MM1201: Material Science (3-0-0)

Dr. Anushree Dutta, Assistant Professor

Dept. of Metallurgical and Materials Engineering
Email Id: [Link]@[Link]

UNIT-IV

NIT Jamshedpur
1
 Principles of solidification
Solidification: Liquid state converts into the solid state. Liquid metal is cooled (Temperature will drop)
and solidify into solid state
Pouring Temperature  Temp at which Liquid is Poured into mold to give shape. Always poured at
somewhat higher temperature that its melting point. The difference of pouring temperature and melting
point is called degree of superheat

Cooling curve of pure metal Cooling curve of Alloy

Solidification

Often, a liquid may supercool below the

freezing point. But once solidification starts,
heat evolution raises the sample temperature
back to the freezing point as shown in Fig.
 Supercooling / Undercooling
• It is apparent that during the cooling of a liquid, an appreciable nucleation rate
(i.e., solidification) will begin only after the temperature has been lowered to
below the equilibrium solidification (or melting) temperature(Tm). This
phenomenon is termed supercooling (or undercooling), and the degree of
supercooling for homogeneous nucleation may be significant (on the order of
several hundred degrees Kelvin) for some systems.
 Solidification of alloys

• In case of alloys, it does not solidify at constant temperature because it

is mixture of two or more component so crystallization in different way.
It does not occur at constant temperature.
 Phase change or phase transformations
• The properties of engineering alloys are optimized by a careful control of the microstructure.

• Phase changes (also called phase transformations) that occur in an alloy determine its
microstructural features.

• For understanding the underlying principles in the control of microstructure through thermal
or thermomechanical treatments, a knowledge of the mechanism and kinetics of phase
changes is essential

Phase. A homogeneous portion of a system that has uniform physical and chemical characteristics.
 Nucleation and Growth Kinetics

1. the formation of tiny particles that are stable to further thermal fluctuations and will
not dissolve; and
2. the increase in the size of these particles.
Step 1 is called nucleation and step 2 is growth.
• The interface that separates the two phases has a surface energy.
• This energy has to be supplied during nucleation.
• It acts as an inhibiting factor for the phase change to occur.
• A very small particle has a large surface area-to-volume ratio and can, therefore, be
unstable.

Ref: Physical Metallurgy by V. Raghavan

 Phase Transformations in Metals
• 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.
• There are two types of nucleation: homogeneous and heterogeneous.
Nucleation
 Homogeneous Nucleation
For the homogeneous type, nuclei of the new phase form uniformly throughout the
parent phase.
There are two contributions to the total free energy change that
accompany a solidification transformation. The first is the free energy
difference between the solid and liquid phases, or the volume free energy,
∆𝐺𝑣 . Its value will be negative if the temperature is below the equilibrium
solidification temperature.
The second energy contribution results from the formation of the solid–
liquid phase boundary during the solidification transformation. Associated
with this boundary is a surface free energy (𝛾), which is positive

• a transformation will occur Critical radius

Critical free energy
spontaneously only when free
energy has a negative value
Ref: Callister & Rethwisch
 Homogeneous Nucleation

embryo
nucleus

In a physical sense, this means that as a solid particle begins to form as atoms in the liquid
cluster together, its free energy first increases. If this cluster reaches a size corresponding to the
critical radius r*, then growth will continue with the accompaniment of a decrease in free
energy.
Ref: Callister & Rethwisch
 Homogeneous Nucleation
This volume free energy change (∆𝐺𝑉 ) is the driving force for the solidification transformation, and its magnitude
is a function of temperature. At the equilibrium solidification temperature , ∆𝐺𝑉 the value of is zero,

It can be shown that is a function of temperature as (∆𝐺𝑉 )

Where,∆𝐻𝑓 is the latent heat of fusion (i.e., the heat given up
during solidification), 𝑇𝑚 is the equilibrium solidification temperature
in kelvin

And

Physically, this means that with a lowering of undercooling temperature (𝑇𝑚 − T) nucleation occurs more
readily.

