Fundamentals Unit 3

Unit 3:

Phase Diagrams
&
Mechanisms of Strengthening of Metals

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 Phase Diagrams Unit 3

o Basics:

 They are called solid solutions, where we have solvent and solute.
 Solvent is the element/ compound which is in major proportion and
solute is the one is smaller proportion.

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 Phase Diagrams Unit 3
o Basics:

 Solvent is the element/ compound which is in major proportion and

solute is the one is smaller proportion.

+ =

Solute (C) Solution (Steel)

Solvent (Fe)

Solid Solid Solid Solution

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 Phase Diagrams Unit 3

o Solubility Limit:

For most alloy systems, there is a maximum concentration of solute atoms

that may dissolve into the solvent to form a solid solution. This maximum
concentration is called solubility limit.

Any further addition of solute

above solubility limit leads to
formation of another solid solution
or compound that has a distinctly
different composition.

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 Phase Diagrams Unit 3

o Solubility Limit:

 If solute available is more than the solubility limit that may lead to formation
of different phase, either a solid solution or compound.
 In general, solubility limit changes with temperature.

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 Phase Diagrams Unit 3

o Solubility Limit:

 Examples in case of Solids

Micrograph of Grey Cast Iron Micrograph of Ductile Cast Iron

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 Phase Diagrams Unit 3

o Solubility Limit:

 Examples in case of Solids

Nb is the light phase, Nb3Si is the dark phase

Nb-Si alloy (Nb is the light phase, Nb3Si

is the dark phase)

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 Phase Diagrams Unit 3
o Phases:
The Phase is a homogeneous portion of a system having same
composition and properties throughout its volume, and is separated from
other portions of the system by a boundary.

 A phase can be solid, liquid or gas.

A Phase can be a pure substance or a solution, provided that the structure

and composition are uniform throughout.

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 Phase Diagrams Unit 3
o Phases:
 The properties of the materials depend largely upon the nature of phases,

 Therefore it is essential to know the conditions at which these phases

exist, and a condition at which a change in phase will occur.

IC engines are made of Cast iron or Al alloys, because

neither pure Fe nor pure Al, can with stand, temperature
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and pressures being built up in the IC engine.
 Phase Diagrams Unit 3
o Phase Diagrams:

 Lets say you are a hiker... scaling Mt.

Everest...
When hungry u decided to boil egg… and
always ended up with running Egg… why ?
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Phase Diagrams Unit 3

At Sea level...
i.e. Atmospheric
Pressure… 1 bar

At Higher Altitude...
i.e. low Atmospheric
Pressure…
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 Phase Diagrams Unit 3
o Phase Diagrams:

Explanation lies in the

water used to boil the Egg...

 Further explanation in
given by phase diagram of
water.

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 Phase Diagrams Unit 3
o Phase Diagrams:
Explanation lies in the
water used to boil the
Egg...

Further explanation in
given by phase diagram of
water.
All of this knowledge is important
to even have a egg at hill resorts…

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 Phase Diagrams Unit 3
o Phase Diagrams:

The information concerning to phase changes in an alloy system is

presented in the form of phase diagram.

Thus a phase diagram is essentially a graphical representation of phases,

which are present in an alloy system at various temperatures, pressures and
compositions.

It represents the state of given system under equilibium (slow cooling/
thermodynamic equilibrium) conditions in which there will be no changes
with time.

Hence, the phase diagram is also called as equilibrium diagram for a a

given system.

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 Phase Diagrams Unit 3

Equilibrium or Phase diagrams indicate:

 Various phases present at different composition and temperature (pressure

is assumed constant, at 1 atm), and their change while heating and cooling

Solid solubility of one element in

another.
 Temperature range over which
solidification of an alloy occurs, &
Temperatures at which different
phases start to melt.
The phase diagram is useful basis
in studying various metallurgical
concepts such as melting,
solidification and structural changes
produced by heat treatment…
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 Phase Diagrams: Unary Phase Diagram: Unit 3

Any material can exist in solid, liquid and vapor phases depending in the
conditions of temperature, pressure and over-all composition.

 For one component system, the variables that determine which phases
exist in equilibrium are temperature and pressure.

