Phase Diagrams-

Introduction

Presented By:
Rajnish Kumar Singh
Assistant Professor
Mechanical Engineering Department
GIET(A), Rajahmundry
Lecture Details:
Unit- 2, Topic- 1
Subject – Metallurgy and Material Science
ME, II Year/ I Semester
 Lesson Objectives
After studying this chapter you should be able to do the following:
 Construct a phase diagram with help of a series of cooling curves.
 Describe the phase diagram and its importance in metallurgy and material science.
 Familiarize with the basic concepts and terminologies related to phase diagram –
Phase, Equilibrium, Component, Variable, Solubility limit etc.
 Describe different experimental methods to draw phase diagrams
 Classify the phase diagrams based upon its degree of freedom.
 Introduction
• To understand the concept of
phase diagram and it’s L L

Temperature →
importance we’ll start with an
alloy system, i.e., Cu-Ni System. L 1453 ℃

• Cu (FCC) 𝑇𝑚 = 1085℃
𝜶+L
• Ni (FCC) 𝑇𝑚 = 1453℃
1085℃
• 𝜶 is substitutional solid solution
S
𝜶
of Cu and Ni. S

• Note:- Pressure is kept constant at 1 atm Cu Ni

0% 20% 40% 60% % Ni →80% 100%
 Introduction
100% 80% 60% 40% 20% 0% Cu
0% 20% 40% 60% 80% 100% Ni

Temperature →
Temperature →

Ni
Cu
0% 20% 40% 60% 80% 100%
Time →
Series of cooling curves for different % Ni →
composition
 Importance of Phase Diagrams
• We can get a number of

Temperature →
information from the diagram. L phase region

• For example take 43% Ni – Alloy, 1453 ℃

we can tell about following just 𝜶+L

from one diagram
 Solidification start temp 1085℃
𝜶 phase region
 Solidification end temp
 Phases present at a given
temp.
• Many other information are also Cu Ni
0% 20% 40% 60% 80% 100%
there, which we’ll discuss later. % Ni →
 What are Phase Diagrams
• Phase diagrams are maps which demarcates regions of stability/ existence of various
phases.
• Map that gives relationship between phases in equilibrium in a system as a function
of Temperature, Pressure and composition.
• The nature and occurrence of these phases depends on:
I. Temperature
II. Pressure
III. Composition
• Also called Equilibrium Diagram or Constitutional Diagram.
Definitions and Basic Concepts – Component
• Component – The independent chemical species, in terms of which composition of a
system is specified, are called components.
System Components Number of components
Cu-Ni System Copper and nickel 2
Ice-Water system H2 O 1
Mild Steel Iron and Carbon 2

• System – A series of possible alloys consisting of the same components.

• Solute and solvent – Component of higher composition is called solvent while all
other components are called solute.
 Solubility Limit
• Solubility Limit: For many alloy systems and at some specific temperature, there is a
maximum concentration of solute atoms 100

that may dissolve in the solvent to form Solubility Limit

80
a solid solution; this is called a solubility

Temperature
60
limit.
Liquid Liquid
• The addition of solute in excess of this 40
Solution Solution
+
Solid sugar
solubility limit results in the formation of 20

another solid solution or compound 0

Sugar 0 20 40 60 80 100
having a distinctly different composition. Water 100 80 60 40 20 0
Composition%
 Definitions and Basic Concepts – Phase
• Phase – A chemically homogenous, physically distinct and mechanically separable
part of a system is called a phase.

• Three phases of matter: Liquid, Solid, Gaseous.

• Pure material as well as solution – Phase
Mixture – More than a phase or multiphase.
• A crystal structure is considered to be of one
phase. Aluminium Copper Alloy
Darker - 𝜶 𝑷𝒉𝒂𝒔𝒆
Fe → BCC (𝛂 − 𝐟𝐞𝐫𝐫𝐢𝐭𝐞), FCC (𝛄 − 𝐚𝐮𝐬𝐭𝐞𝐧𝐢𝐭𝐞) Lighter - 𝜷 Phase

• The sugar–water solution just discussed is one phase, and solid sugar is another.
 Variables in Phase Diagram
• A existence of a particular phase depends upon various conditions like temperature,
pressure and concentration. These are called variables.
• The axes can be:
 Thermodynamic: (T, P, V)
 Composition variables: (C, x %)
• In single component systems (unary systems) the usual variables are T & P.
• In two component phase diagrams the usual variable are T & x % (P is kept constant).
 Experimental methods
1. 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.
 Experimental methods
2. 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.
 Experimental methods
3. 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 microstructure.
 Summary
• Equilibrium phase diagrams are a convenient and concise way of representing the
most stable relationships between phases in alloy systems.
• A phase is some portion of a body of material throughout which the physical and
chemical characteristics are homogeneous.
• The number of components is the minimum number of required chemical
constituents using which compositions of all the phases can be defined.
• Solubility limit is maximum concentration of solute dissolved in solution at a certain
temperature.
• Thermodynamic Variables: T, P, V • Compositional: % wt, %mole
Thank You
 Unary and Gibb’s Phase Rule

