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PHASE DIAGRAMS

THEORY AND APPLICATIONS


Some basic concepts
◆ Phase
• A homogeneous region with distinct
structure and physical properties
• In principle, can be isolated
• Can be solid, liquid or gas
◆ Phase Diagram

• Representation of phases present under a


set of conditions (P, T, Composition etc.)
Concepts…...
◆ Phase transformation
• Change from one phase to another
• E.g. L S, S S etc.
• Occurs because energy change is
negative/goes from high to low energy state
◆ Phase boundary

• Boundary between phases in a phase diagram


A simple phase diagram
System: H2O

Liquid
Phase boundary

Pressure
Solid
Triple point
Vapor (Invariant point)

Temperature
Gibb’s Phase Rule
P+F=C+ P=number of phases
C=number of components
2 F=number of degrees of freedom
F=C-P+2 (number of independent variables)

Modified Gibbs Phase Rule (for incompressible systems)

P+F=C+1
F=C-P+1 Pressure is a constant variable
Application of the phase rule
At triple point, P=3, C=1, F=0
i.e. this is an invariant point

At phase boundary, P=2, C=1, F=1

In each phase, P=1, C=1, F=2


Solidification(cooling) curves
Pure metal Alloy

L L Soldification
begins
TL
L S L+S
Tm
TS
Solidification S
S
complete
Construction of a simple phase diagram
◆ Conduct an experiment
◆ Take 10 metal samples(pure Cu, Cu-
10%Ni, Cu-20%Ni, Cu-30%Ni………, pure
Ni)
◆ Melt each sample and then let it solidify
◆ Record the cooling curves
◆ Note temperatures at which phase
transformations occur
L
T Results L S
L
L TL
L TL TNi
L+S
L S L+S
Pure Ni
TS S
TCu S TS S
Pure Cu Cu-20%Ni
Cu-10%Ni

t
Binary isomorphous phase diagram
Temp L
x x x x TNi
x x x
x
x L+S x
x x
x x
TCu x x x x x x
Cu

S Ni

0 100
10 20 30 40 50 60 70 80 90

Cu %Ni Ni
Composition
Microstructural changes during solidification
Pure metal
L
T
L
S

L S
Tm

t
Microstructural changes during solidification
Alloy
L
T

TL
L+S
TS
S
S

t
Binary isomorphous phase diagram
T L
L T1
L
T2
T3 L+S

T4 L

S
S
CL C0 CS
0 100
10 20 30 40 50 60 70 80 90

A %B B

Composition
Notes
◆ This is an equilibrium phase diagram (slow cooling)
◆ The phase boundary which separates the L from the
L+S region is called LIQUIDUS
◆ The phase boundary which separates the S from the
L+S region is called SOLIDUS
◆ The horizontal (isothermal) line drawn at a specific
temperature is called the TIE LINE
◆ The tie line can be meaningfully drawn only in a
two-phase region
◆ The average composition of the alloy is CO
Notes…..
◆ The intersection of the tie line with the liquidus gives
the composition of the liquid, CL
◆ The intersection of the tie line with the solidus gives
the composition of the solid, CS
◆ By simple mass balance,
CO = fS CS + fL CL
and fS + fL = 1
CO = fS CS + (1- fS) CL
f =
CO
− C L C − C
f S= − f L =
Lever
0 L C S
− CO
S
CS − CL CS C L
Rule CS − C L
Some calculations
◆ In our diagram at T3, CO= A-40%B,
CS=A-90%B and CL=A-11%B

◆ Therefore, fS=29/79 or 37% and


fL=50/79 or 63%
◆ If we take an initial amount of alloy =100 g,
amt. of solid=37 g (3.7 g of A and 33.4 g of B) and
amt. of liquid=63 g (56.07 g of A and 6.93 g of B)
The Eutectic Phase Diagram Liquidus
L α + β (TE, CL=CE) Solidus
Solvus
T
L

β +L
α +L TE β
α
E

α +β
CE

A Wt%B B
Pure A or B
L
T L
S
L
CE
L
β +L α +β
α +L TE β L
α α +β
E
Other alloys
α +β between A and B
CE
L

A B L+α
Wt%B L α +β
α +β
Solidification for alloy of eutectic composition
T
L L

β +L
α +L TE β
α
E
α +β
α +β
CE S

A B
Wt%B
α +β
Eutectic microstructure
Lamellar structure

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T L
L

β +L
α +L β
α TE Proeutectic α

α +β
CE
α +β

A B
Wt%B

α +β
T
L
L

β +L
α +L β
α TE L

α +β
CE α

A B
Wt%B
β particles
The Eutectoid Phase Diagram
γ α + β (TE, Cγ =CE)
T
γ

β +γ
α +γ TE β
α
E

α +β
CE

A Wt%B B
Cooling of an alloy of eutectoid composition
T
γ γ

β +γ
α +γ TE β γ
α
E
α +β
α +β
CE S

A B
Wt%B
α +β
Cooling of an alloy of hypoeutectoid composition
T γ
γ
γ
β +γ
α +γ TE β Pro-eutectiod α
α
E
γ
α +β Pro-eutectiod α α +β

S
A B
Wt%B

α +β