PHASE DIAGRAMS

All binary phase diagrams can be classified according to the appearance of the
following reaction or transformations.

The understanding of phase diagrams for alloy systems is extremely important

because there is a strong correlation between microstructure and mechanical
properties. Development of microstructure of an alloy is related to the
characteristics of its phase diagram. Phase diagrams provide valuable information
about melting, casting, crystallization, and other phenomena.

Definitions and basic concepts

The term component is frequently used in this discussion; components are pure
metals and/or compounds of which an alloy is composed.

“Solvent”

Represents the element or compound that is present in the greatest amount solvent
atoms are also called host atoms.

“Solute”

Is used to denote an element or compound present in a minor concentration.

Solubility limit

For many alloy systems and at some specific temperature there is a maximum
concentration of solute atoms that may dissolve in the solvent to form a solid
solution this is called a solubility limit.The addition of solute in excess of this
solubility limit results in the formation of another solid solution or compound that
has a distinctly different composition.

Equilibrium: State of a system at any specified condition (temperature, pressure,

composition or their combination) 2 or more phases can co-exist in equilibrium
(glass of water containing ice cubes)

Components: Are elements or the compounds that constitute a system

Fe-C, Fe-Ni, Cu-Al systems – 2 component systems

German silver (alloy of Cu-Ni-Zn) - 3 component system

Duralumin (alloy of Al-Mn-Cu-Mg) - 4 component system

Au-Cu system: Components → Au, Cu

Ice-water system: Component → H2O

Degree of Freedom:

Number of independent variables required to describe the state of a system are

called as the Degree of Freedom.Temperature, pressure and the composition of
phases are independent variables.These variables can be varied in the system
without disturbing the existing phase

Phase

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

physical and chemical characteristics. Every pure material is considered to be a
phase, so also is every solid, liquid, and gaseous solution. Each phase has different
physical and chemical properties. If more than one phase is present in a given
system, boundary separating the phases will exist across which there will be a
discontinuous and abrupt change in physical and/or chemical characteristics.Also
when a substance can exist in two or more polymorphic forms (e.g., having both
FCC and BCC structures)

Solids:

i. Single phase solid: is one which has same crystal structure, compositions &
properties throughout the system Examples: Pure Cu (pure metals), pure water,
solid solutions (α-brass, α–iron), Fe3C (homogeneous mixture of two types of
atoms)

ii. Multi phase solids: have different structures, composition & properties at
different regions Examples: Rock, wood, alloys, Fe (BCC & FCC)

Solid solution consists of atoms of at least two different types, the solute atoms
occupy either substitutional or interstitial positions in the solvent lattice and the
crystal structure of the solvent is maintained.
Depending on the ratio of the solvent (matrix) metal atom size and solute element
atom size two types of solid solutions may be formed:

1. Substitutional solid solution (SSS)

a. Ordered substitutional solid solution

b. Disordered or Random substitutional solid solution

2. Interstitial solid solution (ISS)

Substitutional solid solution

If the atoms of the solvent metal and solute element are of similar sizes (not more
than 15% difference) they form substitution solid solution where part of the solvent
atoms are substituted by atoms of the alloying element

a. Ordered SSS

When molten alloy is cooled slowly the diffusion of atoms takes place and re-
arrangement of atoms takes place. This leads to uniform distribution of solute
atoms & solvent atoms. This structure is known as Ordered Substitutional solid
solution or Super Lattice.Concentration of solute atoms will be constant through
the lattice structure

Examples: Cu-Zn, Cu-Ni systems

b. Disordered SSS

If solute atoms are arranged randomly in the solvent atom structure then it is called
Disordered SSS or there will be no uniform distribution of solute atoms in solvent
atomic structure.Concentration of solute atoms can vary considerably through the
lattice structure.Solid solution formation usually causes increase of electrical
resistance and mechanical strength and decrease of plasticity of the alloy.

