1

Chapter 7 Phase Equilibria and

Phase Diagrams
Introduction
The one-component phase diagram
Phase equilibria in a two-component system
The eutectic phase diagram
The peritectic phase diagram
The monotectic phase diagram
Complex diagrams
2
Phase

A chemically and structurally homogeneous region of a material
A part of a system, physically distinct, macroscopically homogeneous,
and of fixed or variable composition.
It is mechanically separable from the rest of the system.
A phase is a region within which all the intensive variables vary
continuously, whereas at least some of them have discontinuities at the
borders between phases.
ice water
ice + water
2 phases = solid phase + liquid phase
I want to drink 2-phase water consisting
of solid phase and liquid phase.
3
Phase diagram
Graphical representation of the combination of temperature, pressure,
composition, or other variables for which specific phases exist at equilibrium.
Phase diagram of Water (H
2
O)
Phase diagram of Carbon dioxide (CO
2
)
State point: a position on the phase diagram
0.47 g/cm
3
@304.25 K & 72.9 atm
4
One-Component Phase Diagrams
Gibbs Phase Rule for systems in equilibrium
Component: a chemical species whose concentration in a phase can be varied
independently of the other species concentration
Number of degrees of freedom in equilibrium is the number of variables (p, T, or
composition) that can be independently adjusted without disturbing equilibrium.
water
F = C P + 2
C- Components
P- Number of phases
F- Degrees of freedom
F = 2
F = 1 F = 1
F = 0 F = 0
F = 2
F = 2
5
Example of One-Component Phase Diagrams
iron
SiO
2
6
Two-Component Phase Diagrams
Temperature
Pressure
Composition for materials A and B
(Composition of one-component
system?)

For one state point in closed system we
need three variables (p, T, & X).
If we fix the pressure,
(T, X(composition)) 2-D space
(p, T, X(composition)) 3-D space
F = C P + 1
F = 2
F = 1
T
X
s
X
l
X
A
+X
B
=X
total
F = C P + 2
C- Components
P- Number of phases
F- Degrees of freedom
F = 2
F = 1 F = 1
F = 0 F = 0
F = 2
F = 2
One-
component
system
7
Two-Component Phase Diagrams
Specification of composition
Atomic percentage (=atomic fraction=atomic number fraction=mole fraction)
Weight percentage (=weight fraction)
( ) ( )
100
/ % / %
/ %
% %
+
= =
B of wt atomic B of wt A of wt atomic A of wt
A of wt atomic A of wt
A of atomic A of mole
( ) ( )
100
% %
%
%
+

=
B of wt atomic B of atomic A of wt atomic A of atomic
A of wt atomic A of atomic
A of wt
Question1) Calculate the atomic fraction of copper in aluminum for a two-
component alloy containing 5 wt % copper. Atomic mass is 63.55 for Cu and 26.98
for Al.
9
Two-Component Phase Diagrams
isomorphous system
has complete solubility of one component in another.
Non-isomorphous system ?
Cu-Ni phase diagram
Both Cu and Ni have the
same crystal structure, FCC,
similar radii,
electronegativity and
valence.
F = C P + 1
10
Two-Component Phase Diagrams
In a single-phase field, the composition
of the phase is the composition of the
alloy
In a two-phase field, the amount of
each phase and the composition of
each phase can be determined using
a tie line and the lever rule
In a single-phase field, the composition
of the phase is the composition of the
alloy
Phase boundaries
liquidus boundary and solidus boundary
X
o
11
System is:
--binary
i.e., 2 components:
Cu and Ni.
--isomorphous
i.e., complete
solubility of one
component in
another; o phase
field extends from
0 to 100wt% Ni.
Consider
C
o
= 35wt%Ni.
Equilibrium cooling
Two-Component Phase Diagrams
Cu-Ni phase diagram
12
If we know T and C
o
(initial composition), then we know the
composition of each phase.
Examples:
Cu-Ni
system
C
0
= 35 wt% Ni
At 1300 C:
Only liquid (L)
C
L
= C
0
(= 35 wt% Ni)
At 1150 C:
Only solid (o)
C
o
= C
0
(= 35 wt% Ni)
At T
B
:
Both o and L
C
L
= C
liquidus
(= 32 wt% Ni)
C
o
= C
solidus
(=43 wt% Ni)
Two-Component Phase Diagrams
13
If we know T and C
o
, then we know the amount of each phase
(given in wt%).
C
0
= 35 wt% Ni
At 1300 C:
Only liquid (L)
W
L
= 100 wt%, W
o
= 0 wt%
At 1150 C:
Only solid (o)
W
L
= 0 wt%, W
o
= 100 wt%
At T
B
:
Both o and L
W
L
= S/(R+S) =
(43-35)/(43-32) = 73 wt%
W
o
= R/(R+S) =
(35-32)/(43-32) = 27 wt%

