CHAPTER 8

Phase Diagrams

Learning Outcome
Week
5

Topic

Learning Outcomes

Phase Diagrams

It is expected that students are able to:

Definition and basic concepts

Gibbs Phase Rules
Phase diagram of pure
substance
Binary phase diagram binary
isomorphous and binary
eutectic
Lever Rule

describe phase diagram of a material

system and apply Gibbs phase rule
describe binary isomorphous and
binary eutectic phase diagrams
draw generic diagram showing all
phase regions and relevant information
determine phase composition and
phase fraction in a mixture using tieline and lever rule
describe microstructure evolution
during equilibrium cooling as metal
solidifies

(Sections 8.1 8.7, omit 8.3

and 8.6)

Introduction: Phase Diagram and Terminology

Phase diagram is a graphical representation of what phases are present
in a material system at various temperature, pressure and composition.
Phase diagram for a mixture is plotted as temperature vs. composition.
For pure substance, phase diagram is plotted as temperature versus
pressure.

Phase Diagram for Alloys or Mixtures

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Introduction (cont.)

Information from phase diagram:

- Represents phases present in metal at different conditions
(temperature, pressure and composition).
- Indicates equilibrium solid solubility of one element in another.
- Indicates temperature range under which solidification occurs.
- Indicates temperature at which different phases start to melt.

Phase: a region in a material system that differs in its structure and/or

composition from another region. For example, liquid water and ice are
two separate phases although they both are composed of H2O.
Phases are separated from each other by a phase boundary.

Component: element, compound or solution in the system. For

example, the components of syrup are water (H2O) and sugar. The
components of brass are copper and zinc. A binary alloy has two
components, a ternary alloy three, etc.

Foundations of Materials Science and Engineering, 5th Edn. Smith and Hashemi

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Phase Diagram of Pure Substances

Pure systems (e.g. water) can exist as solid, liquid, or vapor

phases, depending on temperature and pressure.
Pure water: Along freezing line, two phases (solid-liquid) coexist.
Along vaporization line, liquid and vapor coexist.
At triple point, three different phases coexist.

Foundations of Materials Science and Engineering, 5th Edn. Smith and Hashemi

Gibbs Phase Rule

Gibbs phase rule is an equation that gives the number of phases that can
coexist in equilibrium in a system:

P+F=C+2
P = number of phases that coexist within a system
C = number of components (elements, compounds) in the system
F = degree of freedom for the system
2 = two independent variables (temperature, pressure)
Degree of freedom indicates number of variables (temperature, pressure,
composition) that can be changed without changing number of phases.
For solid-liquid systems, pressure is assumed to be constant,

P+F=C+1
86

Gibbs Phase Rule Pure Component

A: One-phase region
P+F=C+2
1 + F = 1 + 2; thus F = 2
Can change two variables
(T and P) and still have
this system in one phase.

Pure H2O: only

1 component
(water) in the
system. C = 1

B: Two-phase region
P+F=C+2
2 + F = 1 + 2; thus F = 1
Can change only one variable to
keep system in two-phase. If a
particular pressure is specified,
there is only one temperature at
which 2 phases can coexist.

P+F=C+2

C: Three-phase region
P+F=C+2
3 + F = 1 + 2; thus F = 0
Invariant point. T and P
cannot be changed if you
want to keep this system in
3 phases.

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Binary Isomorphous Alloy System Generic Diagram

Isomorphous system: Two elements completely soluble in

each other in both the liquid and solid states. Ex: Cu-Ni system.

Temperature

Three distinct phases:

liquid (L); solid solution (); and
solid + liquid ( + L)
Above liquidus line, alloy exists as a
liquid. We see one liquid phase.
Below solidus line, alloy is a stable
solid. We see only one solid phase; one
crystal structure. Cannot tell between A
and B.
In 2-phase region, solid and liquid in
equilibrium with one other. Composition
of liquid and solid phases at any
temperature can be determined by
drawing a tie-line.
Tie-line connects phases in equilibrium
with each other - essentially an
isotherm.

Foundations of Materials Science and Engineering, 5th Edn. Smith and Hashemi

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Binary Isomorphous Alloy: Cu-Ni System

Cu and Ni have complete liquid solubility and complete solid solubility.

Complete solid solubility occurs because both have FCC crystal structures,
similar atomic radii, similar EN, and same valence state. Satisfies HumeRothery solid solubility rules (Chap. 4)

Foundations of Materials Science and Engineering, 5th Edn. Smith and Hashemi

Solubility and Solubility Limit

Solubility the ability of one element to dissolve
another element.
Solubility limit is the maximum concentration for which
only a single-phase solution occurs. Example: alcohol
has unlimited solubility in water; sugar has limited
solubility in water; oil is insoluble in water.
Same concept applies to solid phases: Cu and Ni are
totally soluble in all proportions (just like water-methanol).
C has a limited solubility in Fe, up to only 2.08%.

10

Solubility Limit in Phase Diagram

Sugar/Water Phase Diagram

Q: What is solubility limit at 20oC?

