Identify the ‘Material’ of the items?

1
A material is a substance or mixture of substances
that constitutes an object. 2
Material Classification

3
Semi-conductors

4
Are these related to Material? 5
 What is Material Science?

Material Science is an interdisciplinary field involving

the study of properties of matter and its applications to
various areas of science and engineering.
6
Materials scientists study the ‘connections’ between the
underlying structure of a material, its properties, its
processing methods and its performance in applications. 7
Characterization analogy!

8
 Characterization

Characterization is the process by which a material's

structure and properties are probed and measured.
9
 Cast iron
‘Cast iron’ covers a family of
ferrous alloys - It is an iron alloy

Cast irons have carbon content

between 2 and 4%

Cast irons can also contain silicon, manganese, sulphur, phosphorous

Low cost material with structural strength similar to steel

10
 Features of Cast iron
Cast iron is used for the fabrication of large structures, such as
machine bases, engine blocks, and large brackets

Cast iron is ideal for casting

because of its ease of flow
when molten
11
 Metallurgical features of Cast iron
Cast iron have good tribological and wear resistant properties

Antiwear cast iron

balls for mining
and cement
industries
Cast Iron Surface Plate

Cast iron have appreciable

resistant to corrosion

Old rust-free Iron Pillar of Delhi Cast Iron Pump Parts

12
 Application of different types of Cast iron

White cast iron impeller

Gray cast iron wheel Malleable cast iron pipe

fitting

Ductile or nodular cast iron valve

13
Does it involves Materials Science?

14
Does it involves Materials Science?

15
Does it involves Materials Science?
16
Does it involves Materials Science?
17
Does it involves Materials Science?
18
Does it involves Materials Science?
19
Does it involves Materials Science?
20
 Material Science
(ME103101ME)

Dr. Kalinga Simant Bal,

Assistant Professor,
Department Of Mechanical Engineering,
National Institute of Technology Raipur. 21
 Course info

Credits: 04 = 3 (L) + 1 (T) Teaching Scheme: Theory 04

Hrs/Week

Prerequisites

Materials Phase

Chemistry Workshop
22
 Syllabus

Unit 1: Structure of Crystalline Solids (12 Hrs)

Unit 2: Elastic-Plastic Deformation (11 Hrs)
Unit 3: Phase Diagram (12 Hrs)
Unit 4: Heat Treatment (09 Hrs)

44 hours

23
 Topics to cover
Unit 1: Structure of Crystalline Solids

Material Science and Engineering,

Structure of Materials,
Solidification of Metals and Alloys.

24
 Recent advantages in
material science and technology and future trends

Materials Genome
Initiative (MGI) is a
federal multi-agency
initiative (by U.S.) for
discovering,
manufacturing, and
deploying advanced
materials twice as fast
and at a fraction of the
cost compared to
traditional methods

25
 MGI led innovations

Next generation of wound film Experimentally synthesized

capacitor hexagonal Co₃N

Transistors within unique

devices having varied
micrometer-scale physical
dimensions

26
 Structures

Ordered No specific Order

structure

27
 Crystalline structure of solid

arrangement of lacks the long-range

atoms is in a Poly = many order
periodically
repeating pattern

28
 Cannon

Part of Material Science

29
Atomic Arrangement via Cannon Balls

30
Lattice

31
Is two-dimensional square lattice possible?

360/90 = 4 YES

32
Is two-dimensional pentagonal lattice possible?

360/108 = 3.333 NO
pentagons
cannot be
made to meet
at a point
bearing
a constant
angle to one
another
33
Is two-dimensional Hexagonal lattice possible?

360/120 = 3
YES

34
 Space Lattice
A space lattice is defined as an infinite array of points
in three dimensions in which every point has
surroundings identical to that of every other point in
the array.

35
Crystal Cell in materials

Unit Cell
36
Unit Cell and Crystal Lattice

• The unit cell of a crystal structure is the smallest group of

atoms possessing the symmetry of the crystal which, when
repeated in all directions, will develop the crystal lattice.
37
Effective number of lattice points in the unit cell

38
 Unit Cell and Space Lattice

The unit cell is the smallest unit which, when repeated

in space indefinitely, will generate the space lattice.
Arrangements of points in space in periodically
repeating patterns.
39
 Space Lattice
A three-dimensional space lattice is generated by repeated
translation of three noncoplanar vectors, a, b and c.

40
 Bravais lattices

14 distinguishable ways of
arranging points in
three-dimensional space
such that each arrangement
conforms to the definition
of a space lattice.

These 14 space lattices are

known as Bravais lattices.
They belong to seven crystal
systems.
41
Schematics of Crystal system: Cubic

Pyrite Gemstone
42
Cubic Crystal system

43
Schematics of Crystal system: Tetragonal

Wulfenite
44
Tetragonal Crystal system

45
Schematics of Crystal system: Orthorhombic

46
Orthorhombic Crystal system

47
Schematics of Crystal system: Rhombohedral

Calcite 48
 Schematics of Crystal system: Hexagonal

The effective number of lattice

points in this unit cell is 3.
49
Schematics of Crystal system: Hexagonal

50
Schematics of Crystal system: Monoclinic

Selenite
51
Schematics of Crystal system: Triclinic

52
Lattice (unit cell) parameters required to specify a
crystal system.

53
 Draw two adjacent FCC unit cells and join the top and
bottom face centres of each cell. Also join these four face
centres to the nearest common corners.

54
There is no end-centred tetragonal lattice in the Bravais list,
but there is an end-centred orthorhombic lattice.

55
 Coordination number (CN)
For metals, each atom has the same
number of nearest-neighbor or touching
atoms, which is the coordination number.

