BPE402

Materials Engineering and Metallurgy

B.Tech, 5th Semester

Veer Surendra Sai University of Technology, Burla, Sambalpur, Odisha

Course Coordinator
1. Renu Kumari
Assistant Professor
Department of Metallurgical & Materials Engineering (MME)
Email: renumetalbit@gmail.com, Mob. No-09564452009
2. Avala Lava Kumar
Assistant Professor
Department of Metallurgical & Materials Engineering (MME)
E-mail : lavakumar.vssut@gmail.com Phone: (+91) (7077110110)
3.

Dr. Sushant Kumar BadJena

Assistant Professor
Department of Metallurgical & Materials Engineering (MME)
Email: skbadjena@gmail.com, Phone: +91 84559 38473

Module-1

1.1 Introduction of Materials Science and Engineering

Materials Science Investigating relationships that exist between the structure and properties of
materials.
Materials Engineering On the basis of these structure-property correlations, designing or
engineering the structure of a material to produce a pre-determined set of properties.
1.1.1

Structure
Structure of a material usually relates to the arrangement of its internal components.

Subatomic - Structure involves electrons within the individual atoms and interactions
with their nuclei.

Atomic level- structure encompasses the organization of atoms or molecules relative to

one another.

Microscopic Which contains large groups of atoms that are normally agglomerated
together.

Macroscopic Viewable with the naked eye.

1.1.2 Property
A property is a material trait in terms of the kind and magnitude of response to a specific
imposed stimulus. Properties are made independent of material shape and size.
Example

A specimen subjected to forces will experience deformation,

A polished metal surface will reflect light.

Properties of solid materials may be grouped into six different categories: (1) mechanical,
(2) electrical, (3) thermal, (4) magnetic, (5) optical and (6) deteriorative.
The four components of the discipline of materials science and engineering and their
interrelationship.
2

1.1.3 Classification of Materials

Solid materials have been conveniently grouped into three basic classifications:
(1) metals, (2) ceramics, and (3) polymers.
1.1.3.1 Metals

Materials in this group are composed of one or more metallic elements (such as iron,
aluminum, copper, titanium, gold, and nickel), and often also nonmetallic elements (for
example, carbon, nitrogen, and oxygen) in relatively small amounts.

Atoms in metals and their alloys are arranged in a very orderly manner.

In comparison to the ceramics and polymers, are relatively dense.

Mechanical Property- relatively stiff and strong , ductile (i.e., capable of large amounts
of deformation without fracture), and are resistant to fracture.

Metallic materials have large numbers of nonlocalized electrons; that is, these electrons
are not bound to particular atoms.Many properties of metals are directly attributable to
these electrons.

Example, metals are extremely good conductors of electricity,and heat, and are not
transparent to visible light; a polished metal surface has a lustrous appearance.

Some of the metals (viz., Fe, Co, and Ni) have desirable magnetic properties.

1.1.3.2 Ceramics

Ceramics are compounds between metallic and nonmetallic elements; they are most
frequently oxides, nitrides, and carbides.

Examples-aluminum oxide (or alumina, Al2O3), silicon dioxide (or silica, SiO2),silicon
carbide (SiC), silicon nitride (Si3N4).

Examples of traditional ceramics clay minerals (i.e., porcelain), cement, and glass.

Properties

Relatively stiff and strongstiffnesses and strengths are comparable to those of the
metals , very hard, extremely brittle (lack ductility),.highly susceptible to fracture.

Thermal and electrical Properties- Insulative to the passage of heat and electricity low
electrical conductivities and are more resistant to high temperatures

Optical characteristics-Ceramics may be transparent, translucent, or opaque.

1.1.3.3 Polymers

Carbon-based compounds.

Chain of H-C molecules. Each repeat unit of H-C is a monomer e.g. ethylene (C2H4),
Polyethylene (CH2 CH2)n.

Polymers include the familiar plastic and rubber materials.

Many of them are organic compounds that are chemically based on carbon, hydrogen,
and other nonmetallic elements (viz. O, N, and Si).

They have very large molecular structures, often chain-like in nature that have a
backbone of carbon atoms. Some of the common and familiar polymers are polyethylene
(PE), nylon, poly (vinyl chloride)(PVC), polycarbonate (PC), polystyrene (PS), and
silicone rubber.

Properties

Low densities, not as stiff nor as strong as ceramics and metals.

Extremely ductile and pliable (i.e., plastic).

Relatively inert chemically and unreactive in a large number of environments.

Limitations

Tendency to soften and/or decompose at modest temperatures, which, in some

instances,limits their use.

Low electrical conductivities and are nonmagnetic.

1.1.4 Composites

A composite is composed of two (or more) individual materials, which come from the
categories discussed aboveviz., metals, ceramics, and polymers.

Objective-to achieve a combination of properties that is not displayed by any single

material

Examples

Cemented carbides (WC with Co binder)

4

Plastic molding compounds containing fillers

Rubber mixed with carbon black

Wood (a natural composite as distinguished from a synthesized composite)

1.1.5 Advance Materials

Materials that are utilized in high-technology (or high-tech) applications are sometimes
termed advanced materials.

Examples

Include electronic equipment (camcorders, CD/DVD players, etc.), computers, fiber-optic

systems, spacecraft, aircraft, and military rocketry, liquid crystal displays (LCDs), and
fiber optics.

These advanced materials may be typically traditional materials types (e.g., metals,
ceramics, polymers) whose properties have been enhanced, and, also newly developed,
high-performance materials.

Advanced materials include semiconductors, biomaterials, and what we may term

materials of the future.

1.1.6 Biomaterials

Biomaterials are employed in components implanted into the human body for
replacement of diseased or damaged body parts.

These materials must not produce toxic substances and must be compatible with body
tissues (i.e., must not cause adverse biological reactions).

All

of

the

above

materialsmetals,

ceramics,

polymers,

composites,

and

semiconductorsmay be used as biomaterials.

ExampleTitanium and its alloy, Co-Cr alloy, stainless steel, zirconia, HA, TiO2 etc.
1.1.7 Semiconductors

Semiconductors have electrical properties that are intermediate between the electrical
conductors (viz. metals and metal alloys) and insulators (viz. ceramics and polymers).

The electrical characteristics of these materials are extremely sensitive to the presence of
minute concentrations of impurity atoms, for which the concentrations may be controlled
over very small spatial regions.

Semiconductors have made possible the advent of integrated circuitry that has totally
revolutionized the electronics and computer industries (not to mention our lives) over the
past three decades.

1.1.8 The Materials Selection Process

Pick Application and determine required Properties.

Properties: mechanical, electrical, thermal, magnetic, optical, deteriorative.

Properties- Identify candidate Material(s)

Material: structure, composition.

Material- Identify required Processing

Processing: changes structure and overall shape

Example: casting, sintering, vapor deposition, doping forming, joining, annealing.

1.2 Defects in Solids

The term defect or imperfection is generally used to describe any deviation from the
perfect periodic array of atoms in the crystal.

The properties of some materials are extremely influenced by the presence of

imperfections such as mechanical strength, ductility, crystal growth, magnetic hysteresis,
dielectric strength, condition in semiconductors, which are termed structure sensitive are
greatly affected by the-relatively minor changes in crystal structure caused by defects or
imperfections.

There are some properties of materials such as stiffness, density and electrical
conductivity which are termed structure-insensitive, are not affected by the presence of
defects in crystals.

It is important to have knowledge about the types of imperfections that exist and the roles
they play in affecting the behavior of materials.

Crystal imperfections can be classified on the basis of their geometry as

1.2.1 Point Defects in Metals

It is a zero dimension defect, associated with one or two atomic positions.
(a)

Vacancies -The simplest of the point defects is a vacancy, or vacant lattice site, one
normally occupied from which an atom is missing. All crystalline solids contain
vacancies and, in fact, it is not possible to create such a material that is free of these
defects, vacant atomic sites in a structure.

(b)

Self-Interstitials- when an atom occupies an interstitial site where no atom would

ordinarily appear, causing an interstitialcy.

1.2.2 Point Defects in Ceramics

(a) Vacancies- vacancies exist in ceramics for both cations and anions.
(b) Interstitials - interstitials exist for cations, interstitials are not normally observed for anions
because anions are large relative to the interstitial sites.

(c)

Frenkel Defect
To maintain the charge neutrality, a cation vacancy-cation interstitial pair occur together.

This is called a Frenkel defect. The cation leaves its normal position and moves to the
interstitial site. There is no change in charge because the cation maintains the same positive
charge as an interstitial.
(d)

Schottky Defect
A cation vacancyanion vacancy pair known as a Schottky defect. To maintain the

charge neutrality, remove one cation and one anion; this creates two vacancies.

1.2.3 Equilibrium number of vacancies

The equilibrium number of vacancies for a given quantity of material depends on and
increases with temperature according to

Where, N is the total number of atomic sites, Qv is the energy required for the formation
of a vacancy, T is the absolute temperature in kelvins, and k is the gas or Boltzmanns constant.
1.38 x 10-23 J/atom-K.
Equilibrium Concentration:

Problem
1.

Find the equilibrium concentration of vacancies in aluminium and nickel at 0K, 300 K and

900K. Given Hf= 68 103 KJ /mol.

Solution(i) at 0K
ex p

68 10
8.314 0

(ii) at 300 K
ex p

68 10
8.314 300

27.26

1.45

10

2. Calculate the equilibrium number of vacancies per cubic meter for copper at 1000oC. The
energy for vacancy formation is 0.9 eV/atom; the atomic weight and density (at 1000oC) for
copper are 63.5 g/mol and 8.4 g/cm3, respectively.
SolutionThe value of N, the number of atomic sites per cubic meter for copper, from its atomic
weight its density and Avogadros number according to

10

10

6.023

10

8.4
63.5 /

=8.0

1028 atoms/m3

Thus, the number of vacancies at 1000oC (1273K) is equal to

N

8.0

10

atoms
exp
m

8.62

0.9 eV
10 eV/K

1273K

= 2.2 1025 vacancies/m3

1.2.4 Effect of point imperfections

The presence of a point imperfection introduces distortions in the crystal.

In the case of impurity atom, because of its difference in size, elastic strains are
created in the regions surrounding the impurity atom.

All these factors tend to increase the potential energy of the crystal called enthalpy.
The work done for the creation of such a point defect is called the enthalpy of
formation of the point imperfection

1.2.5 Line Imperfections

A dislocation is a linear or one-dimensional defect around which some of the atoms are
misaligned. The defects, which take place due to distortion of atoms along a line, in some
direction are called as line defects,.Line defects are also called dislocations.

It is responsible for the phenomenon of slip by which most metals deform plastically.

The two types of dislocations are,

(a)

Edge dislocation

It is a linear defect that centers around the line that is defined along the end of the extra
half-plane of atoms.

The distorted configuration extends all along the edge into the crystal.

Thus as the region of maximum distortion is centered around the edge of the incomplete
plane, this distortion represents a line imperfection and is called an edge dislocation.
11

Edge dislocations are represented by or depending on whether the incomplete

plane starts from the top or from the bottom of the crystal.

These two configurations are referred to as positive and negative edge dislocations
respectively.

(b)

Screw dislocation:

In this dislocation, the atoms are displaced in two separate planes perpendicular to
each other.

It forms a spiral ramp around the dislocation.

The Burgers Vector is parallel to the screw dislocation line.

Speed of movement of a screw dislocation is lesser compared to edge dislocation.

12

(c)

Mixed dislocations
Most dislocations found in crystalline materials are probably neither pure edge
nor pure screw, but exhibit components of both types; these are termed mixed
dislocations.

Burgers vector

The magnitude and direction of the lattice distortion associated with a dislocation is
expressed in terms of a Burgers vector, denoted by a b.

The Burger vector can be found by the gap in the Burger circuit which is obtained by
moving equal distances in each direction around the dislocation.

1.2.6 Surface imperfections

Surface imperfections arise from a change in the stacking of atomic planes on or across a
boundary.

The change may be one of the orientations or of the stacking sequence of atomic planes.

In geometric concept, surface imperfections are two- dimensional. They are of two types
external and internal surface imperfections.

(a) External Surfaces

They are the imperfections represented by a boundary. At the boundary the atomic bonds
are terminated.