A: 65wt% sugar.
If Co < 65wt% sugar: syrup
If Co > 65wt% sugar: syrup +

60
40

L
(liquid solution
i.e., syrup)

20
0

20

40

60

L
(liquid)
+

S
(solid
sugar)
80

C = Composition (wt% sugar)

100
Sugar

Ex: Water-Sugar

Solubility
Limit

80

Water

Max concentration for which

only a solution occurs.

Temperature (C)

Solubility Limit:

100

sugar.

Solubility limit increases with T :

e.g., if T = 100C, solubility limit = 80wt% sugar.
11

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The Lever Rule

The lever rule gives the weight % of the phases in

any two-phase regions.
Wt. fraction of solid phase:

XS =

w0 wL
w S wL

Wt. fraction of liquid phase:

XL =

w S w0
w S wL

12

Foundations of Materials Science and Engineering, 5th Edn. Smith and Hashemi

Interpretation of Phase Diagram

For a given temperature and composition we can use
phase diagram to determine:
a) What phases are present
b) Compositions of the phases in 2-phase region
c) Amount or weight fractions of these phases
b) Finding the composition in a two-phase region:
1. Locate composition and temperature in diagram
2. Draw the tie line from liquidus line to solidus line
and then drop vertical lines to the composition
x-axis.
3. Composition of liquid and solid phases are given
by the intersection of the vertical lines with the
composition axis.

Interpretation of Phase Diagram (cont.)

The Lever Rule
c)

Finding the amount of phases in a two-phase

region:

1. Locate composition and temperature in diagram

2. In two-phase region, draw the tie line
3. Fraction of a phase is determined by taking the length
of the tie line to the phase boundary for the other
phase, divided by total length of the tie line.

Lever rule is a mechanical analogy to the

mass balance calculation. Tie-line in the
two-phase region is analogous to a lever
balanced on a fulcrum.

ML

Phase Diagram: # and the phases present

If we know T and Co, then we know:
-- the number and the phases present.

Example:
A (1100C, 60):

1 phase:

B (1250C,35)

T(C)
1600
1500
1400
1300

B (1250C, 35):
2 phases: L +

Cu-Ni phase
diagram

(FCC solid
solution)

1200
1100
1000
0

L (liquid)

A(1100C,60)
20

40 60 80
wt% Ni

100
15

Phase Diagram: Compositions of the phases

If we know T and Co, then we know:
-- the composition of each phase.
Example:
C o = 35 wt% Ni
At T A = 1320C:
Only Liquid (L)
C L = C o ( = 35 wt% Ni)
At T D = 1190C:
Only Solid ( )
C = C o ( = 35 wt% Ni )

At T B = 1250C:
Both and L

T(C)
T A
1300

T B
1200

T D
20

Cu-Ni system
A
L (liquid)

tie line

B

D

(solid)

30 32 35 40 4 3

C LC
o

50

wt% Ni

C L = C liquidus ( = 32 wt% Ni here)

C = C solidus ( = 43 wt% Ni here)
16

Phase Diagram: Amount of the phases

If we know T and Co, then we know:

-- the amount of each phase (given in wt%).

Example:
C o = 35 wt% Ni

At T A : Only Liquid (L)

W L = 100 wt%, W = 0
At T D : Only Solid ( )
W L = 0, W = 100 wt%
At T B : Both and L
WL

43 35
=
=
= 73 wt%
R +S
43 32
=

R
R +S

= 27 wt%

T(C)
T A
1300

Cu-Ni system

A tie line
L (liquid)
B
R S

T B
1200

T D
20

(solid)

35 4 0 43
32 Co C

C L

3 0

wt% Ni

5 0

17

Binary Isomorphous Alloy: Melting and Cooling

In pure component system, melting occurs at a well-defined melting

temperature (at mp). Consider the temperature y-axis.

In multi-component (alloy) systems, melting occurs through a range of

temperatures, between the solidus and liquidus lines. Solid and liquid
phases are in equilibrium in this temperature range.

Microstructure Development in Binary Isomorphous Alloy

During Slow (Equilibrium) Cooling

Solidification in the 2-phase region (liquid + solid) occurs

gradually upon cooling from liquidus line.
Composition of the solid and the liquid change gradually
during cooling (determined by the tie-line method).
Nuclei of the solid phase form and they grow to consume all
the liquid at the solidus line

19

Microstructure Development in Binary Isomorphous Alloy

During Slow (Equilibrium) Cooling
Phase diagram:

Cu-Ni system.
Consider
Co = 35 wt%Ni.

T(C) L (liquid)
130 0
L: 35 wt% Ni
: 46 wt% Ni

System is:
-- binary: 2 components:
Cu and Ni.
-- isomorphous
i.e., complete
solubility of one
component in
another; phase
field extends from
0 to 100 wt% Ni.

L: 35wt%Ni

Cu-Ni
system

A
32

35

B
C

46
43

D35

24
120 0

L: 32 wt% Ni
: 43 wt% Ni

L: 24 wt% Ni
: 35 wt% Ni

(solid)
110 0
20

30

Adapted from Fig. 9.4,

Callister 7e.

: 35 wt% Ni

35
Co

40

50

wt% Ni
20