SC: CN = 6

FCC: CN = 12 BCC : CN = 8 HCP: CN = 12

Method of determining CN for FCC crystal → Front face atom has 4

corner nearest-neighbor atoms surrounding it, 4 face atoms that
are in contact from behind, and 4 other equivalent face atoms
residing in the next unit cell to the front, which is not shown.
56
 Atomic packing factor
The APF is the sum of the sphere volumes of all atoms within a unit
cell (assuming the atomic hard-sphere model) divided by the unit
cell volume.

For the FCC structure, the APF is 0.74, which is the maximum
packing possible for spheres all having the same diameter.

SC: APF = 0.52 BCC: APF = 0.68 FCC: APF = 0.74 HCP: APF = 0.74
57
[Link]
 Determination of FCC Unit Cell Volume
Calculate the volume of an FCC
unit cell in terms of the atomic
radius R.

The atoms touch one another

across a face-diagonal the length
of which is 4R. Because the unit
cell is a cube, its volume is a³.
From the right triangle on the
face,

58
Computation of the Atomic Packing Factor for FCC

59
 Crystal Directions and Planes
Miller indices is used to specify directions and planes in a crystal.

Components of r along three axes: r1 = 2, r2 = 3 and r3 = 0, so [230].

60
 Find the Miller indices of the direction ‘r’

Assume ‘r’ to pass through origin by drawing vector parallel to it.

_
Components of ‘r’ along three axes: r1 = -1, r2 = 1 and r3 = 0, so [110].
61
Identification of directions in cubic system.

62
 _
The angle between [111] and [112] directions in a
cubic crystal is

63
Miller indices of a crystal plane

64
Find the Miller indices of plane indicated by unit
normal ‘s’

Assume ‘s’ to pass through

smallest intercept by drawing
plane parallel to it
Intercept of ‘s’ along three axes: a = 3, b = 2 and c = ∞, so (230).65
Identification of planes in cubic system.

66
Draw plane (623)

67
Draw a plane at 2a, 5b, 2c.

68
A crystal plane makes intercepts 2a, 2b and 3c on the
crystallographic axes where a, b, c represent the
intercepts of the unit plane. The Millers indices of
the plane will be?

Intercept = 2a, 2b, 3c

Fractional intercept = 2a/a, 2b/b, 3c/c

reciprocal = 1/2, 1/2, 1/3

Miller indices = (332)

69
 Determine the Miller indices of a plane that makes an
intercept of 2 Å, 3 Å and 4 Å on the coordinate axes of an
orthorhombic crystal with a : b : c = 4 : 3 : 2.

a=a b = 3a/4 c = 2a/4

Fractional intercept = 2/a, 3/b, 4/c = 2/a, 4/a, 8/a

Reciprocal = 1/2, 1/4, 1/8

Miller indices = (421)

70
In cubic crystals, a ‘crystal plane’ and a ‘crystal
direction normal to it’ have the same indices.

71
An orthorhombic Crystal whose primitive translations are a
= 1.21 Å, b = 1.84_ Å and C = 1.97 Å respectively. If plane of
miller indices (231) cuts an intercept of 1.21 Å along ‘x’ axis
find the length of intercept at ‘y’ and ‘z’ axes.

Miller indices of plane = 2, 3, -1

intercept of plane = 1/2, 1/3, -1/1

Fractional intercept w.r.t unit cell = 1.21/2, 1.84/3,

-1.97/1
intercept = 1.21 Å, 1.22 Å, -3.94 Å

72
 __
Draw a (110) and a (111) plane inside a cubic unit cell.

Hint: shift origin for drawing plane 73

Determine the Miller indices of the direction that is
common to both these planes.

Hint: shift vector to pass through origin 74

 Interplanar spacing between adjacent planes

The interplanar spacing between

adjacent planes of Miller indices
(hkl), dhkl, is defined as the spacing
between the first such plane and a
parallel plane passing through the
origin.

In cubic crystals, the following relationship gives the interplanar

spacing as a function of the Miller indices and the lattice parameter:

75
Draw a (111) plane and a (222) plane in the unit cell of a
cubic lattice with lattice parameter a. Determine their
distances from a parallel plane through the origin.

76
 Interatomic distance

The wavelength of the X-ray radiation used for crystal diffraction

should be in the same range as that of interatomic distance. 77
X-ray emission

78
 Wave mechanics

79
Professor McBride , Wave Mechanics, Yale Dept. Of Chemistry, 2009
 X-ray Diffraction by crystal

Diffractometer

Crystal Diffraction 80
A Century of Crystallography: the Braggs Legacy, The Royal Institution, Great Britain, 2014
 Physics of X-ray Diffraction

Out of phase, no light

In phase, light

81
A Century of Crystallography: the Braggs Legacy, The Royal Institution, Great Britain, 2014
 The Bragg Law of X-ray Diffraction

The two reflected rays will reinforce each other, only when
the path difference is equal to an integral multiple of the
wavelength. 82
A diffraction pattern of a cubic crystal of lattice parameter a = 3.16 Å is
obtained with a monochromatic x-ray beam of wavelength 1.54 Å.
The first four lines on this pattern were observed to have the following
values:

Determine the interplanar spacing and the Miller indices of the

reflecting planes.

83
Structural characterization using X-ray Diffraction

One crystal (pink)

composed of
multiple sub-cryst
allites (blue)
Polycrystalline sample

84
Crystal imperfections

85
Edge and Screw defects
 Vacancy

atom is missing

If there are n point imperfections, in one mole of a crystal, the

change in the free energy G of the crystal can be written as

N is Avogadro’s number 86
 Variation of Gibbs free energy
The equilibrium state of the crystal will correspond to the
minimum in its free energy.