Surface atoms are not bonded to the maximum number of nearest neighbors, and are
therefore in a higher energy state than the atoms at interior positions. The bonds of these
13

surface atoms that are not satisfied give rise to a surface energy, expressed in units of
energy per unit area (J/m2 or erg/cm2).
(b) Grain Boundaries
The boundary separating two small grains or crystals having different
crystallographic orientations in polycrystalline materials.

(c) Twin Boundaries

A twin boundary is a special type of grain boundary across which there is a specific
mirror lattice symmetry; that is, atoms on one side of the boundary are located in mirrorimage positions of the atoms on the other side.

The region of material between these boundaries is appropriately termed a twin.

Twins result from atomic displacements that are produced from applied mechanical shear
forces (mechanical twins), and also during annealing heat treatments following
deformation (annealing twins).

14

1.2.7 Volume Defects

These include pores, cracks, foreign inclusions, and other phases. They are normally
introduced during processing and fabrication steps.
1.2.8 Effect on property

There are some properties of materials such as stiffness, density and electrical
conductivity which are termed structure-insensitive, are not affected by the presence of
defects in crystals while there are many properties of greatest technical importance such
as mechanical strength, ductility, crystal growth, magnetic.

Hysteresis, dielectric strength, condition in semiconductors, which are termed structure

sensitive are greatly affected by the-relatively minor changes in crystal structure caused
by defects or imperfections.

15

1.3 Diffusion in solids

Diffusion is a process of mass transport by atomic movement under the influence of thermal
energy and a concentration gradient. Atoms move from higher to lower concentration region.

Figure 1. (a) A coppernickel diffusion couple

after

high-temperature

heat

treatment,

showing the alloyed diffusion zone. (b)

Schematic representations of Cu (red circles)
and Ni (blue circles) atom locations within the
couple. (c) Concentrations of copper and nickel
as a function of position across the couple.
Figure 1 shows, pure copper and nickel at the two extremities of the couple, separated by an
alloyed region. Concentrations of both metals vary with position as shown in Figure1(c). This
result indicates that copper atoms have migrated or diffused into the nickel, and that nickel has
diffused into copper.
1.3.1 Diffusion Mechanisms
Diffusion is just the stepwise migration of atoms from lattice site to lattice site. In fact,
the atoms in solid materials are in constant motion. For an atom to make such a move, two
conditions
16

must be met: (1) there must be an empty adjacent site, and (2) the atom must have sufficient
energy to break bonds with its neighbor atoms and then cause some lattice distortion during the
displacement.
(a)

Vacancy Diffusion
In this mechanism involves the interchange of an atom from a normal lattice position to

an adjacent vacant lattice site or vacancy. This process necessitates the presence of vacancies,
and the extent to which vacancy diffusion can occur is a function of the number of these defects
that are present. Diffusing atoms and vacancies exchange positions, the diffusion of atoms in one
direction corresponds to the motion of vacancies in the opposite direction. Both self-diffusion
and inter-diffusion occur by this mechanism.

(b) Interstitial Diffusion

In this diffusion involves atoms that migrate from an interstitial position to a neighboring
one that is empty. This mechanism is found for inter-diffusion of impurities such as hydrogen,
carbon, nitrogen, and oxygen, which have atoms that are small enough to fit into the interstitial
positions. In most metal alloys, interstitial diffusion occurs much more rapidly than diffusion
by the vacancy mode, since the interstitial atoms are smaller and thus more mobile.

17

(I)

Steady-state diffusion

Steady-state diffusion is the situation when the diffusion flux is independent of time. Ficks
first law describes steady-state diffusion and is given by

Where, J is the diffusion flux or the mass

transported per unit time per unit area and dC/dx is
the concentration gradient. D is known as the
diffusion coefficient.
The negative sign in this expression
indicates that the direction of diffusion is down the
concentration gradient, from a high to a low
concentration
ExampleDiffusion of atoms of a gas through a plate of metal for which the concentrations (or
pressures) of the diffusing species on both surfaces of the plate are held constant.
(II)

Non-steady-state diffusion
Most practical diffusion situations are nonsteady-state ones. In this the diffusion flux and

the concentration gradient at some particular point in a solid vary with time, with a net
accumulation or depletion of the diffusing species resulting.
This is described by Ficks second law

18

A solution to this equation can be obtained for a semi-infinite solid with the following boundary
conditions
For t=0, C = C0 at 0 x
For t > 0, C= Cs at x=0
C=C0 at x=
Application of these boundary conditions to Equation 1 yields the solution

1.3.2 Factors affecting Diffusion

(a) Diffusing species
The magnitude of the diffusion coefficient D is indicative of the rate at which atoms
diffuse. Coefficients, both self- and inter-diffusion. The diffusing species as well as the host
material influence the diffusion coefficient. As the value of D is fixed for a given element in a
given material, the extent of diffusion is first decided by the diffusing species itself.
(b) Temperature
Temperature is the most important factor, which influence on the coefficients and diffusion
rates. Temperature dependence of the diffusion coefficient is expresses as

Where, Do is the pre-exponential factor, Qd is the activation energy for diffusion, T is absolute
temperature in kelvin and R is gas constant.

19

Mechanisms/modes of plastic deformation

Plastic deformation in crystalline solid is accomplished by means of various processes
mentioned below; among which slip is the most important mechanism.
Plastic deformation of crystalline materials takes place by mechanisms which are very different
from that for amorphous materials (glasses). Plastic deformation in amorphous materials occur
by other mechanisms including flow (~viscous fluid) and shear banding.

Plastic deformation by dislocation Motion (SLIP)

SLIP is the most important mechanism of plastic deformation . At low temperatures

(especially in BCC metals) twinning may also become important.

At the fundamental level plastic deformation (in crystalline materials) by slip

involves the motion of dislocations on the slip plane (creating a step of Burgers
vector).

Slip is caused by shear stresses (at the level of the slip plane). Hence, a purely
hydrostatic state of stress cannot cause slip.

A slip system consists of a slip direction lying on a slip plane.

Slip is analogous to the mode of locomotion employed by a caterpillar

Dislocations move more easily on specific planes and in specific directions.

Ordinarily, there is a preferred plane (slip plane), and specific directions (slip
direction) along which dislocations move. The combination of slip plane and slip
direction is called the slip system.
20

The slip system depends on the crystal structure of the metal.

The slip plane is the plane that has the most dense atomic packing (the greatest planar
density). The slip direction is most closely packed with atoms (highest linear density).

In CCP, HCP materials the slip system consists of a close packed direction on a close
packed plane.

Just the existence of a slip system does not guarantee slip slip is competing against
other processes like twinning and fracture. If the stress to cause slip is very high (i.e.
CRSS is very high), then fracture may occur before slip (like in brittle ceramics).

For slip to occur in polycrystalline materials, 5 independent slip systems are required.
Hence, materials which are ductile in single crystalline form, may not be ductile in
polycrystalline form. CCP crystals (Cu, Al, Au) have excellent ductility.

At higher temperatures more slip systems may become active and hence
polycrystalline materials which are brittle at low temperature, may become ductile at
high temperature.
Number of slip

Crystal

Slip plane(s)

Slip direction

FCC

{111}

<110>

12

HCP

(0001)

<1120>

BCC

{110}, {112}, {123}

[111]

48

<110>

12

NaCl (Ionic)

{110}
{111} not a slip plane

C (Diamond cubic)

{111}

<110>

TiO2(Rutile)

{101}

<101>

systems

21

Slip in Single Crystal

If a single crystal of a metal is stressed in tension beyond its elastic limit, it elongates
slightly and a step appears on the surface due to the relative displacement of one part of
the crystal with respect to the others and the elongation stops.

Further increase in the load causes movement of another parallel plane, resulting in
another step. Similarly numbers of small steps are formed on the surface of the single
crystal that are parallel to one another and loop around the circumference of the
specimen.

Each step (shear band) results from the movement of a large number of dislocations and
their propagation in the slip system.

Extent of slip in a single crystal depends on the magnitude of shearing stress produced by
external loads, geometry of the crystal structure and the orientation of he active slip
planes with respect to the shearing stress.

Slip begins when the shearing stress on slip plane in the slip direction/Resolved Shear
Stress (RSS) reaches a critical value called the Critical Resolved Shear Stress (CRSS)
and plastic deformation starts (The actual Schmids law)
22

Even if we apply an tensile force on the specimen the shear stress resolved onto the
slip plane is responsible for slip.

RSS is maximum (P/2A) when

If the tension axis is normal to slip plane i.e. =90o or if it is parallel to the slip plane
i.e.

= =45o

= 90o then RSS = 0 and slip will not occur as per Schmids law.

CRSS is a material parameter, which is determined from experiments.

23

Problem
1. Consider a single crystal of BCC iron oriented such that a tensile stress is applied along a
[010] direction.
(a) Compute the resolved shear stress along a (110) plane and in a [111] direction when a
tensile stress of 52 MPa (7500 psi) is applied

(b) If slip occurs on a (110) plane and in a [111]

direction, and the critical resolved shear

stress is 30 MPa (4350 psi), calculate the magnitude of the applied tensile stress
necessary to initiate yielding.
Solution:Determine the value of

,the angle between the normal to the (110) slip plane (i.e., the

[110] direction) and the [010] direction using [u1v1w1] = [110], [u2v2w2] = [010] and the
following equation.

Similarly determine the value of , the angle between

[111]

and [010] directions as

follows:

(1)(0) (1)(1) (1)(0)

cos1 ( 1 ) 54.7 o
[(1) 2 (1) 2 (1) 2 ][(0) 2 (1) 2 (0) 2 ]
3

cos1

Then calculate the value of RSS using the following expression

24

Yield Strength Y

30 MPa
73.4 Mpa
(cos 45)(cos 54.7)

Plastic deformation by Twin

In addition to slip (dislocation movement), plastic deformation can also occur by

twinning.

Twinning results when a portion of the crystal takes up an orientation that is related to the
orientation of the rest of the untwinned lattice in a definite, symmetrical way.

Twinned portion of the crystal is a mirror image of the parent crystal and the plane of
symmetry between the two portions is called twinning plane.

Twinning may favorably reorient slip systems to promote dislocation movement.

25

Twins are generally of two types: Mechanical Twins and Annealing twins

Mechanical twins are generally seen in bcc or hcp metals and produced under
conditions of rapid rate of loading and decreased temperature.

Annealing twins are produced as the result of annealing. These twins are generally
seen in fcc metals.

Annealing twins are usually broader and with straighter sides than mechanical twins.

(a) Mechanical Twins (Neumann bands in iron), (b) Mechanical Twins in zinc produced by
polishing (c) Annealing Twins in gold-silver alloy

Twinning generally occurs when the slip systems are restricted or when the slip systems
are restricted or when something increases the critical resolved shear stress so that the
twinning stress is lower than the stress for slip.

So, twinning generally occurs at low temperatures or high strain rates in bcc or fcc metals
or in hcp metals.

Twinning occurs on specific twinning planes and twinning directions.

26

Bauschinger effect

The Bauschinger effect refers to a property of

materials

where

characteristics

the

change

material's
as

stress/strain

result

of

the

microscopic stress distribution of the material. For

example, an increase in tensile yield strength
occurs at the expense of compressive yield
strength. The effect is named after German
engineer Johann Bauschinger.

The Bauschinger effect is normally associated with

conditions where the yield strength of a metal
decreases when the direction of strain is changed.
It is a general phenomenon found in most
polycrystalline metals.

The basic mechanism for the Bauschinger effect is

related to the dislocation structure in the cold worked metal. As deformation occurs, the
dislocations will accumulate at barriers and produce dislocation pile-ups and tangles.
Based on the cold work structure, two types of mechanisms are generally used to explain
the Bauschinger effect.

27

Work Hardening

Room temperature deformation.

Common forming techniques used to change the cross sectional area:

Dislocations during Cold Work

Dislocations entangle one another during cold work.

Dislocation motion becomes more difficult, which makes the material stronger overall

28

Isotropic grains are approx. spherical,

equiaxed & randomly oriented.

Anisotropic (directional) since rolling

affects grain orientation and shape.

Result of Cold Work

Dislocation density increases, which leads to a increase in yield strength: Materials

becomes harder.

Ductility and tensile strength also increases.

Recovery, Recrystallization & Grain Growth

Recovery

Recovery takes place at low temperatures of annealing.

Apparently no change in microstructure.

