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UNIT 3

PHYSICAL METALLURGY
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
Why do we study phase diagrams?
There is a strong correlation between microstructure and mechanical
properties and development of microstructure can be understood from the
phase diagrams. Moreover phase diagrams can be used to obtain
information about melting, casting, crystallization, etc.
Preeutectoid ferrite
Pearlite (dark layer is ferrite,
Light layer is cementite)
SEM micrograph of plain C steel
with 0.44 wt% C (3000X).
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
PHASE of a System
A physically distinct part of a system that may be mechanically separated
from other distinct parts. (e.g., in a glass of ice water (the system), ice and
water are two phases mechanically distinct phases)

COMPONENTS of a System
The minimum number of chemical constituents that are necessary to
define the complete composition of a system (e.g. for the plagioclase
system, components are NaAlSi
3
O
8
albite & CaAl
2
Si
2
O
8
- anorthite)

VARIABLES that define the STATE of a System
Extensive dependent on the quantity of the system volume, mass,
moles, ...
Intensive properties of the phases of a system that are independent of
quantities (temperature, pressure, density, molecular proportions,
elemental ratios, ...)
Note that ratios of extensive variables become intensive
(V/m = density, V/moles=molar volume)
TYPES of Phase diagrams
Number of Constituents
Unary (like the water one
shown at the beginning)
one constituent
Binary - two constituents ,
like an alloy (we will focus
on these)
Ternary - three
constituents; requires 3-D
diagram
Number of phases
Isomorphous one solid
phase
Polymorphous multiple
solid phases
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
PHASE transformations and phase diagrams
In contrast to pure metals, which solidify at a constant temperature -
freezing point, alloys solidify over a range of temperature, depending on
the alloy components and their concentrations.

In course of solidification and subsequent cooling of solid alloy
processes of phase transformations take place. The phases compositions
and their quantities change with the temperature.

Phase diagrams are used for quantitative description of the phase
transformation and changes.

Phase diagram of an alloy system is a graphical presentation of the
relationships between the phases compositions and their relative amounts
at any given temperature and under equilibrium conditions.
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
Despite the fact, that in real metallurgical processes, especially in the
processes, occurring in solid state, the equilibrium conditions are not
reached, phase diagram is a very useful instrument of analysis and
quantitative evaluations of the alloy behavior.

Phase diagram of an alloy system consisting of two components is called
binary phase diagram.
There are three main types of binary phase diagrams:

1. Complete solid and liquid solution diagram,
2. Eutectic diagram (including Eutectic diagram with partial solubility of
the components in solid state and Eutectic diagram with intermetallic
compound)
3. Peritectic diagram.
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
COMPLETE solid and liquid solution diagram
The diagram has two
curves liquidus
(equilibrium conditions
of liquid phase with first
solid crystals primary
crystals) and solidus
(equilibrium conditions
of last liquid with nearly
complete solid).
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
Consider solidification of an alloy with concentration C. When the alloy
temperature is higher than T
L
, single liquid phase exists (point M on the
diagram).

When the temperature reaches the value T
L
(point M
1
on the liquidus curve)
solidification starts. According to solidus curve (point N
1
)the first solid
crystals have different composition C
1
.

Further cooling of the alloy causes changing of the liquid phase composition
according to the liquidus curve and when the alloy temperature reaches a
certain intermediate value T (position M
T
), liquid phase of composition C
y

and solid phase of composition C
x
are in equilibrium.

Relative amounts of the two phases are determined by their compositions
and may be calculated by the lever rule :

W
S
/ W
L
= M
T
Y / M
T
X or W
S
/ W
L
= (C
Y
-C) / (C-C
X
)
Where:
W
S
weight of the solid phase; W
L
weight of the liquid phase;
M
T
Y and M
T
X length of the corresponding lines in the diagram.
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
EUTECTIC diagram
Eutectic phase diagram
describes behavior of the
alloys, two components
of which are completely
soluble in liquid state and
entirely insoluble in solid
state.

