PHASE DIAGRAMS Handout

FUNDAMENTALS OF
METALLURGY
SUNIL DIVEKAR9823513441
20 April 2023 SUNIL DIVEKAR9823513441 1

PHASE DIAGRAMS
• Definitions and notes: Slides 3 to 8
• Unary Cooling curves: Slides 9 to 13
• Isomorphous phase diagram: Slides 14 to 16
• Definitions and illustration: Slide 17 to 28
• Solid solution: 29 to 38
• Eutectic phase diagram: Slide 39 to 43
• Partial eutectic diagrams: 44 to 52
• Knowing how to apply the following content is
more important than the content itself.
PHASE DIAGRAMS
Phase diagram:
The graph of Temperature versus Composition for
an alloy cooled in equilibrium.
A system is at equilibrium if its free energy is at its
minimum under specified combination of
temperature, pressure, and composition.
When in equilibrium,
a. The characteristics of a system do not change
with time.
b. The system is stable.

PHASE DIAGRAM
• Definition
Phase :
Phase is a homogeneous part of a system. It is
physically distinct, chemically homogeneous
and mechanically separable part of a system
under study.
 Every pure metal is a phase.
 Every solution is a phase.
 A state of matter is a phase
Thus ferrite, Cementite, Austenite, liquid are
phases. Pearlite is a mixture of phases.
PHASE DIAGRAM
Gibbs phase rule.
For a system at equilibrium, an equation given
below that expresses the relationship between
the number of phases present and the number of
externally controllable variables.
F = C -P + n
Where,
F is the number of degrees of freedom of the system
C is the number of components of the system
P is the number of phases in equilibrium
n is the number of external factors like pressure and
temperature.
PHASE DIAGRAMS
Interpretation of the Phase diagram gives basic

information on the following:
1. Critical lines
2. Phases
3. Amount of phases
4. Composition of phases
5. Microstructure

PHASE DIAGRAMS
Phase diagram:
There are various types of Phase diagram:
•Isomorphous
•Eutectic
•Eutectoid
•Peritectic
The type of equilibrium diagram depends on
how the components coexists with each
other.

PHASE DIAGRAM
• Definition
• Alloy is a combination of two or more
elements having metallic properties.
• The element in the largest amount is metal

solvent and is called base metal or parent
metal.
• The other intentionally added element which

can be metal or non metal is solute and is
called as alloying element.
PHASE DIAGRAM
• What happens when a PURE metal solidifies?
Temperature
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SUNIL DIVEKAR9823513441
PHASE DIAGRAM
• Temperature-time graph

PHASE DIAGRAM
• This is called COOLING CURVE
a-b : Liquid
a b-c : Liquid+solid
Liquid
c-d : Solid
Solidification
b c
Solid
Freezing/Melting
tremperature d

PHASE DIAGRAM
• COOLING CURVE
a-b : Liquid
a b-c : Liquid+solid
Liquid
c-d : Solid
Solidification
b c
Solid
SUPERCOOLING
d

PHASE DIAGRAM
• What happens whenTWO PURE metal solidify?
Temperature
Cooling curve of High

melting point Metal
Cooling curve of Low

melting point Metal

Time
PHASE DIAGRAM
Cooling curve for an alloy of a given composition
Solidification starts
Solidification ends

PHASE DIAGRAM
• Consider two metals with different compositions

PHASE DIAGRAM
Such diagrams are called “Phase diagram”

PHASE DIAGRAM
Phase Diagrams: Definition Solidus and liquidus
Liquidus line.
On a binary phase diagram, the line or boundary separating
liquid and liquid-solid phase regions. For an alloy, the
liquidus temperature is the temperature at which a solid
phase first forms under conditions of equilibrium cooling.
Solidus line
On a phase diagram, the locus of points at which
solidification is complete upon equilibrium cooling, or at
which melting begins upon equilibrium heating.

PHASE DIAGRAM
Composition line and Tie line
Composition Line
Tie Line
a
b

PHASE DIAGRAM
Phase Diagrams: Definition of tie line
A horizontal, constant temperature line,

drawn through a point of intersection of given
composition and that temperature, up to the
boundary lines of the two phase fields is
called a tie line

PHASE DIAGRAM
• Lever rule :
Lever rule states that the relative amount of a
given phase is proportional to the length of
the lever arm on the opposite side of the alloy
point of lever
OR
Lever rule states that the ratio of the amount
by weight of the liquid phase to that of solid
phase is inversely proportional to the
corresponding sections of the straight tie line

PHASE DIAGRAM
Phase diagram example: Copper-Nickel
T
E
M LIQUIDUS
P 1452OC
E
R LIQUID
T1OC
A
T
LIQUID & T2OC
U
SOLID
R SOLIDUS
E
1083OC SOLID
100%Cu 60%Cu40%Ni 100%Ni

PHASE DIAGRAM
Phase diagram example: Copper-Nickel
T
E
M LIQUIDUS
P 1452OC
E
R
T1OC
A
T
U T2OC
R SOLIDUS
E
1083OC
100%Cu 60%Cu40%Ni 100%Ni

