PHASE DIAGRAMS

EQUILIBRIUM PHASE DIAGRAMS

Phase Rule
Types of Phase diagrams
Lever Rule

Advanced Reading

Alloy Phase Equilibria

A. Prince
Elsevier Publishing Company, Amsterdam (1966)

Phase Diagrams
Phase diagrams are an important tool in the armory of an materials scientist
In the simplest sense a phase diagram demarcates regions of existence of various phases.
This is similar to a map which demarcates regions based on political, geographical,
ecological etc. criteria.
Phase diagrams are maps*

Thorough understanding of phase diagrams is a must for all materials scientists

Phase diagrams are also referred to as EQUILIBRIUM PHASE DIAGRAMS
This usage requires special attention: though the term used is Equilibrium, in practical
terms the equilibrium is NOT GLOBAL EQUILIBRIUM but MICROSTRUCTURAL
LEVEL EQUILIBRIUM (explanation of the same will be considered later)
This implies that any microstructural information overlaid on a phase diagram is for
convenience and not implied by the phase diagram.
The fact that Phase Diagrams represent Microstructural Level equilibrium is often not
stressed upon.

* there are many other maps that a material scientist will encounter like creep mechanism maps, various kinds of materials selection maps etc.

 Broadly two kinds of phase diagrams can be differentiated* those involving time and
those which do not involve time (special care must be taken in understanding the former
class- those involving time).
In this chapter we shall deal with the phase diagrams not involving time.
This type can be further sub-classified into:
Those with composition as a variable (e.g. T vs %Cu)
Those without composition as a variable (e.g. P vs T)
Temperature-Composition diagrams (i.e. axes are T and composition) are extensively used in
materials science and will be considered in detail in this chapter. Also, we shall restrict
ourselves to structural phases (i.e. phases not defined in terms of a physical property)**
Time-Temperature-Transformations (TTT) diagrams and Continuous-CoolingTransformation (CCT) diagrams involve time. These diagrams are usually designed to
have an overlay of Microstructural information (including microstructural evolution).
These diagrams will be considered in the chapter on Phase Transformations.

* this is from a convenience in understanding point of view

** we have seen before that phases can be defined based either on a geometrical entity or a physical property (sometimes phases based on a
physical property are overlaid on a structural phase diagram- e.g. in a Fe-cementite phase diagram ferromagnetic phase and curie
temperatures are overlaid)

Since terms like Phase and Microstructure are key to understanding phase diagrams, let us
have a re-look at the figure we considered before
Thermo-mechanical
Treatments

Crystal
Atom

Structure
Electromagnetic

Microstructure

Phases

Defects

Casting
Metal Forming
Welding
Powder Processing
Machining

Component

+ Residual Stress
& their distributions

Click here to know more about microstructures

Processing determines shape and microstructure of a component

Vacancies
Dislocations
Twins
Stacking Faults
Grain Boundaries
Voids
Cracks

Let us start with some basic definitions:

DEFINITIONS
Components of a system

Independent chemical species which comprise the system:

These could be: Elements, Ions, Compounds
E.g.
Au-Cu system : Components Au, Cu (elements)
Ice-water system : Component H2O (compound)
Al2O3 Cr2O3 system : Components Al2O3, Cr2O3

Note that
components need not
be only elements

This is important to note that components need not be just elements!!

Phase

This is the typical textbook definition which one would see!!

Physically distinct, chemically homogenous and mechanically separable region of a

system (e.g. gas, crystal, amorphous...).
Gases
Gaseous state always a single phase
mixed at atomic or molecular level

Liquids
Liquid solution is a single phase
e.g. NaCl in H2O
Liquid mixture consists of two or more phases
e.g. Oil in water (no mixing at the atomic/molecular level)

Solids
In general due to several compositions and crystals structures many phases are possible
For the same composition different crystal structures represent different phases.
E.g. Fe (BCC) and Fe (FCC) are different phases
For the same crystal structure different compositions represent different phases.
E.g. in Au-Cu alloy 70%Au-30%Cu & 30%Au-70%Cu are different phases

What kinds of Phases exist?

We have already seen the official definition of a phase:
Physically distinct, chemically homogenous and mechanically separable region of a
system.
However, the term phase is used in diverse contexts and we list below some of these.

Based on state Gas, Liquid, Solid

Based on atomic order Amorphous, Quasicrystalline, Crystalline
Based on Band structure Insulating, Semi-conducting, Semi-metallic, Metallic
Based on Property Paraelectric, Ferromagnetic, Superconducting, ..
Based on Stability Stable, Metastable, (also- Neutral, unstable)
Also sometimes- Based on Size/geometry of an entity Nanocrystalline, mesoporous, layered,

Phase transformation
Phase Transformation is the change of one phase into another.
E.g.:
Water Ice
- Fe (BCC) - Fe (FCC)
- Fe (FCC) - Fe (ferrite) + Cementite (this involves change in composition)
Ferromagnetic phase Paramagnetic phase (based on a property)
Grain
The single crystalline part of polycrystalline metal separated by similar entities by a
grain boundary
Microstructure

An alternate definition based on magnification

(Phases + defects + residual stress) & their distributions

Structures requiring magnifications in the region of 100 to 1000 times
OR
The distribution of phases and defects in a material
Again this is a typical textbook definition which has been included for!!

