE STRAIN: It is defined as the integral of the elemental strain.

l
dl li
True strain ε true =∫ =ln =ln ⁡(1+ε engg )
l0 l lo

Relationship between engineering strain and true strain

δll
Engineering Strain ( e )=
l

l
δll
True strain ( ε )=∫
l0 l

l
True strain ( ε )=∫ Engineering Strain
l0

l
δll l A
¿∫
l0 l
=ln
[] [ ]
l0
=ln 0
A

Where, l is the instantaneous length of the specimen and l0 is the original length.

Relationship between engineering stress and true stress

58
 The true stress (σ). The normal) is the load at any instant divided by the cross-sectional area over

which it acts. The engineering stress (σ). The normals), is the load divided by the original cross-sectional

area.

P
True stress ( σ )= σ). The normal
A

P
Engineering tress ( σ s ) =
A0

The true stress may be determined from the engineering stress as follows:

P
∗A0
P A0
True stress ( σ )= = −−−−−−−( 1)
A A

P= Load acting on specimen

A0 = Original cross sectional area of specimen

A = Instantaneous cross-sectional area

But by the constancy of volume relationships

A0 L
= −−−−−−−−−−−−(2)
A L0

Again, engineering strain (σ). The normale) is the ratio of change in dimension to original dimension.

But the relationship

L−L0 L
Engineering strain ( σe )= = −1
L0 L0

L
( σ e +1 )= −−−−−−(3)
L0

A0 l
= =σ e+1
A l0

59
Using equations (1),(2), and (3), we can write

P
True stress(σ )= ( σ e +1 )=σs (σe +1)
A0

σ =σs (σe+ 1) or σ =σs (1+σe)

Stress-strain diagram for different materials

The stress-strain diagrams for different materials may be grouped under the following two

important headings:

1. Ferrous metals and 2. Non-ferrous metals

1. Stress-strain diagram for ferrous metals:

Figure shows the stress-strain diagram for a few important types of steels, wrought

iron and cast iron. It will be seen from the diagram, that the elastic portion for all the steels

is nearly same. Thus the Young’s moduli for these metals are also approximately the same.

As a matter of fact, the strength of a ferrous metal depends upon the percentage of carbon

content in it. This point is illustrated by the stress-strain curves of wrought iron, which

indicates that the ductility decreases by increasing the percentage of carbon content.

It is noticed from the stress-strain curve of the cast iron (which is a brittle) that there

seems to be no perfectly defined location of the yield point. Therefore it becomes difficult

60
to determine the yield strength of brittle materials. A common method to determine yield

strength for such materials is to draw a straight line parallel to the elastic portion of the

curve at a pre-determined strain ordinate value (say 0.1%). The point, at which this line

intersects the stress-strain curve, is called the yield strength or proof stress, which is at

0.1% of set strain.

Figure shows the stress-strain diagram for a few selected non-ferrous metals. It will

be seen from the diagram, that there is no definite elastic portion of the curves. As a matter

of fact, the elastic properties of non-ferrous metals vary considerably. In the case of alloys,

the stress-strain diagram depends upon their chemical composition.

The deformation of metals may be classified into the following two types depending

upon the nature of strain produced during deformation.

1. Elastic deformation 2. Plastic deformation

Elastic deformation may be defined as the process of deformation which appears and

disappears simultaneously with the application and removal of stress.

Plastic Deformation may be defines as the process of permanent deformation which exists

in a metal even after the removal of the stress. The plastic deformation in crystalline

materials occurs at temperature lower than 0.4 Tm (Tm is the melting temperature in

Kelvin). This may occur under the tensile, compressive or torsional stresses.

There are two mode of plastic deformation namely slip or gliding and twinning. The

slip mode is common in many crystals at ambient and elevated temperatures. At low

temperatures, the mode of deformation changes over to twinning in a number of cases.