PHASE DIAGRAM
Phase diagram: Copper -Nickel
T
E
LIQUIDUS
M
P 1452OC
E
R
T1OC
A a
T c b
U T2OC
R SOLIDUS
E
1083OC Composition of
Composition of
Solid
Liquid
100%Cu 60%Cu40%Ni 100%Ni

Phase diagrams
• Lever rule :
• Amount of phase -
Amount of solid = ac / ab
Amount of liquid = cb / ab
• Composition
Composition of Liquid : Project ‘a’ on composition line
Composition of Solid : project ‘b’ on composition line
PHASE DIAGRAM
T E
Composition Line
E
M
P 1452OC
E
R T1OC
LIQUIDUS
A
T
T2OC
U
R
1083OC SOLIDUS
Composition of Composition of
liquid phase solid phase
100%Cu 60%Cu40%Ni 100%Ni
PHASE DIAGRAM
T E
Composition Line
E LIQUIDUS
M
P 1452OC
E
R T1OC
A SOLIDUS
T
T2OC
U
R
1083OC
100%Cu 60%Cu40%Ni 100%Ni

PHASE DIAGRAM
T E
E
M LIQUIDUS
P 1452OC
E
R T1OC
A
a
T
b
a’ T2OC
U
R b’
1083OC
SOLIDUS Change in
Change in
composition of liquid composition of Solid
100%Cu 60%Cu40%Ni 100%Ni
SOLIDIFICATION OF METALS
• Coring : Coring is the variation in composition

within a dendrite or grain, from its core to
case.
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PHASE DIAGRAM
• An alloy where only two metals are mixed is
called as binary alloy.
• When in liquid state the two elements may be

miscible or non-miscible.

PHASE DIAGRAM
• In binary alloys mutual solubility of metals
varies widely.
• Some are completely soluble in both liquid as
well as solid state throughout their entire
range of composition e.g. Au-Ag, Cu-Ni
• Some are completely insoluble in both liquid
as well as solid conditions. e.g. Lead-
Aluminium
• Some are completely soluble in the liquid
state and only partially soluble in solid state
e.g. Cu-Ag, Fe – Zn
PHASE DIAGRAMS
Phase diagram:
When an alloy is formed between element
metals, the phases may be found in the solid
alloy in any of the following conditions:
1. Solution
2. Compound
3. Mixture
4. Pure element

PHASE DIAGRAMS
Phase diagram:Solid solutions
In Solid solutions-
• The component in the largest amount is metal
solvent and is called base metal or parent
metal.
• The other intentionally added element which
can be metal or non metal is solute and is
called as alloying element.

PHASE DIAGRAMS
Phase diagram: Solid solutions
The solid solution can be
A. Substitutional solution
I. Ordered or
Ordered
II. Disordered
B. Interstitial solution
Disordered
Interstitial
PHASE DIAGRAMS
Substitutional solid solutions are formed under
specific conditions. These conditions are
described by the Hume Rothary rules.
There are 4 Conditions:
1. Atomic size factor
2. Crystal structure factor
3. Electrochemical charge factor
4. Valency factor

PHASE DIAGRAMS
(i) Atomic size factor :
A difference in the size of solute atom and solvent atom distorts lattice
structure. Distortion reduces the possibility of forming solid solution.
For complete solubility the difference in the size of atomic diameters
between solute and solvent must be less than 8%.
Metals like silver and gold have a difference of 0.2%, Nickel and copper
show a difference of 2.7%. Silver-Gold and Nickel-Copper form
complete substitutional solid solutions.
(ii) Crystal structure factor

For solid solubility the crystal structure of the solute and solvent atoms
must be same individually. If the crystal structure of the constituent
metal differs, a conflict arises. Copper and Nickel form complete
substitutional solid solutions and they both have FCC structure.

PHASE DIAGRAMS
(iii) Electronegativity :
The more electropositive one element and the more
electronegative the other, the greater is the
likelihood that they will form an intermetallic
compound instead of a substitutional solid solution
(ii) Valences
Other factors being equal, a metal will have more of
a tendency to dissolve another metal of higher
valency than one of a lower valency.

PHASE DIAGRAM
Simple solution system (e.g., Ni-Cu solution)
Crystal electroneg r (nm)
Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278
• Both have the same crystal structure (FCC) and have

similar electronegativities and atomic radii (W. Hume
Rothery rules) suggesting high mutual solubility.
• Ni and Cu are totally miscible in all proportions.

