CHAPTER 10: PHASE DIAGRAMS

ISSUES TO ADDRESS...

When we combine two elements...

what equilibrium state do we get?

In particular, if we specify...
--a composition (e.g., wt%Cu - wt%Ni), and
--a 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

Phase A
Nickel atom
Copper atom

THE SOLUBILITY LIMIT

Ex: Phase Diagram:

Water-Sugar System

80
60
40

Pu re
W a te r

Answer: 65wt% sugar.

(liquid solution
i.e., syrup)

(liquid)

+
S

(solid
sugar)

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

If Co < 65wt% sugar: sugar

If Co > 65wt% sugar: syrup +

20

Question: What is the

solubility limit at 20C?

Solubility
Limit

sugar.
Solubility limit increases with T:

Pu re
Sugar

Max concentration for

which only a solution
occurs.

100

Te m p e ra tu re (C )

Solubility Limit:

Adapted from Fig.

9.1,
Callister 6e.

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

2

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 (e.g., and ).
AluminumCopper
Alloy

(lighter
phase)

(darker
phase)
Adapted from
Fig. 9.0,
Callister 3e.
3

EFFECT OF T & COMPOSITION

(Co)

watersugar
system

Adapted from
Fig. 9.1,
Callister 6e.

Te m p e ra tu re (C )

Changing T can change # of phases: path A to

B.
B(100,70)path
D(100,90)
Changing Co can change # of phases:
B to
1 phase
2 phases
D.
100
L

80
60
40
20
0

(liquid)

(liquid solution
i.e., syrup)

+
S

(solid
sugar)

A(70,20)

2 phases

20
40
60 70 80
100
Co=Composition (wt% sugar)
4

PHASE DIAGRAMS
Tell us about phases as function of T, Co, P.
For this course:
--binary systems: just 2 components.
--independent variables: T and Co (P = 1atm is always
used).

Phase
Diagram
for Cu-Ni
system

T(C)

2 phases:

1600
1500

L (liquid)
(FCC solid solution)

L (liquid)

1400
1300

(FCC solid
solution)

1200
1100
1000
0

20

40

60

80

3 phase fields:
L
L +

Adapted from Fig. 9.2(a), Callister 6e.

(Fig. 9.2(a) is adapted from Phase
Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International,
Materials Park, OH (1991).

100

wt% Ni

PHASE DIAGRAMS: # and types

of phases

Rule 1: If we know T and Co, then we know:

--the # and types of phases present.

A(1100, 60):
1 phase:
B(1250, 35):
2 phases: L +

1600
1500

L (liquid)

B (1250,35)

Examples:

T(C)

1400
1300
1200

Adapted from Fig. 9.2(a), Callister 6e.

(Fig. 9.2(a) is adapted from Phase
Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International,
Materials Park, OH, 1991).

1100
1000
0

Cu-Ni
phase
diagram

(FCC solid
solution)
A(1100,60)

20

40

60

80

100

wt% Ni
6

PHASE DIAGRAMS: composition of

phases
Rule 2: If we know T and Co, then we
know:

--the composition of each phase.

T(C)
Examples:

Cu-Ni
system

A
TA
C o = 35wt%Ni
tie line
1300 L (liquid)
At TA:
Only Liquid (L)
B
TB
CL = Co ( = 35wt% Ni)

At TD:
(solid)
1200
D
Only Solid ()
TD
C = Co ( = 35wt% Ni
)
20
303235 4043
50
At TB:
C LC o
C wt% Ni
Adapted from Fig. 9.2(b), Callister 6e.
Both and L
(Fig. 9.2(b) is adapted from Phase
C L = Cliquidus ( = 32wt% Ni here)Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
C = Csolidus ( = 43wt% Ni here)OH, 1991.)
7

PHASE DIAGRAMS: weight fractions of phases

Rule 3: If we know T and Co, then we
know:

Cu-Ni
system

Examples:
--the amount of each phase (given in wt%).
T(C)
C o = 35wt%Ni

At TA: Only Liquid (L)

WL = 100wt%, W
=0
At TD: Only Solid ()
WL = 0, W = 100wt%
At TB: Both and L

S
43 35
73wt%
WL
R S 43 32
R
W
R S

TA
1300

TB
1200

TD
20

tie line

L (liquid)
R

B
S
D

(solid)

303235 4043

C LC o

50

C
wt% Ni

= 27wt%

THE LEVER RULE: A PROOF

Sum of weight fractions:WL W 1
Conservation of mass (Ni):Co WL CL W C
Combine above equations:
C Co S
Co CL R

WL
W

C CL R S
C CL R S
A geometric interpretation:
Co
CL
C
R
S

WL

moment equilibrium:

WLR WS
1 W
solving gives Lever Rule
9

EX: COOLING IN A Cu-Ni BINARY

Phase diagram: T(C) L (liquid)

L: 35wt%Ni

Cu-Ni system.