Presented By:
Rajnish Kumar Singh
Assistant Professor
Mechanical Engineering Department
GIET(A), Rajahmundry
Lecture Details:
Unit- 2, Topic- 2
Subject –Material Science and Metallurgy
ME, I Year/ II Semester
 Lesson Objectives
After studying this chapter you should be able to do the following:
 Classify the phase diagrams based upon the number of components present.
 Familiarize with the concept of degree of freedom and understand the Gibbs’ Phase
Rule.
 Introduce Unary phase diagram and it’s different regions.
 Identify triple point on a unary phase diagram and define it.
 Calculate degree of freedom for different regions, phase boundaries and triple point.
 Define Binary phase diagram.
 Classification of Phase Diagrams
Number of Components Name of System
Phase Diagram
One Unary
• Phase diagrams and the systems they
Two Binary
Three Ternary describe are often classified and
Four Quaternary named for the number (in Latin) of
Five Quinary components in the system:
Six Sexinary
Seven Septenary
Eight Octanary
Nine Nonary
 Unary Phase Diagram
• Simplest type of Phase diagram.

1000
b
• It’s a one-component system. The

100
Liquid
phase diagram is for a pure substance, (Water)

Pressure (atm)
10
Solid c
so in this composition is held constant. (Ice) 2 3

1.0
• This means that pressure and temp.

0.1
are the variables. Vapour

0.01
(Stream)
O
• Also called Pressure-Temperature a

0.001
diagram (P-T diagram) -20 0 20 40 60 80 100 120
Temperature(℃)
 Unary Phase Diagram – Phase Boundary
• Lines – a0, b0 and c0 – are called

1000
b
phase boundaries.

100
Liquid
• On any point on these curves the two (Water)

Pressure (atm)
10
Solid c
phases present on either sides are in (Ice) 2 3

1.0
equilibrium with each other.

0.1
• For example, consider heating at 1 atm. Vapour

0.01
(Stream)
• Point 2 – equilibrium between S and L. O
a

0.001
• Point 3 – equilibrium between L and V. -20 0 20 40 60 80 100 120
Temperature(℃)
 Unary Phase Diagram – Triple Point
• All three of the phase boundary curves
intersect at a common point, which is
labeled O, called “Triple Point”
• This means that at this point, all of the
three phases are simultaneously in
equilibrium with one another.
• Its position is distinct, or fixed by definite values of pressure and temperature.
• Any deviation from this point by a change of temperature and/or pressure will cause
at least one of the phases to disappear. So it’s called “Invariant Point”.
 Gibbs Phase Rules
• Gibbs phase rule is a criterion that determines how many phases can coexist within a
system at equilibrium.
F=C–P+N
For a system in equilibrium
or, F+P=N+C
Where,
F – Degrees of Freedom
C – Number of Components
P – Number of Phases
N –Number of Non compositional variables or thermodynamic variables.
 Degree of freedom
• 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”
• 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.
 Gibbs Phase Rules
Variables in a phase diagram
• Variables in the system = Composition variables + Thermodynamic variables

V = P(C-1) + N

• Thermodynamic variables = P + T (usually considered) = 2 (=N)

F=C–P+2
Phase Rule reduces to,
or, F=C–P+1 if pressure is considered constant
 Gibbs Phase Rules – Single Phase Region
• For a single phase region, either solid or liquid
or gaseous phase region, only one phase
exist.
So, F + P = C + 2
or, F + 1 = 1 + 2,
or F = 2
• The single phase region at any point, T and P
can both be varied while still being in the
single phase region with F = 2.
 Gibbs Phase Rules – Phase Boundary
• The Gibbs phase rule here is:
F+P=C+N
or, F + P = C + 2
or, F + 2 = 1 + 2
• The degree of freedom (F) is 1.
i.e. we can chose either T or P and the
other will be automatically fixed.
 Gibbs Phase Rules – Triple Point
• At O, Triple point, All three phases co exist.
So, F + P = C + 2
or, F + 3 = 1 + 2
or, F = 0
• This implies for all three phases to exist, both
temperature and pressure is to be fixed.
• That’s why it is called invariant point, i.e.,
they are fixed for a given system.
 Binary Phase Diagram
• Binary implies that there are two components.
• Pressure changes often have little effect on
Liquid
the equilibrium of solid/ Liquid phases (unless
of course we apply ‘huge’ pressures). 𝛼 + Liquid