By setting dG/dn = 0, we
obtain the equilibrium
concentration

87
 Numerical on Point Imperfection
Find the equilibrium concentration of vacancies in
aluminium and nickel at 0 K, 300 K and 900 K.

Equilibrium concentration

88
 Cont……Numerical on Point Imperfection
Equilibrium concentration

89
 Point defects: Schottky defect and Frenkel defect

NaCl ZnS
KCl AgCl

Found in ionic solids with Found in ionic solids with

(a) high coordination number and (a) low coordination number and
(b) ionic species having similar size. (b) ionic species having different size.
90
Line imperfections: dislocations

An incomplete plane in a crystal

results in an edge dislocation 91
 Burgers Vector

no line imperfection

extra step to return to point P

The magnitude and the direction of this step define the

Burgers vector:

The Burgers vector is perpendicular to the edge dislocation line.

92
Compute the line energy of dislocations in BCC iron. The
Burgers vector in iron is of the 1/2 <111> type. The shear
modulus of iron is 80.2 GN/sq-m.
Line energy of the dislocation =

µ = shear modulus of the crystal

b = Burgers vector

BCC iron (a = 2.87 Å)

b = 2.87 x √3/2 = 2.49 Å

93
 Surface Imperfections
Regions of distortions that lie about a surface having a thickness of
a few atomic diameters

A tilt boundary consists of equally

spaced edge dislocations94
A metal heated to elevated temperatures exhibits grooves on the
surface at positions where the grain boundaries meet the surface.
Assume that the ratio of the surface energy of the free surface to
that of the grain boundary is 3 to 1. Compute the angle at the
bottom of the groove of a boundary, which makes an angle of 90°
with the external surface.

95
Gibbs free energy

96
 Solidification criteria

Free energy ‘g’ of a

material in the liquid (l)
and crystalline forms (β)
as a function of
temperature

Liquid (L) to crystals (β) transformation by nucleation and growth 97

Surface area-to-volume ratio

98
 Effect of grain size
A tiny particle has a large surface area to volume ratio and can
therefore be unstable

As r →0, above ratio can become very large,

Hence, produce unstable particle

Energy of the surface can effectively prevent the initial formation

of a tiny particle.

A particle is said to have nucleated, when it becomes stable and

will not disappear due to thermal fluctuations
99
Nucleation

100
 Kinetics of homogeneous nucleation

r = radius of the particle

g = Gibbs free energy

change per unit volume

γ = Surface energy per

unit area of the
interface

101
 Kinetics of homogeneous nucleation
At (df/dr) = 0, maximum values → critical value

For the L→β transformation

h = enthalpy change (the heat of reaction) per unit volume of the product.
Tm = equilibrium melting point at which g = 0,
T = transformation temperature
ΔT = degree of supercooling
102
Calculate the critical free energy of nucleation of ice from water at
(i) 0°C, (ii) -5°C, and (iii) -40°C. Also, calculate the critical radius at
each temperature. The enthalpy of fusion of ice is 6.02 kJ/mol. The
energy of the ice-water interface, 0.076 J/m², can be taken to be
independent of temperature. Given, Molar volume of ice as 19 cm³

103
Metal ingot structure

104
 Columnar crystal

105
[Link]
Dendritic crystal

106
 Topics to cover
Unit 2: Elastic-Plastic Deformation

Basic Mechanical Properties,

Mechanism of plastic deformation,
Fracture of Metals.

107
Material Properties

108
 Hardness

A = Area of plastic deformation; P = normal load 109

 Strength

Tensile Test in Universal testing 110

Components of a Universal testing machine

111
 Ductility vs. Brittleness

Brittle material

Ductile material

112
Toughness

113
 Impact Testing

Impact testing is used to

determine the ability of the
material to absorb energy
during a shock loading.

This test helps to determine

the toughness, impact
strength, and fracture
resistance of the material.

Charpy testing machine [Link] 114

 Effect of grain size on properties of metals

General relationship of grain size with mechanical properties

Hall–Petch equation d = average grain diameter

115
 Plastic deformation

If operating temperature < 0.4 times the melting temperature

permanent deformation → ‘plastic deformation’ 116

 Plastic deformation in ductile material

[Link] 117
 Critical resolved shear stress

Resolved shear
stress ‘τ’ on a slip
plane along a slip
direction
depends on their
orientation with
respect to the
tensile axis

Schmid's Law

When τ → τ(critical resolved shear stress, CRSS) ⇒ ‘initiation of

plastic deformation’.
118
[Link]
 Role of dislocation in Plastic deformation

Dislocations prevent the synchronized breakage of bonds

between atoms in materials and cause gradual deformation by
making the one-by-one breakage of single bonds possible

[Link] [Link]
119
[Link] [Link]
Shear Strength of ‘Perfect Crystal’ vs. ‘Real Crystal’
Perfect Crystal Real Crystal

Real crystals deform at a much lower stress than predicted by the

model for a perfect crystal → presence of dislocations in real
crystals.

Measured CRSS values should be associated with the stress

required to move a dislocation that is already present in a real
crystal and not with the stress required to shear a perfect crystal.
120
 Plastic deformation via Slip and Twinning

Movement of
atoms by many
interatomic
distances

Movement of atom
is only a fraction of
an interatomic
distance

121
[Link] [Link]
 Strain Hardening

τ = Stress to move a dislocation

τ₀ = Stress to move the dislocation
with zero dislocation density
A = Constant
ρ = Dislocation density

Strain hardening requires the dislocations to interact and impede

each other’s movement due to the interfering effect of the stress
fields of the surrounding dislocations
122
[Link]
Effect of ‘cold working’ on grain boundary

metal is shaped below its

recrystallization
temperature
process of strengthening
metals through plastic
deformation

123
 Season cracking
Cold-worked brass (Dislocations pile-up at grain boundaries) +
high residual stresses + ammonia (selective dissolution of the
boundary region) → cracks along the grain boundaries

High energy concentration at

boundaries causes it to become
anodic with respect to the grain
interior.