System is:
--binary

1300
L: 35wt%Ni
: 46wt%Ni

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

Consider
Co = 35wt%Ni.

A
32

--isomorphous

Cu-Ni
system

35

B
C

46
43

24

36

1200

L: 32wt%Ni
: 43wt%Ni

L: 24wt%Ni
: 36wt%Ni

(solid)
1100
20

30

Adapted from Fig.

9.3, Callister 6e.

35
Co

40

50

wt% Ni
10

CORED VS EQUILIBRIUM PHASES

C changes as we
solidify.
First to solidify has C = 46wt%Ni.
Cu-Ni case: Last to solidify has C = 35wt%Ni.
Fast rate of
Slow rate of
cooling:
cooling:
Cored structure

First to solidfy:
46wt%Ni

Equilibrium
structure
Uniform
C:
35wt%Ni

Last to solidfy:
< 35wt%Ni

11

MECHANICAL PROPERTIES: Cu-Ni

System
Effect of solid solution strengthening
on:

400
TS for
pure Ni

300
TS for pure Cu

200
0 20 40 60 80 100
Cu
Ni

--Ductility (%EL,%AR)

E lo n g a tio n (% E L )

Tensile Stren gth (M Pa)

--Tensile strength (TS)

Composition, wt%Ni

Adapted from Fig. 9.5(a), Callister 6e.

--Peak as a function of Co

60

%EL for pure Cu

%EL for
pure Ni

50
40
30

20
0 20 40 60 80 100
Cu
Ni

Composition, wt%Ni

Adapted from Fig. 9.5(b), Callister 6e.

--Min. as a function of Co
12

BINARY-EUTECTIC SYSTEMS
2 components

Ex.: Cu-Ag system

has a special composition

with a min. melting T.
Cu-Ag
T(C)
system

1200

3 single phase regions

L (liquid)
1000
(L,)
Limited solubility:
L + 779C
L+
800
T
E
: mostly Cu
8.0
71.9 91.2
: mostly Ni
600
TE : No liquid below TE

400
CE : Min. melting T
composition
200
0

20

40

60 CE 80

100

C o, wt% Ag

Adapted from Fig. 9.6,

Callister 6e. (Fig. 9.6 adapted
from Binary Phase Diagrams, 2nd ed., Vol. 1, T.B.
Massalski (Editor-in-Chief), ASM International,
Materials Park, OH, 1990.)

13

EX: Pb-Sn EUTECTIC SYSTEM (1)

For a 40wt%Sn-60wt%Pb alloy at 150C,
find...
T(C)
--the phases present:
+
--the compositions of
the phases:

300

200
150

L (liquid)
L +
18.3

183C
61.9

L+
97.8

100

Pb-Sn
system

20

40
Co

60

80

100

C o, wt% Sn

Adapted from Fig. 9.7,

Callister 6e. (Fig. 9.7 adapted
from Binary Phase Diagrams, 2nd ed., Vol. 3, T.B.
Massalski (Editor-in-Chief), ASM International,
Materials Park, OH, 1990.)
14

EX: Pb-Sn EUTECTIC SYSTEM (2)

For a 40wt%Sn-60wt%Pb alloy at 150C, find...

--the phases present: +

Pb-Sn
T(C)
--the compositions of
system
the phases:
300
C = 11wt%Sn
L (liquid)
C = 99wt%Sn
--the relative amounts 200 L + 183C
L+
18.3
of each phase:
61.9
97.8

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

150

100

0 11 20

40
Co

60

80

99100

C o, wt% Sn

Adapted from Fig. 9.7,

Callister 6e. (Fig. 9.7 adapted
from Binary Phase Diagrams, 2nd ed., Vol. 3, T.B.
Massalski (Editor-in-Chief), ASM International,
Materials Park, OH, 1990.)
15

MICROSTRUCTURES
IN EUTECTIC SYSTEMS-I
Co < 2wt%Sn
Result:

--polycrystal of
grains.