During recovery, some of the stored internal strain energy is relieved through dislocation
motion due to enhanced atomic diffusion at the elevated temperatures.

Leads to reduction in the number of dislocations.

29

This process also removes the residual stresses formed due to cold working significant.
The recovering of physical and mechanical properties varies with the temperature and
time.
Recovery is a relaxation process with the following characteristics:

There is no incubation period

Recovery rate is large at the beginning, and then it slows down till it is near zero
Recovery has a limit value varying with temperature; the higher the temperature, the
greater is the limit value and the shorter is the time needed to reach the limit value
The greater the deformation, the greater is the initial recovery rate, and decrease in grain
size helps to accelerate the recovery process
The characteristic of recovery can be expressed as the following equation:

Where,
t is the time of heating under constant temperature
x is the fraction of property increase caused by cold work after heating
c is a constant related with material and temperature
The value of constant parameter c can be described with the Arrhenius equation:

Recrystallization

After recovery is complete, the grains are still in a relatively high strain energy state.

Recrystallization is the formation of a new set of strain-free and uniaxial grains that have
low dislocation densities.

The temperature at which materials are recrystallized is known as the recrystallization

temperature, Trecrystallization (0.3 0.5) Tm

The driving force to produce the new grain structure is the internal energy difference
between strained and unstrained material.

The new grains form as very small nuclei and grow until they consume the parent
material.
30

Recrystallization is a heterogeneous process and dependent on the deformation state of

steels.
The kinetics of recrystallization depends on nucleation rate, N, and growth rate, G.

Grain Growth

After recrystallization, the strain-free grains will continue to grow if the metal specimen
is left at elevated temperatures. Grains begin to grow via grain boundary immigration;
this phenomenon is called grain growth.

Grain growth is driven by the tendency to decrease the total boundary surface energy by
decreasing the grain boundary area.

Large grains grow at the expense of smaller grains.

(a)

(b)

(c)

(d)

Fig.1.1. (a) Work hardening, (b) recovery, (c) recrystallization, and (d) grain growth during
annealing.

31

Module 2 and 3
I. Solidification
Solidification is basically phase transformation from liquid phase to solid phase. The progress of
a phase transformation takes place in two stages: nucleation and growth. Nucleation involves
the appearance of very small particles, or nuclei of the new phase (often consisting of only a few
hundred atoms), which are capable of growing. During the growth stage these nuclei increase in
size, which results in the disappearance of some (or all) of the parent phase.

Cooling Curve

32

Driving Force
Solidification is undoubtedly the most important processing route for metals and alloys. Consider
a pure metal (Fig. 1). At the fusion temperature Tf, G = 0 so that
Gf = Hf TfSf = 0 or Hf = TfSf
where Hf is the latent heat of fusion, Gf is the Gibbs free energy and Sf is the entropy,i.e
positive for melting.For any temperature T ,
G = H TS
Or G Hf TSf
= Sf (Tf T) = Sf T
Where T is undercooling.
.
Fig. 2.1: Driving Force for nucleation.
The driving force is therefore proportional to the undercooling provided that the latent heat and
the entropy of fusion do not vary much with temperature.
Nucleation
There are two types of nucleation: homogeneous and heterogeneous. The distinction
between them is made according to the site at which nucleating events occur. For the
homogeneous type, nuclei of the new phase form uniformly throughout the parent phase,
whereas for the heterogeneous type, nuclei form preferentially at structural in homogeneities,
such as container surfaces, insoluble impurities, grain boundaries, dislocations, and so on.
Homogeneous Nucleation
Nucleation

without

preferential

nucleation

sites

is

homogeneous

nucleation.

Homogeneous nucleation occurs spontaneously and randomly, but it requires Superheating or

supercooling of the medium.

33

Let us first consider the solidification of a pure material, assuming that nuclei of the solid phase
form in the interior of the liquid as atoms cluster together so as to form a packing arrangement
similar to that found in the solid phase. Furthermore, it will be assumed that each nucleus is
spherical in geometry and has a radius r.

Fig.2.2: Schematic diagram showing the

There are two contributions to the total free energy change that accompany a solidification
transformation.
(i)The first is the free energy difference between the solid and liquid phases, or the volume free

energy, i.e

. where

is the volume free energy change .

(ii)The second is the surface energy, results from the formation of the nucleation of a spherical
solid particle in a liquid, i.e 4

Finally, the total free energy change

is equal to

the sum of these two contributionsthat is

..(1)

Critical Radius(r*)Differentiate the equation (Equation 1) with respect to

r, set the resulting expression equal to zero, and then
solve for critical radius ( r*). That is

Fig.2.3: Schematic plot of free energy versus

radius.
34

and activation free energy (G*)

=
When radius (r) is less than critical radius ( r*),termed as an embryo.
and when radius (r) is greater than critical radius ( r*),termed as an nucle.
(a) Heterogeneous nucleation
Heterogeneous nucleation forms at preferential sites such as phase boundaries, surfaces
(of container, bottles, etc.) or impurities like dust. At such preferential sites, the effective surface
energy is lower, thus diminishes the free energy barrier and facilitating nucleation.
Heterogeneous nucleation occurs much more often than homogeneous nucleation.
Let us consider the nucleation, on a flat
surface, of a solid particle from a liquid
phase. It is assumed that both the liquid
and solid phases wet this flat surface,
that is, both of these phases spread out
and cover the surface.
Figure 2.4: Heterogeneous nucleation of a solid from a liquid.
Taking a surface tension force balance in the plane of the flat surface leads to the following
expression:

where, IL , SI

and

SL is the interfacial energy between interface- liquid, solid interface and

solid liquid respectively. And is the contact angle.

35

Where S() is the function of contact angle as follows:

Geometry of Solidification
The chill zone contains fine crystals nucleated at the mould surface. There is then selective
growth into the liquid as heat is extracted from the mould. If the liquid in the centre of the mould
is undercooled sufficiently there may also be equiaxed grains forming.

Figure 2.4: Geometry of solidification.

36

3. Phase Diagram
Introduction

Phase diagrams are an important tool in the armory of an materials scientist

In the simplest sense a phase diagram demarcates regions of existence of various phases.
(Phase diagrams are maps)

Phase diagrams are also referred to as equilibrium diagrams or constitutional

diagrams. This usage requires special attention: through the term used is equilibrium,
in practical terms the equilibrium is not global equilibrium but Microstructural level
equilibrium.

Broadly two kinds of phase diagrams can be differentiated* those involving time and
those which do not involve time.

In this chapter we shall deal with the phase diagrams not involving time.
This type can be further sub classified into:
Those with composition as a variable (e.g. T vs. %Composition)
Those without composition as a variable (e.g. P vs. T)

Time-Temperature-Transformation

(TTT)

diagrams

and

Continuous-Cooling-

Transformation (CCT) diagrams involve time.

Components of a system

Independent chemical species which comprise the system. These could be Elements,
Ions, Compounds
Example: Au-Cu system : Components Au, Cu (elements)
Ice-water system : ComponentH2O (compound)
Al2O3-Cr2O3 system : ComponentsAl2O3, Cr2O3

Phase

A physically homogeneous and distinct portion of a material system (e.g. gas, crystal,
amorphous)

Gases : Gaseous state always a single phase mixed at atomic or molecule level.
37

Liquids: Liquid solution is a single phase e.g. Nacl in H2O and Liquid mixtures
consists of two or more phases e.g. Oil in water (no mixing at the atomic level)

Solids: In general due to several compositions and crystals structures many phases are
possible.
o For the same composition different crystal structures represent different phases.
E.g. Fe (BCC) and Fe (FCC) are different phases

What kinds of phases exist?

Based on state Gas, Liquid, Solid

Based on atomic order Amorphous, Quasi-crystalline, Crystalline

Based on band structure Insulating, Semi-conducting, Semi-metallic, Metallic

Based on Property Para-electric, Ferromagnetic, Superconducting

Based on stability Stable, Metastable, Unstable

Also sometimes- Based on size/geometry of an entity Nanocrystalline, mesoporous,

layered.

Phase transformation

Phase transformation is the change of one phase into another. For example
Water Ice and -Fe (BCC) -Fe (FCC)

Grain

The single crystalline part of polycrystalline metal separated by similar entities by a grain
boundary

Solute

The component of either a liquid or solid solution that is present to a lesser or minor
extent; the component that is dissolved in the solvent.

Solvent

38

The component of either a liquid or solid solution that is present to a greater or major
extent; the component that dissolves the solute.

System

System has two meanings. First, system may refer to a specific body of material or
object. Or, it may relate to the series of possible alloys consisting of the same
components, but without regard to alloy composition.

Solubility Limit

For many alloy systems and at some specific temperature, there is a maximum
concentration of solute atoms that may dissolve in the solvent to form a solid solution;
this is called a Solubility Limit.

Microstructure

(Phases + defects + residual stress) & their distributions

Structures requiring magnifications in the region of 100 to 1000 times. (or) The
distribution of phases and defects in a material.

Phase diagram

Map that gives relationship between phases in equilibrium in a system as a function of T,

P and composition. Map demarcating regions of stability of various phases

Variables/Axis of phase diagrams

The axes can be:

o Thermodynamic (T, P, V)
o Kinetic (t) or Composition variables (C, %X)

In single component systems (unary systems) the usual variables are T & P

In phase diagrams used in materials science the usual variable are T & %X

In the study of phase transformation kinetics TTT diagrams or CCT diagrams are also
used where the axis are T & t
39

System Components
Phase diagrams and the systems they describe are often classified and named for the number (in
Latin) of components in the system:
Number of components

Name

of

system

or

diagram
One

Unary

Two

Binary

Three

Ternary

Four

Quaternary

Five

Quinary

Six

Sexinary

Seven

Septenary

Eight

Octanary

Nine

Nonary

Ten

Decinary

Experimental Methods
Thermal Analysis: A plot is made of temperature vs. time, at constant composition, the
resulting cooling curve will show a change in slope when a phase change occurs because of the
evolution of heat by the phase change. This method seems to be best for determining the initial
and final temperature of solidification. Phase changes occurring solely in the solid state generally
involve only small heat changes, and other methods give more accurate results.
Metallographic Methods: This method consists in heating samples of an alloy to different
temperatures, waiting for equilibrium to be established, and then quickly cooling to retain their
high temperature structure. The samples are then examined microscopically. This method is
difficulty to apply to metals at high temperatures because the rapidly cooled samples do not
always retain their high temperature structure, and considerable skill is then required to interpret
the observed microstructure correctly.

40

X-ray diffraction: Since this method measures lattice dimensions, it will indicate the
appearance of a new phase either by the change in lattice dimension or by the appearance of a
new crystal structure. This method is simple, precise, and very useful in determining the changes
in solid solubility with temperature.
Gibbs Phase Rule

The phase rule connects the Degrees of Freedom, the number of components in a system
and the number of phases present in a system via a simple equation.

To understand the phase rule one must understand the variables in the system along with
the degrees of freedom.

We start with a general definition of the phrase degrees of freedom.

Degrees of Freedom: The degree of freedom, F, are those externally controllable conditions of
temperature, pressure, and composition, which are independently variable and which must be
specified in order to completely define the equilibrium state of the system.

The degrees of freedom cannot be less than zero so that we have an upper limit to the number of
phases that can exist in equilibrium for a given system.
Variables in a phase diagram

C No. of components

P No. of phases

F No. of degrees of freedom

Variables in the system = Composition variables + Thermodynamic variables

Composition of a phase specified by (C 1) variables (If the composition is expressed in

%ages then the total is 100% there is one equation connecting the composition
variables and we need to specify only (C - 1) composition variables)
41

No. of variables required to specify the composition of all phases: P(C 1) (as there are
P phases and each phase needs the specification of (C 1) variables)

Thermodynamic variables = P + T (usually considered) = 2 (at constant pressure (e.g.

atmospheric pressure) the thermodynamic variable becomes 1)

Total no. of variables in the system = P (C 1) + 2

F < no. of variables F < P (C 1) + 2For a system in equilibrium the chemical

potential of each species is same in all the phases

If , , are phases, then: A () = A () = A ()..

Suppose there are 2 phases ( and phases) and 3 components (A, B, C) in each phase
then : A() = A(), B() = B(), C() = C() i.e. there are three equations. For
each component there are (P 1) equations and for C components the total number of
equations is C(P 1). In the above example the number of equations is 3(2 1) = 3
equations.