124
 Bauschinger effect

Stage-1 Tensile to Stage-2 Compressive to

compressive loading tensile loading

An increase in tensile yield strength occurs at the expense of

compressive yield strength and vice versa
125
[Link]
Stress-strain hysteresis loop (Bauschinger effect)
Observed in ductile materials

Reverse movement of dislocations

aided by back stresses caused
reduction in yield stress 126
 Yield point phenomena
When certain materials such as mild steel are deformed in tension,
it is found that the stress-strain curve is not smooth, but shows
marked irregularities, with negative slopes occurring at or near the
initial yield on the curve.

non homogeneous deformation

After the initial stress

maxima, the deformation
occurs within a narrow
band, which propagates
along the entire length of
the gage section before
the stress rises again. 127
 Mechanism behind Yield point phenomena

Lüders strain (yield strength elongation)

Stretcher strain marks developed usually at 45° to the tensile axis

128
 Cottrell atmosphere and Yield point phenomena

Carbon atom below a dislocation in iron → Cottrell atmosphere

Interaction between accumulated foreign atoms and dislocations,

→ affects the yielding through the formation of Lüders bands

Dislocation pinning and unpinning leads to zigzag-shaped curve

129
Metal forming temperature range

130
 Cold working vs. Hot working

Below re-crystallization Above re-crystallization

temperature temperature

Increases strength, Less energy required for

decrease ductility and deformation
corrosion resistance
Result in surface
Better surface finish oxidation

Better dimensional Allows for large

control deformation 131
 Recovery
The partial restoration of the original characteristics, produced
by reducing the distortion of the crystal lattice without
remarkable changes in microstructure

Excess point imperfections are absorbed

Dislocations of opposite sign mutually annihilate each other

Dislocations of the same sign arrange themselves into

lower energy configurations 132
 Recrystallization
Formation of new equiaxed grains in the heating process of
metal, instead of the oriented fibrous structure of the deformed
metal

No crystal structure change or phase transformation occurs

during recrystallization
133
 Grain Growth
Increase in the average grain size on further annealing, after all
the cold worked material has recrystallized

HEA
T

Atoms tend to jump across boundary to increase overall bond energy

Larger grains grows at the expense of smaller grains

134
Effect of Recovery, Recrystallization and Grain Growth

135
[Link] [Link]
 Fracture of metals

Fracture refers to the failure of a material

under load by breaking into two or more
pieces

Materials subjected to alternating or

cyclic loading fail due to fatigue →
Fatigue fracture

Materials used at high temperatures

can fail due to creep fracture
136
 Ductile Fracture

Ductile fracture is the rupture of a material after a considerable

amount of plastic deformation

Successive stages in the ductile fracture of a Cup and cone fracture

tensile test specimen

Crack starts at the center of the specimen and spreads radially,

with final completion of the fracture on a cone-shaped surface
making an angle of approximately 45° with the tensile axis
137
[Link]
 Brittle Fracture

Brittle fracture is the failure of material without apparent plastic

deformation

Broken pieces when fitted together →

original shape and dimensions of the
specimen are restored

Griffith’s energy balance criterion

c = crack of half length Y = Young’s modulus of the material

γ = surface energy per unit area of the material 138
 Fatigue failure of metals
When a metal is subjected to many applications of the same
load, fracture occurs at much lower stresses than would be
required for failure in a tensile test. The failure of metals under
alternating stresses is known as fatigue

[Link] [Link] 139

Fatigue of metals

140
 Fatigue crack propagation rate

Region I → fatigue threshold region ≡

too low energy for crack to
propagate

Region II → rate of crack growth

changes roughly linearly with a
change in stress intensity fluctuation

Region III → small increases in

the stress intensity amplitude,
produce relatively large increases
in crack growth rate since the
material is nearing the point of
unstable fracture

a = crack length, N = number of cycles

141
 Creep of metals
Creep is the permanent deformation of a material under load as
a function of time

Creep is appreciable only at Temperature and time

temperatures above 0.4 times dependence of creep
the melting temperature deformation →
thermally activated process

142
[Link]
Stages in Creep of metals

Stage I (primary creep) → Creep

rate decreases with time
⇒ work hardening > recovery

Stage II (secondary or steady-state

creep)→ Creep rate is a minimum
and is constant with time
⇒ work hardening = recovery

Stage III (tertiary creep)→ Creep

rate increases with time until
fracture occurs ⇒
necking and failure of sample

143
 Stress-rupture test
Stress rupture test is similar to
creep test except that the test is
always carried out to the failure of
the material

Log-log scale plot

Slope change during test

represents structural change in
material

144
[Link]
 Creep test vs. Stress-rupture test
Test is carried out at lower stress Test is always carried out to the
to avoid tertiary creep or failure failure of the material

Lower loads than stress-rupture Higher loads are used → hence

test higher creep rate

Time period of test = 2000 to Time period of test = 1000 h

10000 h

Total strain = 0.5 % Total strain = 50 %

Testing requires controlling many Testing device is simpler to build,

parameters maintain and operate

Structural change of test specimen Rapid structural change of test

is not rapid specimen is observed
145
 Destructive Testing method
Destructive testing is undertaken in order to understand a
specimen’s performance or material behaviour, these procedures
are carried out to the test specimen’s failure

Tensile test used to determine specific

Compression test material constants or
Hardness test component constants
Flexural test
Charpy impact test
Fatigue test
Creep rupture test
Cupping test
Corrosion Testing

[Link] [Link] 146

 Non-destructive Testing method
Testing and analysis techniques used to evaluate the material
properties, component, structure or system for characteristic
differences without causing damage to the original part.