Phase diagram
Map demarcating regions of stability of various phases.
or
Map that gives relationship between phases in equilibrium in a system as a
function of T, P and composition (the restricted form of the definition sometime considered in materials textbooks)

Variables / Axis of phase diagrams

The axes can be:
Thermodynamic (T, P, V),
Other possibilities include magnetic field intensity (H), electric field (E) etc.

Kinetic (t) or
Composition variables (C, %x)
In single component systems (unary systems) the usual variables are T & P
In phase diagrams used in materials science the usual variables are:T & %x
In the study of phase transformation kinetics Time Temperature Transformation
(TTT) diagrams or Continuous Cooling Transformation (CCT) diagrams are also
used where the axis are T & t

Important points about phase diagrams

(Revision + extra points)

Phase diagrams are also called Equilibrium Phase Diagrams.

Though not explicitly stated the word Equilibrium in this context usually means
Microstructural level equilibrium and NOT Global Equilibrium.
Microstructural level equilibrium implies that microstructures are allowed to
exist and the system is not in the global energy minimum state.
This statement also implies that:
Micro-constituents* can be included in phase diagrams
Certain phases (like cementite in the Fe-C system) maybe included in phase
diagrams, which are not strictly equilibrium phases (cementite will decompose to
graphite and ferrite given sufficient thermal activation and time)
Various defects are tolerated in the product obtained. These include defects
like dislocations, excess vacancies, internal interfaces (interphase boundaries,
grain boundaries) etc.
Often cooling lines/paths are overlaid on phase diagrams- strictly speaking this
is not allowed. When this is done, it is implied that the cooling rate is very slow
and the system is in ~equilibrium during the entire process.
(Sometimes, even fast cooling paths are also overlaid on phase diagrams!)
* will be defined later

The GIBBS PHASE RULE

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
Degrees of Freedom: A general definition
In response to a stimulus the ways in which the system can respond corresponds to the
degrees of freedom of the system

For a system in equilibrium

F=CP+2
or

The phase rule

FC+P=2

F Degrees of Freedom
C Number of Components
P Number of Phases

The Phase rule is best understood by considering examples from actual phase diagrams as
shown in some of the coming slides

Variables in a Phase Diagram

C No. of Components
P No. of Phases
F No. of degrees of Freedom
Variables in the system =
Composition variables + Thermodynamic variables
Composition of a phase specified by (C 1) variables

(e.g. If the composition is expressed in %ages then the total is 100% there is one equation
connecting the composition variables and we need to specify only (C1) composition variables)

No. of variables required to specify the composition of all Phases: P(C 1)

(as there are P phases and each phase needs the specification of (C1) variables)

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

(at constant Pressure (e.g. atmospheric pressure) the thermodynamic variable becomes 1)

Total no. of variables in the system = P(C 1) + 2

F < no. of variables F < P(C 1) + 2

The Gibbs Phase Rule

For a system in equilibrium the chemical potential of each species is same in all the
phases.
If , , , are phases, then: A() = A() = A().

Suppose there are 2 phases ( & phases) and 3 components (A,B,C) in each phase.
Then: A() = A(), B() = B(), C() = C() i.e there are 3 equations
For each component there are (P1) equations and for C components the total number of equations is C(P1)
In the above example the number of equations is 3(21)=3 equations.

F = (Total number of variables) (number of relations between variables)

= [P(C 1) + 2][C(P 1)] = C P + 2

In a single phase system F = no. of variables.

PF

F=CP+2

(for a system with fixed number of components as the number phases increases the degrees of freedom decreases)

It is worthwhile to clarify a few terms at this stage:

Components can go on to make a phase
(ofcourse one can have single component phases as well- e.g. BCC iron phase, ferromagnetic iron phase etc.)

Phases can go on to make a microconstituent

Microconstituents can go on to make a microstructure
(ofcourse phases can also directly go on to make a microstructure)

A way of understanding the Gibbs Phase Rule: F = C P + 2

The degrees of freedom can be thought of as the difference between what you (can) control
and what the system controls

C+2

Degrees of Freedom = What you can control

Can control the no. of
components added and P & T

What the system controls

System decided how many
phases to produce given the
conditions

Variation of the number of degrees of freedom with number of components and number of phases
Phase rule with pressure
fixed (at say 1 atm)

C=2
2 components

C=3
3 components

No. of
phases

Total variables
P(C 1) +2

Degrees of Freedom
C P +2

Degrees of Freedom
C P +1

Not possible

No. of
phases

Total variables
P(C 1) +2

Degrees of Freedom
C P +2

Degrees of Freedom
C P +1

10

3 phase coexistence is an
invariant point

The Gibbs phase rule and its geometrical cousin

There is an interesting connection between the Gibbs Phase Rule and the Euler
Rule for Convex Polyhedra.
The Eulers formula for convex polyhedra can be considered as the geometrically
equivalent Gibbs Phase rule. The diagram below brings out the analogous variables.
Gibbs Phase Rule

V0 V1 + V2 = 2

FC+P=2

or

VE+F=2

V0 = V Vertices
V1 = E Edges
V2 = F Faces
Vertices ~ degrees of Freedom

Faces ~ Phases
Edges ~ Components
For the cube
VE+F=2
8 12 + 6 = 2

Single component phase diagrams (Unary)