This diagram has two
liquidus curves, starting
from the freezing points
of the two metals and
intersecting in a minimum
point eutectic point.
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
Consider solidification of an alloy with concentration C. When the alloy
temperature is higher than T
L
, single liquid phase exists (point M on the
diagram).

When the temperature reaches the value T
L
(point M
1
on the liquidus curve)
solidification starts. The primary crystals, forming in this case are the
crystals of the metal A.

Further cooling of the alloy causes enrichment of the liquid phase with the
metal B according to the liquidus curve and when the alloy temperature
reaches a certain intermediate value T (position M
T
), liquid phase of
composition C
y
and solid phase, consisting of A crystals, are in
equilibrium.

At the temperature equal to T
E
(eutectic temperature) formation of the
primary crystals stops and the remaining liquid phase , having composition
C
E
(eutectic composition), transforms to an intimate mixture of small A
and B solid crystals. This is the eutectic phase transformation.
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
Relative amounts of the primary crystals and the eutectic mixture may be
calculated by the lever rule :
W
P
/ W
E
= (C
E
-C) / C
Where:
W
P
weight of the primary crystals;
W
E
weight of the eutectic mixture.
EUTECTIC diagram with partial solubility of the components in solid state
This kind of phase diagram is a
hybrid of the diagram with
complete solid and liquid solution
and the eutectic diagram (the
metals are completely soluble in
liquid state and entirely insoluble
in solid state).
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
Consider solidification of an alloy with concentration C. When the alloy
temperature is higher than T
L
, single liquid phase exists (point M on the
diagram).

When the temperature reaches the value T
L
(point M
1
on the liquidus curve)
solidification starts. According to solidus curve the first solid crystals
(primary crystals) of the -phase have composition C
1
.

Further cooling of the alloy causes changing of the liquid phase
composition according to the liquidus curve and when the alloy temperature
reaches a certain intermediate value T (position M
T
), liquid phase of
composition C
y
and solid -phase of composition C
x
are in equilibrium.

At the temperature equal to T
E
(eutectic temperature) formation of the
primary crystals stops and the remaining liquid phase, having composition
C
E
(eutectic composition), transforms to a finely divided mixture of small
solid crystals of -phase and -phase (eutectic phase transformation).
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
Relative amounts of the -phase primary crystals and the eutectic mixture
may be calculated by the lever rule:

W
P
/ W
E
= M
2
E / M
2
N
or
W
P
/ W
E
= (C
E
-C) / (C- C

)
Where:
W
P
weight of the -phase primary crystals;
W
E
weight of the eutectic mixture;

Just below the eutectic temperature T
E
the alloy consists of two solid
phase: -phase and -phase, relative amounts of which is determined by
the lever rule:

W

/ W

= M
2
F / M
2
N
or
W

/ W

= (C

-C) / (C- C

)
Where:
W

weight of the -phase;


W

weight of the-phase;
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
HYPO-eutectic alloys

If an alloy composition C is lower, than eutectic composition C
E
,
solidification of the alloy starts from formation of the primary crystals of -
phase according to the left branch of the liquidus curve. These alloys are
called hypo-eutectic.

HYPER-eutectic alloys

If an alloy composition C is higher, than eutectic composition C
E
,
solidification of the alloy starts from formation of the primary crystals of -
phase according to the right branch of the liquidus curve. These alloys are
called hyper-eutectic.

EUTECTOID phase transformation

is analogous to the eutectic transformation, however it occurs with a solid
solution phase, breaking up into a mixture of two finely divided phases of
different compositions.
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
EUTECTIC diagram with intermetallic compound
Intermetallic compound (valence compound) is a phase, having chemical
composition equal to a fixed simple ratio, like CuZn,Cu
3
Sn, Mg
2
Pb, etc.
Sometimes intermetallic compounds exist over a range of composition,
differing from the valence law. Intermetallic compounds of this sort are
called electron compounds or intermediate solutions.
An example of a phase
diagram with intermetallic
compound AB
2
is shown in
figure. This diagram may be
considered as a combination
two different diagrams: A- AB
2

and AB
2
-B.
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
PERITECTIC diagram
Sometimes a solid solution phase,
which has already been formed,
and the residual liquid phase react
and form another solid solution
phase or intermetallic compound,
having a composition between the
compositions of the liquid and the
first solid. This is peritectic
transformation (peritectic reaction).