Acoustic emission Check the usability of

Computed tomography finished components
Eddy current testing (inspection) – no material
Ultrasonic testing parameters are determined
Radiography testing
Thermography
3D X-Ray Microscopy
Dye penetrant inspection
Magnetic particle testing

[Link] [Link] 147

 Topics to cover
Unit 3: Phase Diagram

Definitions and Basic Concepts,

Binary Phase Diagrams,
Iron–Carbon System.

148
 Solubility Limit
Solution – single phase
Mixture – more than one phase

Solubility Limit: Maximum Sugar-water syrup phase diagram

concentration for which
only a single phase
solution occurs.
Solution
OR
The maximum
concentration of the
solute that can dissolve
within the solvent
without the formation of
a second phase rich in
solute. Solubility limit increases with T149
 Phase
A system is an isolated body of matter.

The component(s) are independent chemical species (elements,

ions or compounds) that comprise the system.

A phase is a physically distinct, chemically homogeneous, and

mechanically separable region of a system.

150
 Example of Component and Phase

Aluminum-Copper Alloy

Component: elements or Phases: The physically

compounds which are and chemically distinct
present in the mixture material regions that
(e.g., Al and Cu). result (e.g., α and β).
151
 Phase equilibrium
A system is at equilibrium if
its free energy is at a
minimum under some
specified combination of
temperature, pressure, and
composition.

The characteristics of the system do not change with time but

persist indefinitely; that is, the system is stable.

Phase equilibrium, refers to equilibrium as it

applies to systems in which more than one
phase may exist.
152
 Example of Phase equilibrium
Phase equilibrium is reflected by a constancy with time in the
phase characteristics of a system.
Sugar–water syrup is contained in a
closed vessel and the syrup solution is
in contact with solid sugar at 20 °C

At equilibrium, syrup composition →

65 wt% sugar–35 wt% water, and the
amounts and compositions of the
syrup and solid sugar will remain
constant with time.

Temp^ (system) → 100 °C: previous

equilibrium is temporarily upset as This will continue until the new
the solubility limit has been increased equilibrium syrup concentration is
to 80 wt% -- some of the solid sugar established at the higher
will go into solution in the syrup. temperature. 153
 Gibbs Phase Rule
Gibbs Phase Rule: F = C – P + 2
F = degrees of freedom
C = number of components P = number of phases in equilibrium

The variables of a system include the two external parameters:

temperature and pressure.
Within the system, there are variables that specify the
compositions of the phases present.

Total number of variables = P (C – 1) + 2

The number of independent variables among these gives the

degrees of freedom F, that which cannot be more than the total
number of variables:
F = C – P + 2 ≤ P (C – 1) + 2 154
 Implication of Gibbs Phase Rule
F = C – P + 2 ≤ P (C – 1) + 2

P ↑, F ↓. F </ 0 so that we have an upper limit to the number of

phases that can exist in equilibrium in a given system.

Q: What are the degrees of freedom of a system of two components

when the number of phases is one, two, three, and so on?

The system cannot have more than four phases in equilibrium.

155
 Single-component system (Unary Phase Diagram)
No composition variable and
the only other variables are
P and T.
F=C–P+2

C = 1, P = 1, F = 2 →
vary T and P

C = 1, P = 2, F = 1 →
vary either T or P

C = 1, P = 3, F = 0 →
neither T nor P can
be varied arbitrarily
Pressure-temperature diagram for the one-component system of156iron
 Binary-component systems (Binary Phase Diagrams)
Variables: T, P, C₀ (for each phase in equilibrium) → 3D plot
Pressure changes often produce no significant effect on the
equilibrium and hence neglected → 3D plot reduced to 2D plot
(drawn at atmospheric pressure)
F=C–P+1

Al₂O₃–Cr₂O₃ phase diagram 157

 Phase diagrams
Phase diagrams are maps that give the relationships between
phases in equilibrium in a system as a function of temperature (T),
pressure (P) and composition (C₀).

wt% Ni
Phase Diagram for Cu-Ni system P–T phase diagram for pure H₂O 158
 Binary Isomorphous Systems
System is:
Cu-Ni Phase Diagrams
Binary → 2 components
(Cu and Ni).
Isomorphous → complete
solubility of one component in
another.
Different phase fields:
L, α + L (two phase), α →
separated by phase boundary
lines.
Cu–Ni system is termed
isomorphous because of the
complete liquid and solid
solubility of the two
components.
100 0 Melting point of Cu = 1085 °C
Cu
0 100 Melting point of Ni = 1453 159
°C
Ni
 Interpretation of Phase Diagrams: 1-Phases Present
Locating the T–C₀ point
on the diagram and
noting the phase(s) with
which the corresponding
phase field is labeled

Point B: 35 wt% Ni–

65 wt% Cu at 1250 °C →
both ‘α’ phase and ‘L’
phase at equilibrium

Point A: 60 wt%
Ni–40 wt% Cu at
1100 °C → single ‘α’
phase
Cu-Ni Phase Diagrams 160
Interpretation of Phase Diagrams: 2-Determination of
Phase Compositions (in terms of the concentrations
of the components)
Point A: 60 wt% Ni–40 wt% Cu at 1100 °C → single α phase

Tie-line – connects the phases in

equilibrium with each other -
essentially an isotherm.
Point B: The perpendicular from
the intersection of the tie line
with the liquidus boundary meets
the composition axis at 31.5 wt%
Ni–68.5 wt% Cu → composition of
the liquid phase (CL).

