Chapter 9: Phase Diagrams for

Metallic Systems

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

Phase Equilibria: Solubility Limit

Introduction
Solutions solid solutions, single phase
Mixtures more than one phase
Adapted from Fig. 9.1,
Callister 7e.

Sucrose/Water Phase Diagram

solubility limit at 20C?

Answer: 65 wt% sugar.

If Co < 65 wt% sugar: syrup

Solubility
Limit

80
60

40

(liquid solution
i.e., syrup)

20
0
Pure
Water

Question: What is the

Temperature (C)

Max concentration for

which only a single phase
solution occurs.

100

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

L
(liquid)

+
S
(solid
sugar)

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

Pure
Sugar

Solubility Limit:

Chapter 9 - 2

Components and Phases

Components:
The elements or compounds which are present in the mixture
(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
chapter-opening
photograph,
Chapter 9,
Callister 3e.
Chapter 9 - 3

Effect of T & Composition (Co)

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

watersugar
system

Adapted from
Fig. 9.1,
Callister 7e.

Temperature (C)

100

80

(liquid)

60

L
(liquid solution

40

i.e., syrup)

+
S
(solid
sugar)

A (20C,70)

20
0

2 phases

2 phases

20
40
60 70 80
100
Co =Composition (wt% sugar)
Chapter 9 - 4

Phase Equilibria
Simple solution system (e.g., Ni-Cu solution)
Crystal
Structure

electroneg

r (nm)

Ni

FCC

1.9

0.1246

Cu

FCC

1.8

0.1278

Both have the same crystal structure (FCC) and have

similar electronegativities and atomic radii (W. Hume
Rothery rules) suggesting high mutual solubility.
Ni and Cu are totally miscible in all proportions.
Chapter 9 - 5

Phase Diagrams
Indicate phases as function of T, Co, and P.
For this course:
-binary systems: just 2 components.
-independent variables: T and Co (P = 1 atm is almost always used).

T(C)

Phase
Diagram
for Cu-Ni
system

2 phases:

1600
1500

L (liquid)

1400

us
d
i

u
liq + s
L lidu
so

1300

(FCC solid
solution)

1200
1100
1000

L (liquid)
(FCC solid solution)

20

40

60

80

3 phase fields:
L
L+

Adapted from Fig. 9.3(a), Callister 7e.

(Fig. 9.3(a) is adapted from Phase
Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
OH (1991).

100

wt% Ni

Chapter 9 - 6

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

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

1600

L (liquid)

1500

B (1250C,35)

Examples:

T(C)

1400
1300
1200

Adapted from Fig. 9.3(a), Callister 7e.

(Fig. 9.3(a) is adapted from Phase
Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
OH, 1991).

L (FCC solid
solution)

1100
1000

Cu-Ni
phase
diagram

us
d
i
u
liq
us
d
i
l
so

A(1100C,60)
0

20

40

60

80

100

wt% Ni

Chapter 9 - 7

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
Co = 35 wt% Ni
tie line dus
qu i
i
l
1300 L (liquid)
At T A = 1320C:

+
L s
Only Liquid (L)
B
lidu
T
o
s
B
CL = Co ( = 35 wt% Ni)

At T D = 1190C:
L+
(solid)
1200
D

Only Solid ( )
TD
C = Co ( = 35 wt% Ni)
20
3032 35 4043
50
At T B = 1250C:
CLCo
C wt% Ni
Both and L
Adapted from Fig. 9.3(b), Callister 7e.
9.3(b) is adapted from Phase Diagrams
CL = C liquidus ( = 32 wt% Ni here) (Fig.
of Binary Nickel Alloys, P. Nash (Ed.), ASM
C = C solidus ( = 43 wt% Ni here) International, Materials Park, OH, 1991.)
Chapter 9 - 8

Phase Diagrams:
weight fractions of phases
Rule 3: If we know T and Co, then we know:
Cu-Ni
system

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

Examples:

Co = 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
W

S 43 35 73 wt %
R + S 43 32
R
= 27 wt%
R +S

T(C)

TA

L (liquid)

1300

TB
L

1200

TD
20

tie line dus

i
liqu

B
R S
D

3032 35

CLCo

+
L

us
d
i
l
so

(solid)

40 43

50

C wt% Ni

Adapted from Fig. 9.3(b), Callister 7e.