• Hence, binary phase diagrams are usually

drawn at 1 atmosphere pressure. 𝛼
• T & Composition – these are the usual
variables in binary phase diagrams.
 Summary
• Phase diagram can be classified based upon the number of components, e.g., unary,
binary, ternary etc.
• One component system- Unary Diagram
Two component system- Binary Diagram
• Unary phase diagram has pressure and temperature as variables.
• A phase boundary is a curve on phase diagram where two phase exist in equilibrium.
• Triple point is a point where three phases coexist simultaneously in equilibrium.
• An invariant point is a point where change in any one variable results in loss of one or
more phases.
 Summary
• 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.
• Gibb’s Phase Rule: F + P = N + C
• No. of variables: V = P(C-1) + N

Region Degree of freedom

Single phase region 2
Phase Boundary 1
Triple Point 0
Thank You
 Isomorphous Phase Diagram

Presented By:
Rajnish Kumar Singh
Assistant Professor
Mechanical Engineering Department
GIET(A), Rajahmundry
Lecture Details:
Unit- 2, Topic- 3
Subject – Metallurgy and Material Science
ME, II Year/ I Semester
 Lesson Objectives
After studying this chapter you should be able to do the following:
 Schematically sketch simple isomorphous phase diagrams with help of cooling
curves.
 Label the various phase regions on these diagrams.
 Label Phase equilibrium lines – liquidus and solidus lines on these diagrams.
 Explain 1-2-1 phase for a two phase region in binary phase diagram.
 Evaluate the phases present, their composition and their relative amount a given
point in phase diagram.
 Describe tie line and lever rule to find above information in a two phase region.
 Construction of Isomorphous Diagram
100% 80% 60% 40% 20% 0% Cu
0% 20% 40% 60% 80% 100% Ni

Temperature →
Temperature →

Ni
Cu
0% 20% 40% 60% 80% 100%
Time →
Series of cooling curves for different % Ni →
composition
 Isomorphous Phase Diagrams
• 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 etc.

 Phases in Isomorphous Diagram
• Liquid phase region above liquidus
and solid phase region below
solidus, are single phase region.
• The (L + 𝛼) state is not a semi-solid
state.
• It is mixture of solid of fixed
composition and structure, in
equilibrium with a liquid of fixed
composition.
 Constitution Point
1500
1453 ℃
• It is a point (x, T) on phase diagram
1400 L
represents an alloy of constitution

Temperature →
‘x’ held at a temperature T. 1300

𝜶+L
Three Questions: 1200 A
(40% Ni, 1200℃)
1. What are the phases present?
1100
2. What are the composition of the phases?
1085℃ 𝜶
3. What are the relative amount of phases?
1000
20% 40% 60% 80% 100%
Cu % Ni→ Ni
1. phases present?
2. composition of the phases?
3. Relative amount of phases?
 What are the Phases the Present
1500
• Point A: (80% wt Ni, 1100℃) 1453 ℃

1400 L
Phase : 𝜶- phase

Temperature →
• Point B: (60% wt Ni, 1250℃)
Phase : 𝜶-phase + L-phase
1300

𝜶+L
. B
1200
The 1-2-1 phase rule.
• If we horizontally move from one 1100 . A
single phase region to another single 𝜶
1085℃
phase region, then we will always 1000
have a 2-phase region in between Cu
20% 40% 60% 80% 100%
% Ni→ Ni
them.
 What are Composition of the Phases
What is Composition
• Fraction or ‘%’ of different components.
• wt % wt fraction
• Mole % mole fraction.
• 𝐶0 = Alloy composition
= fraction of a component in whole alloy
• 𝐶𝑃ℎ𝑎𝑠𝑒 = Phase composition
= fraction of a component in given phase
 What are Composition of the Phases
Single phase Region
• Point A: (80% wt Ni, 1100℃)
Phase : 𝜶- phase
• 𝐶0 = 80% wt Ni
• 𝐶𝛼 = Alloy composition
= fraction of a component in whole alloy
• So for single phase region,
. A
Alloy composition = Phase composition
 What are Composition of the Phases
Two phase Region
• Point B: (60% wt Ni, 1300℃)
Phase : 𝐋 + 𝜶- phase
• 𝐶𝐿 & 𝐶𝛼 = ? . B
Tie Line Rule:
Tie-line is an isotherm in the two phase
region running from one boundary to the
other.
𝐂𝐋 𝐂𝛂
𝐶𝐿 = 50%
𝐶𝛼 = 76%
 What are Relative Amounts of the Phases
Single phase Region
• Point A: (80% wt Ni, 1100℃)
Phase : 𝜶- phase
• Since the whole alloy is made up of one
phase only, i.e., 𝛼- phase,
Relative amount of phase 𝛼 in the alloy
. A
= 1 (100%)
 What are Relative Amounts of the Phases
Two phase Region
• Point B: (60% wt Ni, 1300℃)
Phase : 𝐋 + 𝜶- phase
• 𝑓𝐿 & 𝑓𝛼 = ?
Lever Rule:
a
. B
b