Solidus–tie line intersection →

composition for α solid-solution
phase (Cα) of 42.5 wt% Ni–57.5
wt% Cu. Cu-Ni Phase Diagrams 161
Interpretation of Phase Diagrams: 3-Determination of
Phase Amounts (as fraction or as percentage)
Point A: 100 % single α phase

Overall alloy composition is located on

Lever rule may be employed to the tie line.
determine the relative amounts
or fractions of phases in any
two-phase region for a binary
alloy if the T and C₀ are known
and if equilibrium has been
established.

WL and Wα = Mass (weight)

fraction of liquid phase (L) and
solid phase (α), respectively.

162
 Determination of Phase Amounts (as fraction) using
weight percent
Derivation for Lever rule is accomplished through two conservation-of-mass
expressions

C0 = 35 wt% Ni, Cα = 42.5 wt% Ni,

CL = 31.5 wt% Ni

163
Determination of Phases Present and Computation
of Phase Compositions

164
11 wt% Sn–89 wt% Pb 98 wt% Sn–2 wt% Pb
Development of Microstructure in Isomorphous Alloys

Schematic representation of
2 the development of
1260 microstructure during
1250
the equilibrium
1220
solidification (cooling) of
3 35 wt% Ni–65 wt% Cu Alloy.
1190

165
Binary Eutectic Systems

Invariant point

Eutectic isotherm

166
Copper–silver system
 Features of Binary Eutectic Systems

Upon cooling, a liquid phase (L) is transformed into the two solid
phases (α and β) at the temperature T; the opposite reaction occurs
upon heating. This is called a eutectic reaction (eutectic means
“easily melted”).
General rule of binary phase diagrams:
In binary phase diagrams, one or at most two phases may be in equilibrium
within a phase field.

For a eutectic system → three phases (L, α, β) may be in equilibrium only at

points along the eutectic isotherm.

Single-phase regions are always separated from each other by a two-phase

region that consists of the two single phases that it separates: “1-2-1” rule.
167
Development of Microstructure in Eutectic Alloys:
Composition C₁
0 < C₀ < 2 wt% Sn:
--at extreme end
--L → L + α → α (polycrystalline grains).

Pb-Sn Phase Diagrams 168

Development of Microstructure in Eutectic Alloys:
Composition C₂
2 wt% Sn < C₀ < 18.3 wt% Sn:
L → L + α → α → two phases (α polycrystal
+ fine β-phase inclusions)

169
Development of Microstructure in Eutectic Alloys:
Composition C₃

170
 Development of Microstructure in Eutectic Alloys:
Composition C₃ (Eutectic reaction)

This microstructure consists of alternating layers of

lead rich α-phase solid solution (dark layers), and
tin-rich β-phase solid solution (light layers). 171
Development of Microstructure in Eutectic Alloys:
Composition C₄

172
 Development of Microstructure in Eutectic Alloys:
Composition C₄ (Eutectic reaction)
18.3 wt% Sn < C₀ < 61.9 wt% Sn:
L → L + α → α-crystals + eutectic
microstructure (α + β)

Microstructure photograph of a lead–tin alloy at composition of 50 wt% Sn–50

wt% Pb: This microstructure is composed of a primary lead-rich α-phase (large
dark regions) within a lamellar eutectic structure consisting of a tin-rich
β-phase (light layers) and a lead-rich α-phase (dark layers). 173
 Eutectic and Peritectic Reactions

Pb-Sn

Cu-Zn

Cu-Zn

Cu-Sn

Alloy compositions to the left of the eutectic mixture are called hypoeutectic
alloys, and those to the right are called hypereutectic alloys. 174
 Basic feature of Iron–Iron Carbide Phase Diagram
Most steels contain only Fe₃C and not graphite (C). So, instead of
Fe-C diagram, the Fe–Fe₃C diagram is used.

Graphite is more
stable than Fe₃C,
so Fe–Fe₃C
diagram is
considered as
metastable
phase diagram.

175
[Link]
 The Iron–Iron Carbide (Fe–Fe₃C) Phase Diagram
Pure iron melts → 1535°C
Peritectic invariant reaction at
1493°C with 0.18% C:
δ+L↔γ

Eutectic reaction occurs at

1150°C with 4.3% C:
L ↔ γ + Fe₃C

Eutectoid reaction at 725°C

with 0.8% C:
γ ↔ α + Fe₃C
L = Liquid
δ = Delta ferrite
Fe₃C = Cementite Fe–C alloys containing 0–1.4% carbon are called steels.
γ = Austenite Fe–C alloys with more than 2% carbon are called cast irons.
176
α = Alpha ferrite
 Applications of Plain Carbon Steels

Nails made from Rails made from medium Knives made of high
mild steel carbon steel carbon steel

177
 Development of Microstructure in Iron–Carbon Alloys

Microstructure Microstructure of white cast iron. Microstructure of

showing pearlite White regions → cementite. gray cast iron.
formed at eutectoid Dark regions → unresolved Graphite flakes
composition of 0.8% C pearlite are embedded in a
matrix of ferrite
Iridescent (luminous) Formed at cooling of a cast iron
appearance with 3% C Graphite flakes are
under microscope sharp at their tips and
Presence of the large fraction of act as stress raisers.
Pearlite is a This makes gray cast
cementite makes white cast
microconstituent, and iron is brittle under
iron very hard and brittle
not a single phase tensile load.178
 The Influence of Other Alloying Elements

Shifting in the position of the eutectoid with respect to

temperature and to carbon concentration occurs due to alloying
Alloy additions also alter the relative fractions of pearlite and the
proeutectoid phase. 179
 Topics to cover
Unit 4: Heat Treatment

Introduction,
Heat treatment processes,
Surface treatment processes.