Let us start with the simplest system possible: the unary system wherein there is just one
component.
Though there are many possibilities even in unary phase diagrams (in terms of the axis and
phases) , we shall only consider a T-P unary phase diagram.
Let us consider the Fe unary phase diagram as an illustrative example.
Apart from the liquid and gaseous phases many solid phases are possible based on crystal
structure. (Diagram on next page).
Note that the units of x-axis are in GPa (i.e. high pressures are needed in the solid state and
liquid state to see any changes to stability regions of the phases).
The Gibbs phase rule here is: F = C P + 2. (2 is for T & P).
Note that how the phase fields of the open structure (BCC- one in the low T regime () and
one in the high T regime ()) diminish at higher pressures. In fact - phase field completely
vanishes at high pressures.
The variables in the phase diagram are: T & P (no composition variables here!).
Along the 2 phase co-existence lines the DOF (F) is 1 i.e. we can chose either T or P
and the other will be automatically fixed.
The 3 phase co-existence points are invariant points with F = 0. (Invariant point implies
they are fixed for a given system).

F=CP+2

Temperature (C)

Gas

Single phase regions

F=11+2=2
T and P can both be varied while still
being in the single phase region

Liquid
Two phase coexistence lines
F=12+2=1
we have only one independent variable
(we can chose one of the two variables (T
or P) and the other is automatically
fixed by the phase diagram)

(BCC)
1535
1410

(FCC)
(BCC)

(HCP)

Triple points:
3 phase coexistence
F=13+2=0
triple points are fixed points of a
phase diagram (we cannot chose T or P)

Pressure (GPa)
Note the P is in GPa
Very High pressures are required for things to happen in the solid state

The maximum number of phases which can

coexist in a unary P-T phase diagram is 3

Understanding aspects of the iron unary phase diagram

The degrees of freedom for regions, lines and points in the figure are marked in the diagram
shown before
The effect of P on the phase stability of various phases is discussed in the diagram below
It also becomes clear that when we say iron is BCC at RT, we mean at atmospheric pressure
(as evident from the diagram at higher pressures iron can become HCP)

Temperature (C)

Gas

Liquid

Increase P and gas will

liquefy on crossing phase
boundary

This line slopes upward as at constant T if we increase the P the

gas will liquefy as liquid has lower volume (similarly the reader
should draw horizontal lines to understand the effect of pressure
on the stability of various phases- and rationalize the same).
Phase fields of non-close packed structures
shrink under higher pressure

(BCC)

Phase fields of close packed structures expand

under higher pressure

(FCC)
(HCP)
(BCC)

These lines slope downward as: Under

higher pressure the phase with higher
packing fraction (lower volume) is
preferred

Pressure (GPa)
Usually (P = 1 atm) the high temperature phase is the
loose packed structure and the RT structure is close packed.
How come we find BCC phase at RT in iron?

Binary Phase Diagrams

Binary implies that there are two components.
Pressure changes often have little effect on the equilibrium of solid phases (unless
ofcourse we apply huge pressures).
Hence, binary phase diagrams are usually drawn at 1 atmosphere pressure.
The Gibbs phase rule is reduced to:
Variables are reduced to: F = C P + 1. (1 is for T).
T & Composition (these are the usual variables in Materials Phase Diagrams)
Phase rule for condensed phases

F=CP+1
For T

In the next page we consider the possible binary phase diagrams. These have been
classified based on:
Complete Solubility in both liquid & solid states
Complete Solubility in both liquid state, but limited solubility in the solid state
Limited Solubility in both liquid & solid states.

Overview of Possible Binary Phase diagrams

Liquid
Liquid State
State

Complete Solubility in both liquid &

solid states

Isomorphous

Solid
Solid State
State analogue
analogue

Solid state analogue of

Isomorphous

Isomorphous with ordering

Isomorphous with
phase separation

Complete Solubility in both liquid state,

but limited solubility in the solid state

Limited Solubility in both liquid & solid

states

Eutectic

Eutectoid

Peritectic

Peritectoid

Monotectic

Monotectoid

Syntectic

What are the variables/DOF in a binary phase diagram?

We have already seen that the reduced phase rule at 1Atm pressure is: F = C P + 1.
The one on RHS above is T.
The other two variables are:
Composition of the liquid (CL) and composition (CS) of the solid.
The compositions are defined with respect to one of the components (say B):
CLB, CSB

The Degrees of Freedom (DOF, F) are defined with respect to these variables.

System with complete solid & liquid solubility: ISOMORPHOUS SYSTEM

Let us start with an isomorphous system with complete liquid and solid solubility.
If we try to draw a straight line connecting the melting point of A and B (the two
components)- we note that the degree of freedom for any intermediate composition is 1
this line expands into a region (which is a two phase mixture of liquid and solid).
Pure components melt at a single temperature, while alloys in the isomorphous system
melt over a range of temperatures*. I.e. for a given composition solid and liquid will
coexist over a range of temperatures when heated.

M.P. of A

C=1
P=2
F=0

F=CP+1

melting points
are fixed!

M.P. of B

C=2
P=2
F=1

%B

* Assuming that the components do not decompose or sublime.