(Fig. 9.3(b) is adapted from Phase Diagrams of
Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH, 1991.)
Chapter 9 - 9

The Lever Rule

Tie line connects the phases in equilibrium with
each other - essentially an isotherm
T(C)
1300

tie line dus

i
liqu

L (liquid)

1200
20

+
L

TB
L

us
d
i
l
so

+
R

ML

(solid)
R

30C C
40 C

L o

wt% Ni

WL

How much of each phase?

Think of it as a lever (teeter-totter)

50

Adapted from Fig. 9.3(b),

Callister 7e.

C C0
ML
S

ML M R S C CL

M S M L R

C CL
R
0
R S C CL
Chapter 9 - 10

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)
130 0
L: 35 wt% Ni
: 46 wt% Ni

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

Consider
Co = 35 wt%Ni.

A
32

--isomorphous

L: 35wt%Ni

35

B
C

46
43

24
120 0

L+

Cu-Ni
system

L+

L: 32 wt% Ni

36

: 43 wt% Ni

L: 24 wt% Ni
: 36 wt% Ni

(solid)
110 0
20

30

Adapted from Fig. 9.4,

Callister 7e.

35
Co

40

50

wt% Ni
Chapter 9 - 11

Cored vs Equilibrium Phases

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

Fast rate of cooling:

Cored structure

Slow rate of cooling:

Equilibrium structure

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

Uniform C :
35 wt% Ni

Chapter 9 - 12

Mechanical Properties: Cu-Ni System

Effect of solid solution strengthening on:
--Ductility (%EL,%AR)

400
TS for
pure Ni

300
TS for pure Cu

200
0 20 40 60 80 100
Cu
Ni

Composition, wt% Ni

Adapted from Fig. 9.6(a), Callister 7e.

--Peak as a function of Co

Elongation (%EL)

Tensile Strength (MPa)

--Tensile strength (TS)

60

%EL for pure Cu

%EL for
pure Ni

50
40
30
20
0 20
Cu

40

60

80 100
Ni

Composition, wt% Ni

Adapted from Fig. 9.6(b), Callister 7e.

--Min. as a function of Co
Chapter 9 - 13

Binary-Eutectic Systems
has a special composition
with a min. melting T.

2 components

Cu-Ag
system

T(C)

Ex.: Cu-Ag system

1200

3 single phase regions

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

400
CE : Min. melting TE
composition
200
Eutectic transition

L(CE)

(CE) + (CE)

20

40

60 CE 80

100

Co , wt% Ag

Adapted from Fig. 9.7,

Callister 7e.
Chapter 9 - 14

EX: Pb-Sn Eutectic System (1)

For a 40 wt% Sn-60 wt% Pb alloy at 150C, find...
--the phases present: +
T(C)
--compositions of phases:
CO = 40 wt% Sn
C = 11 wt% Sn
C = 99 wt% Sn

--the relative amount

of each phase:

C - CO
S
=
W =
R+S
C - C

300

200
150
100

99 - 40
59
=
=
= 67 wt%
99 - 11
88
C - C
W = R = O
C - C
R+S
=

Pb-Sn
system

40 - 11
29
=
= 33 wt%
99 - 11
88

L (liquid)

L+

183C

18.3

61.9

L+
97.8

S
+

0 11 20
C

40
Co

Adapted from Fig. 9.8,

Callister 7e.

60

80

C, wt% Sn

99100
C

Chapter 9 - 15

EX: Pb-Sn Eutectic System (2)

For a 40 wt% Sn-60 wt% Pb alloy at 200C, find...
--the phases present: + L
T(C)
--compositions of phases:
CO = 40 wt% Sn
C = 17 wt% Sn
CL = 46 wt% Sn

--the relative amount

of each phase:
CL - C O
46 - 40
=
W =
CL - C
46 - 17
6
=
= 21 wt%
29

Pb-Sn
system

300
220
200

L (liquid)

L+
R

L+

S
183C

100

CO - C
23
=
WL =
= 79 wt%
CL - C
29

+
0

17 20
C

40 46 60
80
Co CL C, wt% Sn

Adapted from Fig. 9.8,

Callister 7e.

Chapter 9 - 16

100

Microstructures
in Eutectic Systems: I
Co < 2 wt% Sn
Result:
--at extreme ends
--polycrystal of grains
i.e., only one solid phase.

