Introduction to

Materials Science & Engineering

Chapter 9.
9 Phase Diagrams

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Contents

Introduction

Solubility Limit

Phase Diagrams
g

Microstructural
M crostructura Evolution
E o ut on during
ur ng Cooling
oo ng

Eutectic Systems

Fe C Alloy
Fe-C
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Issues to address
When
Wh we combine
bi two
t
elements...
l
t

What equilibrium state do we get?

In particular,
l
if
f we specify...
f

Composition (e.g., atomic % Ge atomic % Sn), and

Temperature (T )

Then...

How many phases do we get?

What is the composition of each phase?

How much of each phase do we get?

Phase B

Ph
Phase
A

Nickel atom
Copper atom
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 Phase: chemically and structurally homogeneous region of material.

Components: chemically distinct and essentially indivisible
substance.
Solubility limit - maximum concentration of solute that may
dissolve in a solvent at a g
given temperature
p
to form a solid solution.
Precipitate - a solid phase that forms from the original matrix
phase when the solubility
p
y limit is exceeded.
Phase diagram - graphical representation of the phases present
and the
an
th ranges
rang in
n composition,
c mp t n, temperature,
t mp ratur , and
an pressure
pr
ur overr
which the phases are stable.
Gibbs phase rule: F =C + 2 P

C : # components

P : # phases in equilibrium

F : degree of freedom (temperature, pressure, composition.)

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 Binary phase diagram - A phase diagram for a system with two

components.
t
Ternary phase diagram - A phase diagram for a system with three
components.
components
Isomorphous phase diagram - A phase diagram in which components
display unlimited solid solubility.
Liquidus temperature - The temperature at which the first solid
begins to form during solidification.
Solidus temperature - The temperature below which all liquid has
completely solidified.
Intermetallic compound - A compound formed of two or more
metals that has its own unique composition, structure, and
p p
properties.
Eutectic - A three-phase invariant reaction in which one liquid
phase solidifies to produce two solid phases.
5

Peritectic - A three-phase reaction in which a solid and a liquid

combine to produce a second solid on cooling.

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Contents

Introduction

Solubility Limit

Phase Diagrams
g

Microstructural
M crostructura Evolution
E o ut on during
ur ng Cooling
oo ng

Eutectic Systems

Fe C Alloy
Fe-C
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Phases & Solubility

(a) The three forms of water

gas, li
liquid
id & solid
lid are
each a phase.
(b) Water and alcohol have
unlimited solubility.
(c) Salt and water have limited
solubility.
(d) Oil and water have virtually
no solubility.
7

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Solubility Limit
-Liquid copper-nickel are
completely soluble.
- Solid copper-nickel are
p
y soluble, with
completely
copper and nickel atoms
occupying random lattice
sites.

In copper-zinc alloys containing more than 30 at. % Zn,

a second phase forms because of the limited solubility of zinc in copper.

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Solubility Limit
Solubility limit - maximum concentration of solute that may dissolve in a
solvent at a given temperature to form a solid solution.
Precipitate - a new solid phase that forms when the solubility limit is
exceeded.

(Fig. 9-1)

C12H22O11 H2O

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Solubility Limit

Answer: 65 wt
wt. % sugar
If Co < 65 wt. % sugar: syrup

60

40

(liquid solution
i.e., syrup)

20
0

L
(liquid)

+
S
(solid
g )
sugar)

20
40
6065 80
100
Co=Composition (wt% sugar)

Pure
e
Suga
ar

solubility limit at 20C?

Solubility
Limit

80

Pure
e
Wate
er

Question: What is the

100
Tempera
T
ature (C
C)

Phase Diagram of
Water - Sugar System

If Co > 65 wt.
t % sugar: syrup + sugar

10

Solub
Solubility
l ty llimit
m t increases
ncreases with
w th T :
e.g., if T = 100C, solubility limit = 80 wt. % sugar
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Components and Phases

Components:

The elements or compounds which are mixed initially

(e.g., Al and Cu).

Phases:
The physically and chemically distinct material regions
that result.

1 component (H2O)

Aluminum-Copper Alloy

(lighter
phase)
(darker
(d k
phase)

11

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Contents

12

Introduction

Solubility Limit

Phase Diagrams
g

Microstructural
M crostructura Evolution
E o ut on during
ur ng Cooling
oo ng

Eutectic Systems

Fe C Alloy
Fe-C
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Fundamental Concepts
Phase diagram: graphical representation of the phases
present
pr
s nt and
an the
th ranges
rang s in
n compos
composition,
t on, ttemperature,
mp ratur ,
and pressure over which the phases are stable.
Gibbs
G bb phase
h
rule:
l F=C+2P

(Eq. 9-16)

C: # components,
p
P: # p
phases in equilibrium
q
F: degree of freedom (temperature, pressure, composition.)
ex)) H2O,
O C = 1,
1 F=C+2P=3-P
1 phase F = 2
2 phase F = 1
3 phase F = 0 (invariant)
13

* pressure constant F = C + 1 P
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One-Component Phase Diagram

(Fig 9-2)
(Fig.