The two component region expands

with one degree of freedom i.e. we
can chose one variable say the T

Now let us map the variables and degrees of freedom in varions regions of the isomorphous phase diagram
F=CP+1
C=2
P = 1 (liquid)
F=2

Variables T, CLB 2
M.P. of A

T and Composition can

C=1
P=2
F=0

in the two phase region, if

we fix T (and hence exhaust
our DOF), the composition of
liquid and solid in equilibrium
are automatically fixed (i.e. we
have no choice over them).
Alternately we can use our
DOF to chose CL then T
and CS are automatically
fixed.

both be varied while still

being in the single phase
region

Variables
T, CLB, CSB 3

C=2
P=2
F=1
M.P. of B

Variables T, CSB 2

C=2
P=1
F=2
B

A
F=2P
For pure components at any T

F= 3 P
For alloys

%B

F=2P

Gibbs free energy vs composition plot at various temperatures: Isomorphous system

As we know at constant T and P the Gibbs free energy determines the stability of a phase. Hence, a
phase diagram can be constructed from G-composition (Gmixing-C) curves at various temperatures.
For an isomorphous system we need to chose 5 sample temperatures: (i) T1 > TA, (ii) T2=TA, (iii)
TA>T3>TB, (iv) T4=TB, (v) T5<TB.

G of L lower than for all

compositions and hence L is stable

G of L lower than for all

compositions except for pure A.

For compositions
between X1 and X2
the common tangent
construction gives
the free energy of
the L+ mixture

Isomorphous Phase Diagram: an example

A and B must satisfy Hume-Rothery rules for the formation of extended solid solution.
Examples of systems forming isomorphous systems: Cu-Ni, Ag-Au, Ge-Si, Al2O3-Cr2O3.
Note the liquidus and solidus lines in the figure.

T (C)

2200

Liquidus

L+S

2100
S
Solidus

2000

Note that the components

are compounds

Al2O3 10

30

50
%Cr2O3

70

90

Cr2O3

Schematics

ISOMORPHOUS PHASE DIG.

Points to be noted:
Pure components (A,B) melt at a single temperature. (General) Alloys melt over a range of
temperatures.
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 have to be followed.
In some systems (e.g. Au-Ni system) there might be phase separation in the solid state (i.e.
the complete solid solubility criterion may not be followed) these will be considered later
in this chapter as a variation of the isomorphous system (with complete solubility in the
solid and the liquid state).
Click here to know more about

HUME ROTHERY RULES

Both the liquid and solid contain the components A and B.

In Binary phase diagrams between two single phase regions there will be a two phase
region In the isomorphous diagram between the liquid and solid state there is the
(Liquid + Solid) state.
The Liquid + Solid state is NOT a semi-solid state it is a solid of fixed composition
and structure, in equilibrium with a liquid of fixed composition.
In the single phase region the composition of the alloy is the composition.
In the two phase region the composition of the two phases is different and is NOT the
nominal composition of the alloy (but, is given by the lever rule). Lever rule is considered next.

Tie line and Lever Rule

Given a temperature and composition- how do we find the fraction of the phases present along with the composition?

Say the composition C0 is cooled slowly (equilibrium)

At T0 there is L + S equilibrium
Solid (crystal) of composition C1 coexists with liquid of composition C2

We draw a horizontal line (called the Tie

Line) at the temperature of interest (say T0).
Tie line is XY.
Note that tie lines can be drawn only in the
two phase coexistence regions (fields). Though
they may be extended to mark the temperature.

To find the fractions of solid and liquid we

use the lever rule.

 We draw a horizontal line (called the Tie Line) at the temperature of interest (say T0).
The portion of the horizontal line in the two phase region is akin to a lever with the
fulcrum at the nominal composition (C0).
The opposite arms of the lever are proportional to the fraction of the solid and liquid
phases present (this is the lever rule).
At T
0

The fraction of liquid (fl) is (C0 C1)

The fraction of solid (fs) is (C2 C0)

Note: strictly speaking

cooling curves cannot be
overlaid on phase diagrams

f liquid

Cooling
Arm of the lever
proportional to
the liquid

Arm of the lever

proportional to
the solid

L+S

S
C1

C0

%B

C2

C 2 C0
C2 C1

Note that tie line is drawn within the two phase

region and is horizontal.

Fulcrum of the lever

f solid

L
Tie line

T0

C0 C1
C2 C1

Expanded version

At T0
The fraction of liquid (fl) is proportional to (C0 C1) AC
The fraction of solid (fs) is proportional to (C2 C0) CB

Arm of the lever

proportional to
the liquid

Arm of the lever

proportional to
the solid

C
T0

fliquid

B
f solid

Fulcrum of the lever

C1

Extended tie line

C0

C2

AC C0 C1

AB C2 C1
CB C2 C0

AB C2 C1

How does the fraction (or %) of solid and liquid change as we cool (in the two phase region)?
As we cool from T1 to T9 in the two phase region:
The first solid appears at T1 (effectively the fraction of solid at T1 is zero).
The fraction of solid increases according the solid line in the plot below and correspondingly the fraction of liquid decreases.
The last bit of liquid solidifies at T9.
The composition of the solid and liquid in equilibrium with it keeps on changing as we cool (as in upcoming slide).
The total percentage (L + S) is always 100%.