T(C)

400

300

200
TE

100

Adapted from Fig. 9.9,

Callister 6e.

L: Cowt%Sn

L +

: Cowt%Sn

(Pb-Sn
System)

0
10
20
30
Co
C o, wt%
2
(room T solubility limit)

Sn

16

MICROSTRUCTURES
IN EUTECTIC SYSTEMS-II
2wt%Sn < Co < 18.3wt
%Sn
Result:
-- polycrystal with fine
crystals.

L: Cowt%Sn

T(C)

400

L
L

300

L +
200
TE

: C owt%Sn

100

Adapted from Fig.

9.10, Callister 6e.

Pb-Sn
system

0
10
20
30
Co C o, wt%
2
(sol. limit at Troom)
18.3
(sol. limit at TE )

Sn
17

MICROSTRUCTURES
IN EUTECTIC SYSTEMS-III
Co = C E
Result: Eutectic microstructure
--alternating layers of and
T(C)
crystals.
300

Pb-Sn
system
200
TE

L: Cowt%Sn

L +

100

0
0

20
18.3
Adapted from Fig.
9.11, Callister 6e.

L +

183C

+
40

Micrograph of Pb-Sn
eutectic
microstructure

160m

: 97.8wt%Sn Adapted from Fig. 9.12, Callister 6e.

: 18.3wt%Sn
(Fig. 9.12 from Metals Handbook,
60
CE
61.9

80

100
97.8

Vol. 9, 9th ed., Metallography and

Microstructures, American Society
for Metals, Materials Park, OH,
1985.)

C o, wt% Sn

18

MICROSTRUCTURES
IN EUTECTIC SYSTEMS-IV
18.3wt%Sn < Co < 61.9wt%Sn
Result: crystals and a eutectic
microstructure
L: Cowt%Sn

T(C)

300

Pb-Sn
system

200
TE

L +
R
R

100

0
0

L +

S
S

Adapted from Fig.

9.14, Callister 6e.

40
Co

60
61.9

C = 18.3wt%Sn
C L = 61.9wt%Sn
W = S =50wt%
R +S
WL = (1-W) =50wt%

Just below TE :

+
20
18.3

Just above TE :

80

primary
eutectic
eutectic

100
97.8

C o, wt% Sn

C = 18.3wt%Sn
C = 97.8wt%Sn
W = S =73wt%
R +S
W = 27wt%
19

HYPOEUTECTIC &
HYPEREUTECTIC
T(C)
L

300

Adapted from Fig. 9.7,

Callister 6e. (Fig. 9.7
200
TE
adapted from Binary
Phase Diagrams, 2nd
ed., Vol. 3, T.B.
100
Massalski (Editor-inChief), ASM
International, Materials
0
Park, OH, 1990.)

L +

Co

Co

hypoeutectic hypereutectic
20

40

60

80

eutectic

hypoeutectic: Co=50wt%Sn

61.9

100

Co, wt% Sn

97.8

hypereutectic: (illustration only)

eutectic: C o=61.9wt%Sn

175m

(Pb-Sn
System)

18.3

(Figs. 9.12 and

9.15 from Metals
Handbook, 9th
ed.,
Vol. 9,
Metallography
and
Microstructures,
American Society
for Metals,
Materials Park,
OH, 1985.)

L +

160m

Adapted from
eutectic micro-constituent
Fig. 9.15, Callister 6e.
Adapted from Fig. 9.12,
Callister 6e.

Adapted from Fig. 9.15,

Callister 6e.
(Illustration only)

20

IRON-CARBON (Fe-C) PHASE

DIAGRAM
T(C)

L Fe 3C

-Eutectoid (B):
Fe 3C

1600

1400

+L

austenite)

1200

1000

800
600

120m

400
0
(Fe)

Result: Pearlite =
alternating layers of
and Fe3C phases.
(Adapted from Fig. 9.24, Callister 6e.
(Fig. 9.24 from Metals Handbook, 9th
ed., Vol. 9, Metallography and
Microstructures, American Society for
Metals, Materials Park, OH, 1985.)