An example of a phase diagram
with peritectic transformation is
shown in the figure.
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
Consider solidification of an alloy with concentration C. When the alloy
temperature is higher than T
L
, single liquid phase exists (point M on the
diagram).

When the temperature reaches the value T
L
(point M
1
on the liquidus curve)
solidification starts. According to solidus curve (point N
1
)the first solid
crystals (primary crystals) of the -phase have composition C
1
.

Further cooling of the alloy causes changing of the liquid phase composition
according to the liquidus curve and when the alloy temperature reaches a
certain intermediate value T (position M
T
), liquid phase of composition C
y

and solid -phase of composition C
x
are in equilibrium.

At the temperature equal to T
P
(peritectic temperature) formation of the -
phase crystals stops and the remaining liquid phase, having composition C
L

reacts with -phase crystals, forming -phase of composition C
P
(peritectic
phase transformation).

At this temperature remaining -phase crystals have composition C

and all
crystals of -phase have composition C
P
(peritectic composition).
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
Relative amounts of the -phase crystals and the liquid phase just above the
peritectic transformation may be calculated by the lever rule :
W

/ W
L
= (C
L
-C) / (C- C

)
Where:
W

weight of the -phase crystals;


W
L
weight of the liquid phase;

Just below the peritectic temperature T
P
the alloy consists of two solid
phase: -phase and -phase, relative amounts of whichis determined by the
lever rule :
W

/ W

= (C
P
-C) / (C- C

)
Where:
W

weight of the -phase;


W

weight of the-phase;

During further cooling solid solution phases (-phase and -phase) change
their compositions according to the corresponding solvus curves. At the
temperature T
3
-phase crystals have composition C

and all crystals of -


phase have composition C

.
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
If the alloy composition is exactly equal to peritectic composition C
P
, -
phase and liquid phase are consumed completely in the peritectic
reaction. Alloys with composition C lower than C
P
, some quantity of -
phase remains after the peritectic reaction (it may be calculated by the
lever rule).

If the alloy composition C is higher than C
P
, some liquid phase remains
after the peritectic reaction. This remaining liquid transforms to -phase
during the further cooling.
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
SYNTECTIC reaction
A reversible reaction that involves the conversion of two liquid phases,
and, into a solid phase on cooling:

Liquid 1 + Liquid 2

The maximum temperature at which this reaction can occur is the
congruent melting point of the solid phase. Example: The conversion of co-
existing K-rich and Zn-rich phases in the K-Zn system to form an
intermediate solid phase KZn
13
.
MONOTECTIC reaction
The reversible transition, on cooling, of a liquid to a mixture of a second
liquid and a solid:

Liquid1 liquid2 + solid.
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
The eutectoid reaction describes the
phase transformation of one solid into
two different solids (o + c).

The compositions of the two new
phases are given by the ends of the
tie-line through the eutectoid point. The
general eutectoid reaction is therefore:

Solid > solid + solid

or using the names given to these
phases:

Austenite > ferrite + cementite (Fe
3
C)
EUTECTOID reaction
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
EUTECTOID Microstructure
The eutectoid structure in iron has a special name: it is called pearlite
(because it has a pearly look). The schematic and micrograph below show
pearlite. It is important to note that pearlite is not a phase, but a mixture of
two phases: ferrite and cementite.
Austenite containing 0.8% C
changes into ferrite (iron containing
almost no carbon) and cementite
(Fe
3
C, containing 25 at% carbon).
Hence carbon atoms must diffuse
together to form Fe
3
C, leaving
ferrite.
Nuclei of small plates of ferrite and cementite form at the grain boundaries
of the austenite, and carbon diffusion takes place on a very local scale just
ahead of the interface (schematic below). Thus the plates grow, consuming
the austenite as they go, to form pearlite.
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
PERITECTOID reaction
An isothermal, reversible reaction in the solid state, that, on cooling
of a binary, ternary, ... , n system, results in one, two, ... (n 1) new
solid phases. For example, in a binary system containing two solids
and