Draw a vertical line representing the alloy

composition. The vertical line will divide
the tie line into two parts whose lengths
are inversely proportional to the amount
of the phases present.
 What are Relative Amounts of the Phases
Lever Rule:
𝒂 𝒃
The opposite arm of the lever are
. B
proportional to the fraction of the solid
and liquid phases.
𝑎
𝑓𝛼 =
𝑎+𝑏
𝐶0 − 𝐶𝐿
𝑓𝛼 =
𝐶𝛼 − 𝐶𝐿 𝐂𝐋 𝐂𝟎 𝐂𝛂

𝑏 𝐶𝛼 − 𝐶0
𝑓𝐿 = =
𝑎 + 𝑏 𝐶𝛼 − 𝐶𝐿
 Tie and lever Rule: Example
Alloy of 35% wt Ni at 1250℃
a. Phases Present:
L+𝛼
a. Composition of phases present:
Composition of Liquid Phase
= 𝐶𝐿 = 32% wt. Ni 𝒂 𝒃
Composition of 𝛼- Phase
= 𝐶𝛼 = 43% wt. Ni
c. Relative amount of phases present:
Relative amount of 𝛼-phase
𝑎 35−32
= 𝑎+𝑏 = 43−32 = 0.27 = 0.27%
Relative amount of liquid phase
𝑎 43−35 32 35 43
= 𝑎+𝑏 = 43−32 = 0.73 = 73%
 Summary
• Isomorphous diagrams are those for which there is complete solubility in the solid
phase. The copper–nickel system displays this behavior.
• There are 3 phase regions present in isomorphous phase diagram separated by two
phase equilibrium lines – Liquidus and Solidus.
• A constitution point is simply a point on diagram with co-ordinates – (x%, T).
• A phase diagram evaluates following at a constitutional point – Phases present,
composition of the phases, relative amount of phases.
• 1-2-1 Phase rule: A two phase region will always exist between two 1 – phase regions.
 Summary
• A tie-line is an isotherm drawn from one boundary to another in 2-phase region.
• Projection of the end points of tie lines where it touches 1-phase boundary gives us
the composition of respective phases.
• The lever rule is a rule used to determine the mole fraction or the mass fraction of
each phase of a binary equilibrium phase diagram.
Thank You
 Isomorphous Phase Diagram-
Evolution of Microstructures

Presented By:
Rajnish Kumar Singh
Assistant Professor
Mechanical Engineering Department
GIET(A), Rajahmundry
Lecture Details:
Unit- 2, Topic- 4
Subject – Metallurgy and Material Science
ME, II Year/ I Semester
 Lesson Objectives
After studying this chapter you should be able to do the following:
 Describe the development of various microstructures and phase transformations
during equilibrium cooling of an isomorphous alloy.
 Describe the development of various microstructures and phase transformations
during non- equilibrium cooling of an isomorphous alloy.
 Differentiate the cored and equilibrium structure of an isomorphous alloy.
 Evaluate the degree of freedom for various regions of isomorphous phase diagram.
 Equilibrium Cooling
L
(35% Ni)

L
(35% Ni) a
𝛼
(46% Ni)
b
L
(32% Ni)
𝛼 c
(40% Ni)
L
(24% Ni) d
𝛼
(35% Ni) e
𝜶
𝜶
𝜶
𝜶
𝛼
(35% Ni)
 Equilibrium Cooling
Points to be Noted:
• With continued cooling, both compositions and relative amount of each phase will
change.
• Composition of 𝛼- phase and Liquid phase follows the solidus and liquidus line
respectively.
• Relative amount of 𝛼- phase will increase continuously with cooling of alloy and can
be determined at any point with help of lever rule.
• Overall alloy composition remains unchanged, even though there is a redistribution of
Cu and Ni between phases.
 Non-equilibrium Cooling
• In actual practice it is extremely difficult to cool under equilibrium conditions.
• With changes in temperature, there must be readjustments in the compositions of
the liquid and solid phases in accordance with the phase diagram.
• These readjustments are accomplished by diffusional processes.
• Diffusion process is time-dependent.
• To maintain equilibrium during cooling, sufficient time must be allowed at each
temperature for the compositional readjustments.
• Consequently, microstructures other than those previously described develop.
 Non-equilibrium Cooling
L
(35% Ni)