T(C)

L: Co wt% Sn

400
L

300

200

(Pb-Sn
System)

: Co wt% Sn

TE
100

Adapted from Fig. 9.11,

Callister 7e.

L+

0
Co

10

20

30

Co , wt% Sn

2
(room T solubility limit)

Chapter 9 - 17

Microstructures
in Eutectic Systems: II
L: Co wt% Sn

T(C)

2 wt% Sn < Co < 18.3 wt% Sn 400

Result:
Initially liquid +
then alone
finally two phases
polycrystal
fine -phase inclusions

300

L +

200

TE

: Co wt% Sn

100

+
0

Adapted from Fig. 9.12,

Callister 7e.
(sol.

10

20

Pb-Sn
system
30

Co
Co , wt%
2
limit at Troom )
18.3
(sol. limit at TE)

Sn

Chapter 9 - 18

Microstructures
in Eutectic Systems: III
Co = CE
Result: Eutectic microstructure (lamellar structure)
--alternating layers (lamellae) of and crystals.

T(C)
L: Co wt% Sn

300

Pb-Sn
system

200

L+

100

183C

TE

20
18.3

Adapted from Fig. 9.13,

Callister 7e.

40

Micrograph of Pb-Sn
eutectic
microstructure

: 97.8 wt% Sn
: 18.3 wt%Sn

60
CE
61.9

80

160 m
Adapted from Fig. 9.14, Callister 7e.

100
97.8

C, wt% Sn

Chapter 9 - 19

Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister

7e.

Chapter 9 - 20

Microstructures
in Eutectic Systems: IV
18.3 wt% Sn < Co < 61.9 wt% Sn
Result: crystals and a eutectic microstructure
T(C)

L: Co wt% Sn

300

Pb-Sn
system

200

L+
R

TE

100

20
18.3

Adapted from Fig. 9.16,

Callister 7e.

L+

60
61.9

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

Just below TE :
primary
eutectic
eutectic

40

Just above TE :

80

Co, wt% Sn

100
97.8

C = 18.3 wt% Sn
C = 97.8 wt% Sn
W = S = 73 wt%
R+S
W = 27 wt%
Chapter 9 - 21

Hypoeutectic & Hypereutectic

300

T(C)

Adapted from Fig. 9.8,

Callister 7e. (Fig. 9.8
adapted from Binary Phase
Diagrams, 2nd ed., Vol. 3,
T.B. Massalski (Editor-inChief), ASM International,
Materials Park, OH, 1990.)

200

L+
+

100

20

40

hypoeutectic: Co = 50 wt% Sn
(Figs. 9.14 and 9.17
from Metals
Handbook, 9th ed.,
Vol. 9,
Metallography and
Microstructures,
American Society for
Metals, Materials
Park, OH, 1985.)

L+

TE

60

80

eutectic
61.9

hypereutectic: (illustration only)

Adapted from
Fig. 9.17, Callister 7e.

Co, wt% Sn

eutectic: Co = 61.9 wt% Sn

175 m

100

(Pb-Sn
System)

160 m
eutectic micro-constituent
Adapted from Fig. 9.14,
Callister 7e.

Adapted from Fig. 9.17,

Callister 7e. (Illustration
only)
Chapter 9 - 22

Intermetallic Compounds
Adapted from
Fig. 9.20, Callister 7e.

Mg2Pb
Note: intermetallic compound forms a line - not an area because stoichiometry (i.e. composition) is exact. Chapter 9 - 23

Eutectoid & Peritectic

Eutectic - liquid in equilibrium with two solids
L cool +
heat

Eutectoid - solid phase in equation with two solid

phases
intermetallic compound
S2
S1+S3
- cementite

cool
heat

+ Fe3C

(727C)

Peritectic - liquid + solid 1 solid 2 (Fig 9.21)

S1 + L
S2
+L

cool
heat

(1493C)

Chapter 9 - 24

Eutectoid & Peritectic

Cu-Zn Phase diagram

Eutectoid transition

Peritectic transition + L

Adapted from
Fig. 9.21, Callister 7e.

Chapter 9 - 25

Iron-Carbon (Fe-C) Phase Diagram

L + Fe3C

-Eutectoid (B):
+ Fe3C

T(C)
1600

1400
1200

+L

(austenite)

1000

800
600

120 m

Result: Pearlite =
alternating layers of
and Fe3C phases
(Adapted from Fig. 9.27, Callister 7e.)