Both the critical radius, 𝑟 ∗ and the activation free energy (∆𝐺 ∗ ) decrease as increasing the undercooling
temperature (𝑇𝑚 − T) which lead to fine grain structure.
 Heterogeneous Nucleation
for the heterogeneous type, nuclei form preferentially at structural inhomogeneities, such as container
surfaces, insoluble impurities, grain boundaries, dislocations, and so on.

Heterogeneous nucleation
The activation energy (i.e., energy barrier) for nucleation is lowered
when nuclei form on preexisting surfaces or interfaces, since the
surface free energy is reduced.
Foreign particle
Homogeneous and Heterogeneous nucleation

This ∆𝐺 ∗ lower for heterogeneous means that a smaller

energy must be overcome during the nucleation
process (than for homogeneous), and, therefore,
heterogeneous nucleation occurs more readily

1
𝑆 𝜃 = 2 − 3 cos 𝜃 + 𝑐𝑜𝑠 3 𝜃
4
Homogeneous and Heterogeneous Nucleation
 Growth
• The growth step in a phase transformation begins once an embryo has exceeded
the critical size, and becomes a stable nucleus.
• Note that nucleation will continue to occur simultaneously with growth of the new
phase particles; of course, nucleation cannot occur in regions that have already
transformed to the new phase.

Where, 𝐺ሶ = Growth rate, Q (the activation energy) and C (a preexponential) are independent
of temperature
 PHASES
A chemically homogeneous, physically distinct and mechanically separable part of system
is called PHASE

• A phase may be defined as a homogeneous portion of a system that has uniform

physical and chemical characteristics. Every pure material is considered to be a
phase.

Three phase of matter: Liquid, Solid, Gas

Solid phase: Different crystal structure will be considered different phases

Example: At room temperature, Crystal structure of Fe is BCC called as 𝛼 phase
At high temperature, Crystal structure of Fe is FCC called as 𝛾 phase
 Component and Phase
Component: The independent chemical specifies (element, compound) in terms of which
the composition of a system is specified are called component.

components are pure metals and/or compounds of which an alloy is composed.

For example, in a copper–zinc brass, the components are Cu and Zn.

System Components Phase

Water 𝐻2 𝑂 (Single component) Liquid phase (Single phase)

Water  ice 𝐻2 𝑂 (Single component) Liquid + solid phases (two phases)

Brine NaCl + 𝐻2 𝑂 (Two components) Liquid solution (Single phase)

Mild Steel Fe, Carbon (Two components) α, Fe3 C (at Room temperature)
 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.

The addition of solute in excess of this solubility limit results in the formation of
another solid solution or compound that has a distinctly different composition.
 Phase diagram
• Much of the information about the control of the phase structure of a
particular system is conveniently and concisely displayed in what is called a
phase diagram, also often termed an equilibrium diagram

Now, there are three externally controllable parameters that will affect phase structure—
viz. temperature, pressure, and composition—and phase diagrams are constructed when
various combinations of these parameters are plotted against one another

Types of Phase Diagram : Based on number of components

1. Unary Diagram (Single component system)
2. Binary Diagram (Two component system)
3. Ternary Diagram (Three component system)

Phase diagram. A graphical representation of the relationships among environmental constraints (e.g., temperature
and sometimes pressure), composition, and regions of phase stability, ordinarily under conditions of equilibrium.
 ONE-COMPONENT (OR UNARY) PHASE DIAGRAMS

Perhaps the simplest and easiest

type of phase diagram to understand
is that for a one-component system,
in which composition is held constant
(i.e., the phase diagram is for a pure
substance); this means that pressure
and temperature are the variables

Triple point: sometimes it is

also termed an invariant point,
Figure: Pressure–temperature phase diagram for H2O.
Intersection of the dashed horizontal line at 1 atm pressure with its position is distinct, or fixed
the solid–liquid phase boundary (point 2) corresponds to the by definite values of pressure
melting point at this pressure (T 0C). Similarly, point 3, the and temperature.
intersection with the liquid–vapor boundary, represents the
boiling point (T 100C).
Binary Phase Diagrams
The copper–nickel system is termed isomorphous
because of this complete liquid and solid solubility of
the two components
Furthermore, with regard to phase boundaries, the
line separating the L and 𝛼 + L phase fields is termed
the liquidus line.
The solidus line is located between the 𝛼 and
𝛼 + L regions, below which only the solid phase a exists

A : point (x, T) on the phase diagram represents an alloy of

composition x (here x represents 60 wt.% Ni and 40 wt % Cu)
held on equilibrium at temperature T (here T is 1100C)
 INTERPRETATION OF PHASE DIAGRAMS
Three important question can be answer by interpretation of phase diagram
(1) the phases that are present,
(2) the compositions of these phases, and
(3) the percentages or fractions of the phases.