𝛼
(46% Ni)
a
𝛼
(46% Ni)
(40%Ni) b

𝛼 c
(46% Ni)
(40%Ni) d
(35% Ni)

e
𝛼
(46% Ni)
(40%Ni)
(35% Ni)
 Coring
• The final solid under non equilibrium cooling 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 • Fast rate of cooling: • Slow rate of cooling:
Cored structure Equilibrium structure
to as coring or dendritic
segregation.
• The faster the rate of cooling,
the greater will be the coring or
segregation.
 Gibb’s Phase Rule for Binary Phase Diagram
• Gibbs phase rule is a criterion that determines how many phases can coexist within a
system at equilibrium.
F+P=C+N

• Here F is degree of freedom, P is no of phases present, C is No of components in the

system.
• N = No of thermodynamic variables or non compositional variables = Temp and
pressure
• In binary phase diagrams (which also includes isomorphous) pressure is kept
constant. F+P=C+1
 Gibb’s Phase Rule- Isomorphous Diagram
V = P(C-1) + 1
F+P=C+1 Liquid Phase
C=2
P=1
F=2
V=2
Solid 𝜶- Phase
(L+α)
C=2
C=2
P=1
P=2
F=1
F=2
V=3 V=2
 Variation in Isomorphous Phase diagram
• It is possible to have a system in which the liquidus
and solidus lines go through a minimum or a
maximum.
• The alloy composition x behaves just like a pure
metal.
• There is no difference in the liquid and solid
composition.
 Variation in Isomorphous Phase diagram
• 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 congruent-melting alloys.
Because alloy x has the lowest melting point in the
series.
 Variation in Isomorphous Phase diagram
• When the atomic size difference is
about 15% as in Au-Ni system, a
two-solid-phase field appears in the
phase diagram at lower
temperature and is called a
miscibility gap.
• Au-Ni system shows formations of
solid solutions in all proportions.
 Summary
• During equilibrium cooling, compositions of 𝛼-phase and L-phase follows the solidus
and liquidus line, while the overall alloy composition remains the same.
• During non – equilibrium, cooling rate is too rapid to allow diffusion to take place.
• During non – equilibrium, solidus line shifts to the higher solute contents, while
liquidus line is altered.
• A cored structure or dendritic structure is obtained under non – equilibrium cooling.
Region Degree of freedom
L & 𝛼- region 2
𝛼 + L- region 1
Thank You
 Eutectic Phase Diagram

Presented By:
Rajnish Kumar Singh
Assistant Professor
Mechanical Engineering Department
GIET(A), Rajahmundry
Lecture Details:
Unit- 2, Topic- 5
Subject – Metallurgy and Material Science
ME, II Year/ I Semester
 Eutectic Phase Diagram
Type III: Completely soluble in liquid but only partially soluble in solid state

α-phase –
Solid Solution of B in A

β-phase – L
Solid Solution of A in B
L+𝛂 L +𝛃
Solvus– Line indicating 𝛂 𝛃
Maximum Solubility Eutectic Line
𝜶+𝛃
 Eutectic Point
• The minima on liquidus is called
eutectic point
• It can be seen that at eutectic point,
the alloy solidifies at a single temp,
called Eutectic Temperature.
• Composition is called Eutectic
composition.
Eutectic Point resembles the solidification of a pure
metal but differs in the sense that it gives two
different phases.
𝐋𝐢𝐪𝐮𝐢𝐝 ⇔ 𝐒𝐨𝐥𝐢𝐝 𝟏 + 𝐒𝐨𝐥𝐢𝐝 𝟐
The above reaction is called Eutectic Reaction
 Pb-Sn Alloy System
• Pb-Sn alloy system is a great
example of Binary Eutectic Phase
Diagram.
• Pb-Sn alloys are used for soldering.
• Low melting alloy
• Strength (more than pure elements)

• Eutectic – Easily Melt

• At eutectic composition an alloy
has lowest melting temperature
and hence it can be easily melt.
 Eutectic Diagram – Single Phase Region
Three Questions:
A (10% Sn, 250℃)
1. The phases present?
 𝜶 L