% of Solid or L iquid

100
80
60

Fraction of Liquid (%)

Fractionof Solid (%)

40
20
0
1

4
5
6
Temperature Label

Points to be noted
For a composition C0
At T0 Both the liquid and the solid phases contain both the components A and B
To reiterate: The state is NOT semi-solid but a mixture of a solid of a definite composition (C1) with a
liquid of definite composition (C2)
If the alloy is slowly cooled (maintaining ~equilibrium) then in the two phase region (liquid + solid
region) the composition of
the solid will move along the brown line and the composition of the liquid will move along the blue line.
The composition of the solid and liquid are changing as we cool!

Isomorphous Phase Diagrams

Any composition
melts above the
linearly
interpolated
melting point

Below T1 (820C) for some range of compositions the solid

solubility of Au in Ni (and vice-versa) is limited.

Note that
Ag & Au are so similar that the phase diagram
becomes a thin lens (i.e. any alloy of Au & Ag melts
over a small range of temperatures as if it were
nearly a pure metal!!).
Any composition melts above the linear interpolated
melting point.

Note here that there is solid solubility, but it is not complete at

low temperatures (below the peak of the 1 + 2 phase field
dome)
(we will have to say more about that soon)

T1

Funda Check

One phase or many phases? the concept of the phase field

We have noted that different crystal structures of the same component are different phases.
Different compositions of the same crystal structure differ in lattice parameter and
constitute different phases.
Sometimes in the region of stability of a phase (say ), different compositions are
referred to (casually) as -phase.
The region should be called a Phase Field and different compositions are actually different
phases.
The solid solution based on a component is often written in brackets. E.g. (Cu) marked in
the phase diagram implies a solid solution of Cu with another component (say Ag).

Funda Check

Is the lever rule right? (I.e. does it give the right phase fractions?)

Let A and B be the two components constituting the

binary phase diagram. Consider co-existing phases (with
composition C1) and (with composition C2) with a mean
composition C0. f denotes the fraction of a particular
phase. Let be the compositions expressed in terms of the
percentage of B.

Using lever rule: f

C2

C1

x1B

C0 x0B

C0 C1 x0 x1
C C0 x2 x0
, f 2

C2 C1 x2 x1
C2 C1 x2 x1

Amount of B in C0 (L) = Amount of B in + Amount of B in

x0 x1
x2 x0
x0 x2 x1 x2 x1 x2 x0 x1
x0 f x2 f x1 =
x0
x2
x1 =
x
x
x
x
x
x

2
1

2 1
2 1

x2B

Extensions of the simple isomorphous system: Congruently melting alloys

We have seen that a pure metal melts at a single temperature (Why?!!).
An alloy typically melts over a range of temperatures. However, there are special compositions which
can melt at a single temperature like a pure metal. One of these is the congruent melting compositionin a variation of the isomorphous phase diagram. Some systems show this type of behaviour.
Intermediate compounds also have this feature as we shall see later.
Elevation in MP

Case A

Variables T, CL

B,

CS 3
B

Depression in MP

Case B

C=2
P=2
F = 1?? (see below)

Congruently melting alloys just like a pure metal

Is the DOF 1? No: in requiring that CLB = CSB we have exhausted the degree of freedom. Hence T
is automatically fixed DOF is actually zero!

 These isomorphous phase diagrams with congruent melting compositions can be understood as two
simple isomorphous diagrams with C0 as one of the components:
i.e. A-C0 is one and C0-B is the other.

%C0

Extensions of the simple isomorphous system: What does this imply w.r.t the solid state phases?
Elevation in the MP means that the solid state is more stable (crudely speaking the
ordered state is more stable) ordering reaction is seen at low T.
Depression in MP means the liquid state (disordered) is more stable phase separation
is seen at low T. (Phase separation can be thought of as the opposite of ordering. Ordering (compound formation) occurs for
ve values of Hmix, while phase separation is favoured by +ve values of Hmix.

AB bonds stronger than AA and BB bonds

AA and BB bonds stronger than AB bonds

Solid stabilized Ordered solid formation

Liquid stabilized Phase separation in the solid

state

Case B

E.g. Au-Ni

Case A

Examples of isomorphous systems with phase

separation and compound formation

Au-Ni: model system to

understand phase separation

Au-Pt system with phase

separation at low temperatures

Au-Pd system
with 3
compounds

Phase separation in a AlCrFeNi alloy (with composition

Al28.5Cr27.3Fe24.9Ni19.3) into BCC + B2 phases

Ti-Zr: With solid

state analogue of
isomorphous phase
diagram

Congruent transformations
We have seen two congruent transformations. The list is as below.
Melting point minimum
Melting point maximum
Order disorder transformation
Formation of an intermediate phase