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Comparison between elastic and plastic deformation:

Elastic deformation Plastic deformation

1 It is a deformation, which appears and disappe It is a permanent deformation whic

ars with the application and removal of stress h exists even after the removal of
stress

2 This deformation is the beginning of the progr This takes place after the elastic de
ess of deformation formation has stopped

3 It takes place over a short range of stress-strain It takes over a wide range of stress-
curve strain curve.

4 In elastic deformation, the strain reaches its ma In plastic deformation, the strain oc
ximum value after the stress has reached its ma curs simultaneously with the applic
ximum value ation of stress

Critical Resolved Shear Stress (CRSS):

At room temperature, deformation occurs very easily by slip mechanism. Slip begins

when the shear stress on the slip plane in the slip direction reaches a critical value called as

Critical Resolved Shear Stress.

Consider a single crystal in the form of cylinder, subjected to an axial load as shown in

the figure. Cross sectional area of the crystal is ‘A’ and axial force acting on it is ‘P’ along

the axis.

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 .

As a result of axial load, let the slip takes place along the shaded plane shown in the

figure. The angle between the slip direction and tensile axis is ^ and the angle between the

normal slip plane and tensile axis is Φ. The component of axial force acting on the slip

plane in the slip direction is P cos^.

Only this component of force is effective in moving the dislocation.Slipping takes

place along the shaded plane (slip plane). ^ + Φ = 90

A
The area of slip plane, which is inclined at an angle Φ is
cos ∅

Mathematically critical resolved shear stress (τc)c)

component of load along the slip plane

¿
area of the slip plane

Pcos ^ P cos ^ cos ∅

τ c= = =σ cos ^ cos ∅
A A
cos ∅

This is equation is known as Schmid’s Law.

The term ‘cos ^ cos ∅' is treated as Schmid’s factor. The following points are

important for the values of critical resolved shear stress.

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 1. If the slip direction is at right angles to the tensile axis (^=90º), then Cos ^= cos90º

= 0, therefore τc)c= 0.

2. If the plane is parallel to the tensile axis (Φ=90º) then cosΦ= cos90º= 0, therefore

τc)c= 0

3. If both the slip plane and slip directions are inclined at an angle of 45º to the

tensile axis, then τc)c = σ). The normal cos 45ºcos45º

1 1 σ
CRSS=σ =
√ 2 √2 2
4. It will be seen that for all combinations of Φ and ^, the critical resolved shear stress

will always be less than σ). The normal/2 (i.e. half the tensile stress).

The value of CRSS is a constant for a material at a given temperature. If many slip

planes and slip directions of the same type are possible in a crystal, then the active plane is

the one on which the CRSS is reached first as the specimen is subjected to increasing

applied stress.

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 PHASE DIAGRAMS

Phase Rule:

Phase rule may be defined as “ Provided the equilibrium between the phases is not

influenced by gravity, electric, magnetic and surface tension forces, and only influenced by

pressure, temperature and concentration and then the sum of phases (P) and degrees of

freedom(F) exceeds the number of components (C) by two”

P + F = C+2 or F = C – P + 2

Phase (P): Phase is defined as that part of a system which is chemically homogeneous,

physically distinct and mechanically separable. The phase can be separated from other part

of the system by a definite boundary.

Equilibrium: A state of balance, which exists or tends to be attained between the phase in

the structure of an alloy after a chemical and physical change.

Number of components C:Smallest number of independent chemical constituents by

means of which the composition of each can be expresses.

Degree of freedom, F: The number of variables such as pressure, temperature and

composition of the constituents in a system which needs to be fixed to keep the system

under equilibrium.

Phase equilibrium diagrams permit us to predict the types of phase than can be

formed under certain set of conditions of temperature, pressure and composition.

Uses of phase equilibrium diagrams:

1. It applies to physical as well as chemical phase reactions.

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 2. It provides a convenient basis for classification of equilibrium states of systems

with the help of phases, components and degrees of freedom.

3. It applies to macroscopic systems and hence information about molecular structures

is not essential.

4. Phase rule does not take any cognizance of the nature or the amounts of substances

present in the system.

5. It indicates that different systems having the same degrees of freedom behave in a

similar fashion. Further, it helps in predicting the behavior of a system under

different conditions of the governing variables.