A:
1. Phase present: -phase
2. Composition of phase: 60 wt.% Ni and 40 wt.% Cu
equilibrium at 1100 C
3. Fraction of phase: 100% of -phase
INTERPRETATION OF PHASE DIAGRAMS

B:
1. Phase present: L, -phase
2. Composition of phase: 𝑪𝑳 (Composition of liquid
phase 31 wt.% Ni), 𝑪 (Composition of -phase 43
wt.% Ni) and 𝑪𝟎 (alloy composition 34 wt.% Ni )
equilibrium at 1250 C
3. Fraction of phase: Fraction of liquid and -phase are
estimated by LEVER rule
Fraction of phase: Fraction of liquid and -phase are 𝑪𝑳  31 wt.% Ni, 𝑪  43 wt.% Ni and 𝑪𝟎  34 wt.% Ni
estimated by LEVER rule

Fraction of liquid phase

43 − 34
=
43 − 31
= 0.75

Type equation here.

34 − 31
=
43 − 31
= 0.25

𝑊𝐿 + 𝑊𝑎 = 1
 THE GIBBS PHASE RULE
This rule represents a criterion for the number of phases that will coexist within a system
at equilibrium, and is expressed by the simple equation

P is the number of phases present

The parameter F is termed the number of degrees of

freedom or the number of externally controlled variables
(e.g., temperature, pressure, composition) which must be
specified to completely define the state of the system.

The parameter C represents the number of components

in the system.

N is the number of non-compositional variables (e.g.,

temperature and pressure)
THE GIBBS PHASE RULE Binary temperature– composition phase
diagrams, specifically the copper–silver system,
Since pressure is constant (1 atm), the
parameter N is 1—temperature is the only non-
compositional variable.

Furthermore, the number of components C is 2

(viz. Cu and Ag), and

Single-phase fields on the phase diagram (e.g.,

and , , liquid regions). Since only one phase
is present, P =1 and

It means that two independent variable (both

Temperature and composition)
are required to defined the system
 THE GIBBS PHASE RULE

It means that one

• For the situation wherein two phases independent variable (either
coexist, for example,  L,  + L, and  Temperature or composition)
phase regions. are required to defined the system
THE GIBBS PHASE RULE

For binary systems, when three phases are present,

there are no degrees of freedom

This means that the compositions of all three

phases as well as the temperature and composition
are fixed.
BINARY EUTECTIC SYSTEMS
eutectic reaction (eutectic means easily
melted)

TE is called the eutectic isotherm.

Eutectic Alloy (Cu-Ag alloys):

Eutectic Composition: 71.9 wt.% Ag
Eutectic temperature: 779C
Invariant reaction

1) Eutectic reaction:
one liquid  two different solid (cooling)
2) Eutectoid reaction:
One solid phase  two different solid phase (cooling)
3) Peritectic reaction:
One liquid + one solid  one different solid phase
(cooling)
4) Peritectoid reaction:
Two different solid phase  one solid phase (cooling)
THE IRON–IRON CARBIDE (Fe–Fe3 C) PHASE DIAGRAM

composition still be expressed in

“wt% C” rather than wt% Fe3 C”;
6.70 wt% C corresponds to 100
wt% Fe3 C

Phases are:
Liquid
𝛿 − Ferrite: BCC crystal structure
Austenite (𝛾): FCC crystal structure
-Ferrite: BCC crystal structure
Cementite (𝐹𝑒3 𝐶): orthorombic
 Invariant point at Fe-Fe3 C
Eutectic reaction