F = (Total number of variables) (number of relations between variables)

= [P(C 1) + 2] [C(P 1)] = C P + 2

In a single phase system F = Number of variables

P F (For a system with fixed number of components as the number phases increases
the degrees of freedom decreases.

Unary Phase Diagram

Let us start with the simplest system possible: the unary system wherein there is just one
component.

Though there are many possibilities even in unary phase diagram (in terms of the axis
and phases), we shall only consider a T-P unary phase diagram.

Let us consider the water (H2O) unary

phase diagram

The Gibbs phase rule here is: F=C-P+2

(2 is for T&P) (no composition variables
here)

42

Along the 2 phase co-existence (at B & C) lines the degree of freedom (F) is 1 i.e. we
can chose either T or P and the other will be automatically fixed.

The 3 phase co-existence points (at A) are invariant points with F=0. (Invariant point
implies they are fixed for a given system).

The single phase region at point D, T and P can both be varied while still being in the
single phase region with F = 2.

The above figure represents the phase

diagram for pure iron. The triple point
temperature and pressure are 490C and
110 kbars, respectively. , and refer to
ferrite, austenite and -iron, respectively.
is simply the higher temperature
designation of .

Binary Phase Diagram

Binary implies that there are two components.

Pressure changes often have little effect on the equilibrium of solid phases
(unless of course we apply huge pressures).

Hence, binary phase diagrams are usually drawn at 1 atmosphere pressure.

The Gibbs phase rule is reduced to:

Variables are reduced to : F = C P + 1 (1 is for T).

T & Composition (these are the usual variables in materials phase diagrams)

In the next page we consider the possible binary phase diagrams. These have been
classified based on:
43

 Complete solubility in both liquid & solid states

Complete solubility in both liquid state, but limited solubility in the
solid state
Limited solubility in both liquid & solid states

Isomorphous Phase Diagram

Isomorphous phase diagrams form when there is complete solid and liquid
solubility.

Complete solid solubility implies that the crystal structure of the two components
have to be same and Hume-Rothery rules to be followed.

Examples of systems forming isomorphous systems: Cu-Ni, Ag-Au, Ge-Si,

Al2O3-Cr2O3

Both the liquid and solid contain the components A and B.

In binary phase diagrams between two single phase regions there will be a two
phase region In the isomorphous diagram between the liquid and solid state
there is the (Liquid + Solid) state.

44

The Liquid + Solid state is NOT a semi-solid state it is a solid of fixed

composition and structure, in equilibrium with a liquid of fixed composition.

In some systems (e.g. Au-Ni system) there might be phase separation in the solid
state (i.e.,the complete solid solubility criterion may not be followed) these
will be considered as a variation of the isomorphous system (with complete
solubility in the solid and the liquid state.

Cooling curves: Isomorphous system

Isomorphous Phase Diagram

This very simple case is one complete liquid and solid solubility, an isomorphous
system.
The example is the Cu-Ni alloy of Fig. 3.1.
The complete solubility occurs because both Cu and Ni have the same crystal structure
(FCC), near the same radii, electronegativity and valence.
The liquidus line separates the liquid phase from solid or solid + liquid phases. That is,
the solution is liquid above the liquidus line.
45

The solidus line is that below which the solution is completely solid (does not contain a
liquid phase

Figure 3.1: The coppernickel phase diagram.

Tie line and Lever rule

Chemical Composition of Phases: To determine the actual chemical composition of the phases
of an alloy, in equilibrium at any specified temperature in a two phase region, draw a horizontal
temperature line, called a tie line, to the boundaries of the field . These points of intersection are
dropped to the base line, and the composition is read directly.
Relative Amounts of Each Phase:

To determine the relative amounts of the two phases in equilibrium at any specified
temperature in a two phase region, draw a vertical line representing the alloy and a
horizontal temperature line to the boundaries of the field.

46

The vertical line will divide the horizontal line into two parts whose lengths are inversely
proportional to the amount of the phases present. This is also known as Lever rule.

The point where the vertical line intersects the horizontal line may be considered as the
fulcrum of a lever system.

The relative lengths of the lever arms multiplied by the amounts of the phases present
must balance.

Tie line and Lever rule

We draw a horizontal line (called the Tie Line)at the temperature of interest (say T0). Let
Tie line is XY.

Solid (crystal) of composition C 1 coexists with

liquid of composition C 2

Note that tie lines can be drawn only in the two

phase coexistence regions (fields). Though they
may be extended to mark the temperature.

To find the fractions of solid and liquid we use

the lever rule.

The portion of the horizontal line in the two phase region is akin to lever with the
fulcrum at the nominal composition (C0)

The

opposite

arms

of

the

lever

are

proportional to the fraction of the solid and

liquid phase present (this is lever rule).

47

Variations of Isomorphous System

An alloy typically melts over a range of temperatures. However, there are special compositions
which can melt at a single temperature like a pure metal. There is no difference in the liquid and
solid composition. It begins and ends solidification at a constant temperature with no change in
composition, and its cooling curve will show a horizontal line. Such alloys are known as a

congruent-melting alloys, sometimes known as a pseudo-eutectic alloy. Ex: Cu-Au, Ni-Pd.

Congruently melting alloys just like a pure metal

48

Is the DOF 1? No: in requiring that

we have exhausted the degree of

freedom. Hence T is automatically fixed DOF is actually Zero..!

Variations of Isomorphous System

Elevation in the MP means that the solid state is more stable (crudely speaking the
ordered state is more stable) ordering reaction is seen at low T.

Depression in MP means the liquid state (disordered) is more stable phase separation
is seen at low T. (phase separation can be thought of as the opposite of ordering.
Ordering (compound formation) occurs for ve values for H mix).

Equilibrium Cooling

49

Figure: The above figure represents the very slow cooling, under equilibrium conditions, of a
particular alloy 70A-30B will now be studied to observe the phase changes that occur

This alloy at temperature T0 is a homogeneous single-phase liquid solution (a) and

remains so until temperature T1is reached. Since T1is on the liquidus line, freezing or
solidification now begins.

The first nuclei of solid solution to form 1 will be very rich in the higher melting point
metal A and will be composed of 95A-5B (by tie line rule). Since the solid solution in
forming takes material very rich in A from the liquid, the liquid must get richer in B. Just
after the start of solidification, the composition of the liquid is approximated as 69A-31B
(b).

When the lower temperature T2 is reached, the liquid composition is at L2. The only solid
solution in equilibrium with L2 and therefore the only solid solution forming at T2 is 2.
Applying tie line rule, 2 is composed of 10B. Hence, as the temperature is decreased,
not only does the liquid composition become richer in B but also the solid solution.

At T2 ,crystals of 2 are formed surrounding the 1 composition cores and also separate
dendrites of z (see figure in below).

50

In order for equilibrium to be established at T2, the entire solid phase must be a
composition 2. This requires diffusion of B atoms to the A-rich core not only from the
solid just formed but also from the liquid. This is possible in crystal growth (c).

The composition of the solid solution follows the solidus line while the composition of
liquid follows the liquidus line, and both phases are becoming richer in B.

At T3 (d), the solid solution will make up approximately three-fourths of all the material
present.

Finally, the solidus line is reached at T4, and the last liquid L4, very rich in B, solidifies
primarily at the grain boundaries (e).

However, diffusion will take place and all the solid solution will be of uniform
composition (70A-30B), which is the overall composition of the alloy (f).

There are only grains and grain boundaries. There is no evidence of any difference in
chemical composition inside the grains, indicating that diffusion has made the grain
homogeneous.

51

Non Equilibrium Cooling - Coring

In actual practice it is extremely difficult to cool under equilibrium conditions. Since

diffusion in the solid state takes place at a very slow rate, it is expected that with
ordinary cooling rates there will be some difference in the conditions as indicated by
the equilibrium diagram.

Consider again 70A-30B alloy, solidification

starts at T1 forming a solid solution of
composition 1 .

At T2 the liquid is L2 and the solid solution

now forming is of composition 2 . Since
diffusion is too slow to keep pace with
crystal growth, not enough time will be
allowed to achieve uniformity in the solid, and the average composition will be
between 1 and 2, say 2.

As the temperature drops, the average composition of the solid solution will depart
still further from equilibrium conditions. It seems that the composition of the solid

52

solution is following a nonequilibrium solidus line 1 to 5, shown dotted lines in

figure.

The liquid, on the other hand, has essentially the composition given by the liquidus
line, since diffusion is relatively rapid in liquid. At T3 the average solid solution will
be of composition 3 instead of 3.

Under equilibrium cooling, solidification should be complete at T4 ; however, since

the average composition of the solid solution 4 has not reached the composition of
the alloy, some liquid must still remain. Applying lever rule at T4 gives 4 = 75% and
L4 = 25%.

Therefore, solidification will continue until T5 is reached. At this temperature the

composition of the solid solution 5 coincides with the alloy composition, and
solidification is complete. The last liquid to solidify, L5, is richer in B than the last
liquid to solidify under equilibrium conditions.

The more rapidly the alloy is cooled the greater will be the composition range in the
solidified alloy. Since the rate of chemical attack varies with composition, proper
etching will reveal the dendritic structure microscopically (see below figure). The
final solid consists of a cored structure with a higher-melting central portion
surrounded by the lower-melting, last-to-solidify shell. The above condition is
referred to as coring or dendritic segregation.

To summarize, nonequilibrium cooling results in an increased temperature range

over which liquid and solid are present; Since diffusion has not kept pace with
crystal growth, there will be a difference in chemical composition from the center to
the outside of the grains. The faster the rate of cooling, the greater will be the above
effects.

Eutectic Phase Diagram

Very few systems exhibit an isomorphous phase diagram (usually the solid solubility of
one component in another is limited).

Often the solid solubility is severely limited through the solid solubility is never zero
(due to entropic reasons).

53

In a Simple eutectic system (binary), there is one composition at which the liquid freezes
at a single temperature. This is in some sense similar to a pure solid which freezes at a
single temperature (unlike a pure substance the freezing produces a two solid phases both
of which contain both the components).

The term Eutectic means easy melting The alloy of eutectic composition freezes at a
lower temperature than the melting point s of the constituent components.

This has important implifications e.g. the Pb-Sn eutectic alloy melts at 183 C, which
is lower than the melting points of both Pb (327C) and Sn (232C) Can be used for
soldering purposes (as we want to input least amount of heat to solder two materials).

In the next page we consider the Pb-Sn eutectic phase diagram.

Microstructural Characteristics of Eutectic System

54

To reiterate an important point: Phase diagram do not contain microstructural

information (i.e. they cannot tell you what the microstructures produced by cooling is.
Often microstructural information is overlaid on phase diagram for convenience.
Hence, strictly cooling is not in the domain of phase diagram but we can overlay
such information keeping in view the assumptions involved.

55

Application of Lever rule in Eutectic System

Peritectic Phase Diagram

56

Like the eutectic system, the Peritectic reaction is found in systems with complete liquid
solubility but limited solid solubility.

In the Peritectic reaction the liquid (L) reacts with one solid () to produce another solid
(). L+

Since the solid forms at the interface between the L and the , further reaction is
dependent on solid state diffusion. Needless to say this becomes the rate limiting step and
hence it is difficult to equilibrate peritectic reactions (as compared to say eutectic
reactions).

In some Peritectic reactions (e.g. the Pt-Ag system previous page). The (pure) phase
is not stable below the Peritectic temperature (TP = 1186 C for Pt- Ag system) and splits
into a mixture of (+) just below TP.

Monotectic Phase Diagram

In all the types discussed previously, it was assumed that there was complete solubility in
the liquid state. It is quite possible, however, that over a certain composition range two
liquid solutions are formed that are not soluble in each other.

Another term for solubility is miscibility. Substances that are not soluble in each other,
such as oil and water, are said to be immiscible. Substances that are partly soluble in each
other are said to show a miscibility gap, and this is related to Monotectic Systems.

When one liquid forms another liquid, plus a solid, on cooling, it is known as a
Monotectic Reaction.

It should be apparent that the Monotectic reaction resembles the eutectic reaction, the
only difference being that one of the products is a liquid phase instead of a solid phase.

An example of an alloy system showing a Monotectic reaction is that between copper

and lead given in next page. Notice that in this case the L1 + L2 is closed.