L+Fe3C
S

+Fe3C

727C = T
eutectoid

S
+Fe3C
1

0.77

C e u te c to id

1148C

Fe 3 C (c e m e n tite )

2 important
points
-Eutectic (A):

6.7

4.30 C , wt% C
o
Fe 3C (cementite-hard)
(ferrite-soft)

Adapted from Fig. 9.21,Callister 6e. (Fig. 9.21

adapted from Binary Alloy Phase Diagrams, 2nd
ed.,
Vol. 1, T.B. Massalski (Ed.-in-Chief), ASM
International, Materials Park, OH, 1990.)
21

HYPOEUTECTOID STEEL
T(C)

1600

+L

1200
austenite)

1000

800

+Fe3C
r s

727C

R S

w =s/(r+s) 600
w =(1-w )

400
0 Co
pearlite

0 .7 7

L+Fe3C

1148C

+Fe3C
1

wpearlite =w

w =S/(R+S)
wFe3C =(1-w )
Adapted from
Fig. 9.27,Callister
6e. (Fig. 9.27 courtesy Republic Steel
Corporation.)

(Fe-C
System)

Fe 3 C (c e m e n tite )

1400

6.7

C o, wt% C
100m

Adapted from Figs.

9.21 and
9.26,Callister 6e. (Fig.
9.21 adapted from
Binary Alloy Phase
Diagrams, 2nd ed.,
Vol. 1, T.B. Massalski
(Ed.-in-Chief), ASM
International,
Materials Park, OH,
1990.)

Hypoeutectoid
steel

22

HYPEREUTECTOID STEEL
T(C)

1600

Fe 3C

+L

austenite)

1200

L+Fe3C

1148C

1000

+Fe3C

wFe3C =r/(r+s)600
w =(1-w Fe3C)

400
0
pearlite

800

0 .7 7

S
1

Co

+Fe3C
2

wpearlite =w
w =S/(R+S)
wFe3C =(1-w )
Adapted from
Fig. 9.30,Callister
6e. (Fig. 9.30
copyright 1971 by United States Steel
Corporation.)

(Fe-C
System)

Fe 3 C (c e m e n tite )

1400

6.7

C o, wt% C

Adapted from Figs.

9.21 and
9.29,Callister 6e. (Fig.
9.21 adapted from
Binary Alloy Phase
Diagrams, 2nd ed.,
Vol. 1, T.B. Massalski
(Ed.-in-Chief), ASM
International,
Materials Park, OH,
1990.)

60m Hypereutectoid
steel

23

ALLOYING STEEL WITH MORE

ELEMENTS

Ti

1200

Mo

Si

1000
Cr

800

Mn

600

Ni

12

Ceutectoid changes:

C e u te c to id (w t% C )

T E u te c to id ( C )

Teutectoid changes:

wt. % of alloying elements

Adapted from Fig. 9.31,Callister 6e. (Fig.

9.31 from Edgar C. Bain, Functions of the
Alloying Elements in Steel, American
Society for Metals, 1939, p. 127.)

0.8
0.6

Ni
Cr

0.4

Si

0.2
0
0

Ti Mo
4

W
8

Mn
12

wt. % of alloying elements

Adapted from Fig. 9.32,Callister 6e. (Fig.

9.32 from Edgar C. Bain, Functions of the
Alloying Elements in Steel, American
Society for Metals, 1939, p. 127.)

24

APPLICATION: REFRACTORIES
Need a material to use in high temperature furnaces.
Consider Silica (SiO2) - Alumina (Al2O3) system.
Phase diagram shows:
mullite, alumina, and crystobalite (made up of SiO2)
tetrahedra as candidate refractories.
2200
T(C)
2000

3Al2O3-2SiO 2
Liquid
(L)

1800

1400
0

alumina + L
mullite
+L

crystobalite
+L

1600

mullite

mullite
+crystobalite

20

alumina
+
mullite

Adapted from Fig.

12.27, Callister 6e.
(Fig. 12.27 is adapted
from F.J. Klug and R.H.
Doremus, "Alumina
Silica Phase Diagram
in the Mullite Region",
J. American Ceramic
Society 70(10), p.
758, 1987.)

40
60
80
100
Composition (wt% alumina)

25

SUMMARY
Phase diagrams are useful tools to determine:
--the number and types of phases,
--the wt% of each phase,
--and the composition of each phase

for a given T and composition of the system.

Alloying to produce a solid solution usually
--increases the tensile strength (TS)
--decreases the ductility.

Binary eutectics and binary eutectoids allow for

a range of microstructures.

26

ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems: