PHASE DIAGRAMS

Phase Rule
Types of Phase diagrams
Lever Rule
Alloy Phase Equilibria
A. Prince
Elsevier Publishing Company, Amsterdam (1966)
Advanced Reading
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.
Phase Diagrams
* 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-Cooling-
Transformation (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)
Atom Structure
Crystal
Electro-
magnetic
Microstructure Component
Thermo-mechanical
Treatments
Phases Defects +
Casting
Metal Forming
Welding
Powder Processing
Machining
Vacancies
Dislocations
Twins
Stacking Faults
Grain Boundaries
Voids
Cracks
+ Residual Stress
Processing determines shape and microstructure of a component
& their distributions
Since terms like Phase and Microstructure are key to understanding phase diagrams, let us
have a re-look at the figure we considered before
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 H
2
O (compound)
Al
2
O
3
Cr
2
O
3
system : Components Al
2
O
3
, Cr
2
O
3

Let us start with some basic definitions:
This is important to note that components need not be just elements!!
Note that components
need not be only
elements
Phase
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 H
2
O
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
This is the typical textbook definition which one would see!!
What kinds of Phases exist?
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,
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.
Microstructure
Structures requiring magnifications in the region of 100 to 1000 times
OR
The distribution of phases and defects in a material
Grain
The single crystalline part of polycrystalline metal separated by similar entities by a
grain boundary
Phase Transformation is the change of one phase into another.
E.g.: Water Ice
o- Fe (BCC) - Fe (FCC)
- Fe (FCC) o- Fe (ferrite) + Cementite (this involves change in composition)
Ferromagnetic phase Paramagnetic phase (based on a property)
Phase transformation
Again this is a typical textbook definition which has been included for!!
An alternate definition based on magnification
(Phases + defects + residual stress) & their distributions
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
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!)
Important points about phase diagrams (Revision + extra points)
* will be defined later
The GIBBS PHASE RULE
F = C P + 2 For a system in equilibrium
F C + P = 2
or
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
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
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 phase rule
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
i.e. C P + 2 < P(C 1) + 2
In a single phase system F = no. of variables
P F (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)
Degrees of Freedom = What you can control What the system controls
F = C + 2 P
Can control the no. of
components added
and P & T
System decided how
many phases to
produce given the
conditions
A way of understanding the Gibbs Phase Rule:
The degrees of freedom can be thought of as the difference between what you (can) control
and what the system controls
No. of phases
Total variables
P(C 1) +2
Degrees of Freedom
C P +2
1 3 3
2 4 2
3 5 1
4 6 0
C = 2
No. of phases
Total variables
P(C 1) +2
Degrees of Freedom
C P +2
1 4 4
2 6 3
3 8 2
4 10 1
C = 3
3 components
2 components
Variation of the number of degrees of freedom with number of components and number of phases
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.
V
0
V
1
+ V
2
= 2 V E + F = 2
or
V
0
= V Vertices
V
1
= E Edges
V
2
= F Faces
Edges ~ Components
Vertices ~ degrees of Freedom
Faces ~ Phases
F C + P = 2 Gibbs Phase Rule
8 12 + 6 = 2
For the cube
V E + F = 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 (o) and
one in the high T regime(o)) diminish at higher pressures. In fact o- phase field completely
vanishes even below 4 GPa pressure.
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).
1535
1410
o (BCC)
c (HCP)
(FCC)
o (BCC)
Liquid
Gas
Pressure (GPa)
T
e
m
p
e
r
a
t
u
r
e

(

C
)

Triple points:
3 phase coexistence
F = 1 3 + 2 = 0
triple points are fixed points of a
phase diagram (we cannot chose T or P)
Two phase coexistence lines
F = 1 2 + 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)
Single phase regions
F = 1 1 + 2 = 2
T and P can both be varied while still
being in the single phase region
F = C P + 2
The maximum number of phases which can
coexist in a unary P-T phase diagram is 3 Note the P is in GPa
Very High pressures are required for things to happen in the solid state
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)
o (BCC)
c (HCP)
(FCC)
o (BCC)
Liquid
Gas
Pressure (GPa)
T
e
m
p
e
r
a
t
u
r
e