Eutectic Phase Diagram

Very few systems exhibit an isomorphous phase diagram (usually the solid solubility of
one component in another is limited).
Often the solid solubility is severely limited- though the solid solubility is never zero (due
to entropic reasons).
In a simple eutectic system (binary), there is one composition at which the liquid freezes to
two solids at a single temperature. This is in some sense similar to a pure solid which
freezes at a single temperature (unlike a pure substance the freezing produces a two solid
phases- both of which contain both the components).
The term EUTECTIC means Easy Melting The alloy of eutectic composition freezes at
a lower temperature than the melting points of the constituent components.
This has important implications e.g. the Pb-Sn* eutectic alloy melts at 183C, which is
lower than the melting points of both Pb (327C) and Sn (232C) can be used for
soldering purposes (as we want to input least amount of heat to solder two materials).
In the next page we consider the Pb-Sn eutectic phase diagram.
As noted before the components need not be only elements. E.g. in the A-Cu system a
eutectic reaction is seen between (Solid solution of Cu in Al) and (Al2Cu- a
compound).
* Actually - eutectic alloy (or (Pb)-(Sn) eutectic alloy)

Liquidus

T (C)

327C

300
200

Eutectic reaction
L+

+L
D

Teutectic = TE

TE

232C

Solidus
E

100

183C

L+

+
Solvus
18%

Pb 10

30
CE

Eutectic reaction (the proper

way of writing the reaction)

50
%Sn

70
Ceutectic = CE

Cool

62% Sn

183 C

CE

97%

62%

90

Sn

CE

18% Sn 97% Sn

CE

CE

Note that Pb is CCP, while Sn at RT is Tetragonal (tI4, I41amd) therefore complete solid solubility across compositions
is ruled out!!

Note the following points:

and are terminal solid solutions (usually terminal solid solutions are given symbols ( and )); i.e. is a solid solution of
B (Sn) in A (Pb).
(In some systems the terminal solid solubility may be very limited: e.g. the Bi-Cd system).
has the same crystal structure as that of A (Pb in the example below) and has the same crystal
structure as B (Sn in the example below).
Typically, in eutectic systems the solid solubility increases with temperature till the eutectic point (i.e.
we have a sloping solvus line). In many situations the solubility of component B in A (and viceversa) may be very small.
The Liquidus, Solidus and Solvus lines are as marked in the figure below.

Liquidus

327C

300

Eutectic reaction
L+

232C

T (C)

Solidus

+L

200
100

183C

L+

+
Solvus
62%

18%

Pb 10

30

50
%Sn

97%

70

90

Sn

 At the eutectic point E (fig. below) 3 phases co-exist: L, &

The number of components in a binary phase diagram is 2 the number of degrees of freedom F = 0.
This implies that the Eutectic point is an Invariant Point for a given system it occurs at a fixed
composition and temperature.
For a binary system the line DF is a horizontal line.
Any composition lying between D and F will show eutectic solidification at least in part (for
composition E the whole liquid will solidify by the eutectic reaction as shown later).
The percentage of and produced by eutectic solidification at E is found by considering DF as a
E
lever with fulcrum at E.
D
F

T (C)

300
200

+L

Eutectic reaction
L+

L+

C=2
P=3
F=0

100

Increasing solubility of B in A with T

A 10

30

%B

50

70

90

Further points:
Extension of the boundary line between a single phase region and adjacent two-phase
region, should lie in the two phase region (red dashed lines as in figure below).
The eutectic reaction is a phase reaction and not a chemical reaction.

Examples of Eutectic microstructures As pointed out before microstructural information is often overlaid on phase
diagrams. These represent microstructures which evolve on slow cooling.
Al-Al2Cu lamellar eutectic

Pb-Sn lamellar eutectic

Sn

2 m

Though we label the microstructure

as Pb-Sn lamellar eutectic it is
actually a - eutectic.

Composition plot across lamellae

Pb

(Al)

Al2Cu
(note that one of the components is a compound!)

Gibbs free energy vs composition plot at various temperatures: Eutectic system

Isomorphous to Eutectic

AA and BB bonds stronger than AB bonds

Liquid stabilized

A eutectic system can be visualized as arising from an isomorphous system with depression in
MP, as below.
L+

L+

L
L+

1
A

L + 1

2
1 + 2

1 + 2
B

1 + 2

L + 2

2
B

Solidification of Eutectic and Off-eutectic compositions

To reiterate an important point: phase diagrams do not contain microstructural information (i.e. they cannot tell you
what is the microstructure produced by cooling). Often microstructural information is overlaid on phase diagrams for
convenience. Hence, strictly cooling is not in the domain of phase diagrams- but we can overlay such information
keeping in view the assumptions involved.
For the following explanations refer to the Pb-Sn eutectic diagram and the diagram considered next. Solidification of
three range(s) of compositions need to be understood: (i) to the left of CE, (ii) between CE and CE and (iii) CE.
(iii) On cooling an eutectic composition (CE or C3E in the next page), at the eutectic temperature (TE), both the
constituents (say & ) of the eutectic reaction will simultaneously form from the liquid. In practice (based on
other factors) one of the constituents may form before the other. The entire solidification takes place at a single
temperature- TE.
On slow cooling, the microstructure produced by the eutectic reaction could be lamellar, Chinese script (like), etc.
This distribution of phases (say lamellar) is called a microconstituent.

(i) On cooling a composition to the left of CE

The phase will start solidifying from the liquid and between 1a and 1b there will be a mixture of and L.
Between 1b and 1c there will be only phase.
Below 1c (as the solubility of B in reduces) phase will precipitate out of (and we will have a mixture of +
).
(ii) On cooling a composition between CE and CE
Between 2a and 2b, the phase will start solidifying from the liquid and we will have a mixture of L + (this is
known as the proeutectic- implying that it is pre-eutectic ). On cooling towards TE the composition of the
liquid travels along the 2a-E curve.
On reaching TE (i.e. point 2b) the liquid remaining after the solidification of proeutectic- will solidify as a eutectic
mixture (according to the eutectic reaction).
For a composition between CE and CE the situation is similar to case (ii) above except that we will get proeutectic-
instead of proeutectic-. And for a composition beyond CE the situation is similar to case (i) above (except that we
will get instead of ).