+
A reversible reaction in a system containing two solid solution
phases, and in which decomposes into and a new
phase .

+
MONOTECTOID reaction
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
THREE-Phase Reactions
Involves 3 distinct phases
Occurs at a single point
Often times is associated
with special properties or
characteristics for that
material
Eutectic L => S1 + S2
Eutectoid S1 => S2+ S3
Peritectic L + S1 => S2
Peritectoid S1 + S2 => S3
Monotectic L1 => S1 + L2
Miscibility gap; Oil and
water region, where two
liquid phases coexist
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
EQUILIRIUM diagram
Phase diagrams also called equilibrium diagrams or constitution
diagrams are a very important tool in the study of alloys. It may be
defined as a plot of the composition of phases as a function of
temperature in any alloy system under equilibrium conditions.
Equilibrium diagrams may be classified according to the relation of
the components in the liquid and solid states as follows:

1. Components completely soluble in the liquid state.
(a) Completely soluble in the solid state.
(b) Partly soluble in the solid state.
(c) Insoluble in the solid state.
2. Components partially soluble in the liquid state.
(a) Completely soluble in the solid state.
(b) Partly soluble in the solid state.
3. Components completely insoluble in the liquid state.
(a) Completely insoluble in the solid state.
Dr. Ashok Kumar Srivastava

OP Jindal Institute of Technology
COMPONENTS completely soluble in liquid and solid states
The first type of equilibrium diagram in which the components are
completely soluble in the liquid state is most common in engineering
alloys.

One method of determining the temperatures at which phase
changes occur in a system consists of following the temperature as
a function of time as different alloys in the system are very slowly
cooled. The data obtained in this manner form a cooling curve for
each of the alloy.

If the equilibrium diagram of the antimony-bismuth system is to be
determined, consider first a sample of pure antimony cooling slowly
from the molten state. The cooling curve for this alloy is shown in
Figure (a).
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
A hold occurs in the cooling curve starting at x and ending at y.
Solidification begins at the time corresponding to point x and is
completed at the time corresponding to point y, i.e., solidification
occurs at the constant temperature T
sb
. The temperature remains
constant during the process of solidification because of the
liberation of heat of fusion.
Cooling curves
for
Sb-Bi system
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
The cooling curve (b) shows for an alloy of antimony and bismuth
containing 25%-Bi and 75%-Sb. Examination shows that
solidification begins at the break, or point x, and continues until the
point is reached. At point y cooling rate changes again. This point y
is designated as a recovery. The structure of the solid material
consists of homogeneous grains, i.e., all grains are exactly of the
same composition.

Consider an alloy containing 50%-Sb and 50%-Bi. The cooling
curve of this alloy is shown in figure (c). The break, x and the
recovery, y occur at lower temperatures than for the previous alloy.

Consider an alloy containing 75%-Bi and 25%-Sb. The cooling
curve of this alloy is shown in figure (d). The break, x and the
recovery, y occur at lower temperatures than in the preceding cases.
The structure of the solid alloy will consist of homogeneous grains of
solid solution.
Dr. Ashok Kumar Srivastava

OP Jindal Institute of Technology
The cooling curve of pure Bi is shown in figure (e). Solidification
begins at point x and is completed at point y. One may conclude
from this discussion that pure metals solidify at constant
temperature and their cooling curves exhibit only a hold, whereas
the cooling curves of solid solutions exhibit a break and a recovery.
The results obtained from
the cooling curves may
now be plotted of
temperature as a function
of composition called the
equilibrium or phase
diagram, as shown in the
following diagram.
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
The temperature at which solidification begins is designated by x in
the cooling curves, will form the liquidus curve. The temperatures at
which solidification is completed is designated by y in the cooling
curves, will form the solidus curve of the equilibrium phase diagram.

