CHAPTER 9: 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

Chapter 9- 1

THE SOLUBILITY LIMIT

Solubility Limit:

100

Max concentration for

which only a solution
occurs.

Answer: 65wt% sugar.

60

40

(liquid solution
i.e., syrup)

+
S
(solid
sugar)

20
0

If Co < 65wt% sugar: sugar

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

20
40
6065 80
100
Co =Composition (wt% sugar)
Adapted from Fig. 9.1,
Callister 6e.

Solubility limit increases with T:

e.g., if T = 100C, solubility limit = 80wt% sugar.
Chapter 9- 2

eruP
raguS

solubility limit at 20C?

L
(liquid)

eruP
ret aW

Question: What is the

80

) C( er ut ar ep meT

Ex: Phase Diagram:

Water-Sugar System

Solubility
Limit

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.
Chapter 9- 3

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).

T(C)
Phase
Diagram
for Cu-Ni
system

2 phases:

160 0
150 0

L (liquid)
(FCC solid solution)

L (liquid)

140 0
us
d
i
liqu

130 0

L+

us
d
i
l
so

120 0

(FCC solid
solution)

110 0
100 0
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

Chapter 9- 5

PHASE DIAGRAMS: # and types of phases

Rule 1: If we know T and Co, then we know:
--the # and types of phases present.

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

T(C)
160 0
150 0

L (liquid)

140 0
) 53, 05B(
21

130 0
120 0
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).

L+

110 0
100 0
0

Cu-Ni
phase
diagram

dus
i
u
liq
us
d
i
l
so

(FCC solid
solution)
A(1100,60)

20

40

60

80

100

wt% Ni

Chapter 9- 6

PHASE DIAGRAMS: composition of phases

Rule 2: If we know T and Co, then we know:
--the composition of each phase.

Examples:

T(C)

Cu-Ni
system

A
TA
C o = 35wt%Ni
tie line us
quid
i
l
L
(liquid)
130 0
At T A :
+
L
Only Liquid (L)
s
B
lidu
o
s
TB
CL = Co ( = 35wt% Ni)

At T D:
L+
(solid)
120 0
D
Only Solid ( )
TD
C = Co ( = 35wt% Ni )
20
3032 35 40 43
50
At T B :
CLCo
C wt% Ni
Adapted from Fig. 9.2(b), Callister 6e.
Both and L
(Fig. 9.2(b) is adapted from Phase Diagrams of
CL = Cliquidus ( = 32wt% Ni here) Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH, 1991.)
C = Csolidus ( = 43wt% Ni here)
Chapter 9- 7

PHASE DIAGRAMS: weight fractions of phases

Rule 3: If we know T and Co, then we know:
--the amount of each phase (given in wt%).

Examples:

T(C)

C o = 35wt%Ni
At T A : Only Liquid (L)
WL = 100wt%, W = 0
At T D: Only Solid ( )
WL = 0, W = 100wt%
At T B : Both and L

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

Cu-Ni
system

= 27wt%

TA
130 0

L (liquid)

TD
20

+
L

TB
120 0

tie line us
id
liqu

R
L+

D
3032 35

CLC o

dus
soli

(solid)
40 43

50

C
wt% Ni

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

(Fig. 9.2(b) is adapted from Phase Diagrams of
Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH, 1991.)
Chapter 9- 8

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

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

WL

Co CL R
W
C CL R S
moment equilibrium:

WLR WS
1 W
solving gives Lever Rule
Chapter 9- 9

EX: COOLING IN A Cu-Ni BINARY

Phase diagram:
Cu-Ni system.

System is:
--binary
i.e., 2 components:
Cu and Ni.

T(C) L (liquid)
1300
L: 35wt%Ni
: 46wt%Ni

Consider
Co = 35wt%Ni.

A
35
32

--isomorphous
i.e., complete
solubility of one
component in
another; phase
field extends from
0 to 100wt% Ni.

L: 35wt%Ni

B
C

46
43

24
1200

L+

L: 32wt%Ni

36

L+

: 43wt%Ni

L: 24wt%Ni
: 36wt%Ni

(solid)
1100
20

30

Adapted from Fig. 9.3,

Callister 6e.

Cu-Ni
system

35
Co

40

50

wt% Ni
Chapter 9- 10

CORED VS EQUILIBRIUM PHASES

C changes as we solidify.
Cu-Ni case: First to solidify has C = 46wt%Ni.
Last to solidify has C = 35wt%Ni.

Fast rate of cooling:

Cored structure

Slow rate of cooling:

Equilibrium structure

First to solidfy:
46wt%Ni
Last to solidfy:
< 35wt%Ni

Uniform C :
35wt%Ni

Chapter 9- 11

MECHANICAL PROPERTIES: Cu-Ni System

Effect of solid solution strengthening on:
--Tensile strength (TS)

--Ductility (%EL,%AR)
60

400

%EL for
pure Ni

50

TS for
pure Ni

300

40
30

200
0 20 40 60 80 100
Cu
Ni

Composition, wt%Ni

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

--Peak as a function of Co

) LE %
( noi t agnol E

TS for pure Cu

aP M
( ht gnert S eli s ne T

%EL for pure Cu

20
0 20
Cu

40

60

80 100
Ni

Composition, wt%Ni

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

--Min. as a function of Co
Chapter 9- 12

BINARY-EUTECTIC SYSTEMS
has a special composition
with a min. melting T.