Order-disorder transformation

Generally in the formation of a substitutional type of solid solution the solute atoms do not
occupy any specific position but are distributed at random in the lattice of the solvent. The alloy
is said to be in “Disordered” condition. If it cooled slowly, undergo rearrangement of the atoms
where the solute atoms move into definite positions of lattice. This solution is known as ordered
solid solution or super lattice.
On the equilibrium diagram, the ordered solutions are frequently designated as α I, βI, etc. or αII,
βII, etc. and the area in which they are found is usually bounded by a dot-dash line.

Types of solubility

1. Unlimited Solid Solubility:

 Solute and solvent are mutually soluble at all concentrations

 Example: Cu-Ni system

 Meets the requirements of the Hume-Rothery Rules

 Result is a single phase alloy

2. Limited or Partial Solid Solubility:

 There is a limit to how much of the solute can dissolve in the solvent before
“saturation” is reached

 Example: Pb - Sn and most other systems

 Does not meet the requirements of Hume-Rothery Rules

 Results in a multi-phase alloy

General Conditions for unlimited solid solubility

For an alloy system to have unlimited solid solubility certain basic rules or
conditions are needed to be satisfied.

These conditions are called as Hume-Rothery Rules

They are:

1) Atomic size factor

2) Crystal Structure

3) Electro-negativity

4) Valences

Hume-Rothery rules

1. Atomic size factor: The atoms or ions must be of similar size, with no more
than 15% difference in their atomic radius, in order to minimize the lateral

2. Crystal Structure: The material must have same crystal structure, or else
there will be a point at which a transition occurs from one phase to a second
phase with a different structure.

3. Electro Negativity: The atoms should have same electro negativities. The
more electro +ve one element and more electro -ve the other elements, the
greater is the likelihood that they will form an inter metallic compound
instead of a solid solution.

4. Valence: A metal of lower valence will have more tendency to dissolve

more of a metal of higher valence than vice-versa. The difference in the
valency of solute & solvent atoms should be less or else it encourages
formation of compounds rather than solid solutions

2. Interstitial solid solution

When solute atoms of small atomic radii fit into the spaces or voids or interstices
of the lattice structure of the larger host or solvent (or parent or matrix) atoms,
Interstitial solid solutions are formed.The atomic diameter of interstitial atoms
must be substantially smaller than that of host atoms.Normally maximum
allowable concentration of interstitial atom is less than 10%.Those atoms having
atomic radii less than 0.1 nm are likely to form interstitial solid solution.

Favorable conditions for formation of interstitial solid solution

1. Solvent is metal

2. Solute is a non metal

3. The atomic radii differences between solute & solvent is very high

4. Solubility of solute in solvent should be very less (otherwise interstitial

compound formation takes place)

5. The solute and solvent should have similar electro negativity

Equilibrium Phase Diagrams

A diagram that depicts existence of different phases of a system under equilibrium

is termed as Phase diagram. It is also known as Equilibrium diagram or
Constitutional diagram.

What it Represents?

Equilibrium phase diagrams represent the relationships between temperature and

the compositions and the quantities of phases at equilibrium.

Uses or Objectives of Phase/Equilibrium Diagrams

1. To show phases that is present at different compositions and temperatures

under slow cooling (equilibrium) conditions.

2. To indicate equilibrium solid solubility of one element / compound in

another.

3. To indicate temperature at which an alloy starts to solidify and the range of

solidification.

4. To indicate the temperature at which different phases start to melt.

5. To determine amount of each phase in a two-phase mixture.

Classification of Phase Diagrams

Based on the number of components in the system

1. Unary phase diagrams - 1 component systems

2. Binary phase diagrams - 2 component systems
3. Ternary phase diagrams - 3 component systems, and so on.

Unary phase diagrams - 1 component systems

Binary phase diagrams - 2 component systems

These diagrams constitute two components .Example: 2 metals (Cu and Ni) or a
metal and a compound (Fe and Fe3C) or 2 compounds (Al2O3 and Si2O3) etc.Phase
rule is applicable for all binary diagrams.Binary diagrams are usually drawn
showing variations in temperature and composition only.