(

C
)

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).
These lines slope downward as: Under
higher pressure the phase with higher
packing fraction (lower volume) is
preferred
Increase P and gas will
liquefy on crossing phase
boundary
Phase fields of non-close packed structures
shrink under higher pressure
Phase fields of close packed structures expand
under higher pressure
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)
F = C P + 1
Phase rule for condensed phases
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.
Complete Solubility in both liquid state,
but limited solubility in the solid state
Overview of Possible Binary Phase diagrams
Isomorphous
Isomorphous with phase separation
Isomorphous with ordering
Complete Solubility in both liquid &
solid states
Limited Solubility in both liquid & solid
states
Eutectic
Peritectic
Liquid State Solid State analogue
Eutectoid
Peritectictoid
Monotectic
Syntectic
Monotectoid
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 (C
L
) and composition (C
S
) of the solid.
The compositions are defined with respect to one of the components (say B):
C
L
B
, C
S
B
The Degrees of Freedom (DOF, F) are defined with respect to these variables.
What are the variables/DOF in a binary phase diagram?
A B
System with complete solid & liquid solubility: ISOMORPHOUS SYSTEM
%B
T

M.P. of B
M.P. of A
C = 1
P = 2
F = 0
C = 2
P = 2
F = 1
A B
The two component region expands
with one degree of freedom i.e. we
can chose one variable say the T
F = C P + 1
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.
* Assuming that the components do not decompose or sublime.
melting points
are fixed!
A
B
%B
T

M.P. of B
M.P. of A
C = 1
P = 2
F = 0
C = 2
P = 1
F = 2
C = 2
P = 1 (liquid)
F = 2
Variables T, C
S
B
2
Variables T, C
L
B
2
Variables
T, C
L
B
, C
S
B
3
F = 2 P
F= 3 P
C = 2
P = 2
F = 1
F = 2 P
F = C P + 1
Now let us map the variables and degrees of freedom in varions regions of the isomorphous phase diagram
T and Composition can
both be varied while still
being in the single phase
region
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 C
L
then T
and C
S
are automatically fixed.
For pure components at any T
For alloys
Al
2
O
3
Cr
2
O
3

%Cr
2
O
3

T

(

C
)

2000
2100
2200
10 30
50 70 90
L
L + S
Solidus
Liquidus
S
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, Al
2
O
3
-Cr
2
O
3
.
Note the liquidus and solidus lines in the figure.
Schematics
Note that the components
are compounds
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).
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.
HUME ROTHERY RULES Click here to know more about
Say the composition C
0
is cooled slowly (equilibrium)
At T
0
there is L + S equilibrium
Solid (crystal) of composition C
1
coexists with liquid of composition C
2

Tie line and Lever Rule
Given a temperature and composition- how do we find the fraction of the phases present along with the composition?
We draw a horizontal line (called the Tie
Line) at the temperature of interest (say T
0
).
To find the fractions of solid and liquid we
use the lever rule.
%B
A B
T

L
L + S
S
C
0
C
1
C
2

T
0

Cooling
Fulcrum of the lever
Arm of the lever
proportional to
the solid
Arm of the lever
proportional to
the liquid
Note: strictly speaking cooling
curves cannot be overlaid on
phase diagrams
Tie line
1 2
1 0
C C
C C
f
liquid

=
At T
0

The fraction of liquid (f
l
) is o (C
0
C
1
)
The fraction of solid (f
s
) is o (C
2
C
0
)
1 2
0 2
C C
C C
f
solid

=
We draw a horizontal line (called the Tie Line) at the temperature of interest (say T
0
).
The portion of the horizontal line in the two phase region is akin to a lever with the
fulcrum at the nominal composition (C
0
).
The opposite arms of the lever are proportional to the fraction of the solid and liquid
phases present (this is the lever rule).
Expanded version
Tie line
C
0
C
1
C
2