2. The composition of the phases?

. A L+𝜶
 Same as Alloy composition: 𝜶 L+𝜷 𝜷
10% Sn
3. The relative amount of phases? 𝜶+𝜷
 100% 𝜶
 Eutectic Diagram – Two Phase Region
Three Questions:
B (30% Sn, 200℃)
1. The phases present?
L
 Liquid and 𝜶
2. The composition of the phases? L+𝜶
 Liquid: 48% Sn 𝜶 14 ‘ B 18 L+𝜷 𝜷
 𝜶 : 16% Sn
3. The relative amount of phases? 𝜶+𝜷
 Liquid = 18/ 32 = 0.56 = 56%
 𝜶 = 14/32 = 0.44 = 44%
16 48
 Lever rule: Exercise
For a 40 wt% Sn-60 wt% Pb alloy at 150°C,
i. Find the phases present
• α And β
ii. Composition of phases,
α  11% Sn (point 𝐶𝛼 )
β  99% Sn (point 𝐶𝛽 ) 150° C
R S
iii. % of phases:
𝑆 99 −40
𝑊𝛼 = = = 67 wt%
𝑅+𝑆 99 −11

𝑅 40 −11
𝑊𝛽 = = = 33 wt%
𝑅+𝑆 99 −11 11 99
40
 Copper Aluminium Phase Diagram

Temperature (℃)→
660℃
θ-phase – 𝑳
Intermetallic
compound of Al
and Cu (CuAl2 ) 𝜶+𝑳 32.7% 𝜽+L
𝑪𝒖𝑨𝒍𝟐
548℃ 𝜶 (𝜽)
α-phase – 5.7% Eutectic Line 52.5%
Solid Solution
of Cu in Al
𝜶+𝜽

Al
0 10 20 30 40 50 60
Cu % Wt→
 Eutectic Reaction
548℃
L (32.7%Cu) α (5.7%Cu) +𝜃 (52.5%Cu)

• α and θphases have different

compositions neither of which 660℃
is the same as that of the 𝑳

liquid. 𝜽+L 𝜽
5.7% 𝜶 + 𝑳
• There must necessarily be a 548℃ 𝜶 52.5%
32.7%
redistribution of the lead and
𝜶+𝜽
tin components by Diffusion.
Al
0 10 20 30 40 50 60
Cu % Wt→
 Intermediate Solid Phases

Terminal Solid
Solution Intermediate phases Intermediate phases

• Boundaries with • Single phase region between terminal • Single phase region between terminal
pure element Phases Phases
 Intermediate alloy phase/ Compounds
• The isomorphous and eutectic phase diagrams discussed thus far are relatively
simple.
• Those for many binary alloy systems are much more complex as they contain
Intermediate solid Phases.
• The most common intermediate alloy phases are:-
 Intermetallic Compounds or Valence Compounds
 Interstitial Compounds
 Electron Compounds
 Invariant Reactions
Reaction Symbolic Upon cooling Example
Equation
Eutectic L ⇿ α + β A Liquid phase produces two solid Fe-C, 4.27%C, 1147°C
phase
Eutectoid α ⇿ β + γ A solid phase produces two solid Fe-C, 0.80 %C, 723°C
phase
Peritectic L + α ⇿ β A Liquid phase and a solid phase Fe-C, 0.16 %C, 1495°C
produces one solid phase
Peritectoid α + β ⇿ γ two solid phases produces an Ni-Zn
another solid phase
 Invariant Reactions
Reaction Symbolic Upon cooling Example
Equation
Montectic L1 ⇿ α + L2 A Liquid phase produces a Ni-Zn
solid phase and a liquid
phase
Thank You
 Iron- Cementite Phase Diagram

Presented By:
Rajnish Kumar Singh
Assistant Professor
Mechanical Engineering Department
GIET(A), Rajahmundry
Lecture Details:
Unit- 2
Subject – Metallurgy and Material Science
ME, II Year/ I Semester
 Lesson Objectives
After studying this chapter you should be able to do the following:
 Identify and describe different allotropes of iron.
 Explain the carbon solubility in different allotropes of Iron.
 Draw Iron – Cementite phase diagram and locate different phases present in it at
different temperature and composition.
 Describe properties of different phases present in Iron – Cementite phase diagram.
 Allotropic Transformations
• Several metals/materials may exist in more than one type of crystal structure
• On changing temperature (or pressure), their crystal structure changes. This is known
as Allotropy.
• Allotropes are variants of a substance consisting of only one type of atom but having
different molecular configuration and physical properties.
• Example
i. Graphite and diamond are allotropes of carbon having different properties.
ii. Iron – BCC at lower temperature but FCC at higher temperature
 Allotropy in Iron
δ - Iron
𝑳
• Body-centered cubic (BCC) crystal structure. 1𝟓𝟑𝟗℃
• Same as α – iron but at high temperature
• Carbon Solubility- varies with temperature (0.08% 𝛅 − 𝐢𝐫𝐨𝐧
max at 1493℃) 1𝟑𝟗𝟒℃