6. It helps in deciding whether the given number of substances together would exist in

equilibrium under a given set of conditions or whether some of them will have to

be inter-converted or eliminated.

7. To calculate relative amount of phases present

8. To determine the number, type and composition of phases present in an alloy- at

particular temperature.

9. To predict temperature at which freezing or melting will begin.

10. To predict microstructure of an alloy at given temperature

11. It acts as a heat treatment road map about the changes taking place during various

transformations.

Limitations of the phase equilibrium diagrams: (limitations of phase rule):

1. Phase rule can be applied only for systems in equilibrium. It is not of much help in

case of systems which attain the equilibrium state very slowly.

2. All the phases of the system must be present under the same conditions of

temperature, pressure and gravitational force.

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 3. It applies only to a single equilibrium state. It does not indicate the other possible

equilibria in the system.

4. Phase rule considers only the number of phases but not their quantities. Even a

minute quantity of the phase, when present, accounts towards the number of

phases. Hence much care has to be taken in deciding the number of phases existing

in the equilibrium state.

5. The solid and liquid phases should not be so finely sub-divided as to bring about

deviation from their normal values of vapor pressure.

6. Does not tell anything about the size of micro constituents present.

7. Does give about physical and mechanical properties of materials.

Classification of phase equilibrium diagrams: Classified into four types

Unary; Binary; Ternary; Multiple

67
68
Iron-Iron carbide equilibrium Diagram

The existing phase relationships of iron-iron carbide system are usually expressed

in terms of the percentage content of carbon. In this respect, the phase diagram, sown in

the figure is not complete, since it is plotted only for carbon content (in weight Per cent)

less than 6.69% which corresponds to the composition of iron carbide (Fe3C), called

cementite. The part of the diagram relating to the carbon content higher than 6.69% is,

however, not of commercial significance and is usually ignored.

It is a common practice to divide the diagram into two parts on the basis of carbon

content. Alloys containing <2% carbon are known as steels and those containing more

than 2% carbon are known as cast irons. Since the exact carbon content in the steels

region is of greater importance. Steels are further subdivided into hypoeutectoid steel from

69
0.008% carbon up to 0.77% carbon and hypereutectoid steel from 0.77% up to 2% carbon.

Compositions containing up to 0.008% carbon are regarded as commercially pure iron.

Referring to the diagram it will be seen that the curve ABCD is the liquidus line.

Above this line, there is only the liquid phase of molten iron containing dissolved carbon.

The curve AEFGCH is solidus line below which all compositions of iron and carbon are

solid. The regions between these two lines represent two-phase fields of solid and liquid.

The iron-iron carbide diagram is characterized by three horizontal lines, EFB, GCH

and JKL, each representing an isothermal reaction involving three phases and occurring at

an invariant point (fixed temperature and composition) on the equilibrium diagram.

These reactions and the invariant points are:

(i) Peritectic reaction at point F 90.18% carbon, at 1495 ºC)

Liquid (0.5%) + δ (0.08% C) heating← →cooling γ (0.018% C)

(ii) Eutectic reaction at point ‘C’ (4.3% carbon, 1148 ºC)

Liquid (4.3%) heating← →cooling γ (2.11% C) + Fe3C (6.69% C)

Combination of two Right hand side products is called as ‘Eutectic mixture

(Ledeburite).

(iii) γ (0.77% C) heating← →cooling α ( 0.022% C) + Fe3C ( (6.69% C)

Combination of two Right hand side products is called as ‘Eutectoid

mixture (Pearlite). The eutectoid reaction is characterized by the

decomposition of a solid phase into two different solid phases.

Most of the structures which appear on the iron-iron carbide diagram have been

assigned definite names: ferrite, austenite, cementite, pearlite and ledeburite.

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 Interstitial solid solution of carbon dissolved in α (bcc)- iron is called ferrite. α-iron

dissolves only 0.008 per cent carbon at room temperature. The solubility, however,

increases with temperature, the maximum solubility being 0.218 per cent carbon at 727 ºC.

Interstitial solid solution of carbon dissolved in γ (fcc)- iron is called austenite.