The important point to note that even for off-eutectic compositions between CE and CE
part of the liquid solidifies by the eutectic reaction

C2

C1

C4
The solidification
sequence of C4 will be
similar to C2 except
that the proeutectic
phase will be

C3

Special eutectic diagrams

Eutectic system without terminal solid
solubility: Bi-Cd
Technically it is incorrect to draw
eutectic phase diagrams with zero solid
solubility.
This would imply that a pure component
(say Bi in the example considered) melts
over a range of temperatures (from P to
271.4C) which is wrong.
Also, let us consider an example of a
point P (which lies on the eutectic
line PQ). At P the phase rule becomes:
F = CP+1 = 13+1 = 1 !!!
Note that the above is an alternate way
of arriving at the obvious contradiction
that at P on one hand we are saying
that there is a pure component and on the
other hand we are considering a three
phase equilibrium (which can happen
only for Bi-Cd alloys).

Technically this is incorrect:

there has to be some terminal
solid solubility

Correct version of the diagram with

some terminal solid solubility.

Special eutectic diagrams

Eutectic system with terminal solid

solubility on one side: Ag-Ge

With terminal
solid solubility
on both sides

Solved
Example

During the solidification of a off eutectic (Pb-Sn) composition (C0), 90 vol.% of the solid
consisted of the eutectic mixture and 10vol.% of the proeutectic phase. What is the value
of C0?

Density data for and : Let us start with some observations: Pb is heavier than Sn and hence the density of is more than that of .
Since the proeutectic phase is the composition is hyperpeutectic (towards the Sn side). The volume
= 10300 Kg/m3
fractions
(in %) are usually calculated by taking the area fractions by doing metallography (microstructure) and
= 7300 Kg/m3
then converting it into volume fractions (usually volume fraction is assumed to be equal to area fractions).

Eutectic Data:
183C
62 wt.% Sn

Cool

62% Sn

183 C

18% Sn 97% Sn

Using the fact that there is 10 vol% phase:

Wt. fraction of proeutectic =

Wt. of
0.1 7300

Wt. of the alloy (0.1 7300) (0.9 eutectic mix )

Kg
97 62
62 18
Where, eutectic mix 10300
7300
4563 4066 8629 3
m
97 18
97 18

Substituting in equation (1): Wt. fraction of proeutectic = 0.086

Using lever rule: 0.086

C0 0.62
, C0 = 0.650 = 65.0%
0.97 0.62

(1)

Peritectic Phase Diagram

Like the eutectic system, the peritectic reaction is found in systems with complete liquid
solubility but limited solid solubility.
In the peritectic reaction the liquid (L) reacts with one solid () to produce another solid ().
L + .
Since the solid forms at the interface between the L and the , further reaction is
dependent on solid state diffusion. Needless to say this becomes the rate limiting step and
hence it is difficult to equilibrate Peritectic reactions (as compared to say eutectic
reactions). Figure below.
In some peritectic reactions (e.g. the Pt-Ag system- next page), the (pure) phase is not
stable below the peritectic temperature (TP = 1186C for Pt-Ag system) and splits into a
mixture of ( + ) just below TP.

Pt-Ag Peritectic system

Melting points of the

components vastly different

Peritectic reaction
L+

TP

Note that below TP pure is not

stable and splits into ( + )

CP
Formal way of writing
the peritectic reaction

CP
L

66.3% Ag 10.5% Ag

L
P

CP

CPL
Cool

1186 C

42.4% Ag

CP

Isomorphous to Peritectic

L+

B
L

L + 1

L + 1 (2)

L+

1 + 2

1 + 2

1
B

1 + 2

2
B

Examples: Some important phase diagrams

Some phase diagrams are technologically important and via these further aspects of the
utility of phase diagrams can be learnt.
The Fe-C (or more precisely the Fe- Fe3C) diagram is an important one. Cementite is a
metastable phase and strictly speaking should not be included in a phase diagram. But the
decomposition rate of cementite is small and hence can be thought of as stable enough to
be included in a phase diagram. Hence, we typically consider the Fe- Fe3C part of the Fe-C
phase diagram.
Another technologically (and from a perspective of physical Metallurgy) important phase
diagram is the Al-Cu system (especially the Al rich end of the phase diagram).

The Fe-Cementite phase diagram

A portion of the Fe-C diagram- the part from pure Fe to 6.67 wt.% carbon (corresponding
to cementite, Fe3C)- is technologically very relevant.
Cementite is not a equilibrium phase and would tend to decompose into Fe and graphite.
This reaction is sluggish and for practical purpose (at the microstructural level) cementite
can be considered to be part of the phase diagram. Cementite forms as it nucleates readily
as compared to graphite.
Compositions up to 1.5%C are called steels and beyond 2%C are called cast irons. In reality
the classification should be based on castability and not just on carbon content.