Only one Triple point represents

equilibrium between Solid, Liquid
and Vapor.

The Unary Phase Diagram of Water

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 Phase Diagrams: Unary Phase Diagram: Unit 3

There are three triple points, but only one of them represents
equilibrium between Solid, Liquid and Vapor.

 In case of Fe, there are three different solid phases which exists:

 α – Fe and δ – Fe;
both have BCC structure.

 γ – Fe has FCC structure.

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The Unary Phase Diagram of Fe
 Phase Diagrams: Binary Systems: Unit 3

Different metals can combine in different ways in solids as well as

liquids. Depending upon the solubility characteristics of two metals, binary
phase diagram (two component system) can be classified as:

Isomorphous Systems: Two components are completely soluble in each

other in both liquid and solid states, and exist in a single phase for all
composition of the alloy.

Eutectic Systems: Here two components are completely soluble in liquid

state and completely insoluble in the solid state.
L
Cooling
Liquid Solid 1 + Solid 2
Heating Solid 1 + Solid 2

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 Phase Diagrams: Binary Systems: Unit 3

Eutectoid System: Phase diagrams in which transformation will takes

place in solid state. i.e. one solid decomposes into two different solids.
Solid 1

Cooling
Solid 1 Solid 2 + Solid 3
Heating Solid 2 + Solid 3

Peritectic System: Here melting points of two metals differ considerably,

and a liquid phase combined with solid phase to produce new solid phase.

Cooling Liquid + Solid 1

Liquid + Solid 1 New Solid
Heating
New Solid

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 Phase Diagrams Unit 3

Binary Isomorphous Systems:

An isomorphous system is one in which two metals are completely

soluble in each other in liquid as well as solid states. These systems are
called solid solutions.

It Compromises of three

regions:

A liquid phase above

Liquidus line

A solid phase below

Solidus line, and region
between both is the mixture
of liquid and solid phase.
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 Phase Diagrams Unit 3

Binary Isomorphous Systems:

There are only two phases in the phase diagram, the liquid and the solid phases.

These single-phases regions are

separated by a two-phase region
where both liquid and solid co-
exist.

The area in the figure above the line

marked liquidus (A’bB’)
corresponds to the region of
stability of the liquid phase,

The area below the solidus line

(A’dB’) represents the stable region
for the solid phase.
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 Phase Diagrams Unit 3

Binary Isomorphous Systems:

There are only two phases in the phase diagram, the liquid and the solid phases.

For the interpretation of the

phase diagram, let’s consider
the vertical line ae drawn
corresponding to composition
of 50% A +50% B and assume
that the system is undergoing
equilibrium cooling.

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 Phase Diagrams Unit 3

Binary Isomorphous Systems:

The point a on the line ae signifies that for that particular temperature and
composition, only liquid phase is stable. This is true up to the point b which lies
on the liquidus line, representing the starting of solidification.

Completion of solidification of
the alloy is represented by the
point, d.

Point e corresponds to single

phase solid region up to the room
temperature.

Point c lies in the two-phase

region made of both liquid and
solid phases.
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Corresponding micro-structural changes are also shown in figure.
 Phase Diagrams Unit 3

Binary Isomorphous Systems: (Nikle – Cu System)

 The points A and B represent the melting point of pure Nickel (1455 oC)
and pure Copper (1083 oC)

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 Phase Diagrams Unit 3

Binary Isomorphous Systems: (Nikle – Cu System)

 The points A and B represent the melting point of pure Nickel (1455 oC)
and pure Copper (1083 oC)

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 Phase Diagrams Unit 3

Lever rule:
Between Liquidus and Solidus lines, both phases, liquid and solid co-exist
under equilibrium, and the relative amounts of both liquid and solid at given
temperature and composition can be calculated by applying Lever Rule.

 Consider an alloy of two

components A and B.

At temperature, T the

alloy of a given composition
will consists two phases,
liquid and solid.

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 Phase Diagrams Unit 3

Lever rule:
 To obtain the relative amounts of liquid and solid, draw a vertical line
representing the alloy (W) and horizontal temperature line (t) to intersect the
liquidus and solidus lines at L and S respectively.