S
+Fe3C
727C = Teutectoid

400
0
(Fe)

S
1

0.76

L+Fe3C

C eutectoid

1148C

+Fe3C
4

Fe3C (cementite)

2 important
points
-Eutectic (A):

6.7

4.30
Co, wt% C
Fe3C (cementite-hard)
(ferrite-soft)

Adapted from Fig. 9.24,Callister 7e.

Chapter 9 - 26

Hypoeutectoid Steel

T(C)

1600

+L

1200
(austenite)
1000
800

+ Fe3C
r s

727C

RS

w =s/(r +s) 600

w =(1- w )
400
0

(Fe)
pearlite

L+Fe3C

1148C

+ Fe3C
1

C0

0.76

w pearlite = w

(Fe-C
System)

Fe3C (cementite)

1400

Adapted from Figs. 9.24

and 9.29,Callister 7e.
(Fig. 9.24 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
100 m Hypoeutectoid
steel

w =S/(R+S)
w Fe3C =(1-w )

pearlite

proeutectoid ferrite
Adapted from Fig. 9.30,Callister 7e.

Chapter 9 - 27

Hypereutectoid Steel

T(C)

1600

+L

1200
(austenite)

1000

800

w Fe3C =r/(r +s)

w =(1-w Fe3C )

R
600

400
0
(Fe)
pearlite

L+Fe3C

1148C

+Fe3C

0.76

Fe3C

(Fe-C
System)

s
S

1 Co

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

+Fe3C
2

Fe3C (cementite)

1400

Adapted from Figs. 9.24

and 9.32,Callister 7e.
(Fig. 9.24 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

60 mHypereutectoid
steel

pearlite

proeutectoid Fe3C
Adapted from Fig. 9.33,Callister 7e.

Chapter 9 - 28

Example: Phase Equilibria

For a 99.6 wt% Fe-0.40 wt% C at a temperature
just below the eutectoid, determine the
following
a) composition of Fe3C and ferrite ()
b) the amount of carbide (cementite) in grams
that forms per 100 g of steel
c) the amount of pearlite and proeutectoid
ferrite ()

Chapter 9 - 29

Chapter 9 Phase Equilibria

Solution: a) composition of Fe3C and ferrite ()
b) the amount of carbide
(cementite) in grams that
forms per 100 g of steel

CO = 0.40 wt% C
C = 0.022 wt% C
CFe C = 6.70 wt% C
3

1600

1200

0.4 0.022

x 100 5.7g
6.7 0.022

(austenite)

94.3 g

+ Fe3C
727C

S
+ Fe3C

600
400
0

L+Fe3C

1148C

1000
800

Fe3C 5.7 g

+L

Fe C (cementite)

Fe3C
Co C
1400

x100 T(C)
Fe3C CFe3 C C

C CO

Co , wt% C

6.7

CFe

3C

Chapter 9 - 30

Chapter 9 Phase Equilibria

c. the amount of pearlite and proeutectoid ferrite ()
note: amount of pearlite = amount of just above TE

1600

1400

T(C)
+L

Co C

x 100 51.2 g 1200

(austenite)
C C
1000

+ Fe3C

800

pearlite = 51.2 g
proeutectoid = 48.8 g

727C

RS
600
400
0

L+Fe3C

1148C

+ Fe3C
1

C CO C

Co , wt% C
Chapter 9 - 31

Fe C (cementite)

Co = 0.40 wt% C
C = 0.022 wt% C
Cpearlite = C = 0.76 wt% C

6.7

Alloying Steel with More Elements

Ti

Mo

Si

Cr
Mn
Ni

wt. % of alloying elements

Adapted from Fig. 9.34,Callister 7e. (Fig. 9.34
from Edgar C. Bain, Functions of the Alloying
Elements in Steel, American Society for Metals,
1939, p. 127.)

Ceutectoid changes:
Ceutectoid (wt%C)

T Eutectoid (C)

Teutectoid changes:

Ni
Cr
Si
Ti Mo

Mn

wt. % of alloying elements

Adapted from Fig. 9.35,Callister 7e. (Fig. 9.35
from Edgar C. Bain, Functions of the Alloying
Elements in Steel, American Society for Metals,
1939, p. 127.)

Chapter 9 - 32

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 - 33

ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:

Chapter 9 - 34