180
 Heat Treatment
Property-enhancing operation - Heat treatment - are performed
to improve mechanical or physical properties of the work
material

Heating

Soaking

Cooling

Heat treatment involves various

heating and cooling procedures
performed to effect microstructural
changes in a material, which in turn
affect its mechanical properties
181
[Link]
 Purpose of Heat Treatment

Applied before shaping (e.g., to

soften the metal so that it can
be more easily formed while
hot)

To relieve the effects of

strain hardening that occur
during forming, so that the
material can be subjected to
further deformation

182
 Sequence of Heat Treatment
Accomplished at or near the end of the sequence to achieve the
final strength and hardness required in the finished product

Heat treatment Machining

Forging
183
Heat Treatment and corresponding features

[Link]
184
 Time-temperature-transformation (T-T-T) curve
T-T-T curve shows how cooling rate affects the transformation of
liquid into various possible phases

Transformed
fraction as
function of time

Transformation
rate as function
185
of temperature [Link]
 T-T-T curve for eutectoid steel

T-T-T curve shows the transformation of austenite into other phases as a

function of time and temperature for a composition of about 0.80% C steel 186
 Micro constituents in steel

Austenite/delta ferrite Ferrite Bainite

Martensite Pearlite

187
[Link]
Austenite and Ferrite

Austenite is an phase in iron-carbon alloy,

in which the iron was in the
face-centred-cubic (gamma-iron) form.
Austenite in iron-carbon alloys is generally
only evident above 723°C, and below 1500°
C, depending on carbon content.

Ferrite is a phase in iron-carbon alloys, in

which the iron was in the body-centred
cubic (alpha- or delta-iron) morphology.
Alpha ferrite forms by the slow cooling of
austenite, with the associated rejection of
carbon by diffusion.
188
Pearlite and Martensite

Pearlite is usually formed during the slow

cooling of iron alloys, and can begin at a
temperature of 1150°C to 723°C.
Pearlite is a lamellar (alternate plate like
structure) combination of ferrite and
cementite (Fe3C).

Martensite is formed in steels when the

cooling rate from austenite is sufficiently
fast.
It is a very hard constituent, due to the
carbon which is trapped in solid solution.
189
 Bainite

Bainite is formed at cooling rates slower

than that for martensite formation and
faster than that for ferrite and pearlite
formation.

Upper bainite generally Lower bainite generally

forms at temperatures forms at temperatures
between 550 and 400°C. between 400 and 250°C.
Carbon rejection is easy. Carbon rejection is difficult.
190
 Heat Treatment processes

Hardening Austenitizing Strengthening

Quenching

At low Tempering At high

temperature temperature

200 °C to 400 °C 550 °C to 700 °C

High High strength

hardness and toughness191
Phase diagram for Iron-carbon

192
 Plot for Heat Treatment processes

Austenitizing involves heating

the steel to a sufficiently high
temperature that it is
converted entirely or partially
to austenite.

The quenching step involves cooling the austenite rapidly enough

to avoid passing through the nose of the TTT curve.

Tempering is a heat treatment applied to hardened steels to

reduce brittleness, increase ductility and toughness, and relieve
stresses in the martensite structure.
193
 Hardening

If the steel is to be very hard and

wear-resistant, a high degree of
hardness is essential. The steel is
tempered accordingly at relatively
low temperatures. This process is
referred to as hardening. 194
 Hardenability
Hardenability refers to the relative capacity of a steel to be hardened by
transformation to martensite.

It is a property that
determines the depth
below the quenched
surface to which the
steel is hardened, or
the severity of the
quench required to
achieve a certain
hardness penetration.

Hardenability does not refer to the maximum hardness that can be attained in
the steel that which depends on the carbon content.
The hardenability of a steel is increased through alloying with chromium,
manganese, molybdenum and nickel. 195
 Precipitation hardening
Precipitation hardening involves the formation of fine particles
(precipitates) that act to block the movement of dislocations and
thus strengthen and harden the metal.

Solution treatment
Quenching

Precipitation treatment

It is the principal heat treatment for strengthening alloys of Al, Cu,

Mg, Ni, and other nonferrous metals. 196
 Stages of Precipitation hardening

Solution treatment involves heating the

alloy to a temperature Ts above the
solvus line into the alpha phase region
and hold for a period sufficient to
dissolve the beta phase.

Quenching is done to room

temperature to create a supersaturated
solid solution.

Precipitation treatment involves

heating the alloy to a temperature TP,
below Ts, to cause precipitation of fine
particles of the beta phase. 197
 Tempering

Martensite is hard and brittle

Tempering is a heat treatment applied to hardened steels to

reduce brittleness, increase ductility and toughness, and relieve
stresses in the martensite structure.
It involves heating
and soaking at a
temperature below
the austenitizing
level for about 1
hour, followed by
slow cooling.
198
 Microstructural change after Tempering
Tempering results in precipitation of very fine carbide particles
from the martensitic iron–carbon solution, and gradually
transforms the crystal structure from BCT to BCC.

The new structure formed as a

result of tempering is called
tempered martensite.

A slight reduction in strength

and hardness accompanies the
improvement in ductility and
toughness.
The temperature and time of the tempering treatment control the
degree of softening in the hardened steel, because the change
from untempered to tempered martensite involves diffusion.
199
 Austempering
Austempering is the process of heat treatment where the steel is
heated to austenitizing temperature, held there for sufficient
period of time to produce homogeneous austenite.