Heat treatments can be done to alter the properties of the steel by modifying the
microstructure we will learn about this in the chapter on Phase Transformations. This
may involve production of metstable phases like martensite (not found in the equilibrium
phase diagram).
As before we will use slow cooling curves to see the microstructures produced. The part
of the phase diagram of interest is: (i) with less than ~2% C and (ii) less that ~1100C.
Phases of interest are listed in the table below.
Phase

Structure

Austenite ()

FCC (CCP)

Ferrite ()

BCC

Cementite (Fe3C)

Orthorhombic

Crystal structure of Cementite

Fe-Cementite diagram
Three reactions are seen in the Fe rich side: (i) Peritectic, (ii) Eutectic & (iii) Eutectoid.
Peritectic
L+

Eutectic
L + Fe3C

1493C

Note: we can also draw the

true Fe-C diagram (not
shown here). Sometime one
of these diagrams is shown
in dashed lines and overlaid
on a single diagram.

L+

Eutectoid
+ Fe3C

Acm
A3

1147C

2.06
+ Fe3C

T
Fe
RT~0.008

723C

A1

0.025

For Pure Fe
1538C

(BCC)
1394C

(FCC)

Of the three reactions the eutectoid reaction is

technologically important

0.8
0.16

%C

4.3

912C

(BCC)

6.7

Fe3C

The portion of the phase diagram, which is technologically relevant is shown in the figure below

Ferrite

Ferrite

C1
Austenite

Pearlite

Pearlite a micro-constituent
(Not a phase)

C1 C2C3

Grain boundary

C2

C3

Similar* to C1 but
the proeutectoid
phase is Cementite

*Similar in solidification sequence not in properties

Fe3C

Pro-eutectoid
Cementite along
prior Austenite
grain boundaries

 Pearlite is a micro-constituent with alternating lamellae of cementite and ferrite.

SEM micrograph of pearlite in

Eutectoid composition (0.8%C)
steel

Pearlite
Pro-eutectoid
Cementite along
prior Austenite
grain boundaries

SEM micrograph of pearlite in

Hyper-eutectoid composition
(1.0%C) steel

Structure of Etched Pearlite in AFM

Composition of EN9 alloy in wt.%: C-0.5, Si-0.25, Mn-0.70, S-0.05, P-0.05

Processing: Hot rolled steel sample annealed at 700C and followed by slow cooling
Hardness: 180-230 BHN (Avg. = 205 BHN)
Images taken on Solver Pro NT-MDT- semi contact mode.

Images courtesy: Prof. Sandeep Sangal and K. Chandra Sekhar (MSE, IITK).

Funda Check
Components need not be only elements- they can be compounds like Al2O3, Cr2O3.
Phase diagrams usually do not correspond to the global energy minimum- hence often
microstructures are tolerated in phase diagrams.
Phase diagrams give information on stable phases expected for a given set of
thermodynamic parameters (like T, P). E.g. for a given composition, T and P the phase
diagram will indicate the stable phase(s) (and their fractions).
Phase diagrams do not contain microstructural information- they are often overlaid on
phase diagrams for convenience.
Metastable phases like cementite are often included in phase diagrams. This is to extend
the practical utility of phase diagrams.
Strictly speaking cooling curves (curves where T changes) should not be overlaid on
phase diagrams. (Again this is done to extend the practical utility of phase diagrams assuming that the cooling is slow).

Solved
Example

Two separate alloys are cooled from the phase field: (i) one hyper-eutectoid and other
(ii) hypoeutectoid. Assuming that in both cases the pro-eutectoid phase forms along the
grain boundaries and its phase fraction is 6%, determine the carbon composition of the two
alloys.

Given: Case-1: 6% ferrite (, proeutectoid phase) along grain boundaries (GB),

At 723C

Case-1: referring the Fe-C diagram 0.06

0.8 C1
, C1 = 0.75% C
0.8 0.025

Case-2: referring the Fe-C diagram 0.06

C2 0.8
, C2 = 1.15% C
6.67 0.8

Case-2: 6% cementite (Fe3C, proeutectoid phase) along GB.

+ Fe3C

723C

0.025
94%

6%

C2

Fe
RT~0.008

C1

0.8

%C

End

Solved
Example
Data for Cu:
Hf (Cu vacancy) = 120 103 J/mole
R (Gas constant) = 8.314 J/mole/K

F=CP+1
Variables T, CLB 2

M.P. of A

C=2
P=2
F=1

C=1
P=2
F=0

C=2
P=1
F=2

Variables T, CLB, CSB 3

Say T1 is chosen
The compositions CLB & CSB are automatically chosen by the system

M.P. of B
Variables T, CSB 2

C=2
P=1
F=2

A
2P

3P

%B

2P

Cooling
Hypereutectic
composition

300

200

Liquid (melt)

+L

L+

Proeutectic

100
+
Pb 10

30

50

70

90 Sn

Grain boundary

Eutectic
Mixture of
+

Cooling

C1

C2

C3
+ Fe3C

+ Fe3C

Fe

Eutectoid
+ Fe3C
0.02

0.8
%C

1700

L
L+

1500
T (C)

Peritectic reaction
L+

1300

Melting points of
the components
vastly different

1100

900

Ag 10

30

50
%Pt

70

90

Pt