At a temperature of T
i
in the equilibrium diagram of the Sb-Bi
system, the composition of the liquid and the composition of the
solid solution are determined by the intersection of this temperature
horizontal with the liquidus and solidus curves, respectively. Any
alloy that exists within the area enclosed by the liquidus and solidus
curves will have one degree of freedom and will be considered as
univariant.

In this type of phase diagram, all alloys that exist below the solidus
curve will consist of homogeneous solid solutions. Ex.- Phase
diagrams of Ni-Cu, Au-Ag, Cr-Mo and W-No.
Dr. Ashok Kumar Srivastava

OP Jindal Institute of Technology
COMPONENTS completely soluble in Liquid State & Insoluble in Solid States
Cooling curves
for
Bi-Cd system
The cooling curve for pure Bi is shown in figure (a). Solidification starts at
the temperature corresponding to x and is completed at the point y. The
cooling curves for an alloy containing 20% Cd and 80% Bi is shown in
figure (b). This curve exhibits a break at point x at a temperature lower than
the temperature at which solidification of pure Bi occurred. The cooling
curve the continues at lower rate of cooling until point y is reached, where
there is a hold and it will continues for a certain length of time until point z.
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
The structure of this solid alloy will consist of large grains of pure Bi
formed during the cooling from x to y and in addition to that an
intimate mixture of crystals of Bi and Cd which formed at the
constant temperature corresponding to the time interval from y to z.
This latter combination is a eutectic.

The cooling curve for an alloy containing 40% Cd and 60% Bi is
shown in figure (c). This cooling curve is unique in that it has only a
hold, occupying the time interval x-y. This alloy in the solid state is
composed entirely of an intimate mixture of grains of Cd and grains
of Bi, forming the eutectic. This is the eutectic alloy of this system.

An alloy containing 75% Cd and 25% Bi is shown in figure (d).
Solidification begins at the break x. A eutectic begins to form at point
y and the solidification is completed at point z. The solid alloy will
consist of large grains of Cd and the eutectic.
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
The cooling curve of pure Cd exhibit only a hold is shown in figure
(e). Solidification starts at x and is completed at point y. The
temperatures at which solidification begins and ends for all of these
alloys are plotted in the temperature-composition diagram to form
the equilibrium diagram shown in the above figure.
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
The lever rule is tool used to determine weight percentages of each
phase of a binary equilibrium phase diagram. It is used to
determine the percent weight of liquid and solid phases for a given
binary composition and temperature that is between the liquidus
and solidus.
LEVER rule
Before any calculations can be made a tie line is drawn on the
phase diagram to determine the percent weight of each element; on
the phase diagram to the right it is line segment LS. This tie line is
drawn horizontally at the compositions temperature from the liquid to
the solidus. The percent weight of element B at the liquidus is given
by w
l
and the percent weight of element B at the solidus is given by
w
s
. The percent weight of solid and liquid can then be calculated
using the following lever rule equations:
Calculations
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
Calculations Contd








The lever rule allows to calculate the relative amounts of phases present in
a binary mixture when the compositions of the phases are known and the
overall composition is known. Let us suppose that b moles of a binary
mixture of known composition x
B
to a closed system and you allow to
equilibrate at some T and P resulting in a mixture of two phases: a moles of
phase A and c moles of phase c
Mole balance on species I

x
A
x
C x
B
a mol c mol
b mol
A C
C A B
cx ax bx + =
Overall mole balance

BA of length
CB of length
x x
x x
c
a
x x c x x a
bx ax x c a
c a b
A B
B c
B C A B
C A B
=