Also, although the terminal solids are indicated as and , the solubility is actually so
small that they are practically the pure metals, copper and lead.
57

The Eutectoid Reaction

This is a common reaction in the solid state. It is very similar to the eutectic reaction
but does not involve the liquid . In this case, a solid phase transforms on cooling into
two new solid phases. The general equation may be written as..!

The resultant Eutectoid mixture is extremely fine, just like the eutectic mixture.
Under the microscope both mixtures generally appear the same, and it is not possible
to determine microscopically whether the mixture resulted from a eutectic reaction or
eutectoid reaction.

An equilibrium diagram of Cu-Zn, illustrating the eutectoid reaction is shown in

figure.

In copper (Cu) Zinc (Zn) system contains two terminal solid solutions i.e. these are
extreme ends of phase diagram and , with four intermediate phases called , ,
and . The phase is termed an ordered solid solution, one in which the copper and
zinc atoms are situated in a specific and ordered arrangement within each unit cell.

58

In the diagram, some phase boundary lines near the bottom are dashed to indicate that
there positions have not been exactly determined. The reason for this is that at low
temperatures, diffusion rates are very slow and inordinately long times are required for
the attainment of equilibrium.

Again only single- and two- phase regions are found on the diagram, and the same and
we can utilize the lever rule for computing phase compositions and relative amounts.

The commercial material brasses are copper-rich copper-zinc alloys: for example,
cartridge brass has a composition of 70 wt% Cu-30 wt% Zn and a microstructure

consisting of a single phase.

59

The Peritectoid Reaction

This is a fairly common reaction in the solid state and appears in many alloy systems.
The peritectoid reaction may be written as

The new solid phase is usually an intermediate alloy, but it may also be a solid solution
.The peritectoid reaction has the same relationship to the peritectic reaction as the
eutectoid has to the eutectic. Essentially, it is the replacement of a liquid by a solid.

The peritectoid reaction occurs entirely in the solid state and usually at lower
temperatures than the peritectic reaction, the diffusion rate will be slower and there is less
likelihood that equilibrium structures will be reached.

Consider Silver (Ag) Aluminium (Al) phase diagram (in next page) containing a
peritectoid reaction.

If a 7% Al alloy is rapidly cooled from the two phase area just above the peritectoid
temperature the two phases will be retained, and the microstructure will show a matrix of
with just a few particles of . When we cool at below the peritectoid temperature by
holding we get single phase .

60

Monotectoid Reaction : Al-Zn Phase Diagram

Syntectic Reaction : Ga I Phase Diagram

61

Summary of Invariant reactions

Allotropic Transformations

As we discussed earlier that several metals may exist in more than one type of crystal
structure depending upon temperature , Iron, Tin, Manganese and Cobalt are examples of
metals which exhibit this property , known as Allotropy.

On an equilibrium diagram, this allotropic change is indicated by a point or points on the

vertical line which represents the pure metal. This is illustrated in below figure. In this
diagram, the gamma solid solution field is looped. The pure metal Fe and alloys rich in
Fe undergo two transformations.

62

Order-disorder Transformations

Ordinarily in the formation of substitutional type of solid solution the solute atoms do not
occupy any specific position but are distributed at random in the lattice structure of the
solvent. The alloy is said to be in a disordered condition.

Some of these random solid solutions, if cooled slowly, undergo a rearrangement of the
atoms where the solute atoms move into definite positions in the lattice. This structure is
known as an ordered solid solution or superlattice.

Ordering is most common in metals that are completely soluble in the solid state, and
usually the maximum amount of ordering occurs at a simple atomic ratio of the two
elements.

For this reason, the ordered phase is sometimes given a chemical formula, such as AuCu
and AuCu3 in the gold-copper alloy system. On the equilibrium diagram, the ordered
solutions are frequently designated as , , etc. or , , etc., and the area in which
they are found is usually bounded by a dot-dash line.

When the ordered phase has the same lattice structure as the disordered phase, the effect
of ordering on mechanical properties is negligible. Hardening associated with the
ordering process is most pronounced in those systems where the shape of the unitcell is
changed by ordering.

Regardless of the structure formed as a result of ordering, an important property change

produced, even in the absence of hardening, is a significant reduction in electrical
resistance. Notice the sharp decrease in electrical resistivity at the compositions which
correspond to the ordered phases AuCu and AuCu3.

63


Allotropic Transformations in Iron

Iron is an allotropic metal, which means that it can exist in more than one type of lattice
structure depending upon temperature. A cooling curve for pure iron is shown below:

Iron Cementite Phase Diagram

The Fe-C (or more precisely the Fe-Fe3C) diagram is an important one. Cementite is a
metastable phase and strictly speaking should not be included in a phase diagram. But
the decomposition rate of cementite is small and hence can be thought of as stable
enough to be included in a phase diagram. Hence, we typically consider the Fe-Fe3C part
of the Fe-C phase diagram.

64

A portion of the Fe-C diagram the part from pure Fe to 6.67 wt.% carbon
(corresponding to cementite, Fe3C) is technologically very relevant.

Cementite is not a equilibrium phase and would tend to decompose into Fe and graphite.
This reaction is sluggish and for practical purpose (at the microstructural level) cementite
can be considered to be part of the phase diagram. Cementite forms as it nucleates readily
as compared to graphite.

Compositions upto 2.1%C are called steels and beyond 2.1% are called cast irons. In
reality the calssification should be based on castability and not just on carbon content.

Heat treatments can be done to alter the properties of the steel by modifying the
microstructure we will learn about this in coming chapters.

65

Figure: Iron Cementite Phase Diagram

Carbon Solubility in Iron

Solubility of carbon in Fe = f (structure, temperature)
Where is carbon located in iron lattice?

66

Characteristics of phases appeared in Fe-Fe3C phase diagram

Ferrite ()

It is an interstitial solid solution of a small amount of

carbon dissolved in iron. The maximum solubility
is 0.025%C at 723C and it dissolves only 0.008%C
at room temperature. It is the softest structure that
appears on the diagram

The crystal structure of ferrite () is B.C.C

Tensile strength 40,000 psi or 275 Mpa

Elongation 40% in 2 in.

Hardness - < 0 HRC or < 90 HRB

Cementite (Fe3C)

Cementite or iron carbide, chemical formula Fe3C, contains 6.67%C by weight and it is a
metastable phase.

It is typically hard and brittle interstitial compound of low tensile strength (approx. 5000
psi) but high compressive strength.

It is the hardest structure that appears on the diagram.

67

Its crystal structure is orthorhombic

Pearlite ( + Fe3C)

Pearlite is the eutectoid mixture containing 0.80 %C and is formed at 723C on very
slow cooling.

It is very fine platelike or lamellar

mixture of ferrite and cementite. The
fine

fingerprint

mixture

called

pearlite is shown in below figure.

Tensile strength 120,000 psi or 825

Mpa

Elongation 20 percent in 2 in.

Hardness HRC 20, HRB 95-100, or BHN 250-300

Austenite ()

It is an interstitial solid solution of a small amount of

carbon dissolved in iron. The maximum solubility is
2.1%C at 1147C.

The crystal structure of Austenite () is F.C.C

Tensile strength 150,000 psi or 1035 Mpa

Elongation 10% in 2 in.

Hardness - 40 HRC and Toughness is high.

68

Ledeburite (+ Fe3C)

Ledeburite is the eutectic mixture of austenite and

cementite. It contains 4.3%C and is formed at
1147C

Structure of ledeburite contains small islands of

austenite are dispersed in the carbide phase.

Not stable at room temperature

Ferrite ()

Interstitial solid solution of carbon in iron of

body centered cubic crystal structure. ( iron )
of

higher lattice parameter (2.89) having

solubility limit of 0.09 wt% at 1495C with

respect to austenite. The stability of the phase
ranges between 1394-1539C.

This is not stable at room temperature in plain

carbon steel. However it can be present at
room temperature in alloy steel especially duplex stainless steel.

Microstructures involved in eutectoid mixture

Eutectoid reaction

Phase changes that occur upon passing from the region

into the + Fe3C phase field.

Consider, for example, an alloy of eutectoid composition

(0.8%C) as it is cooled from a temperature within the
phase region, say 800C that is, beginning at point a in
figure and moving down vertical xx. Initially the alloy is
composed

entirely

of

the

austenite

phase

having

composition 0.8 wt.% C and then transformed to + Fe3C

69

[pearlite].

The microstructure for this eutectoid steel that is slowly cooled through eutectoid
temperature consists of alternating layers or lamellae of the two phases and Fe3C

The pearlite exists as grains, often termed colonies; within each colony the layers are
oriented in essentially the same direction, which varies from one colony to other.

The thick light layers are the ferrite phase, and the cementite phase appears as thin
lamellae most of which appear dark.

Hypo eutectoid region

Hypo eutectoid region 0.008 to 0.8 %C

Consider vertical line yy in figure, at about

875C, point c, the microstructure will consist
entirely of grains of the phase.

In cooling to point d, about 775C, which is within

the + phase region, both these phases will
coexist as in the schematic microstructure Most of
the small particles will form along the original
grain boundaries.
70

Cooling from point d to e, just above the eutectoid but still in the + region, will
produce an increased fraction of the phase and a microstructure similar to that also
shown: the particles will have grown larger.

Just below the eutectoid temperature, at point f, all the phase that was present at
temperature e will transform pearlite. Virtually there is no change in phase that
existed at point e in crossing the eutectoid temperature it will normally be present as
a continuous matrix phase surrounding the isolated pearlite colonies.

Thus the ferrite phase will be present both in the pearlite and also as the phase that
formed while cooling through the + phase region. The ferrite that is present in the
pearlite is called eutectoid ferrite, whereas the other, is termed proeutectoid (meaning
pre- or before eutectoid) ferrite.

Hyper eutectoid region

Hyper eutectoid region 0.8 to 2.1 %C

Consider an alloy of composition C1 in figure that,

upon cooling, moves down the line zz. At point g
only the phase will be present and the
microstructure having only gamma grains.

Upon cooling into the + Fe3C phase field say to

point h the cementite phase will began to form
along the initial grain boundaries, similar to the
phase in point d. this cementite is called
proeutectoid cementite that which forms before the

71

eutectoid reaction.

As the temperature is lowered through the eutectoid to point I, all remaining austenite of
eutectoid composition is converted into pearlite; thus the resulting microstructure consists
of pearlite and proeutectoid cementite as microconstituents.

Application of Lever rule in Fe-Fe3C phase diagram

72

Critical temperature lines

In general, A0 Subcritical temperature, A1 - lower critical temperature, A3 - upper

critical temperature, A4 Eutectic temperature, A5 Peritectic temperature and Acm /+cementite phase field boundary.

While heating we denoted as Ac1, Ac2, Ac3 etc., c stands for chauffage (French word),
which means heating and while cooling we denoted as Ar1, Ar2, Ar3 etc., r stands for
refroidissement, (French word) which means cooling.

73

Martensitic Transformations

Under slow cooling rates, the carbon atoms are able to diffuse out of the austenite
structure and it leads to gamma to alpha transformation . This process involves nucleation
and growth and it is time dependent.

With a still further increase in cooling rate, insufficient time is allowed for the carbon to
diffuse out of solution, and although some movement of the iron atoms takes place, the
structure cannot become B.C.C. while the carbon is trapped in solution.

The resultant structure is called Martensite, is a supersaturated solid solution of carbon

trapped in a body-centered tetragonal structure and it is a metastable phase.

The highly distorted lattice structure is the prime reason for the high hardness of
martensite.

After drastic cooling, martensite appears microscopically as a white needlelike or acicular

structure or lenticular, sometimes described as pile of straw.

Shape of the Martensite formed Lenticular (or thin parallel plates)

Associated with shape change (shear)

This condition requires:

o Bain distortion Expansion or contraction of the lattice along certain
crystallographic directions leading to homogenous pure dilation
o Secondary Shear Distortion Slip or twinning

74

o Rigid Body rotation

Martensitic transformation can be understood by first considering an alternate unit cell

for the Austenite phase as shown in the figure below.

If there is no carbon in the Austenite (as in the schematic below), then the Martensitic
transformation can be understood as a ~20% contraction along the c-axis and a ~12%
expansion of the a-axis accompanied by no volume change and the resultant structure
has a BCC lattice (the usual BCC-Fe) c/a ratio of 1.0.