In austempering, steel is first

quenched to the left of and below
the nose of the T-T-T curve to a
temperature at which bainite
formation is feasible.

Time is allowed for isothermal

transformation to bainite to
proceed to completion.

Benefits include high hardness

and toughness. 200
 Martempering (or Marquenching)
Martempering involves an interrupted quench of austenitized steel
to reduce the overall cooling rate.
Minimize → residual stress generated in the martensite, potential
for distortion and cracking.
The steel is quenched into an
oil or molten salt bath held just
above or slightly below the Ms
temperature until a uniform
temperature is attained, but
less than the time required for
bainite transformation to
initiate.
Gradual cooling below the Mf
followed by tempering
completes the process. 201
 Application of Austempering and Martempering

Austempering process Martempering process

Austempered product Martempered product 202

 Annealing
Annealing consists of heating the metal to a suitable
temperature, holding at that temperature for a certain time
(called soaking), and slowly cooling.

It is performed:

(1) to reduce hardness and brittleness,

(2) to alter microstructure to obtain

desirable mechanical properties,
(3) to soften metals for improved
machinability or formability,

(4) to recrystallize cold-worked

(strain-hardened) metals,

(5) to relieve residual stresses induced by

prior processes.
203
Annealing Process

204
Annealing feature

205
 Normalizing
Full annealing is associated with ferrous metals (usually low and
medium carbon steels); it involves heating the alloy into the
austenite region, followed by slow cooling in the furnace to
produce coarse pearlite.

Normalizing involves similar

heating and soaking cycles,
but the cooling rates are
faster.

The steel is allowed to cool in

air to room temperature. This
results in fine pearlite, higher
strength and hardness, but
lower ductility than the full
anneal treatment.
206
Normalizing Process

207
Normalizing feature

208
Effect of heat treatment on properties of materials

209
NST 37-2 Steel
 Surface Treatment
Surface Treatments are
thermo-chemical treatments
applied to steels in which the
composition of the part surface is
altered by addition of carbon,
nitrogen, or other elements.

These processes are applied to low

carbon steel parts to achieve a
hard, wear-resistant outer shell
while retaining a tough inner core.

The term case hardening is often

used for these treatments.
210
 Surface Treatment processes

Surface treatments introduces compressive stresses at the surface

and improve the resistance to crack propagation in brittle materials.
211
Types of Surface treatment

212
 Carburizing
Carburizing is the most common surface-hardening treatment.

It involves heating a part of low

carbon steel in the presence of a
carbon-rich environment so that C is
diffused into the surface.

The surface is converted to

high carbon steel, capable
of higher hardness than the
low-C core.

213
 Methods of Carburizing-1: Pack carburizing
Use of carbonaceous materials such as charcoal or coke packed in
a closed container with the parts, producing thick layer on the
part surface of 0.6 mm – 4.0 mm.

214
 Methods of Carburizing-2: Gas carburizing
Use of hydrocarbon fuels such as propane (C₃H₈) inside a sealed
furnace to diffuse carbon into the parts, producing case thickness
of 0.13 mm - 0.75 mm.

215
 Methods of Carburizing-3: Liquid carburizing
Employs a molten salt bath containing sodium cyanide (NaCN),
barium chloride (BaCl₂), and other compounds to diffuse carbon
into the steel, at 872 °C to 925 °C, well into the austenite range.

This process produces surface layer thicknesses generally between

those of the other two treatments (1 and 2). 216
 Nitriding
Nitriding is a treatment in which nitrogen is diffused into the
surfaces of special alloy steels to produce a thin hard casing
without quenching.

Case thicknesses →
0.025 mm - 0.5 mm
with hardness up
to HRC 70.

Nitriding is effective for steel These elements form nitride

contain alloying ingredients compounds that precipitate as
such as Al (0.85% to 1.5%) or very fine particles in the casing
Cr (5% or more). to harden the steel.
217
 Nitriding methods
1) Gas nitriding, in
which the steel
parts are heated in
an atmosphere of
ammonia (NH₃) or
other nitrogen-rich
gas mixture.
2) liquid nitriding, in
which the parts are
dipped in molten
cyanide salt baths.

Both processes are

carried out at around
500 °C.
218
 Cyaniding
Fast and efficient case-hardening process for low-carbon steels

Part heated to 871 °C – 954 °C in a Quenched (15 minutes to 180

bath of sodium cyanide- minutes) in water or oil to remove
carbonate-chloride salt solution any residual cyanide

thin, hard shell (between 0.25

and 0.75 mm) produced
used on bolts, nuts, screws and
small gears
lower operation time →
less distorted parts
drawback of cyaniding is that
cyanide salts are poisonous. 219
 Carbonitriding

Carbonitriding is a
treatment in which
both carbon and
nitrogen are absorbed
into the steel surface,
usually by heating in a
furnace containing
carbon and ammonia.

220
 Features of Carbonitriding
It involves the diffusion of C
and N into austenite, with
surface hardening produced by
martensite formation

Case thicknesses → 0.07 mm - 0.5 mm.

It is used to increase wear resistance and surface hardness
through the creation of a hardened surface layer. 221
 References
Materials Science and Engineering by V. Raghavan
Materials Science and Engineering by William D. Callister, Jr

Engineering Physical Metallurgy by Yuri Lakhtin

Materials Science and Engineering by Reza Abbaschian, Lara Abbaschian,. Robert E. Reed-Hill

Fundamentals of Modern Manufacturing: Materials, Processes, and Systems by Mikell P.

Groover

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