Temperature (℃)
γ-iron
• Face-centered cubic (FCC) structure. 𝛄 − 𝐢𝐫𝐨𝐧
• Carbon Solubility- varies with temperature (2.1%
max at 1147℃) 910℃

α - iron 𝛂 − 𝐢𝐫𝐨𝐧
• Body-centered cubic (BCC) structure.
• Carbon Solubility- varies with temperature
(0.022% max at 727℃)
Room Temperature
 1538 L
𝜹 − 𝒇𝒆𝒓𝒓𝒊𝒕𝒆

𝜹+𝑳
1493

1394
𝑳+𝜸
𝐓𝐞𝐦𝐩𝐞𝐫𝐚𝐭𝐮𝐫𝐞 (℃) →

𝑭𝒆𝟑 𝑪 + 𝑳

1147
𝜸 − 𝑨𝒖𝒔𝒕𝒆𝒏𝒊𝒕𝒆
910

𝑭𝒆𝟑 𝑪 − 𝑪𝒆𝒎𝒆𝒏𝒕𝒊𝒕𝒆
𝜸 +𝑭𝒆𝟑 𝑪
𝜶 − 𝑭𝒆𝒓𝒓𝒊𝒕𝒆

𝜶+𝜸
727

𝜶 +𝑭𝒆𝟑 𝑪

Fe
0.8 2.1 wt %C →
0.022

0 4.2 6.67
 Iron- Cementite Phase Diagram
Fe – C diagram and Fe - Fe3C diagram
• First ever Phase diagram. Done by Roberts –Austen in 1898.
• Fe-C phase diagram should be of composition range from 0% → 100%C by wt.
• At 6.67%C, we find an intermetallic compound which is called Cementite (𝑭𝒆𝟑 𝑪).
• At this composition (6.67% C) composition axis stops.
• Beyond this composition alloy is too brittle to be of any importance, so all practical
Iron – Carbon Diagram terminates at 6.67%C.
• That’s why Iron – Cementite is more appropriate name.
 Iron- Cementite Phase Diagram (simplified)
Less significant 𝛿 − 𝑓𝑒𝑟𝑟𝑖𝑡𝑒 part omitted
1538℃

1493℃
L
𝑳+𝜸 𝑭𝒆𝟑 𝑪 + 𝑳
1147 ℃
𝐓𝐞𝐦𝐩𝐞𝐫𝐚𝐭𝐮𝐫𝐞 (℃) →

4.2%
𝜸 − 𝑨𝒖𝒔𝒕𝒆𝒏𝒊𝒕𝒆 2.1%

910℃

𝑭𝒆𝟑 𝑪 − 𝑪𝒆𝒎𝒆𝒏𝒕𝒊𝒕𝒆
𝜸 +𝑭𝒆𝟑 𝑪
𝜶+𝜸
𝜶 − 𝑭𝒆𝒓𝒓𝒊𝒕𝒆

0.022% 0.8% 727℃

𝜶 +𝑭𝒆𝟑 𝑪

Fe
0 wt %C → 6.67
 α-Ferrite
• It is an interstitial solid solution of a small
amount of carbon dissolved in α iron.
• The crystal structure of ferrite (α) is
B.C.C.
• It is the softest structure that appears on
the diagram.
• Soft and ductile, low strength.

The maximum solubility is 0.025%C at 723°C and

it dissolves only 0.008%C at room temperature.
 Cementite (Fe 3C)
• Cementite or Iron carbide – chemical formula Fe 3C.
• Contains 6.67%C by weight (fixed Composition)
• It is a metastable phase.
• Forms when %C exceeds 𝛼 − 𝑓𝑒𝑟𝑟𝑖𝑡𝑒 𝑜𝑟 𝛾-austenite
solubility limit.
• Mechanically – Very Hard and Brittle
• It is the hardest structure that appears on the diagram.
• Its crystal structure is orthorhombic.
 Austenite (γ)
• It is an interstitial solid solution of a small amount of carbon dissolved in γ- iron.
• The maximum solubility is 2.1%C at 1147℃.
• The crystal structure of Austenite (γ) is F.C.C
• Soft and ductile, low strength.