The Lever rule states that the

vertical line divides the horizontal
line into two parts (LO and OS)
whose lengths are inversely
proportional to the amount of
phases present.

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 Phase Diagrams Unit 3

Lever rule:
 The lever rule may be used to determine the relative amounts of phases at
equilibrium in any two phase region for a binary alloy as below…

 Amount of Solid Phase (%) :

S = LO X 100
LS

 Amount of Liquid Phase (%) :

L = OS X 100
LS

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 Phase Diagrams Unit 3

Lever rule:
 To determine the phase composition, locate the temperature (T) and
composition point (O) on the phase diagram.

The tie line through (O)

extends across the two phase
region and terminates at the
phase boundary lines (L & S) on
either side.

The perpendicular lines drawn

through these points on the
composition axis determine the
composition in respective phases.

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Phase Diagrams Binary Eutectic System: Unit 3
Problems

a) ~ 1350 oC

b) ~ 59 % Ni + 41 Cu

c) ~ 1390 oC

d) ~ 81 % Ni + 19% Cu
 Phase Diagrams Unit 3

Lever rule:
 Wight Fractions and Volume Fractions

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 Phase Diagrams Unit 3

Lever rule:
 Wight Fractions and Volume Fractions

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 Phase Diagrams Unit 3

Gibbs Phase Rule:

 J. W. Gibbs derived an equation that enables the number of phases which can
be present in equilibrium in a given system.

 This equation is called Gibbs phase rule which is stated as:

P + F =C + N
Where,
P = Number of Phases in equilibrium,
F = Degree of Freedom in the system (number of variable factors),
C = Number of Components (chemical elements) making the system,
N = Number of external factors (changes depends on the system)

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 Phase Diagrams Unit 3

Gibbs Phase Rule:

For Unary Phase Diagrams: Two Possible Variables are Temperature and pressure;
so N = 2

P + F =C + 2
if c = 1
P F
1 2
2 1
3 0
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 Phase Diagrams Unit 3

Gibbs Phase Rule:

For Binary Phase Diagrams: The only possible variables is Temperature, so N = 1

Pressure = 1 atm.

P + F =C + 1
if c = 2
P F
1 2
2 1
3 0
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 Phase Diagrams Unit 3

Binary Eutectic System:

 In eutectic system components A and B are completely soluble in liquid

state but completely insoluble in solid state.

Cooling
Liquid Solid 1 + Solid 2
Heating

Solid 1 + Solid 2

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 Phase Diagrams Unit 3

Binary Eutectic System:

 Ta and Tb are represents the freezing points of A and B respectively.

 Both A and B have

respective liquidus lines and
At Equilibrium
solidus lines.

These curves intersect at

point E, known as eutectic
point or Invariant Point (for
this composition near 50 – 50
% of A and B.

Eutectic temperature is
the minimum temperature at
which solidification occurs.38
 Phase Diagrams Unit 3

Binary Eutectic System:

 In eutectic system components A and B are completely soluble in liquid

state but completely insoluble in solid state.

Phase Rule:

P + F =C + 1
No. of phases (P) = 3
( +  + liquid)
No. of Components (C) = 2
(A & B)

F= 0
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Phase Diagrams Binary Eutectic System Unit 3
At Equilibrium

Liquidus
Solidus
BCC
Liquid (L)
α α+L +L 
BCC

Solvus
α+

Cu Ag
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Phase Diagrams Binary Eutectic System Unit 3
At Equilibrium Pb - Sn System
Phase Diagrams Binary Eutectic System Unit 3
At Equilibrium Pb - Sn System
Phase Diagrams Binary Eutectic System Unit 3
At Equilibrium Pb - Sn System
Phase Diagrams Binary Eutectic System Unit 3
At Equilibrium Pb - Sn System
Phase Diagrams Binary Eutectic System Unit 3
At Equilibrium Water - Salt System

This is the reason why

salt is added to water to
melt it
Phase Diagrams Binary Eutectic System Unit 3
At Equilibrium Pb – Bi System

Lead (Pb is toxic so it is

replaced by Bismuth (Bi)
Phase Diagrams Binary Eutectic System Unit 3
Problems
Phase Diagrams Binary Eutectic System Unit 3
Problems
Phase Diagrams Binary Eutectic System Unit 3
Problems