T
0

Fulcrum of the lever
Arm of the lever
proportional to
the solid
Arm of the lever
proportional to
the liquid
0 1
2 1
liquid
C C
f
AB C
AC
C

= =

At T
0

The fraction of liquid (f
l
) is proportional to (C
0
C
1
) AC
The fraction of solid (f
s
) is proportional to (C
2
C
0
) CB
2 0
2 1
solid
C C
f
AB
C
C
B
C

= =

B A
C
0
20
40
60
80
100
1 2 3 4 5 6 7 8 9
Temperature Label
%


o
f


S
o
l
i
d

o
r

L
i
q
u
i
d
Fraction of Liquid (%)
Fractionof Solid (%)
How does the fraction (or %) of solid and liquid change as we cool (in the two phase region)?
As we cool from T
1
to T
9
in the two phase region:
The first solid appears at T
1
(effectively the fraction of solid at T
1
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 T
9

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%.
For a composition C
0

At T
0
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 (C
1
) with a
liquid of definite composition (C
2
)
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 is changing as we cool!
Points to be noted
%B
A B
T

Tie line
L
L + S
S
C
0
C
1
C
2
T
0
Cooling
%B
A B
T

Tie line
L
L + S
S
C
0
C
1
C
2
T
0
Cooling
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 o), different compositions are
referred to (casually) as o-phase.
The region should be called a Phase Field and different compositions are actually different
phases.
Solved
Example
Data for Cu:
AH
f
(Cu vacancy) = 120 10
3
J/mole
R (Gas constant) = 8.314 J/mole/K
A B
A B
Extensions of the simple isomorphous system: Congruently melting alloys
Congruently melting alloys- just like a pure metal
But in requiring that C
L
B
= C
S
B
we have exhausted the degree of freedom. Hence T is
automatically fixed DOF is actually zero!
Variables T, C
L
B
, C
S
B
3
C = 2
P = 2
F = 1?? (see below)
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 composition- in a variation of the isomorphous phase diagram.
- Intermediate compounds also have this feature as we shall see later.
Elevation in MP
Depression in MP
Case A
Case B
AA and BB bonds stronger than AB bonds
Liquid stabilized Phase separation in the solid
state
AB bonds stronger than AA and BB bonds
Solid stabilized Ordered solid formation
o
1
& o
2
are different only in lattice parameter
A B
L
o
L + o
o
1

o
2

o
1
+ o
2
E
.
g
.

A
u
-
N
i

A B
L
o
L + o
o + o

o
Ordered solid
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.
Case A
Case B
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
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 o (Solid solution of Cu in Al) and u (Al
2
Cu- a
compound).
Eutectic Phase Diagram
Pb Sn
%Sn
T

(

C
)

100
200
300
10 30
50 70 90
L
o
o + |
|
L + |
o + L
Liquidus
Solvus
Solidus
18%
62%
97%
183C
232C
327C
183
62% 18% 97%
Cool
C
L
Sn Sn Sn
o |

+
Eutectic reaction (the proper way
of writing the reaction)
Eutectic reaction
L o + |
C
eutectic
= C
E

T
eutectic
= T
E

E
C
o
E
C
|
E
C
o
E
C
|
E
C
E
F D
E
T
Note the following points:
o and | are terminal solid solutions; i.e. o is a solid solution of B (Sn) in A (Pb).
(In some systems the terminal solid solubility may be very limited: e,g.***).
o 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 vice-
versa) may be very small.
The Liquidus, Solidus and Solvus lines are as marked in the figure below.
Pb Sn
%Sn
T

(

C
)

100
200
300
10 30
50 70 90
L
o
o + |
|
L + |
o + L
Liquidus
Solvus
Solidus
18%
62% 97%
183C
232C
327C
Eutectic reaction
L o + |
A B
%B
T

(

C
)