Eutectoid reaction

Peritectic reaction

Cooling
 (0.09wt.%C) + L (0.53wt.%C)  (0.17wt.%C)
Heating
Eutectoid composition

pearlite because it has

the appearance of mother
of pearl when viewed
under the microscope at
low magnifications
Hypoeutectoid Alloys
Hypereutectoid Alloy
The influence of alloy composition on the ability of a steel alloy to transform to
martensite for a particular quenching treatment is related to a parameter called
hardenability.
Hardenability curves for five different steel alloys, each containing 0.4 wt% C

4340–1.85 Ni, 0.80 Cr, and 0.25 Mo;

4140–1.0Cr and 0.20 Mo;
8640–0.55 Ni, 0.50 Cr,and 0.20 Mo;
5140–0.85 Cr; and
1040 is an unalloyed steel
The Jominy End-Quench Test
The most simple and convenient method
of determining the Hardenability is the
Jominy End-Quenched test

The mode of quenching results in different

rate of cooling along the length of the test
piece.

A bar of steel having good Hardenability

shows higher hardness readings for greater
distance from the quenched end.
The Jominy End-Quench Test (Results)
Correlation of hardenability and continuous cooling
information for an iron–carbon alloy of eutectoid
composition

The quenched end is cooled most rapidly

and exhibits the maximum hardness; 100%
martensite is the product at this position for
most steels.
Cooling rate decreases with distance from
the quenched end, and the hardness also
decreases with change of phases.
With diminishing cooling rate more time is
allowed for carbon diffusion and the
formation of a greater proportion of the
softer pearlite, which may be mixed with
martensite.
 Annealing treatments of Cold-Worked Metals
RECOVERY, RECRYSTALLIZATION, GRAIN GROWTH

Cold working :
Cold work is a process of deforming a metal below its
recrystallization temperature. During the cold working
following changes are taken place
1. Defect density increases
2. Change in grain shape
3. Increase in strain energy due to increase in defects density

The cold work strengthens the material by increasing dislocations in the crystal matrix. The
rolling of cleaned steel through a carbide die at ambient temperatures is called cold rolling, and
is widely used to increase strength, reduce ductility, and improve size, shape and straightness.
 RECOVERY
Recovery occurs at low temperatures and reduces
or eliminates work hardening effects. Interestingly,
the grain structure is not affected, leaving existing
grain boundaries (size) intact. As a result of recovery
at low temperatures, small changes in hardness
occur due to decrease in dislocation density as
created by the initial cold work.

1. Defect density decreases through atomic diffusion

2. No Change in grain shape
3. Annhilation of opposite sign dislocations
4. Low angle boundaries are created by interaction of
same sign dislocations.

In addition, physical properties such as electrical

and thermal conductivities and the like are
recovered to their Pre cold-worked states
 Cold-worked (33%CW) Initial stage of recrystallization
RECRYSTALLIZATION after heating 3s at 580 C)

Even 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
equiaxed grains that have low dislocation densities
and are characteristic of the precold-worked
condition.
The new grains form as very small nuclei and grow until Complete recrystallization
they completely consume the parent material, processes Parcial recrystallization
after heating 4s at 580 C) after heating 8s at 580 C)
that involve short-range diffusion.
 New strain-free grains are formed
 Driving force : Strain energy associated with
dislocations
 Recrystallization temperature:
A temperature at which 50% recrystallization happen
in 1hour.

Also, during recrystallization, the mechanical properties that were changed as a result of cold working are
restored to their precold-worked values; that is, the metal becomes softer, weaker, yet more ductile.
 Grain growth after 15 min Grain growth after 10 min
Grain growth at 580 C at 700 C
After recrystallization is complete, the strain-free grains
will continue to grow if the metal specimen is left at the
elevated temperature this phenomenon is called grain
growth

driving force for grain growth: Reduction in grain boundary

Surface energy

Grain growth occurs by the migration of grain boundaries.

Obviously, not all grains can enlarge, but large ones grow
at the expense of small ones that shrink

For many polycrystalline materials, the grain diameter d

varies with time t according to the relationship

The mechanical properties at room temperature of a fine-grained metal are usually superior (i.e.,
higher strength and toughness) to the of coarse-grained ones. Therefore, material with coarse grains
exhibits poor strength with high ductile