All binary systems consist only one liquid phase, i.e. a component is completely
soluble in the other component when both are in liquid state.Binary systems are
classified according to their solid solubility.Binary phase diagram is one in which
temperature and compositions are variable parameters and pressure is held constant
normally 1 atm. Binary phase diagrams are maps that represent the relationships
between temperature and the compositions and quantities of phases at equilibrium
which influence the microstructure of an alloy.

The addition of impurity atoms to a metal will result in the formation of a solid
solution and/or a new second phase, depending on the kinds of impurity, their
concentrations, and the temperature of the alloy.

When two different metals (say A & B) are mixed in their liquid state, they form a
homogeneous solution (i.e. “chemically and structurally” same throughout)

When this liquid (A+B) is solidified, the new solid produced may retain the
homogeneity that was present in the liquid state, and such a solid is known as solid
solution.

Types of binary phase diagrams

Reaction Symbolic Equation Schematic Representation

Eutectic L↔α+β

Eutectoid α↔β+γ

Peritectic L+α↔β

Peritectoid α+β↔γ

Roult’s Law

It states that, the freezing point of a pure substance will be lowered by the addition
of second substance provided later is soluble in the pure substance when liquid
state & insoluble in solid state.
Type: 1 BINARY ISOMORPHOUS SYSTEM

Copper Nickel System Binary Isomorphous alloy

Construction of Binary Phase Diagrams

 Let A & B pure metals with melting points TA & TB respectively

 Prepare number of alloys of A & B with varying compositions ranging from

0 to 100%

 Draw cooling curves for all the alloys

 Note critical temperatures from all the cooling curves

Interpretation of phase diagrams

For a binary system of known composition and temperature that is at equilibrium at

least three kinds of information are available

1. The phases that are present

 2. The compositions of these phases and

3. The percentages or fractions of the phases.

To find the composition in phase diagram [Lever Rule]

Since only two phases are present, the sum of their mass fractions must be equal to
unity

Wα + WL = 1 ------------- 1

The mass of one the component that is present in both of the phases must be equal
to the mass of that component in the total alloy OR

WαCα + WLCL = CO ------------- 2

𝐂𝛂−𝐂𝐎 𝐂𝐨−𝐂𝑳
WL = & Wα=
𝐂𝛂−𝐂𝐋 𝐂𝛂−𝐂𝐋

Practise 1:

Sample % of A % of B Solidification Solidification

No. (By wt.) starting temp ending temp
(By wt.)

1 100 0 TA TA

(Pure
A)

2 90 10 800 750

3 80 20 T3 T4

4 70 30 785 705

5 60 40 T7 T8
6 50 50 755 675

7 40 60 T11 T12

8 30 70 715 645

9 20 80 T15 T16

10 10 90 650 615

11 0 100 TB TB

(Pure
B)

Find:

1. T3, T4, T7, T8, T11, T12, T15, T16 Temperatures

2. Amount of liquid and solid at 40%A and 60%B at 7000C

Type 2. Eutectic with no solid SOLUBILITY

Some components are so dissimilar that their solubility in each other is nearly
negligible. At Relatively low temperatures there is a two-phase field for pure solids
A and B consistent such that the two components (A and B) cannot dissolve in
each other. Second the solidus is a horizontal line that corresponds to the eutectic
temperature.