The lever rule
Two-Component Phase Diagrams
Cu-Ni
system
14
The Lever Rule in a Two-Component System
( )
( )
L
L S
S
total
L
f
X X
X X
M
M
=

=
0
( )
( )
S
L S
L
total
S
f
X X
X X
M
M
=

=
0
15
Hamsters ?
Type A
Type B
Assumption: Type B hibernates earlier than Type A.
Type A starts hibernation in colder day
than Type B does.
B is solidified at higher T than A.
Type A Type B
They hibernate.
16
When Types A and B got together, they had a party.
In summer, they mix and
happily play together.
Closed system
Closed system
As the weather gets colder and colder.
They start hibernating
One phase Two phases
Z Z Z Z..
No More Active (solid) phase.
Composition of type B:
X
B
=80 %
Still Active (liquid) phase.
Composition of type B:
X
B
=28.6 %
Total composition is not changed (X
B, total
=50 %).
Total composition: X
B, total
=50 %
W
L
=58.3 % W
S
=41.7 %
18
Two-Component Phase Diagrams
( )
( )
( )
( )
1
1
1
l s
o l l s s
l s
o l s s s
o l l s s s
o l s s l
o l
s
s l
f f
X X f X f
f f
X X f X f
X X X f X f
X X f X X
X X
f
X X
+ =
= +
=
= +
= +
=

( )
( )
s o
l
s l
X X
f
X X

Composition, X
B
T
e
m
p
e
r
a
t
u
r
e
19
The Lever Rule in a Two-Component System
( )
( )
L
L S
S
total
L
f
X X
X X
M
M
=

=
0
( )
( )
S
L S
L
total
S
f
X X
X X
M
M
=

=
0
20
Effect of Cooling Rate
Fast cooling rate
More local heterogeneity

Slow cooling rate
More homogeneous structure
Just slow Very slow
21
Two-Component Phase Diagrams
Composition of the
liquid for each alloy
Composition of the
solid for each alloy
Alloy 1: 0.2
Alloy 2: 0.3
Alloy 3: 0.5
Alloy 4: 0.6
Alloy 5: 0.8
Alloy 1: 0.8
Alloy 2: 0.8
Alloy 3: 0.8
Alloy 4: 0.8
Alloy 5: 0.8
Composition X
0
for each alloy
Alloy 1: 0.2
Alloy 2: 0.2
Alloy 3: 0.2
Alloy 4: 0.2
Alloy 5: 0.2
For Alloy 2,
83 . 0
2 . 0 8 . 0
3 . 0 8 . 0
=

=
L
f 17 . 0
2 . 0 8 . 0
2 . 0 3 . 0
=

=
S
f
0.3
Composition, X
B
T
e
m
p
e
r
a
t
u
r
e
22



At temperature T2
0.77 0.60
0.77 0.50
0.63
l
l
f
f

=
0.60 0.50
0.77 0.50
0.37
s
s
f
f

=
At temperature T3
0.72 0.60
0.72 0.45
0.44
l
l
f
f

=
0.60 0.45
0.72 0.45
0.56
s
s
f
f

=
Analysis of an Isomorphous Phase Diagram
X
0
=0.60
Temperature f
l
x
l
f
s
X
s
T1 1 0.6 0 0.85
T2 0.63 0.5 0.37 0.77
T3 0.44 0.45 0.56 0.72
T4 0.29 0.4 0.71 0.68
T5 0 0.3 1 0.6
23
Two-Component Phase Diagrams
isomorphous system has complete solubility of one component in
another.
Cu-Ni phase diagram
An isomorphous system is only possible
for substitutional solid solution.