=
=
+ = +
+ =
) ( ) (
) (
B
OP Jindal Institute of Technology
Dr. Ashok Kumar Srivastava

Calculations Contd


At material equilibrium, the number of degrees of freedom (F)
required to fully specify the state of the system is given by:






2 + = P C F
F = number of degrees of freedom (intensive properties)

P = number of phases present

C = number of components; The smallest number of
components which can be represented by chemical equations
) (
2
) ( ) (
3
g s s
CO CaO CaCO +
How many degrees of freedom in this system?
OP Jindal Institute of Technology
Dr. Ashok Kumar Srivastava

GIBBS Phase Rule


Consider water in equilibrium with its vapour in a closed system







Example: The Gibbs Phase Rule
1 2 2 1
2
= + =
+ = P C F
Specifying one intensive variable (eg.
Temperature or pressure) will fully
specify the system

For any given pressure, there is only
one boiling temperature for pure water

How many degrees of freedom are
there at the triple point? (B)
P
T
T
c
A
B
C
D
E
Schematic representation of the phase diagram for water
Vapour
Liquid
solid
Supercritical
fluid
P
c
P
T
T
c
A
B
C
D
E
Schematic representation of the phase diagram for water
Vapour
Liquid
solid
Supercritical
fluid
P
c
P
T
T
c
A
B
C
D
E
Schematic representation of the phase diagram for water
Vapour
Liquid
solid
Supercritical
fluid
P
c
OP Jindal Institute of Technology
Dr. Ashok Kumar Srivastava

Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
Component
The elements or compounds which are present in the system
(alloying elements)

Phase
Homogeneous portion of a system that has uniform physical and
chemical characteristics

Single phase systems are termed homogeneous
e.g. melts, pure metals

Multiphase (two or more phases) are heterogeneous.
Most of the metallic alloys are heterogeneous systems.
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
Some simple types of alloy behavior can be classified as:
1. Two components are completely soluble in the liquid state:
2. Two components are partially soluble in the liquid state
(Monotectic reaction)
3. Two components are insoluble in liquid as well as solid state. Two
layers are formed in the liquid state. When cooled, two metals
solidify individually at respective freezing temperatures separating
into two distinct layers depending on the density of the metals. There
is almost no diffusion between layers. Such combinations are not
dealt here as these are no consequence.
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
Solidification
Solidification is process of changing atomic coupling. The liquid state
of metal melt transforms to a solid state. The system is driven to
minimize the free energy. If the temperature decreases, the
equilibrium between liquid and solid state is violate, and nuclei of
solid state (phase) can rise.
G = G
L
- G
S


Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
Solidification: Nucleation Processes
Homogeneous nucleation
nuclei form in the bulk of liquid metal
requires supercooling (typically 80-300C max)

Heterogeneous nucleation
much easier since stable nucleus is already present
Could be wall of mold or impurities in the liquid
phase
allows solidification with only 0.1-10C supercooling
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
Nucleation
nuclei (seeds) act as template to grow crystals
for nucleus to form rate of addition of atoms to nucleus must
be faster than rate of loss
once nucleated, grow until reach equilibrium
Driving force to nucleate increases as we increase AT
supercooling (eutectic, eutectoid)
superheating (peritectic)

Small supercooling few nuclei - large crystals

Large supercooling rapid nucleation - many nuclei,
small crystals

Solidification: Nucleation Processes Contd...
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
r* = critical nucleus: nuclei < r* shrink; nuclei>r* grow (to reduce energy)
AG
T
= Total Free Energy
= AG
S
+ AG
V

Surface Free Energy- destabilizes
the nuclei (it takes energy to make
an interface)
t = A
2
4 r G
S
= surface tension
Volume (Bulk) Free Energy
stabilizes the nuclei (releases energy)
u
A t = A G r G
V
3
3
4
volume unit
energy free volume
= A
u
G
Homogeneous Nucleation & Energy Effects
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
Solidification
T H
T
r
S
m
A A