2 components

Ex.: Cu-Ag system

Cu-Ag
system

T(C)
1200

3 single phase regions

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

400
CE: Min. melting T
composition
200
0

20

40

60 CE 80

100

Co , 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.)
Chapter 9- 13

EX: Pb-Sn EUTECTIC SYSTEM (1)

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

Pb-Sn
system

T(C)
300

L (liquid)
L +

200

18.3

150

L+

183C
61.9

97.8

100

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.)
Chapter 9- 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
L +
--the relative amounts

L+
200
183C
of each phase:
18.3
61.9
97.8

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

150
100

0 11 20

40
Co

60

80

C o , wt% Sn

99100

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.)
Chapter 9- 15

MICROSTRUCTURES
IN EUTECTIC SYSTEMS-I
T(C)

Co < 2wt%Sn
Result:

400

L: C o wt%Sn
L

--polycrystal of grains.

300

200
TE

100

Adapted from Fig. 9.9,

Callister 6e.

L +
(Pb-Sn
System)

: Co wt%Sn

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

30

wt% Sn

Chapter 9- 16

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

L: C o wt%Sn

T(C)
400

L
L

300

L +
: C o wt%Sn

200
TE

100

+
0

Adapted from Fig. 9.10,

(sol.
Callister 6e.

10

20

Pb-Sn
system
30

Co C o , wt%
2
limit at T room )
18.3
(sol. limit at T E)

Sn

Chapter 9- 17

MICROSTRUCTURES
IN EUTECTIC SYSTEMS-III
Co = CE
Result: Eutectic microstructure
--alternating layers of and crystals.
T(C)
L: C o wt%Sn
300

Pb-Sn
system

L +

200
TE

100

20
18.3
Adapted from Fig. 9.11,
0

Callister 6e.

Micrograph of Pb-Sn
eutectic
microstructure

L +

183C

40

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

80

100
97.8

C o, wt% Sn

160m
Adapted from Fig. 9.12, Callister 6e.
(Fig. 9.12 from Metals Handbook, Vol. 9,
9th ed., Metallography and
Microstructures, American Society for
Metals, Materials Park, OH, 1985.)
Chapter 9- 18

MICROSTRUCTURES
IN EUTECTIC SYSTEMS-IV
18.3wt%Sn < Co < 61.9wt%Sn
Result: crystals and a eutectic microstructure
T(C)

300

Pb-Sn
system

L: C owt%Sn

L +

200
TE

R
R

L +

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

Just below T E:

100

Just above T E:

C = 18.3wt%Sn

+
20
18.3

Adapted from Fig. 9.14,

Callister 6e.

40
Co

60
61.9

80

primary
eutectic
eutectic

100
97.8

C o, wt% Sn

C = 97.8wt%Sn
W = S =73wt%
R+S
W = 27wt%
Chapter 9- 19

HYPOEUTECTIC & HYPEREUTECTIC

T(C)
L

300

Adapted from Fig. 9.7,

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

L +

Co

Co

20

(Pb-Sn
System)

hypoeutectic hypereutectic
40

60

80

eutectic

hypoeutectic: C o =50wt%Sn

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 +

61.9

100

Co , wt% Sn

97.8

hypereutectic: (illustration only)

eutectic: C o =61.9wt%Sn

175 m

160 m

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)
Chapter 9- 20

IRON-CARBON (Fe-C) PHASE DIAGRAM

L Fe3C

-Eutectoid (B):
Fe 3C

T(C)
1600

1400
1200

+L

austenite)

1000

800

600

120 m

+Fe 3C

727C = T eutectoid

400
0
(Fe)

S
+Fe3 C
1

0.77

di otcC
etue

Result: Pearlite =
alternating layers of
and Fe 3 C 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+Fe 3C
S

1148C

) etit neem
Fec(3 C

2 important
points
-Eutectic (A):

6.7

4.30
C o, wt% C
Fe3 C (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.)
Chapter 9- 21

HYPOEUTECTOID STEEL
T(C)
1600

1400

1200

+L

austenite)

1000
800

+Fe3 C
r s

727C

RS

w =s/(r +s) 600

w =(1-w )

400
0
pearlite

+Fe3 C
1

Co

77.0

L+Fe 3 C

1148C

w pearlite = w

w =S/(R+S)
w Fe3C =(1-w )
Adapted from
Fig. 9.27,Callister
6e. (Fig. 9.27 courtesy Republic Steel Corporation.)

) etit neem
Fec(3C

(Fe-C
System)
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.-inChief), ASM
International, Materials
Park, OH, 1990.)

6.7

C o, wt% C
100 m

Hypo eutectoid
steel

Chapter 9- 22

HYPEREUTECTOID STEEL
T(C)
1600

1400

+L

austenite)

L+Fe 3 C

1148C

1000

+Fe3 C

w Fe3C =r/(r +s)600

w =(1-w Fe3C)
400
0
pearlite

800

S
+Fe 3C
1

Co

w pearlite = w
w =S/(R+S)
w Fe3C =(1-w )
Adapted from

) eti t ne emF
ec( 3 C

Fe 3 C

1200

77.0

(Fe-C
System)

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.-inChief), ASM
International, Materials
Park, OH, 1990.)

6.7

Co , wt% C
60m Hypereutectoid
steel

Fig. 9.30,Callister
6e. (Fig. 9.30
copyright 1971 by United States Steel Corporation.)

Chapter 9- 23

ALLOYING STEEL WITH MORE ELEMENTS

Teutectoid changes:
Mo

Si
W

1000
Cr

TE
di ot c et u

800
Mn
600

Ni
0

12

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.)

t w(
di ot c et C
ue ) C %

) C(

0.8

Ti

1200

Ceutectoid changes:

0.6

Ni
Cr

0.4

Si

0.2

Ti Mo

0
0

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.)

Chapter 9- 24

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.

Chapter 9- 25