In the presence of Carbon in the octahedral voids of CCP (FCC) -Fe (as in the schematic
below) the contraction along the c-axis is impeded by the carbon atoms. (Note that
only a fraction of the octahedral voids are filled with carbon as the percentage of C in Fe
is small).
75

However the a1 and a2 axis can expand freely. This leads to a product with c/a ratio (c/a)
>1

In this case there is an overall increase in volume of ~4.3% (depends on the carbon
content) the Bain distortion.

The Martensitic transformation occurs without composition change

The transformation occurs by shear without need for diffusion and is called diffusion less
transformation

The atomic movements (shearing) required are only a fraction of the inter atomic spacing

The

shear

changes

the

shape

of

the

transforming

region

results in considerable amount of shear energy

plate-like shape of Martensite

The amount of martensite formed is a function of the temperature to which the sample is
quenched and not of time

Hardness of martensite is a function of the carbon content but high hardness steel is
very brittle as martensite is brittle

Steel is reheated to increase its ductility this process is called TEMPERING

The martensite transformation, for many years, was believed to be unique for steel.
However, in recent years, this martensite type of transformation has been found in a
number of other alloy systems, such as iron-nickel, copper-zinc, and copper-aluminum.

The basic purpose of hardening is to produce a fully martensitic structure, and the
minimum cooling rate ( per second) that will avoid the formation of any of the softer
products of transformation is known as the critical cooling rate.

76

The critical cooling rate, determined by chemical composition and austenitic grain size, is
an important property of a steel since it indicates how fast a steel must be cooled in order
to form only martensite

Time-Temperature-Transformation (TTT) Diagrams

Davenport and Bain were the first to develop the TTT diagram of eutectoid steel. They
determined pearlite and bainite portions whereas Cohen later modified and included MS
and MF temperatures for martensite.

There are number of methods

used to determine TTT diagrams. The most popular

method is salt bath techniques combined with metallography and hardness measurement
with addition of this we have other techniques like dilatometry, electrical resistivity
method, magnetic permeability, in situ diffraction techniques (X-ray, neutron), acoustic
emission, thermal measurement techniques, density measurement techniques and
thermodynamic predictions.

TTT

diagrams, also called as Isothermal (temperature constant) Transformation

diagrams.

TTT diagrams give the kinetics of isothermal transformations.

For every composition of steel we should draw a different TTT diagram.

For the determination of isothermal transformation (or) TTT diagrams, we consider

molten salt bath technique combined with metallography and hardness measurements.

In molten salt bath technique two salt baths and one water bath are used. Salt bath I is
maintained at austenising temperature (780C for eutectoid steel). Salt bath II is
maintained at specified temperature at which transformation is to be determined (below
Ae1), typically 700-250C for eutectoid steel. Bath III which is a cold water bath is
maintained at room temperature.

In bath I number of samples are austenite at A1+20-40C for eutectoid, A3+20-40C for
hypo-eutectoid steel and ACm+20-40C for hyper-eutectoid steels for about an hour.

Then samples are removed from bath I and put in bath II and each one is kept for
different specified period of time say t1, t2, t3, t4,..........,tn etc. After specified times, the
samples are removed and quenched in cold water. The microstructure of each sample is

77

studied using metallographic techniques. The type, as well as quantity of phases, is

determined on each sample.

78

As pointed out before one of the important utilities of the TTT diagrams comes from
the overlay of micro-constituents (microstructures) on the diagram.

Depending on the T, the (+ Fe3C) phase field is labeled with micro-constituents like
Pearlite, Bainite.

The time taken to 1% transformation to, say pearlite or bainite is considered as

transformation start time and for 99% transformation represents transformation finish.

We had seen that TTT diagrams are drawn by instantaneous quench to a temperature
followed by isothermal hold.

Suppose we quench below (~225C, below the temperature marked Ms), then
Austenite transforms via a diffusionless transformation (involving shear) to a (hard)
phase known as Martensite. Below a temperature marked Mf this transformation to
Martensite is complete. Once is exhausted it cannot transform to ( + Fe3C).

Hence, we have a new phase field for Martensite. The fraction of Martensite formed
is not a function of the time of hold, but the temperature to which we quench
(between Ms and Mf).

Strictly speaking cooling curves (including finite quenching rates) should not be
overlaid on TTT diagrams (remember that TTT diagrams are drawn for isothermal
holds!).

79

TTT diagram for Hypo eutectoid steel

In hypo- (and hyper-) eutectoid steels (say
composition C1) there is one more branch to the
C curve-NP (next slide: marked in red).
The part of the curve lying between T1 and TE
(marked in fig : next slide) is clear, because in
this range of temperatures we expect only proeutectoid to form and the final microstructure
will consist of and . (E.g. if we cool to Tx and
hold).
The part of the curve below TE is a bit of a mystery (since we are instantaneously
cooling to below TE, we should get a mix of + Fe3C

what is the meaning of a pro-

eutectoid phase in a TTT diagram? (remember pro- implies pre-)

80

 Suppose we quench instantaneously an hypo-eutectoid composition C1 to Tx we should

expect the formation of +Fe3C (and not pro-eutectoid first).
The reason we see the formation of pro-eutectoid first is that the undercooling w.r.t to
Acm is more than the undercooling w.r.t to A1. Hence, there is a higher propensity for the
formation of pro-eutectoid .

TTT diagram for Hyper eutectoid steel

Similar to the hypo-eutectoid case, hyper-eutectoid compositions C2 have a +Fe3C
branch.
For a temperature between T2 and TE (say Tm (not melting point- just a label)) we land
up with +Fe3C.
For a temperature below TE (but above the nose of the C curve) (say Tn), first we have
the formation of pro-eutectoid Fe3C followed by the formation of eutectoid +Fe3C.

81

Transformation to Pearlite

The transformation product above the nose region is pearlite. The pearlite microstructure
is the characteristic lamellar structure of alternate layers of ferrite and cementite.

As the transformation temperature decreases, the characteristic lamellar structure is

maintained, but the spacing between the ferrite and carbide layers becomes increasingly
smaller until the separate layers cannot be resolved with the light microscope.

As the temperature of transformation and the fineness of the pearlite decreases, it is

apparent that the hardness will increase.

82

Nucleation and growth

Heterogeneous nucleation at grain boundaries

Interlamellar spacing is a function of the temperature of transformation

Lower temperature finer spacing higher hardness

83

Transformation to Bainite

In between the nose region of approximately 510C and the Ms temperature, a new, darketching aggregate of ferrite and cementite appears. This structure, named after E.C.Bain,
is called bainite.

At upper temperatures of the transformation range, it resembles pearlite and is known as

upper or feathery bainite. At low temperatures it appears as a black needlelike structure
resembling martensite and is known as lower or acicular banite.

84

 Pearlite is nucleated by a carbide crystal, bainite is nucleated by a ferrite crystal, and this
results in a different growth pattern.
Acicular, accompanied by surface distortions
** Lower temperature carbide could be carbide (hexagonal structure, 8.4% C)
Bainite plates have irrational habit planes
Ferrite in Bainite plates possess different orientation relationship relative to the parent
Austenite than does the Ferrite in Pearlite

Continuous Cooling Transformation diagrams

The TTT diagrams are also called Isothermal Transformation Diagrams, because the
transformation times are representative of isothermal hold treatment (following a
instantaneous quench).
In practical situations we follow heat treatments (T-t procedures/cycles) in which
(typically) there are steps involving cooling of the sample. The cooling rate may or may
not be constant. The rate of cooling may be slow (as in a furnace which has been switch
off) or rapid (like quenching in water).

85

 Hence, in terms of practical utility TTT curves have a limitation and we need to draw
separate diagrams called Continuous Cooling Transformation diagrams (CCT), wherein
transformation times (also: products & microstructure) are noted using constant rate
cooling

treatments.

diagram

drawn for a given cooling rate

(dT/dt) is typically used for a range
of cooling rates (thus avoiding the
need for a separate diagram for
every cooling rate).
However, often TTT diagrams are
also used for constant cooling rate
experiments- keeping in view the
assumptions

&

approximations

involved.
The CCT diagram for eutectoid steel is considered next.
Important difference between the CCT & TTT transformations is that in the CCT case
Bainite cannot form.

86

Module 4

4.1 Heat Treatment

A heat treatment can be defined as the process to subject a material to a predetermined timetemperature profile in the solid state to achieve desired combination of properties through
alteration of microstructural features, such as, grain size, phase distribution, etc.

General heat treatment processes

Annealing
Annealing cycles are varied according to the temperature and the method of cooling used.
Annealing temperatures may be classified as:

Subcritical annealing (below the lower critical temperature, A1)

Intercritical annealing (above A1 but below the upper critical temperature, A3 in

hypoeutectoid steels, or Acm in hypereutectoid steels)

Supercritical annealing to achieve full austenitization of either hypo- or hyper-eutectoid

steels.

Some commonly used heat treatment cycle superimposed on Fe-C equilibrium diagram is shown
in Fig.4.1.

87

Fig.4.1 Approximate temperature ranges for various heat treatments applied to steels.

Full Annealing

The temperatures for full annealing are typically 50C (90F) above the upper critical
temperature (A3) for hypoeutectic steels and the lower critical temperature (A1) for
hypereutectoid steels.

It is referred to as full annealing because it achieves full austenitization of hypoeutectoid

steels.

88

The indicated temperatures for full annealing are a supercritical anneal for hypoeutectoid
steels, but are in the range of an intercritical anneal for hypereutectoid steels.

Full annealing produces a microstructure that is softer and more amenable to other
processing such as forming or machining.

In addition, stainless and high-alloy steels may be austenitized (fully annealed) and
quenched to minimize the presence of grain boundary carbides or to improve the ferrite
distribution.

The temperatures for full annealing are in approximately the same range of
austenitization temperatures for water quenching (Fig. 4.1) but are below austenitization
temperatures for either normalizing or hardening by oil quenching.

Recrystallization Annealing

When cold worked metals are heated to a sufficiently high temperature, the badly
deformed cold worked grains are replaced by new strain-free grains.

This process is referred to as recrystallization, which is distinct from the recovery process
during stress relief. At a constant temperature, recovery starts rapidly and then decreases
with time. On the other hand, recrystallization, which is a nucleation and growth process,
starts slowly and then builds up to a maximum rate before rapidly leveling off.
Recrystallization annealing of steel is done at subcritical temperatures (Fig. 4.1).

Recrystallization annealing of cold worked metal can produce a new grain structure
without inducing a phase change. The recrystallization temperature is often defined as
the temperature required for the microstructure to undergo 50% recrystallization in 30
min, and for complete recrystallization in approximately one hour.

Although there is a trade-off between time and temperature, temperature is a much more
dominant variable than time. Recrystallization occurs more rapidly at higher
temperatures. For most kinetic processes, increasing the temperature by approximately
11C (20F) doubles the reaction rate. Once recrystallization is complete, further heating
causes grain growth to occur. The recrystallized grain size is dependent on both the
recrystallization time and temperature, particularly the temperature. Higher temperatures
tend to promote larger grain sizes.

89

The temperature required for recrystallization is not exactit depends on the

composition of the alloy and in particular on the amount of cold work performed.
Therefore, recovery may affect the recrystallization temperature, because the tendency
toward recrystallization is lowered when appreciable recovery has occurred; that is, a
higher temperature may then be required to cause recrystallization. In addition, grain size
affects the nucleation rate and the recrystallization temperature. For equal amounts of
cold work, a lower recrystallization temperature and shorter recrystallization time occurs
for fine-grained metal than in coarse grained metal.

Stress Relief Annealing

Annealing at subcritical temperatures (below Ac1) includes three different temperature

regions (Fig. 4.1). The first is the temperature range for stress-relief annealing.

Annealing involves uniform heating of a structure, or portion thereof, and holding at this
temperature for a predetermined period of time, followed by uniform cooling. Stress
relief temperatures are sufficiently high to help activate the microstructural process of
recovery, such that stored internal strain energy is relieved by rearrangement of
dislocations into lower-energy configurations without any change in the shape and
orientation of grains.

Stress-relief heat treating is used to relieve stresses from cold working. Care must be
taken to ensure uniform cooling, particularly when a component is composed of variable
section sizes. If the rate of cooling is not constant and uniform, new residual stresses can
result that are equal to or greater than those that the heat-treating process was intended to
relieve.