Pressure-temperature diagram for H2O. Notice the solid-liquid

line sloping to the left.
left At normal pressure (1 atm or 760 torr),
torr)
the melting temperature is 273 K.

14

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Isomorphous Phase Diagram

Complete liquid and solid solutions

(Fig. 9-3)

Constant p
pressure:
- 2009-10-28
15

F = C + 1 P, C = 2, F = 3 - P

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Phase Diagrams
Tell us about the phases as a function of T, Co, and P
For this course:
- Binary systems: just 2 components
p
variables: T and Co (at P = 1 atm)
- Independent
1600

T(C)

1500

L (liquid)

1400

Cu-Ni

1300

Phase diagram

1200

L (liquid)
(FCC solid solution)

(FCC solid
solution)
l ti )

1100
16

1000
0

20

40

60

80

100 wt%

Ni

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Phase Diagrams: Number and Types of Phases

Rule 1: If we know T and Co, then we know:
- the number and types
yp of phases
p
present.
p
T(C)
1600

A(1100, 60):
A(1100
1 phase:

1500

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

1300

L (liquid)
B(12
250,35)

Examples:

1400

1200
1100

17

1000
0

Cu-Ni
phase diagram

(FCC solid
solution)
A(1100,60)

20

40

60

80

100

wt% Ni
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Phase Diagrams: Composition of Phases

Rule 2: If we know T and Co, then we know:
- the composition of each phase.
Examples:
Co = 35wt%Ni
At TA:
Only Liquid (L)
CL = Co ( = 35wt% Ni)
At TD:
Only Solid ()
C = Co ( = 35wt% Ni)

T(C)

TA
130 0

tie line

L (liquid)
B

TB

120 0
At TB:
TD
Both and L
CL = Cliquidus ( = 32wt% Ni here)
20
C = Csolidus ( = 43
43wt%
t% Ni h
here))
18

Cu-Ni system (Fig. 9-3)

D
3 032

35
C LC o

(solid)

4 0 43

50

C wt% Ni
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Phase Diagrams: Fractions of Phases

Rule 3: If we know T and Co, then we know:
- the amount of each phase (given in wt. or at. %).
Examples:
Co = 35wt%Ni
At TA: Only Liquid (L)
WL = 100wt%, W = 0
At TD: Only Solid ()
WL = 0, W = 100wt%
At TB: Both and L
What would be WL and W?

WL =

19

S
44 35
=
= 75wtt %
+
R S 44 32

T(C)
TA
1300

TB

Cu-Ni system
A
ti li
tie
line

L (liquid)

1200

TD
20

303235

C LC o

(solid)

4044

50

C
wt% Ni

R
35 32
=
= 25wt %
W = +
R S 44 32
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The Lever Rule (Proof)

Sum of weight fractions:

WL + W = 1

(Example 9-1)

Conservation of mass (Ni): Co = WL CL + W C

Combine above equations:
C Co = S
=
WL
C CL R + S
A geometric interpretation
interpretation:
Co
CL
C
R
S

WL
20

Co CL = R
W =
C CL R + S
moment equilibrium:

WLR = WS
1 W
solving gives Lever Rule
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Contents

21

Introduction

Solubility Limit

Phase Diagrams
g

Microstructural
M crostructura Evolution
E o ut on during
ur ng Cooling
oo ng

Eutectic Systems

Fe C Alloy
Fe-C
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Cooling in a Cu-Ni Binary (equilibrium)

Phase diagram: Cu-Ni system.

(Fig. 9-4 incorrect)

System is:
- binary
2 components: Cu and Ni

- isomorphous

complete
p
solubility
y
A phase field extends
From 0 to 100 wt. % Ni

Consider
Co = 35 wt. % Ni

What would be the

22

microstructures?
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Cooling
g in Cu-Ni
(nonequilibrium)

(skip)
( i 9-5)
(Fig.
9 )

Consider

Co = 35 wt. % Ni.