The substitution occurs randomly on their
FCC lattice sites because the Cu and Ni
atoms are so similar.


Cu-Ni alloy
Excellent corrosion resistance
Used for water-cooled heat exchangers
The size difference between the solute and solvent must be no greater than ~15%.
The electronegativities of the two atomic species must be comparable.
The valence of the two species must be similar.
The crystal structures of the two species must be the same.
Hume-Rothery Rules
24
Two-Component Phase Diagrams
Four isomorphous systems
Formation of substitutional solid solution
All the Hume-Rothery rules are satisfied.
Cu-Ni Ge-Si
Ag-Au NiO-MgO
25
Free Energy and Phase Diagram
At High T
At Low T At intermediate T
X
o
A
B
C
A B
C
26
When Types A and B got together, they had a party.
The free energy determines the composition!
The composition is adjusted to minimize the free energy.
In summer, they mix and
happily play together.
Closed system
Closed system
As the weather gets colder and colder.
They start hibernating
One phase Two phases
Z Z Z Z..
No More Active (solid) phase.
Composition of type B:
X
B
=80 %
Still Active (liquid) phase.
Composition of type B:
X
B
=28.6 %
Total composition is not changed (X
B, total
=50 %).
Total composition: X
B, total
=50 %
W
L
=58.3 % W
S
=41.7 %
27
Free Energy and Phase Diagram
How to use the chemical potential?
Liquidus and solidus line is determined at the points
where the chemical potentials of the phases are the
same.
How to minimize the Gibbs free energy?

Constraint 1:


Constraint 2:


Constraint 3:
solid solid liquid liquid total
f G f G G + =
solid B solid liquid B liquid B
f X f X X
, , , 0
+ =
1 = +
solid liquid
f f
Chemical potential, (definition):
T p
i
X
G
,
|
|
.
|

\
|
c
c
=
We use chemical potential to describe the phenomenon.
G: free energy
X
i
: composition (number of molecule or atom of material i)
p: pressure
T: temperature
28
1. A:B=50:50
X
0,B
=0.50
A A
A A
A
A
A
A A A
B
B
B
B
B
B
B
B
B
B
B
B
A
A
A A
A A
A
A
A
A A A
B
B
B
B
B
B
B
B
B
B
B
B
A
A
2. In the 2-phase region, the system will have
solid phase immediately in the liquid phase.
But they want to minimize the free energy by changing the composition (X
B
).
Liquid phase wants to increase the X
B
.
Solid phase wants to decrease the X
B
.
Solid phase
Liquid phase
Liquid phase
29
G
min,S
G
min,L
A A
A A
A
A
A
A A A
B
B
B
B
B
B
B
B
B
B
B
B
A
A
3. This could be done by moving B from solid
phase to liquid phase.
B
Liquid phase increases the X
B
.
Solid phase decreases the X
B
.
0
,
<
|
|
.
|

\
|
c
c
=
T p
i
liquid
liquid
X
G

0
,
>
|
|
.
|

\
|
c
c
=
T p
i
solid
solid
X
G

As long as the free energy can be reduced, the solid phase will keep giving B to the liquid
phase.
For a while, X
B,Solid
and X
B,Liquid
will approach the minimum points, G
min,S
and G
min,L
, respectively.
(highly) Negative slope
(slightly) Positive slope
Solid phase
Liquid phase
The liquid phase want to get more B.
The solid phase want to give out more B.
30
G
min,S
G
min,L
A A
A A
A
A
A
A A A
B
B B
B
B
B
B
B
B
B
B
A
A
4. Although X
B,Solid
arrives at G
min,S
, X
B,Liquid