This name comes from the Greek word eutektos meaning "easily melted." In this
case the material with the eutectic composition is fully melted at the eutectic
temperature. Any composition other than the eutectic will not fully melt at the
eutectic temperature.
For many binary systems the two components are partially soluble in each other.
The result is a phase diagram intermediate between the two cases we have treated
so far. These single-phase regions are comparable to the SS region. As a result the
two solid-solution phases α and β are distinguishable and they frequently have
different crystal structures. The use of Tie lines to determine the compositions of α
and β in the two-phase regions is similar to previous sections. The Pb-Sn system is
a good example of a binary eutectic with limited solid solution.
TYPE 3:- METALS COMPLETELY SOLUBLE IN THE LIQUID STATE BUT ONLY
PARTLY SOLUBLE IN SOLID STATE:

Fig: Phase diagram illustrating partial solid solubility

The phase diagram is shown in fig, TA & TB are the melting point of pure metal A & pure metal
B respectively. TE is the eutectic temperature. The liquidus line is TA E TB & solidus line is
TA FEGTB . Single phase and two phase diagrams are shown in the figure. Alloys in this system
never solidify crystals of pure A or pure B, but always a solid solution or mixture of solid
solutions. The single phase  and  solid solution areas are labeled. The remaining three, two
phases areas may now be labeled as liquid+  , Liquid+  &  +  .

At TE the  solid solution dissolves a max of 20% B as shown by point F. and  solution a max
of 10% A as shown by point G. with decrease in temperature the max amount of solute that can
be dissolved decreases as indicated by the line FH & GJ. These lines are called solvus lines and
indicate the solubility of B in A or A in B solution.

Equilibrium cooling of alloys at different composition of A & B is discussed below.

Alloys 1 composed of 95A-5B, when liquidus line is crossed at T1, it will begin to solidify by
forming crystals of  solid solutions, extremely rich in A. This process continues with the liquid
getting richer in B and gradually moving down along the liquidus line. The  solid solution also
become richer in B, is moving down along the solidus line. When the solidus line is crossed at
T4, the entire solid will be homogenous  solid solution & remain so till room temperature.

Alloy 2. 30A-70B is a eutectic composition and remains liquid until the eutectic temperature is
reached at point E. Liquid under goes eutectic reaction. The eutectic mixture is made of  &  .
The eutectic reaction may be written as,
Cooling
LIQUID  +
Heating
The relative amount of  &  at E is calculated as,

EG 20
=  100 =  100 = 28.6%
FG 70

EF 50
=  100 =  100 = 71.4%
FG 70

Because change in solubility of B in A, (line FH) and A in B (line GJ), the relative amount of 
and  varies for eutectic mixture at room temperature, and it is calculated as

KJ 25
=  100 =  100 = 29.4%
HJ 85

HK 60
=  100 =  100 = 70.6%
HJ 85
Alloy 3, 60A-40B remains liquid until the liquidus line is reached at T3. The liquid starts to
solidify crystals of pro eutectic (primary) α solid solution very much rich in A. As the
temperature decreases, the liquid becomes richer & richer in B, gradually moving down & to the
right along the liquidus line until it reaches point E.
Just above the eutectic temperature following condition exist.

Phases Liquid Primary α

Chemical composition 30A-70B 80A-20B
Relative amounts 40% 60%

Remaining (40%) solidify at E forming crystals of  and β alternatively. The microstructure

appears as shown in figure.

Alloy 4. 85A-15B follows the same process as described for alloy 1. The microstructure and
cooling curve is shown in the figure below. Solidification starts at T2 and is completed in T5. As
the alloy cools the solvus line is reached at point N. The α solution now is saturated in B. Below
this temperature under condition of slow cooling, the excess B must come out of solution. Since
A is soluble in B, the precipitate doesn’t come out as the pure metal B, but rather the β solid
solution. At room temperature the alloy will consist largely of α with a small amount of excess β.
The strength of an alloy is determined by the phase that is continuous throughout the alloy. In
this phase diagram although β-solution constitutes only 5% of the alloy it exists as continuous
network along the grain boundaries.