Stress-relief heat treating can reduce distortion and high stresses from welding that can
affect service performance. The presence of residual stresses can lead to stress-corrosion
cracking (SCC) near welds and in regions of a component that has been cold strained
during processing.

90

Spheroidizing

Depending on the time-temperature exposure of a steel, the cementite carbides in a steel

can form different morphologies, such as the lamellar cementite of pearlite, or a network
of cementite along prior austenite grain boundaries in a hypereutectoid steel.

The shape and distribution of the carbides can be modified by heat treatment, and
spheroidization treatments are used to produce carbides with a more spherical
morphology.

Because spherical shapes have lower surface energy than angular shapes, the lamellar
shape of cementite in pearlite changes morphology to form spheroids. Portions of the
lamellae pinch off (dissolve) to form a spheroid from the remaining portions of
lamellae. This process can occur over a long period of time, or it can be accelerated by
heat treatment. Depending on the steel, spheroidized carbides can lead to improved
machinability, toughness, and formability.

In hypoeutectoid steels, prolonged holding at a temperature just below Ae1 accelerates

the process of spheroidization. The process may take several hours. To improve on
kinetics for full spheroidization, some treatments involve heating and cooling alternately
between temperatures that are just above Ac1 and just below Ar1.

In low-carbon steels, the typical purpose of spheroidizing is to improve the cold

formability of steels. The formability of steel is altered significantly depending on
whether carbides are spheroids or present as lamellae in pearlite. Low-carbon steels are
seldom spheroidized for machining, because in the spheroidized condition they are
excessively soft and gummy, cutting with long, tough chips.

In hypereutectoid steels (C > 0.77%) and tool steels, spheroidization is done to improve
machinability and improve toughness. Heating of hypereutectoid steels above Ac1 is
done to create dispersed cementite particulates. Heating to dissolve the carbide prevents
reformation of a carbide network. If a temperature slightly above Ac1 is to be used, good
loading characteristics and accurate temperature controls are required for proper results;
otherwise, it is conceivable that Ac1 may not be reached and that austenitization may not
occur.

91

Normalizing

Steel is normalized to refine grain size, make its structure more uniform, make it more
responsive to hardening, and to improve machinability.

When steel is heated to a high temperature, the carbon can readily diffuse, resulting in a
reasonably uniform composition from one area to the next. The steel is then more
homogeneous and will respond to the heat treatment more uniformly.

Normalizing is an austenitizing heating cycle followed by cooling in still or slightly

agitated air. Typically, the temperatures for normalizing (Fig. 4.1) are approximately
55C (100F) above the upper critical line (that is, above Ac3 for hypoeutectoid steels and
above Acm for hypereutectoid steels).

To be properly classed as a normalizing treatment, the heating portion of the process

must produce a homogeneous austenitic phase prior to cooling. Fig. 4.2 compares the
time-temperature cycle of normalizing to that of full annealing.

Fig. 4.2 Comparison of normalizing and full annealing heat treatment cycle.

92

Hardening

The maximum hardness of any steel is associated with a fully martensitic structure. This
microstructure can be produced only if the cooling rate applied is higher than the critical
cooling rate for the corresponding steel.

Hardenability is defined as the susceptibility to hardening by rapid cooling, or as the

property, in ferrous alloys, that determines the depth and distribution of hardness
produced by quenching. Both of these definitions emphasize hardness. As discussed
previously, the source of hardening is the formation and presence of martensite, and
therefore a third definition of hardenability, the capacity of a steel to transform partially
or completely from austenite to some percentage of martensite at a given depth when
cooled under some given conditions, more accurately describes the physical process
underlying hardening.

Severity of Quench

The effectiveness of a given quenching medium is ranked by a parameter referred to as

its severity of quench. This measure of cooling or quenching power is identified by the
letter H and is determined experimentally by quenching a series of round bars of a
given steel.

Table I lists H values for a number of commonly used quenches. Note that apart from the
nature of the quenching medium, the vigorousness of the shake determines the severity of
the quench. When a hot solid is put into a liquid medium, gas bubbles form on the surface
of the solid (interface with medium). As gas has a poor conductivity the quenching rate is
reduced. Providing agitation (shaking the solid in the liquid) helps in bringing the liquid
medium in direct contact with the solid; thus improving the heat transfer (and the cooling
rate).

93

Table I. Severity of quench (H) for various quenching media

Jominy test for Hardenability

Fig. 4.3 shows the shape and dimensions of a Jominy specimen and the fixture for
supporting the specimen in a quenching system.

The specimen is cooled at one end by a column of water; thus, the entire specimen
experiences a range of cooling rates between those associated with water and air cooling.

After quenching, parallel flats are ground on opposite sides of the specimen, and hardness
readings are taken every 116 in. from the quenched end and plotted as shown in Fig. 4.4.

Hardenability differences between different grades of steels can be readily compared if

Jominy curves are available. For example, Fig. 4.5 shows hardenability differences
between different grades of alloy steels containing 0.5% C. Higher hardness persists to
greater distances from the quenched end in the more hardenable steels.

Fig. 4.3: Jominy-Boegehold specimen for end-quench test for hardenability.

94

Fig. 4.4 Method of plotting hardness

data from an end-quenched Jominy
specimen.

Fig.4.5 Results of end-quench tests for

four different grades of alloy steels, all
containing 0.5% C.

Tempering

Martensite in steels can be a very strong and in its as quenched condition rather brittle.
It is then necessary to modify its mechanical properties by heat treatment in the range
150700oC. This process is called tempering, in which the microstructure approaches
equilibrium under the influence of thermal activation.

The general trend during the tempering of martensite therefore begins with the rejection
of excess carbon to precipitate carbides but the substitutional solutes do not diffuse
during this process. The end result of tempering is a dispersion of coarse carbides in a
ferritic matrix which bears little resemblance to the original martensite.

It should be borne in mind that in many steels, the martensite reaction does not go to
completion on quenching, resulting in varying amounts of retained austenite which might
decompose during the tempering process.

The effect of tempering temperature on the hardness of steel is shown in Fig.4. 6.

Tempering of Plain Carbon Steels

On reheating as-quenched martensite, the tempering takes place in four distinct but
overlapping stages:
95

Stage 1: up to 250C: precipitation of -iron carbide; partial loss of tetragonality in

martensite.
Stage 2: between 200C and 300C: decomposition of retained austenite.
Stage 3: between 200C and 350C: replacement of -iron carbide by cementite;
martensite loses tetragonality.
Stage 4,: above 350C: cementite coarsens and spheroidizes; recrystallization of ferrite.

Fig. 4.6 Hardness of ironcarbon martensites tempered 1 h at 100700oC.

Martempering

Martempering is a heat treatment for steel involving austenitisation followed by step

quenching, at a rate fast enough to avoid the formation of ferrite, pearlite or bainite to a
temperature slightly above the martensite start (Ms) point. A schematic of above the
process is shown in Fig.4 7.

96

The advantage of martempering lies in the reduced thermal gradient between surface and
center as the part is quenched to the isothermal temperature and then is air cooled to room
temperature.

Residual stresses developed during martempering are lower than those developed during
conventional quenching because the greatest thermal variations occur while the steel is in
the relatively plastic austenitic condition and because final transformation and thermal
changes occur throughout the part at approximately the same time. Martempering also
reduces or eliminate ssusceptibility to cracking.

Fig.4. 7: Schematic representation of the Martempering process.

Austempering

Austempering process is similar to the Martempering process except that the sample after
the homogenization of temperature from surface and temperature, instead of quenching,

97

held at that temperature above Ms for sufficient time (in the bainite transformation range)
to produce banitic microstructure.

A schematic of this process is shown in Fig. 4.8. An advantage of this process over
Martempering is that the tempering can be avoided. Other advantages include, Higher
ductility, Resistance to shock, Uniform hardness, Tougher and more wear restiance,
Higher impact and Fatigue Strengths.

Fig. 4.8. Schematic representation of the Martempering process.

98

Surface Hardening

Numerous industrial applications require a hard wear resistant surface called the case,
and a relatively soft, tough inside called the core. Example: Gears

They are two different categories. They are thermo chemical and thermo mechanical
treatments. Thermo chemical treatment is related to change in chemical composition and
In Thermo mechanical treatment, there is no change of chemical composition of the steel
and are essentially shallow- hardening methods.

A detailed flow chart is given below related to surface hardening treatments.

Carburizing

Carburizing is the most widely used method of surface hardening. Here, the surface
layers of a low carbon steel (<0.25) is enriched with carbon up to 0.8-1.0%. The
source of carbon may be a solid medium, a liquid or a gas.

In all cases, the carbon enters the steel at the surface and diffuses into the steel as a
function of time at an elevated temperature. Carburizing is done at 920-950C. at this
temperature the following reaction takes place
Fe 2 CO
F e (c) CO

Where Fe(c) represents carbon dissolved in austenite. the rate of diffusion of carbon in
austenite, at a given temperature is dependent upon the diffusion coefficient and the
carbon concentration gradient.

The carburizing equation given previously, Fe+2CO

Fe(c) + CO2 is reversible and

may proceed to the left, removing carbon from the surface layer if the steel is heated
in an atmosphere containing carbon dioxide (CO2). This is called decarburization.
99

Decarburization may be prevented by using an endothermic gas atmosphere in the

furnace to protect the surface of the steel from oxygen, carbon dioxide and water
vapor.

An endothermic gas atmosphere is prepared by reacting relatively rich mixtures of air

and hydrocarbon gas (usually natural gas) in an externally heated generator in the
presence of a nickel catalyst.

Liquid carburizing

Liquid carburizing is a method of case hardening steel by placing it in a bath (8%

NaCN, 82% BaCl2 and 10% NaCl) of molten cyanide so that carbon will diffuse
from the bath into the metal and produce a case comparable to one resulting from
pack or gas carburizing.

Liquid carburizing may be distinguished from cyaniding by the character and

composition of the case produced. The cyanide case is higher in nitrogen and lower in
carbon; the reverse is true of liquid carburized cases.

BaCl2 2 NaCN
Ba (CN ) 2 2 NaCl

Ba ( CN ) 2 Fe
Fe ( C ) Ba ( CN ) 2
Pack carburizing

In pack carburizing, the article s to be carburized are packed in a box, embedding

them in a powdery mixture of 85% charcoal and 15% of energizers such as BaCO3 .
The box is sealed with fireclay and loaded into the furnace kept at 930C. The
residual air in the box combines with carbon to produce CO. The energizer
decomposes as below :

BaCO

BaO

CO

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CO

C
2 CO

The carbon enters the steel through the following reaction:

Fe 2 CO
F e (c) CO

If selective carburization is to be done, copper is electroplated to a thickness of ~0.05

mm in regions where carburization is not desired. Alternatively, a refractory paste of
fireclay mixed with asbestos can be applied. Control of temperature and penetration
depth is less in pack carburizing as compared to liquid and gas carburizing. Also,
direct quench from the carburizing temperature to harden the surface is not possible.

Gas Carburizing

The steel is heated in contact with carbon monoxide and/or a hydrocarbon which is
readily decomposed at the carburizing temperature.

A mixture consisting of 5-15% methane (or propane) in a neutral carrier gas is used.
The methane decomposes according to the following reaction:

CH 4 Fe
2 H 2 Fe(c)
The carbon potential of the gas mixture increases with increasing concentration of
methane. Too large a concentration or too high a gas velocity releases carbon faster
than it can be absorbed and may result in soot formation on the surface.

Closer control of temperature and case depth is possible in gas carburizing, as

compared to pack carburizing. Also, post quenching can be done directly.

Heat treatment after carburizing

Since steel is carburized in the austenite region, direct quenching from the carburizing
temperature will harden both the case and core will harden both the case and core if
the cooling rate is greater than the critical cooling rate. Direct quenching of coarse
grained steels often leads to brittleness and distortion, so that this treatment should be

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applied only to fine grained steels. A diagrammatic representation of various

hardening treatments for carburized steels shown in next slide.