For the below Problem, Kindly project the Pb – Sn phase

Diagram in the class and solve the problem manually
This two slides are just for your convince.
Phase Diagrams Binary Eutectic System Unit 3
Problems
Phase Diagrams Binary Eutectic System Unit 3
Problems
Phase Diagrams Binary Eutectic System Unit 3
Problems
 Phase Diagrams: Binary Systems: Unit 3

Eutectoid and Peritectic System:

Eutectoid System: Phase diagrams in which transformation will takes

place in solid state. i.e. one solid decomposes into two different solids.
Solid 1

Cooling
Solid 1 Solid 2 + Solid 3
Heating Solid 2 + Solid 3

Examples of Eutectoid reactions are: Iron – Carbon, Cu – Zn; Al- Mn,

Cu-Sn.

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Phase Diagrams Eutectoid and Peritectic System Unit 3

Eutectoid (E): (560 oC, 74 wt % Zn)

Ni – Ti System
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 Phase Diagrams: Binary Systems: Unit 3

Eutectoid and Peritectic System:

Peritectic System: Here melting points of two metals differ considerably,

and a liquid phase combined with solid phase to produce new solid phase.

Cooling Liquid + Solid 1

Liquid + Solid 1 New Solid
Heating
New Solid

 Examples of Peritectic System are : Iron – Carbon;

Silver – Platinum;
Cu - Zn

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Phase Diagrams Eutectoid and Peritectic System Unit 3

Peritectic (P): (598 oC, 78.6 wt % Zn)

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 Phase Diagrams Unit 3
The Iron Carbide Phase Diagram:

 Various crystal structures and relative hardness of various important

phases seen in Iron- Carbide diagram:
S. No Phase Crystal Relative
Structure Hardness
1 Ferrite – Solid Solution of BCC Very Soft
Carbon in α – iron
2 Austenite – Solid Solution FCC Soft
of Carbon in γ- iron
3 Cementite – Compound of Orthorhombic Very Hard
Iron and Carbon
4 Pearlite – Layers of Ferrite - Medium Hard
and Cementite
5 Ledeburite – Mixture of - Hard
Austenite and Cementite 57
Phase Diagrams The Iron Carbide Phase Diagram Unit 3

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Phase Diagrams The Iron Carbide Phase Diagram Unit 3

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 Phase Diagrams: The Iron Carbide Phase Diagram Unit 3

Eutectic, Eutectoid and Peritectic System:

Iron – Carbon diagram is a complex phase diagram with three invariant

reactions: Eutectic, Eutectoid and Peritectic.

Eutectic System: Eutectic reaction occurs at 1130 oC and composition

of 4.3 % C. The Liquid (4.3% C) transforms into eutectic mixture of
Austenite and Cementite. The reaction can be written as:

Cooling
Liquid Austenite + Cementite
Heating

The Eutectic mixture is called as Ledeburite

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 Phase Diagrams: The Iron Carbide Phase Diagram Unit 3

Eutectic, Eutectoid and Peritectic System:

Iron – Carbon diagram is a complex phase diagram with three invariant

reactions: Eutectic, Eutectoid and Peritectic.

Eutectoid System: This is a solid state reaction which occurs at 723 oC

and composition of 0.8 % C. The Austenite (0.8% C) decomposes into
ferrite (0.025 %C) and Cementite (6.67%C).

Cooling
Austenite Ferrite + Cementite
Heating

The Eutectoid Mixture is called as Pearlite

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 Phase Diagrams: The Iron Carbide Phase Diagram Unit 3

Eutectic, Eutectoid and Peritectic System:

Iron – Carbon diagram is a complex phase diagram with three invariant

reactions: Eutectic, Eutectoid and Peritectic.

Peritectic System: This is a solid state reaction which occurs at 1492 oC

and composition of 0.18 % C. The liquid (0.5% C) combines with δ- iron
(0.08% C) to produce Austenite (0.18 % C). This reaction can be written
as:
Cooling
Liquid + δ – Iron Austenite
Heating

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Phase Diagrams The Iron Carbide Phase Diagram Unit 3

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LPU

End of UNIT - 3

Please read the book.