[Ex:- Lead antimony equilibrium diagram]

Fig: Microstructure of an 85A-15 alloy. a) After slow cooling; b) after reheating and rapid
cooling to room temperature; c) after aging.
 PERITECTIC REACTION:-

In the Peritectic reaction a liquid and a solid react isothermally to form a new solid on cooling.
The reaction is expressed in general as,
Cooling
Liquid + Solid1 New solid
Heating

Fig:- Phase diagram showing the formation of an incongruent melting intermediate phases by a Peritectic
reaction.

TA DETB : Liquidus line TP :Peritectic Temperature

TATPGJTETB : Solidus line TE : Eutectic Temperature

TA : M.P of A

TB : M.P of B

Alloy 1, 90%A-10%B:

The alloy remains liquid until the liquidus line is reached at T1 . Solidification now takes place by
forming crystals of the pure A. As the temperature falls, the amount of liquid decreases.

Let us know the condition exist just above the peritectic temperature TP :

Phases Liquid Solid A

Composition 60A%-40%B 100% A
TP F FD
Relative amount ×100=25% ×100=75%
TP D TP D
The condition just below the peritectic temperature is:

Phases Solid Am Bn Solid A

Composition 70%A-30%B 100%A
TP F FG
Relative amount ×100=33% ×100=67%
TP G TP G
The liquid contains 60%A and Am Bn contains 70%A. The liquid is not rich enough in A to form
the compound by itself. The liquid must therefore react with just the right amount of solid A, in
this case 75% – 67% = 8% to bring its composition to that of the compound Am Bn . The following
reaction must have taken place at the peritectic temperature.
Composition : 60%A 100%A 70%A

Equation : Liquid + Solid ‘A’ Solid ‘ Am Bn ’

Rel.Amount : 25% + 8% 33%

The reaction takes place all around the surface of each grain of solid A where the liquid touches
it. When the correct composition is reached, the layer solidifies into Am Bn material surrounding
every grain of A. Further reaction is slow since it must wait for the diffusion of atoms through
the peritectic wall of Am Bn in order to continue. When diffusion is completed, all the liquid will
have been consumed and since only 8% of pure A was required for the reaction, there will be
67% of A left. The final microstructures will show grains of primary A surrounded by compound
Am Bn .

Fig: Slow cooling of a 90%A-10%B alloy showing the

Microstructure at different temperature
For an alloy composition to left of G, will have same type solidification as that of alloy 1. The
difference will be in the amount of excess A remaining after the occurring of the peritectic
reaction is complete. The closer the alloy composition the alloy composition is to the compound,
the less primary A will remain.

Alloy 2, 65%A-35%B:

The alloy remains liquid above the temperature T2 , and it solidifies pure A when the liquidus line
is crossed at T2 . Solidification continues, the liquid becomes richer in ‘B’. When the point ‘H’ is
reached the liquid composition is 60%A-40%B. now applying the lever rule for the alloy at the
point H,

35 5
×100= 87.5% liquid & ×100= 12.5% Solid A
40 40

Since the line GD is not part of the solidus line, some liquid must remain after the reaction takes
place. It is therefore the solid A which must disappear in reacting with some of the liquid to form
the compound Am Bn .

The same reaction will takes place again:

Composition : 60%A 100A 70A

Reaction : Liquid + Solid A 

Cooling
 Am Bn

The amount of liquid entering into the above reaction may be determined by applying the lever
rule below the reaction temperature.

GH 5
Liquid (percent) = ×100 = ×100 = 50%
DG 10

Since there was 87.5% liquid before the reaction & 50% liquid after the reaction, it is apparent
that 37.5% of the liquid reacted with 12.5% of solid A to give 50% of the compound Am Bn at the
peritectic temperature Tp . As the cooling continues, the liquid now separates crystals of Am Bn .
The liquid becomes richer in B, and its composition gradually moves down and to the right along
the liquidus line until it reaches point E, the eutectic temperature.

