Equilibrium diagrams

Phase diagrams are the diagrams which indicate the phases

existing in the system at any temperature and composition
Plotting is done by using following methods:
Thermal analysis
Metallography
Dialometry
X-ray diffraction
Magnetic measurement
Thermodynamic data analysis
Electrical resistivity
State: It refers to the present condition of a system.
Components: These are the elements present in the
system
System: A substance or group of substances that
are unaffected by surroundings is called a system
(or)
A part of universe under study .
Systems classification:
-unary system
-binary system
-ternary system
Variable: A particular phase exists under various
conditions of temp, pressure and concentration.

Importance of phase diagrams
What phases are in equilibrium for selected alloy
composition and at a desired temperature
To study the solidification of metals and alloys
To determine the chemical composition of each
phase
To calculate the quantity of each phase that is
present
Structure changes because of heat treatment
Gibbs Phase Rule
Under equilibrium condition the following rule must be
satisfied,
P + F = C + 2
where,
P = Number of phases existing in system under
consideration
F = Degree of freedom i.e., number of variables that
can be changed independently without changing the
number of phases existing in the system
C = Number of components in the system
2 represents two of the variables

Types of cooling curves
For pure metals
For binary solid solution alloys
For binary eutectic alloys
For off-eutectic binary alloys
Cooling curve for pure metal
Cooling curve for binary solid
solution alloy
Cooling curve for binary eutectic
alloys
Cooling curve for binary off-eutectic
alloys
Polymorphism (Allotropy)
Variation in temperature and pressure,
result in change in crystal structure. Such
change in crystal structure is called
polymorphism
Materials of same composition and of
different crystal structures are called
polymorphs.
Classification of Polymorphic
transformations
1. Enantiotropy: These are mutually
transformable reversibly at some temp
called transition temp.
Ex: Fe, Zr, Ti..,.
2. Monotropy: These forms are irreversible
in solid state.
Ex: Phosphorous, alumina..,.
Plotting of equilibrium diagrams
1. Prepare large number of alloys of varying
compositions (say 10%)




(1,11 are pure metals and 2-10 are alloys)

%Cu
100 90 80 70 60 50 40 30 20 10 0
%Ni 0 10 20 30 40 50 60 70 80 90 100
M.
No.
1 2 3 4 5 6 7 8 9 10 11
2. Plot cooling curves of the above materials
3. Note down the liquidus and solidus
temperatures of these materials
4. Transfer these temperatures to a temp Vs
composition graph
5. Draw smooth curves through the L
1
to L
11
and S
1
to S
11
6. And the resulting loop type of curve is
called as the equilibrium diagram.
Plotting of equilibrium diagrams
Lever rule
It is used for finding out the amounts of phases existing in a binary
system for a given alloy at any temperature under consideration
Amount of B = Amount of B + Amount of B
in the alloy in the solid in the liquid
Z = S x D + L x C
= SD + (1-S)C
i.e. Z-C = S(D-C)
Therefore, S = Z-C = F-C
D-C D-C
= arm length CF
arm length CD
= opposite length of arm
total length of arm

Amount of solid = arm CF/arm CD
Amount of liquid arm FD/arm CD
Therefore, amount of solid x arm FD = amount of
liquid x arm CF
The point F acts as a fulcrum point and the tie line
CD acts as a lever arm and hence it is called the
lever rule
Unary phase diagram
Binary phase diagrams
Isomorphous systems
Eutectic systems
Partial eutectic systems
Layer type systems
Monotectic system
Eutectic system
Peritectic system
Eutectoid system
Peritectoid systems
Isomorphous system
Two components are completely soluble in
each other in both liquid and solid states,
and exist in a single phase for all
composition of the alloy
Examples: Cu-Ni, Cu-Au and Au-Ag
Eutectic systems
Here, the two metals are having complete
solubility in the liquid state and complete
insolubility in the solid
Examples: Pb-As, Bi-Cd, Th-Ti and Au-Si
Bi-Cd
Binary phase diagram for a eutectic
system
Cooling of hypoeutectic alloy with
Z% B
Cooling of eutectic alloy with Z% B
Cooling of hypereutectic alloy with
Z% B
Partial Eutectic System
Ag - 6 Cu
Ag - 20 Cu
Eutectic alloy
Layer type system
Two metals which show complete insolubility in
both liquid and solid states
Examples: Cu-Mo, Ag-Fe
Monotectic Transformation
Other binary transformations
Ternary system
Applications of phase diagrams
To predict M.P and F.P temperatures for any specific alloy
composition
To determine the number of phases, types of phases,
composition of phases present at a specific temperature
To calculate the relative amount of phase present in a two
phase alloy
To predict the microstructure of an alloy at any given
temperature
To choose the composition to develop best properties
Non-equilibrium cooling
Coring
Prevention of coring
Coring is prevented by the following
methods:
1.Cooling under equilibrium conditions
2.Annealing after normal solidification
Relationship between equilibrium
diagram and properties of alloys
If there is complete solubility of compounds in solid
state:
If there is insolubility of components
in solid state
If there is partial solubility in solid
state