is still
far from G
min,L
.
B
Furthermore, the magnitude of chemical potential

liquid
, is still large in comparison to
solid
(=0).
0
,
<
|
|
.
|

\
|
c
c
=
T p
i
liquid
liquid
X
G

0
,
=
|
|
.
|

\
|
c
c
=
T p
i
solid
solid
X
G

Therefore, the liquid phase still get B from the solid phase.
Due to this, X
B,Solid
will pass through G
min,S
and go up.
For a while, X
B,Liquid
will keep going down towards G
min,L
.
(Still) negative slope
zero slope
B
B
0
,
<
|
|
.
|

\
|
c
c
=
T p
i
liquid
liquid
X
G

0
,
<
|
|
.
|

\
|
c
c
=
T p
i
solid
solid
X
G

Please note that the chemical potentials are all negative If the solid composition passes
through the G
min,S
. Both phases want to get more B.
Solid phase
Liquid phase
The situation is like Tug of War.
31
G
min,S
G
min,L
A A
A A
A
A
A
A A A
B
B
B
B
B
B
B
B
B
A
A
5. Since the solid phase has lost B too much,
G
solid
becomes larger (which means that the solid
phase becomes unstabler).
B
G
solid
and G
liquid
arrive at the points (4) and (5),
respectively.
Now, the solid phase and the liquid phase have the same chemical potential, which means
that they need B component to the same extent.
The B component cannot move any more between those phases.
Therefore, X
B,Solid
and X
B,Liquid
are determined at the points (4) and (5).
If we do this for other X
0,B
for various temperature, we will get various pairs of (4) and (5).
a collection of (4): solidus line
a collection of (5): liquidus line
B
B
0
,
<
|
|
.
|

\
|
c
c
=
T p
i
liquid
liquid
X
G

0
,
<
|
|
.
|

\
|
c
c
=
T p
i
solid
solid
X
G

solid liquid
=
Solid phase
Liquid phase
32
A
B
Q) We have a composition X
B
0
(at T=T
0
) which is in the two-phase region as shown in the
following phase diagram and the corresponding free energy plot. The solid phase and the
liquid phase have different compositions: X
B
S
for the solid phase and X
B
L
for the liquid phase.
(1) From the plot, it is clear that the free energy of solid phase at composition
X
B
0
(point 2) is lower than the free energy of liquid phase (point 1), which seems
that the solid phase is preferred at X
B
0
. Then, why does the system have to have
the two phases at X
B
0
?
By having two phases (solid phase and liquid phase), the system can reduce free
energy even further. It is obvious that the free energy at point (3) obtained from
2 phases is lower than the free energy at point (2) obtained from the pure solid
phase.

(2) To determine points A and B, we need to use the chemical potential. Please
write down the definition of the chemical potential with the explanations for
parameters.





G: free energy
X
i
: composition (number of molecule or atom of material i)
p: pressure
T: temperature T p
i
X
G
,
|
|
.
|

\
|
c
c
=
33
A
B
Q) We have a composition X
B
0
(at T=T
0
) which is in the two-phase region as shown in the
following phase diagram and the corresponding free energy plot. The solid phase and the
liquid phase have different compositions: X
B
S
for the solid phase and X
B
L
for the liquid phase.

(3) At the points A and B, the chemical potentials have (positive, negative) value.
What is the meaning of this?
Both phases want to get more B.