23

X
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Contents

24

Introduction

Solubility Limit

Phase Diagrams
g

Microstructural
M crostructura Evolution
E o ut on during
ur ng Cooling
oo ng

Eutectic Systems

Fe C Alloy
Fe-C
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Binary Eutectic Systems

Greek - Easily melting

A special composition (Fig. 9-7)

with an easy
y melting
m
gT

2 components

Eutectic
E
i reaction
i
L +
____
+

25

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Binary Eutectic Systems

2 components
Ex.: Cu-Ag system

3 single phase regions

(L,, )
Limited solubility:
: mostly Cu
: mostly Ag
TE : No liquid below TE
C E : Min. melting T
composition

It h
has a special
i l composition
iti
with a minimum melting T.
T(C)

(Fig. 9-7)

120 0

L (liquid)

10 00
TE 800

L+
8.0

600

Cu

71 .9 91.2

400
200
0

L+

779C
779
C

20

40

60 C E 80

Composition (wt. %)

10 0

Ag

- 2009-11-02
26

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Example: Pb-Sn Eutectic System

For a 40 wt. % Sn 60 wt. % Pb alloy at 150C, find...
- the phases present: +
(Fig. 9-8)
- the compositions of the phases:
(Fig. 9-9)
C = 11 wt. % S
Sn
T(C)
( )
C = 99 wt. % Sn
300
L (liquid)
(li id)
- the relative amounts
L+
of each phase:

L+
L
200
00
183C
183
C

59
= 67 wt %
W =
88
29
= 33 wt %
W =
88
27

18.3

150
1 00

0 11 20

Pb

61.9

97.8

+
40

60

80

Composition (wt. %)

9910 0

Sn

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Microstructures in Eutectic Systems - I

Co < 2 wt. % Sn

T(C)
4 00

L: Co

Result
R s lt
polycrystal of grains

3 00

2 00
TE

L +
(Pb S
(Pb-Sn

: C o wt%Sn

1 00

System)

0
Co
28

(Fig. 9-11)

wt. % Sn

10

20

30

C o , wt% Sn

2
(room T solubility limit)

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Microstructures in Eutectic Systems - II

2 wt. % Sn < Co < 18.3 wt. % Sn

(Fig. 9-12)
L: C o wt.% Sn

T(C)
( )

Result polycrystal
with fine crystals.

400

L
300

L+

+ X

1 00

29

: C o wt%Sn

200
TE

Pb-Sn
system

10

20

30

C o C o , wt.
2.0
2
0
18.3
(solubility limit at Troom )
(solubility limit at TE )

% Sn
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Microstructures in Eutectic Systems - III

Co = CE
Result Eutectic microstructure --- alternating
layers of and crystals.
crystals
(Fig. 9-13)
T(C)
300

200
TE

L+

30

20
18.3

L+

183C
183
C

1 00

0
0

L: C o wt%Sn

(Fig. 9-14)

Pb-Sn system

40

: 97.8wt%Sn
: 18.3wt%Sn
60
CE
61.9

80

160m

100
97.8

C o , wt% Sn

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Formation of Eutectic Lamellar Structure

(Fig. 9-15)

31

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Microstructures in Eutectic Systems

18.3 wt. % Sn < Co < 61.9 wt. % Sn
Result: crystals
y
and an eutectic microstructure
(Fig. 9-16)
T(C)

Pb-Sn
Pb
Sn
system

200
TE

L+
R
R

1 00

0
0

(Fig. 9-17)
32

300

S
S

40
Co

C = 18.3 wt. % Sn

L+

C L = 61.9 wt. % Sn
W = S =50 wt. %
R+S
WL = (1-Wa ) =50 wt. %

Just below TE :

C = 18.3 wt. % Sn

+
20
18.3

Just above TE :

L: C o wt%Sn

60
61.9

80

primary
p
im
eutectic
eutectic

100
97.8

C o , wt.
t % Sn
S

C = 97.8
9
wt. % Sn
W = S =73 wt. %
R+S
W = 27 wt. %
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Invariant Reactions
___
____

33

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Other Examples
((Fig.
g 9-20))

34

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Other Examples
(Fig 9-21)
(Fig.
9 21)

35

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Other Examples
(Fig. 9-22)

36

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Contents

37

Introduction

Solubility Limit

Phase Diagrams
g

Microstructural Evolution during

C li
Cooling

Eutectic Systems

Fe C Alloy
Fe-C
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Fe-C phase diagram

iron
Austenite
(FCC)

(Fig. 9-24)
A

iron
F
Ferrite
i
(BCC)
soft & ductile

A; eutectic
B; eutectoid
38

B
Cementite ((Fe3C))
hard & brittle

C concentration
t ti
0.008w%
0
008 %
2.14w%
2
14 %
67 %
6.7w%
iron
steel
cast iron
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Summary
Phase diagrams are useful tools to determine:

The number and types of phases.

The at. % or wt. % of each phase.

The fraction of each phase.

phase
For the given T and composition of the system.

Binary alloys allow various ranges of microstructures.

Problems from Chap. 9

39

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Prob 9
Prob.
9-3
3

Prob 9
Prob.
9-4
4

Prob 9
Prob.
9-5
5

Prob.
Prob 9
9-8
8

Prob. 9-9

Prob. 9-11

Prob. 9-12

Prob. 9-17

P b 9-27
Prob.
9 27

P
Prob.
b 9
9-28
28

Prob.
P b 9
9-36
36

Prob.
P b 9
9-45
45
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