The maximum solubility is 2.1%C at 1147°C

 Important reactions in Fe-Fe3C Diagram
4.2% C and 1147℃
Eutectic reaction:
0.16% C and 1493℃ 𝑳(4.2% C) ↔ 𝛄 (2.1%C) + 𝐅𝐞𝟑 𝐂(6.67%C)
Peritectic reaction:
𝛅(0.11% C) + L(0.51%C) ↔ γ (0.16%C)

0.8% C and 727℃

Eutectoid reaction:
𝜸(0.8% C) ↔ 𝛂 (0.02%C) + 𝐅𝐞𝟑 𝐂(6.67%C)
 Summary
• Allotropes are variants of substance having different molecular configuration and
physical configuration and physical properties.
• Iron-cementite diagram extends from 0% to 6.67% C on the composition axis.
• Important phases found on the Iron–Iron carbide phase diagram are –
 Ferrite (BCC) - It is an interstitial solid solution of carbon dissolved in α iron.
 Cementite or iron carbide - Chemical formula Fe3 C, contains 6.67%C by weight.
- It is a metastable phase.
 γ-austenite (FCC) - It is an interstitial solid solution of a small amount of carbon
dissolved in γ- iron.
Thank You
 Development of phases
in
Iron- Cementite Phase Diagram
Presented By:
Rajnish Kumar Singh
Assistant Professor
Mechanical Engineering Department
GIET(A), Rajahmundry
Lecture Details:
Unit- 2,
Subject – Metallurgy and Material Science
 Lesson Objectives
After studying this chapter you should be able to do the following:
 Describe the development of eutectoid mixture by equilibrium cooling of alloy having
eutectic composition.
 Differentiate between eutectoid, Hypoeutectoid and hypereutectoid regions in iron –
cementite diagram.
 Describe the development of Hypoeutectoid mixture under equilibrium cooling.
 Describe the development of eutectoid mixture by equilibrium cooling.
 Calculate the relative amount and composition of phases in two phase region by
application of tie line and lever rule.
 Eutectoid Reaction
• One of the most important
reaction in iron carbon phase
diagram.
• Occurs at 0.8% carbon alloy
composition and 727℃
Temperature.
• Just above 727℃ alloy is in 𝜸-
phase, as we cool it below
𝛄 (0.8% C) ↔ 𝜶 (0.02%C) + 𝑭𝒆𝟑 𝑪 (6.67%C)
727℃ it enters (𝛂 + 𝐅𝐞𝟑 𝐂).
 Development of Eutectoid Phase

a
• Alternating layers of (𝛼 + 𝐹𝑒3 𝐶).
• Lamellar structure.
• It is called Pearlite b
 Pearlite
• Pearlite is the eutectoid mixture containing 0.80%C and is formed at 727℃ on very
slow cooling.
• Composition: (𝛂 - 0.02%C + 𝐅𝐞𝟑 𝐂 - 6.67%C) Overall: 0.8%C
• It is very fine plate like or lamellar mixture
of ferrite and cementite.

Pearlite is a not a phase but

combination of two phases
(ferrite+ cementite)
 Hypoeutectoid and Hypereutectoid

Eutectioid alloy
(Pealite)

Hypoeutectiod
alloy Hypereutectiod alloy
 Development of Hypoeutectoid Phase

a
a
b
b
Proeutectoid 𝛼 c
c d

Pearlite
d Proeutectoid 𝜶
+
Proeutectoid 𝛼 Pearlite

Pearlite
 Development of Hypereutectoid Phase

a a
b b

Proeutectoid c
𝐶𝑒𝑚𝑒𝑛𝑡𝑖𝑡𝑒 c d
Proeutectoid

Pearlite
𝒄𝒆𝒎𝒆𝒏𝒕𝒊𝒕𝒆
d +
Proeutectoid
𝐶𝑒𝑚𝑒𝑛𝑡𝑖𝑡𝑒 Pearlite

Pearlite
Equilibrium Phases at Room Temperature

Proeutectoid 𝒄𝒆𝒎𝒆𝒏𝒕𝒊𝒕𝒆
Pearlite

Proeutectoid 𝜶 +
+ Pearlite
Pearlite
Microstructures
Proeutectoid 𝛼

Pearlite

Proeutectoid
𝐶𝑒𝑚𝑒𝑛𝑡𝑖𝑡𝑒
Network

Pearlite
 Lever Rule in Iron-Carbon Diagram
For a 99.6 wt% Fe-0.40 wt% C at a temperature just below the eutectoid.
Determine the following:
a) The amount of total Fe3C & ferrite (α)
b) The amount of pearlite and pro-eutectoid ferrite (α)
c) The amount of total Fe3C & ferrite (α)
 Summary
• Eutectoid Reaction:
• The microstructural product of an iron–carbon alloy of eutectoid composition is
pearlite, a microconstituent consisting of alternating layers of ferrite and cementite.
• The microstructures of alloys having carbon contents less than the eutectoid (i.e.,
Hypoeutectoid alloys) are composed of a proeutectoid ferrite phase in addition
to pearlite.
• Pearlite and proeutectoid cementite constitute the microconstituents for
hypereutectoid alloys—those with carbon contents in excess of the eutectoid
composition.
Thank You