100
200
300
10 30
50 70 90
L
o
o + |
|
L + |
o + L
Eutectic reaction
L o + |
Increasing solubility of B in A with T
C = 2
P = 3
F = 0
At the eutectic point E (fig. below) 3 phases co-exist: L, o & |
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 show eutectic solidification- as shown later).
The percentage of o and | produced by eutectic solidification at E is found by considering DF as a
lever with fulcrum at E.
E
F
D
E
F
D
A B
L
L + o
o
A B
L
o
L + o
o
1
o
2

o
1
+ o
2
A
B
L
o
1
o
2

L + o
o
1
+ o
2
A B
L
o
1

o
2

L + o
1

o
1
+ o
2
L + o
2

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.
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.
- On cooling an eutectic composition (C
E
), at the eutectic temperature (T
E
), both the constituents (say o & |) 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- T
E
.
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.
- On cooling a off-eutectic composition
Solidification of Eutectic and Off-eutectic compositions
C
1

C
2

C
3
C
4

The solidification
sequence of C
4
will be
similar to C
2
except
that the proeutectic
phase will be |
Cooling
Pb Sn
100
200
300
10 30
50 70 90
L
o
o + |
|
L + |
o + L
Hypereutectic
composition
|
Proeutectic
|
o + |
Eutectic
Mixture of
o
|
Grain boundary
Liquid (melt)
T

(

C
)

900
1300
1500
Ag Pt
%Pt
10 30
50 70 90
L
o
o + |
|
L + |
Peritectic Phase Diagram
1100
1700
Melting points of
the components
vastly different
Peritectic reaction
L + | o
Isomorphous to Peritectic
A B
L
o
L + o
A B
L
L + o
1
(o
2)

o
1
o
2

o
1
+ o
2
A B
L
L + o
1

o
1

o
2

o
1
+ o
2
A B
L
o
L + o
o
1
o
2

o
1
+ o
2
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- Fe
3
C) 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.

Examples: Some important phase diagrams
A portion of the Fe-C diagram- the part from pure Fe to 6.67 wt.% carbon (corresponding
to cementite)- 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.
The composition upto *% C are called steels and beyond * are called cast irons.
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 Fe-Cementite phase diagram
Phase Structure
Austenite () FCC (CCP)
Ferrite (o) BCC
Cementite (Fe
3
C) Orthorhombic
Crystal structure of Cementite
%C
T

Fe
Fe
3
C
6.7
4.3
0.8
0.16
2.06
Peritectic
L + o
Eutectic
L + Fe
3
C
Eutectoid
o + Fe
3
C
L
o
L +

+ Fe
3
C
o
1493C
1147C
723C
Fe-Cementite diagram
0.025
RT~0.008
%C
T

0.8
0.02
Eutectoid
o + Fe
3
C
o

+ Fe
3
C
o+
o + Fe
3
C
Fe
Cooling
C
1
C
2

%C
T

0.8
0.02
Eutectoid
o + Fe
3
C
o

+ Fe
3
C
o+
o + Fe
3
C
Fe
C
3

C
1
C
2
C
3

C
1

C
2

C
3

Fe
3
C
o
Grain boundary
Pearlite a microconstituent (Not a phase)
SEM micrograph of pearlite
Funda Check
Q & A
Components need not be only elements- they can be compounds like Al
2
O
3
, Cr
2
O
3
.
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.
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.
Structure of Etched Pearlite in AFM
Images courtesy: Prof. Sandeep Sangal and K. Chandra Sekhar (MSE, IITK).
A
B
%B
T

M.P. of B
M.P. of A
C = 1
P = 2
F = 0
C = 2
P = 1
F = 2
C = 2
P = 1
F = 2
Variables T, C
S
B
2
Variables T, C
L
B
2
Variables T, C
L
B
, C
S
B
3
2 P
3 P
C = 2
P = 2
F = 1
2 P
F = C P + 1
Say T
1
is chosen
The compositions C
L
B
& C
S
B
are automatically chosen by the system