5
At this temperature, there is only ×100 or 10% liquid left. Since the liquid has reached the
50
eutectic point, it now solidifies into the eutectic mixture Am Bn +B. This alloy, at room
temperature, will consist of 90% primary or proeutectic Am Bn surrounded by 10% of eutectic
( Am Bn +B) mixture. The figure below shows the cooling curve and the microstructure at various
temperatures during the slow cooling of a 65%A-35%B alloy.

Transformation in the solid state

There are several equilibrium changes and reactions which takes place entirely in the solid state.

1. Allotropy

Several metals which exist in more than one type of crystal structure depending upon
temperature. Iron, tin, Manganese & cobalt are examples of metals which exhibit this property,
known as allotropy.
OR
It is the property possessed by certain elements to exist in two or more distinct forms that are
chemically identical but have different physical properties.
Ex:- In the case of iron the crystal structure has one form at room temperature and another at
high temperature. When heated above 910oC the atomic structure changes from body centered
cubic to face centered cubic but reverts again when cooled.

On an equilibrium diagram, this allotropic change is indicated by a point or points on the vertical
line which represents the pure metal.
 Fig: Hypothetical equilibrium diagram showing metal A undergoing two allotropic changes.

In the above diagram, the gamma solid solution field is “looped”. The pure metal rich in A
undergo two transformations. Many of equilibrium diagram involving iron such as Fe-Si, Fe-Mo,
Fe-Cr show this looped solid solution field. Since the type of iron that exists in this temperature
range is gamma loop, this field is usually called the gamma loop.

THE EUTECTOID REACTION

This is a common reaction in the solid state. In this case, a solid phase transforms on cooling into
two new solid phases. The general equation for a eutectoid reaction can be written as,
Cooling
Solid1 Solid 2 + Solid 3
Heating
The resultant eutectoid mixture is extremely fine, just like the eutectic mixture. Under the
microscope both mixture generally appear same. An equilibrium diagram of a eutectoid reaction
is shown in the below figure,
 Fig: Phase diagram showing eutectoid reaction.

Liquidus line : TA ETB

Solidus line : TA FGTB
Point N : Eutectoid point.
Line OP : Eutectoid temperature line.

The eutectic mixture is composed of the phases that occur at both the ends of the eutectic
temperature line, namely γ solid solution (point F) and β solid solution (point G). Point M
indicates the allotropic change for the pure metal A.
Alloy 1

It is slow cooled; γ solid solution is formed when the liquidus line is crossed at X1. More and
more γ is formed until the solidus line is crossed at X2. It remains a uniform solid solution until
the solidus line is crossed at X3.
The pure metal A undergo now an allotropic change, forming the α solid solution. The α solid
solution dissolves much less of B than does the γ solid solution. Some of the B atoms that are
dissolved in the area that will undergo the allotropic change must now diffuse out of that area.
When sufficient diffusion of B atoms has taken place, the remaining A atoms rearrange
themselves into the new crystals structure, forming the α solid solution. The composition of the
remaining γ is gradually moving down and to the right along the solvus line MN. When the alloy
reaches the eutectoid temperature X4, the remaining γ has now reached the eutectoid point N. and
this γ must now transform by the eutectoid reaction, forming alternate layers of α & β with
extremely fine mixture. The reaction may be written as,
Cooling
γ α+β
Heating
The microstructure at room temperature consists of primary α which was formed between X3 and
X4, surrounded by the eutectoid mixture of α + β is shown in the following figure,

The cooling curve for the alloy 1 is given in the below figure,

Peritectoid Reaction

This is a common reaction in the solid state and appears in many alloy systems. Here two solid
phases react to form a new solid phase upon cooling. The peritectoid reaction may be written as
Cooling
Solid1 + Solid 2 New solid3
Heating

The new solid formed may be solid solution or an intermediate phase. Here, two solid phases α
and β react at the peritectoid temperature line EF to form the new solid phase γ which is an
intermediate phase. The equation can be written as
Cooling
α+β γ
Heating