Though γ-iron has larger interstitial holes than α-iron, not all the available holes are filled

at any time. This is because of crowding of carbon atoms into the interstices produces

strains in the structure. Maximum solubility is 2.11 per cent carbon at 1148ºC.

Cementite or iron-carbide is an intermetallic compound of composition Fe3C

containing 6.69% carbon. This does not signify, however, that cementite consists of Fe3C

molecules; but rather it means that the crystal lattice contains iron and carbon atoms in the

ratio of 3:1. It has an orthorhombic unit cell with 12 iron atoms and 4 carbon atoms per

unit cell. Cementite is very hard.

Pearlite is the eutectoid mixture containing 0.8% per cent carbon and is formed at the

eutectoid temperature 727 degrees on very slow cooling. It consists of alternate plates of

cementite and ferrite. Ledeburite is the eutectic mixture containing 4.3% carbon and is

formed at 1148 degrees. It is a mixture of austenite and cementite.

Lines JKL, IK and GK represent the transition temperatures for the transformation of

one solid phase into another under equilibrium conditions. Line JKL is usually refereed as

lower critical temperature line while lines IK and GK are referred to upper critical-

temperature lines.

Effect of alloying additions:

Alloying additions are carried out to

i. increase the hardenability

ii. to improve the strength at ordinary temperatures

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 iii. To improve the mechanical properties at high and lower temperatures

iv. To improve toughness at any minimum hardness and strength

v. to increase wear resistance

vi. To increase corrosion resistance

vii. To improve magnetic properties.

The alloying elements can be classified according to their ability to distribute in the

two main constituents of annealed steel:

A) Elements that dissolve in ferrite.

B).Elements which combine with carbon to form simple or complex carbides.

The alloying additions have the effect of slowing down the transformation reactions.

Quench cracks can also be avoided.

• Manganese added to the extent of 14-15% to the iron produces a new variety of

steels called ‘Hadfield steels’.

• Any element dissolved in ferrite increases the hardness and strength because of

solution hardening.

• Chromium, cobalt, vanadium, tungsten and titanium carbides possess outstanding

hardness and wear resistance.

• Types of steels used in chemical industries:

• Different types of steels and cast irons are used for the fabrication of chemical

equipment.

• Ferrous wrought alloys

• Cast alloys

• High temperature resistance alloys

Wrought Irons: the strength of wrought iron is very low compared to steel. The ductility

72
of these materials is on par with that of low carbon steels. Their endurance limit is low and

is incapable of heat treatment. They find their application in piping carrying potable and

waste water, processing tanks, gratings, trash racks in sewage, deck house sheathing on

ships rudders etc.

Cast irons: may be suitable for certain chemical media at low concentrations and low

temperatures. For high temperature services cast irons are not suitable as it might form

scales. Its ductile property is very poor hence it is not shock resistant.

Addition of silicon to cast iron which gives rise to another class of cast irons called ‘silicon

irons’ which possess significant corrosion resistance properties (very resistance to acid as

well as alkali attack, salts, organic compounds).

• They have very poor mechanical and thermal properties.

• Mild steels: normally contain 0.25-0.35%. Suitable heat treatment alters the form

of cementite and the desired properties may be achieved. These steels are used

with a coating another metal such as tin plate.

• Stainless steels used

• : 1. Martensitic 2. Ferritic 3. Austenitic types

Martensitic steel: 12-20% of Cr with controlled amount of ‘C’. TYPE 410, this type can

be hardened by heat treatment which increases their tensile strength by about three-fold.

Their corrosion resistance is interior to stainless steels used in mild corrosive

environments.

Ferrititic stainless steels: Cr upto 15-30% with carbon content about 0.1%. High

chromium content improves its corrosion resistance. Type 430. used in nitric plants, high

temperature environments up to 1000-1100 degrees

Austenitic stainless steels: superior to corrosion resistant properties than the ferritic and

73
martensitic steels. These steels are very tough and ductile. The tensile strength can be

improved through annealing. Type 304

Low carbon stainless steels: 304L, 308L and 316L (C-0.03%)

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