(4) At T=T
0
, the tie line meets points A and B with the solidus line and the liquidus
line, respectively, which means that the composition of the solid phase and liquid
phase are X
B
S
(point 4) and X
B
L
(point 5). Please explain how to use the chemical
potential to determine the points 4 and 5.
To obtain phase equilibrium, each phase needs to have the same chemical potential
for material. The chemical potential is the slope of the free energy plot, so that the
free energy curves for solid phase and liquid phase have the common tangent line
that has the same slope.
34
Eutectic Phase Diagrams
Composition, X
B
T
e
m
p
e
r
a
t
u
r
e
T
A
T
B
Composition, X
B
T
e
m
p
e
r
a
t
u
r
e
T
A
T
B
Feeling?
eutektos, meaning 'easily melted.'
Eutectic Phase Diagrams
Composition, X
B
T
A
T
B
X
1
X
E
X
2
A B
T
e
m
p
e
r
a
t
u
r
e
X
o
X
|
T
X
s
X
l
T
X
s
X
l
T
X
o
X
|
One-phase liquid
Two-phase solid
One-
phase
solid
One-
phase
solid
two-
phase
two-
phase
Eutectic Phase Diagrams
F = 2, specify
temperature
and composition
F = 1, specify
temperature or the
composition of one
of the phases
F = 0, temperature
and compositions
of the phase are
fixed.
Composition, X
B
T
A
T
B
X
1
X
E
X
2
A B
T
e
m
p
e
r
a
t
u
r
e
F = 2
F = 2
F = 2
Eutectic point
F = 1
F = 1
F = 1
F = 0
38
Eutectic Phase Diagrams
Symbolic expression: Liquid Solid 1 + Solid 2

L o + |
Eutectic Reaction
Through eutectic point in eutectic
isotherm, one-phase Liquid state
becomes two-phase Solid state.
39
Eutectic Phase Diagrams
Question) from the following eutectic phase diagram
(1) Your system is located in two- phase
region (L+ ) with X
0
=0.27. If you cool it
down slowly (equilibrium cooling), what
would be the fraction of primary solid ()
at the eutectic temperature?
588 . 0
20 37
27 37
27 . 0
0
0
=

=
=
o
o
X X
X X
f
X
L
L
P
(2) From the same system, what would be the fraction of liquid at the eutectic
temperature?
412 . 0
20 37
20 27
0
=

=
o
o
X X
X X
f
L
eut
L
40
Eutectic Phase Diagrams
Question) from the following eutectic phase diagram
(3) From the liquid (eutectic composition) in
question (2), what amount of o and | will
be formed just below the eutectic isotherm?
679 . 0
20 73
37 73
=

=
o |
|
o
X X
X X
f
eut
L
321 . 0
20 73
20 37
=

=
o |
o
|
X X
X X
f
eut
L
Therefore, the fraction of alloy composed of the eutectic o and | obtained from
the eutectic liquid in question (2) is
280 . 0 679 . 0 412 . 0 = = =
o o
f f f
eut
L
eut
( ) 132 . 0 679 . 0 1 412 . 0 = = =
| |
f f f
eut
L
eut
412 . 0
20 37
20 27
0
=

=
o
o
X X
X X
f
L
eut
L
41
Eutectic Phase Diagrams
Question) from the following eutectic phase diagram
(4) What is the total amount of o phase in the
alloy at a temperature just below the eutectic
temperature?
868 . 0 280 . 0 588 . 0 = + = + =
eut P total
f f f
o o o
868 . 0
20 73
27 73
0
=

=
o |
|
o
X X
X X
f
total
The amount of o =
o phase (from 2-phase region (L+o))
+ o phase (from eutectic liquid from L+o)
Portion of solid (o) via eutectic liquid in (L+o)
eut
f
o
P
f
o
Portion of solid (o) in two-phase (L+o)
Another way..
42
Peritectic Phase Diagrams
Symbolic expression: Liquid + Solid 1 Solid 2

L + o |
1. Peritectic Point and Peritectic
isotherm!
2. Through peritectic point, Liquid+
solid becomes solid.
43
Peritectic Phase Diagram
X1=0.125 wt %

X2=0.170 wt %

X3=0.350 wt %
Question) Determine the composition and relative amounts of each phase
present just above and below the peritectic isotherm for each of the three
alloy compositions indicated.
f
L
f
o
f

f
L
f
o
f

f
L
f
o
f

X1=0.125
X2=0.170
X3=0.350
just above just below
X1 X2
X3
0.09 0.17 0.53
+ L+
L+
L