TREATMENT
A

CASE

CORE

best

adapted to fine Refined; Excess carbide not dissolved

Unrefined; soft and machinable

grained steels
B-best adapted to fine Slightly coarsened; some solution of Partially refined; stronger and tougher
grained steels

excess carbide

C-best adapted to fine

grained steels
D-best

coarse grained steels

to

grained steels only

F-adapted

Somewhat coarsened; solution of excess Refined: maximum core strength and

carbide

favored;

austenite

retention hardness; better combination of strength

promoted in highly alloyed steels.

treatment

E-adapted

than A

to

grained steels only

for Refined

solution

of

excess

and ductility than B

carbide Refined; soft and machinable; maximum

favored; austenite retention minimized

fine Unrefined with excess carbide dissolved;
austenite retained; distortion minimized
fine Refined; solution of excess carbide
favored; austenite retention minimized

toughness and resistance to impact

Unrefined but hardened

Unrefined; fair toughness

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Cyaniding and Carbonitriding

In this case that contain both carbon and nitrogen are produced in liquid salt baths
(cyaniding) or by use of gas atmospheres (carbonitriding). The temperatures used are
generally lower than those used in carburizing, being between 750-900C.

Exposure is for a shorter time, and thinner cases are produced, up to 0.010in. For
cyaniding and up to 0.030in. For carbonitriding.

In Cyaniding is done in a liquid bath of NaCN, with the concentration varying between
30 and 97%. Both carbon and nitrogen enter the steel via the following reactions:

2 NaCN O2
2 NaCNO

3 NaCNO
NaCN Na2CO3 C 2 N

The temperature used for cyaniding is lower than that for carburizing and in the range of
800-870C. the time of cyaniding is 0.5-3 hour to produce a case depth of 0.25 mm or
less.

Carbonitriding is a case-hardening process in which a steel is heated in a gaseous

atmosphere of such composition that carbon and nitrogen are absorbed simultaneously.

This process is also known as dry cyaniding or gas cyaniding. It is the gas carburizing
process modified by the addition of anhydrous ammonia.

The decomposition of ammonia provides the nitrogen, which enters the steel along with
carbon.

A typical gas mixture consists of 15% NH3, CH4, and 80% of neutral carrier gas. The
temperature used is 750-900C. With increasing temperature, a greater proportion of
carbon enters the steel.

The presence of nitrogen in the austenite accounts for the major differences between
carbonitriding and carburizing. Carbon-nitrogen austenite is stable at lower temperatures
than plain-carbon austenite and transforms more slowly on cooling. Carbonitriding
therefore can be carried out at lower temperatures and permits slower cooling rates than
carburizing in the hardening operation.

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Nitriding

In contrast to the processes described before, nitriding is carried out in the ferrite region.
Consequently, no phase change occurs after nitriding .

This part to be nitrided should possess the required core properties prior to nitriding. Pure
ammonia decomposes to yield nitrogen which enters the steel:

2 NH 3
2 N 3H 2
The solubility of nitrogen in ferrite is small. Most of the nitrogen that enters the steel
forms hard nitrides (e.g. Fe3N). A typical nitriding steel contains alloying elements of
1%Al, 1.5%Cr and 0.2%Mo. Al, Cr, and Mo form very hard and wear resistant nitrides.

The temperature of nitriding is 500-590C. the time for a case depth of 0.02mm is about
2 hour. In addition with wear resistance, it also increases the resistance of a carbon steel
to corrosion in moist atmospheres.

A common problem encountered in nitriding is the formation of

nitride (Fe4N) on the

outer layers of the case , known as the white layer, as it looks white under the
microscope. This layer is very brittle and tends to crack. It must be removed by final
grinding operation. Its formation can be minimized by maintaining the correct ratio of
NH3/ H2 in the gas mixture during the heat treatment.
Thermal Energy Treatments

For large work pieces, such as mill rolls, large gears and complicated cross sections,
in such cases, flame hardening is done by means of an oxyacetylene torch. Heating
should be done rapidly by the torch and the surface quenched, before appreciable heat
transfer to the core occurs.

Four methods are generally use for Flame Hardening

Stationary (Spot): Torch and work is stationary

Progressive: Torch moves over a work piece
Spinning: Torch is stationary while work piece rotates
Progressive-spinning: Torch moves over a rotating work piece.

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Induction Hardening

Here, an alternating current of high frequency passes through an induction coil enclosing
the steel part to be heat treated. The induced emf heats the steel. the depth up to which the
heat penetrates and rises the temperature above Ac3 is inversely proportional to the square
root of the AC frequency.

Correspondingly, the hardened depth decreases with increasing frequency in induction

hardening, the heating time is usually a few seconds. Immediately after heating water jets
are activated to quench the surface . Martensite is produced at the surface, making it hard
and wear resistant. The microstructure of the core remains unaltered. Induction hardening
is suitable for mass production of articles of uniform cross section

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Laser Hardening

Laser hardening treatment is widely used to harden localized areas of steel and cast iron
machine components. This process is sometimes referred to as laser transformation
hardening to differentiate it from laser surface melting phenomena.

There is no chemistry change produced by laser transformation hardening, and the

process, like induction and flame hardening, provides an effective technique to harden
ferrous materials selectively.

As laser beams are of high intensity, a lens is used to reduce the intensity by producing a
defocused spot of size ranging from 0.5 to 25 mm. proper control of energy input is
necessary to avoid melting.

Laser transformation hardening produces thin surface zones that are heated and cooled
very rapidly, resulting in very fine Martensitic microstructures, even in steels with
relatively low hardenability. High hardness and good wear resistance with less distortion
result from this process.

Laser hardening has the advantage of precise control over the area to be hardened, an
ability to harden reentrant surfaces, very high speed of hardening and no separate
quenching step (the quench is effected by the mass of the unheated material).

The disadvantage is that the hardening is shallower than in induction and flame
hardening.
Electron Beam (EB) Hardening

Electron Beam (EB) hardening is like laser treatment, is used to harden the surfaces of
steels. The EB heat treating process uses a concentrated beam of high-velocity electrons
as an energy source to heat selected surface areas of ferrous parts. Electrons are
accelerated and are formed into a directed beam by an EB gun.

After exiting the gun, the beam passes through a focus coil, which precisely controls
beam density levels (spot size) at the work piece surface and then passes through a
deflection coil.

To produce an electron beam, a high vacuum of 10-5 torr is needed in the region where
the electrons are emitted and accelerated. This vacuum environment protects the emitter
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from oxidizing and avoids scattering of the electrons while they are still traveling at a
relatively low velocity.

Like laser beam hardening, the EB process eliminates the need for quenchants but
requires a sufficient work piece mass to permit self quenching.

A mass of up to eight times that of the volume to be EB hardened is required around and
beneath the heated surfaces. Electron beam hardening does not require energy absorbing
coatings, as does laser beam hardening.

107

Engineering Materials
Stainless Steels

Stainless Steels are a large group of special alloys developed primarily to withstand
corrosion. These steels contain chromium in excess of 12% by weight which imparts
stainless characteristics to iron alloys.

AISI Grades of stainless steels:

Martensitic Stainless Steel

These are primarily straight chromium steels with 11.5 to 18% Cr, 0.15% C, 1.25% Mn,
and 1%Si.
Common examples are 403, 410, 416, 420, 440A, 501 & 502 (AISI grades).

Used for turbine blades and corrosion resistant applications.

Heat Treatment
Process Annealing 650 - 760 o C, increase ductility and machinability
Austenitizing 925 -1065

C followed by oil quenching or air cooling, increase

corrosion resistance and strength

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Austenitic Stainless Steel

These are chrome-nickel (3xx type) or chrome -nickel- manganese(2xx type) alloys.

Total content of Ni and Cr is at least 23%.

Difficult to machine but can be improved by addition of selenium of sulfur.

Best high temperature strength and scaling resistance. Hence shows best corrosion
resistance

Used in chemical industry and for household and sanitary fittings.

Heat Treatment

Cold working causes work hardening but hot working can easily be done.

Annealing at high temperatures Recrystallization and carbide solution

Solution treatment Dissolution of chromium carbides

Tool Steel

Tool steel refers to a variety of carbon and alloy steels that are particularly well-suited
to be made into tools.

Characteristics include high hardness, resistance to abrasion (excellent wear), an

ability to hold a cutting edge, resistance to deformation at elevated temperatures (redhardness).
109

Tool steel are generally used in a heat-treated state.

Ferritic Stainless Steel

These are primarily straight chromium steels with 14 to 27% Cr. Carbon is restricted both
to maintain high toughness and ductility and to prevent austenite formation (As carbon
expands the gamma loop)

These steels can be cold formed easily and hence are used for deep drawn parts such as
vessels for food and chemical industries and for architectural and automotive trim.

Heat Treatment
Can be cold or hot worked.

Annealing 760 - 966oC, recrystallization of cold-worked structures achieves

maximum softness, ductility and corrosion resistance.

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Uses
Shock resisting tool steels Intended for applications requiring toughness and resistance
to shock-loading such as hammers, chisels, punches, driver bits and others.

111

 Water hardening tool steels Shallow hardened and relatively low resistance to
softening. They are suitable for woodworking tools, hand-metal cutting tools such as
taps and reamers and cutlery.

Steels for Room Temperature Use (Classified according to their quenching media)

Water hardened grades (W) Plain carbon steels with 0.6-1.0 %C. These have a low
hardenability, ie., martensite only to a depth of 0.5 in. V can be added (forms V4C3)to
improve the hardness and wear resistance of these steels.
Shock resistant grades (S) Contain small amounts of Cr or Mo and are quenched in
oil. They have lower C contents (0.5%) to improve impact strength.
Oil hardened grades (O) Small percentages of Cr and W with 0.9 %C. The have
medium hardness and are used to short run cold forming dies.
Air hardening grades (A) Greater amounts of Cr and Mo and 1 %C. Used for
complicated shapes and thread rolling. Mo and W are relatively expensive so they are
only added in small amounts to give much improved hardenability.
High carbon, high Cr grades (D grade) 12 %Cr and 1.5-2.25 %C are extremely wear
resistant and used for long run dies and for gauges. Chromium is a relatively low cost
addition for increasing hardenability with the excess Cr, Cr23C6 is also formed, which
improves wear resistance.
Steels for High Temperature Use

Chromium hot working steels (H grades) 5-7 % Cr, 0.4-1.0% V, 1.5-7.0% W,

1.5% Mo, 0.35% C. Medium hot working for Mg and Al extrusion die-casting dies.

Tungsten hot working steels (H ) 9.5-12 % W, 3.5-12.0 % Cr, 0.35 % C. Hot

working, extrusion and forging dies for brass, nickel and steel.

Tungsten high speed steel (T) 12-18 % W, 4.0 % Cr, 1-5 % V, 0.7-1.5 % C.
Original high speed (HS) cutting steel with excellent HT wear resistance.

Molybdenum HS steel (M) 3.5-8.0 % Mo, 1.5-6.0 % W, 4.0 % Cr, 1-5 % V, 5 %

Co, 0.8-1.5 % C. Used for 85% of US cutting steels before the advent of ceramic
cutting tools.

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High Speed Steel (HSS)

HSS is a subset of tool steel, commonly used in tool bits and cutting tools. It is often used
in power saw blades and drill bits.
They are characterized by high carbon contents, sometimes up to 1.5%, and major
additions of strong carbide forming elements such as chromium, molybdenum, tungsten
and vanadium. Up to 12% Co is also included in some of the more complex grades.
It can withstand higher temperatures without losing its temper (hardness) which allows it
to cut faster than high carbon steel, hence the name.
Other characteristics include high hardness, resistance to abrasion (excellent wear), an
ability to hold a cutting edge, resistance to deformation at elevated temperatures (redhardness).
Modulus Of elasticity: 221GPa, Density : 8767 kg/m3 ( durability & hardness), Thermal
Conductivity: 21W/m/K
HSS are mainly of two types: Tungsten based ones (T grades), Molybdenum based ones
(M grades)

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Reference
W.D Callister, Materials Science and Engienering, Wiley Inida (P) Ltd., 2007.
C. Reardon, Metallurgy for the Non-Metallurgist, ASM, Second Edition, 2011.
H. K. D. H. Bhadeshia and R. W. K. Honeycombe, Steels: Microstructure and Properties,
Elsevier, Third Edition, 2006.
G. Krauss, Steels: Processing, Structure and Performance, ASM, First Edition, 2005.
H. Avner,Introduction to Physical Metallurgy,McGraw Hill Education (India) Private Limited.
A. Subramaniam & Kantesh Balani (IITK) MHRD, Govt. of India through NMEICT
V. Raghavan,Materials Science and Engineering (5th Edition),Prentice-Hall of India Pvt. Ltd.,
2004.
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