PHASE DIAGRAM
Eutectic phase diagram: Metals soluble in liquid state, insoluble
in Solid state
Liquidus line : AeB

Solidus line : AcedB
Eutectic Point at ‘e’
Eutectic temperqature line: ced
The solid formed will have a

microstructure that will have
a mixture of pure A and pure B

PHASE DIAGRAM
Eutectic phase diagram: Metals soluble in liquid state, insoluble in
Solid state.
Example: Bismuth Cadmium
Hypo Hyper
Pro

PHASE DIAGRAM
in Solid state
Cooling an alloy with eutectic composition
point wise description
Eutectic “A+B”
1. Alloy in Liquid state 1

2. Eutectic transformation at
constant temperature
2
3
The two solids generally solidify side by side in alternate layers,

giving a typical microstructure recognised as eutectic structure.
3. Negligible change in structure
PHASE DIAGRAM
in Solid state Eutectic “A+B”
Proeutectic “A”
Cooling an alloy with proeutectic
Composition point wise
description
1
2. Solidification begins by nucleation of proeutectic
‘A’ phase.
3
3. Eutectic transformation at constant temperature
4
The two solids generally solidify side by side

in alternate layers, giving a typical microstructure
recognised as eutectic structure,
The microstructure will have proeutectic solid ‘A’ and eutectic mixture of ‘A +B’
PHASE DIAGRAM
in Solid state Eutectic “A+B”
Proeutectic “B”
Cooling an alloy with hypereutectic
Composition point wise description
1
1. Alloy in Liquid state
2. Solidification begins by nucleation of proeutectic 2
‘B’ phase.
3
3. Eutectic transformation at constant temperature
4
The two solids generally solidify side by side

The microstructure will have proeutectic solid ‘A’ and eutectic mixture of ‘A +B’
PHASE DIAGRAM
Partial Eutectic phase Diagram:
The two components (A & B) are completely soluble in liquid state and
partially soluble in solid state.
A Liquidus
Liquid
F
Liquid + a Liquid + b
a B E G b
Temperature
OC
a+ b
H
100 %A C 100 %B
Composition, Weight percent B
PHASE DIAGRAM
Phase diagram: Metals soluble in lquid state ,
partially soluble in Solid state
Liquidus
Solidus
Solvus

PHASE DIAGRAM
Phase Diagrams: Definition Solvus
Solvus line.
The locus of points on a phase diagram
representing the limit of solid solubility as a
function of temperature.

PHASE DIAGRAM
The two components (A & B) are completely soluble in
liquid state and partially soluble in solid state
Liquidus: AEF
A Liquidus
Solidus : ABEGF Liquid
Sovus: ABC and FGH F
a B E Gb
Temperature
OC
a+ b
H
100 %A C 100 %B
Composition, Weight percent B
PHASE DIAGRAM
The two components (A & B) are completely soluble in
a is the solid solution of B in A
b is the solid solution of A in B
A Liquidus
Liquid
F
Temperature
a B E G b
OC
a+ b
H
100 %A C Composition, Weight percent B 100 %B
PHASE DIAGRAM
Partial Eutectic phase Diagram:The two components (A & B) are
completely soluble in liquid state and partially soluble in solid state
Cooling an alloy with eutectic A Liquidus
1
composition point wise Liquid
description: F
2. Eutectic transformation at
Temperature
a B E G b
OC
a+ b
3
H
The two solid solutions generally solidify side by side

PHASE DIAGRAM
Partial Eutectic phase Diagram:The two components (A & B) are completely soluble in
Cooling an alloy with Hypo
eutectic composition 1
A Liquidus
point wise description
2 Liquid
1. Alloy in Liquid state F
2. Solidification begins by Liquid + a Liquid + b
nucleation of proeutectic
‘a’ phase. a B 3 E G b
3. Eutectic transformation atTemperature
OC
a+ b
4 H
The two solid solutions generally solidify side 4. Negligible change in

by side in alternate layers, giving a typical structureThe
microstructure recognised as eutectic microstructure will have
structure, proeutectic solid ‘a’ and
eutectic mixture of ‘a+b’
PHASE DIAGRAM
Partial Eutectic phase Diagram:The two components (A & B) are completely soluble in
Cooling an alloy with
hypereutectic composition
A Liquidus
point wise description 1
Liquid
1. Alloy in Liquid state 2 F
2. Solidification begins by Liquid + a Liquid + b
nucleation of proeutectic
‘b’ phase. a B E 3 G b
3. Eutectic transformation atTemperature
OC
a+ b
4 H
The two solid solutions generally solidify side by side in alternate layers,
giving a typical microstructure recognised as eutectic structure,
The microstructure will have proeutectic solid ‘b’ and eutectic mixture of ‘a+b’
PHASE DIAGRAM
Equilibrium diagram: Metals soluble in lquid state , partially
soluble in Solid state

PHASE DIAGRAM
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FUNDAMENTALS OF

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Interpretation of the Phase diagram gives basic

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• The element in the largest amount is metal

• The other intentionally added element which

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Cooling curve of High

Cooling curve of Low

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A horizontal, constant temperature line,

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100%Cu 60%Cu40%Ni 100%Ni

100%Cu 60%Cu40%Ni 100%Ni

100%Cu 60%Cu40%Ni 100%Ni

100%Cu 60%Cu40%Ni 100%Ni

• Coring : Coring is the variation in composition

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• When in liquid state the two elements may be

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(ii) Crystal structure factor

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• Both have the same crystal structure (FCC) and have

• Ni and Cu are totally miscible in all proportions.

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Liquidus line : AeB

The solid formed will have a

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1. Alloy in Liquid state 1

The two solids generally solidify side by side in alternate layers,

The two solids generally solidify side by side

The two solids generally solidify side by side

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The two solid solutions generally solidify side by side

The two solid solutions generally solidify side 4. Negligible change in

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