=
2
*
r* decreases as AT increases
AH
S
= latent heat of solidification
T
m
= melting temperature
= surface free energy
AT = T
m
- T = supercooling
r* = critical radius
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
ISOTHERMAL Transformation Diagrams
2 solid curves are plotted:
one represents the time
required at each temperature
for the start of the
transformation;
the other is for transformation
completion.
The dashed curve
corresponds to 50%
completion.
The austenite to pearlite
transformation will occur only
if the alloy is supercooled to
below the eutectoid
temperature (727C).
Time for process to complete
depends on the temperature.
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
Iron-carbon alloy with
eutectoid composition.

A: Austenite
P: Pearlite
B: Bainite
M: Martensite
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
ISOTHERMAL Transformation Diagrams Contd
Eutectoid iron-carbon
alloy; composition,
C
o
= 0.76 wt% C
Begin at T > 727C
Rapidly cool to 625C
and hold isothermally.
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
S
t
r
e
n
g
t
h

D
u
c
t
i
l
i
t
y

Martensite
bainite
fine pearlite
coarse pearlite
spheroidite
General Trends
POSSIBLE
Transformations
Dr. Ashok Kumar Srivastava

OP Jindal Institute of Technology
- Smaller AT:
colonies are
larger
- Larger AT:
colonies are
smaller
(a) Pearlite
(high diffusion
rate) and (b)
fine pearlite
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
A ternary phase diagram has three components. The three
components are usually compositions of elements, but may include
temperature or pressure also. This type of diagram is three-
dimensional but is illustrated in two-dimensions for ease of drawing
and reading. Instead of being a rectangular plot, it is a triangle.
Ternary phase diagrams exist for many metallic alloys, but are also
widely used in ceramics. Stainless steel (Fe-Ni-Cr) is a perfect
example of a metal alloy that is represented by a ternary phase
diagram. Stainless steel is a very common metal alloy. Almost
everyone knows of an everyday object that is made with stainles
steel.


WHAT is a ternary phase diagram?
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
Ternary phase diagrams are needed so that three components can
be compared at once. For example, stainless steel has iron, nickel,
and chromium compositions. To view all three compositions at the
same time, a triangular plot is set up with an element at each of the
vertexes with the temperature and pressure stated. In ceramic
systems, sometimes compounds are located at the vertexes instead
of elements. The derivation of the ternary plot is too complicated to
go into, but the analytical deviation of a binary system is available
along with the experimental method of determining the phase
diagram
Dr. Ashok Kumar Srivastava

OP Jindal Institute of Technology
TERNARY Phase Diagrams
Construction
Ternary phase diagrams are constructed by projecting the liquidus
surfaces of a three dimensional diagram (a triangular prism in which
T is plotted on the vertical axis against the compositions of three
components on the base of the prism) onto the compositional ternary
diagram.
On such diagrams or projections, these temperatures are shown as
dashed contours. The intersection of two liquidus surfaces is also
projected on the same compositional ternary and is known as a
boundary curve. The areas between boundary curves where one
liquid coexists with a solid are known as "primary fields. Because T is
still a variable on these ternary projections, we can still apply the
condensed phase rule to determine the variance of a system.
Dr. Ashok Kumar Srivastava



OP Jindal Institute of Technology
In alloys containing three components (ternary systems), the phase
diagram consist of a three-dimensional figure, the base of which is
an equilateral-composition triangle, and the temperature is plotted
vertically. An example of a ternary diagram of very simple character
is shown in the following figure for the Cd-Pb-Bi system.
Dr. Ashok Kumar Srivastava





OP Jindal Institute of Technology
ORDER-Disorder Transformations
Solid solutions are composed of atoms of different elements
distributed in a random fashion on a space lattice. Sometimes the
atoms in a solid solution within a specific range of composition may,
at a certain temperature, assume a definite arrangement to form an
ordered structure.
An example of a system in which
an ordered structure occurs on
cooling is shown in the diagram of
the Cu-Au system.