Chapter 9 - 1

Chapter 9 - 2

Chapter 9 - 3

Chapter 9 - 4

Chapter 9 - 5

Chapter 9 - 6

Chapter 9 - 7

Chapter 9: Phase Diagrams

ISSUES TO ADDRESS...
When we combine two elements...
what is the resulting equilibrium state?
In particular, if we specify...
-- the composition (e.g., wt% Cu - wt% Ni), and
-- the temperature (T)
then...
How many phases form?
What is the composition of each phase?
What is the amount of each phase?

Phase B

Phase A
Nickel atom
Copper atom

Chapter 9 - 8

znrlk Snr

Phase Equilibria: Solubility Limit

Solution solid, liquid, or gas solutions, single phase zelti
Mixture more than one phase Karm Adapted from Fig. 9.1,
Callister & Rethwisch 8e.

Sugar/Water Phase Diagram

Solubility Limit:

(liquid)

60

40

(liquid solution
i.e., syrup)

20

Answer: 65 wt% sugar.

At 20C, if C < 65 wt% sugar: syrup
At 20C, if C > 65 wt% sugar:
syrup + sugar

+
S
(solid
sugar)

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

Sugar

solubility limit for sugar in

water at 20C?

Solubility
Limit

80

Water

Question: What is the

Temperature (C)

Maximum concentration for

which only a single phase
solution exists.

100

Chapter 9 - 9

Components and Phases

Components:

(Bileen)

The elements or compounds which are present in the alloy

(e.g., Al and Cu)

Phases:

(Faz)

The physically and chemically distinct material regions

that form (e.g., a and b).
AluminumCopper
Alloy

Adapted from chapteropening photograph,

Chapter 9, Callister,
Materials Science &
Engineering: An
Introduction, 3e.

b (lighter
phase)

a (darker
phase)

Chapter 9 - 10

Effect of Temperature & Composition

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

watersugar
system

Adapted from Fig. 9.1,

Callister & Rethwisch 8e.

Temperature (C)

100

2 phases

80

(liquid)

60

L
(liquid solution

40

i.e., syrup)

+
S
(solid
sugar)

A (20C,C = 70)

20

2 phases

20
40
60 70 80
100
C = Composition (wt% sugar)
Chapter 9 - 11

Criteria for Solid Solubility

Simple 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 soluble in one another for all proportions.

Chapter 9 - 12

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

T(C)
Phase
Diagram
for Cu-Ni
system

2 phases:

1600
1500

L (liquid)
a (FCC solid solution)

L (liquid)

1400
1300

a
(FCC solid
solution)

1200
1100
1000

20

40

60

80

3 different phase fields:

L
L+a
a
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (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 - 13

Isomorphous Binary Phase Diagram

Phase diagram:
Cu-Ni system.

System is:

T(C)
1600
1500

L (liquid)

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

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

Cu-Ni
phase
diagram

1400
1300

a
(FCC solid
solution)

1200
1100
1000

20

40

60

80

100

wt% Ni

Adapted from Fig. 9.3(a), Callister &

Rethwisch 8e. (Fig. 9.3(a) is adapted from
Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
Materials Park, OH (1991).
Chapter 9 - 14

Phase Diagrams:
Determination of phase(s) present
Rule 1: If we know T and Co, then we know:
-- which phase(s) is (are) present.

A(1100C, 60 wt% Ni):

1 phase: a
B(1250C, 35 wt% Ni):
2 phases: L + a

1600

L (liquid)
B (1250C,35)

Examples:

T(C)
1500
1400
1300

A(1100C,60)

1100
1000

a
(FCC solid
solution)

1200
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
Materials Park, OH (1991).

Cu-Ni
phase
diagram

20

40

60

80

100

wt% Ni

Chapter 9 - 15

Phase Diagrams:
Determination of phase compositions
Rule 2: If we know T and C0, then we can determine:
-- the composition of each phase.

Examples:
Consider C0 = 35 wt% Ni
At TA = 1320C:
Only Liquid (L) present
CL = C0 ( = 35 wt% Ni)
At TD = 1190C:
Only Solid (a) present
Ca = C0 ( = 35 wt% Ni)
At TB = 1250C:
Both a and L present
CL = C liquidus ( = 32 wt% Ni)
Ca = C solidus ( = 43 wt% Ni)

Cu-Ni
system

T(C)

TA
1300

TB
1200
TD
20

tie line

L (liquid)
B
D
3032 35

CL C0

a
(solid)
4043

50

Ca wt% Ni

Adapted from Fig. 9.3(a), Callister &

Rethwisch 8e. (Fig. 9.3(a) is adapted from
Phase Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International, Materials
Park, OH (1991).
Chapter 9 - 16

Phase Diagrams:
Determination of phase weight fractions
Rule 3: If we know T and C0, then can determine:
-- the weight fraction of each phase.

Examples:
Consider C0 = 35 wt% Ni
At TA : Only Liquid (L) present
WL = 1.00, Wa = 0
At TD : Only Solid ( a) present
WL = 0, Wa = 1.00
At TB : Both a and L present

WL

Wa

S
R +S

43 35
0.73
43 32

R
= 0.27
R +S
The Lever Rule

Cu-Ni
system

T(C)

TA
1300

TB
1200
TD
20

tie line

L (liquid)
B
R S
D
3032 35

CL C0

a
(solid)

40 43

50

Ca wt% Ni

Adapted from Fig. 9.3(a), Callister &

Rethwisch 8e. (Fig. 9.3(a) is adapted from
Phase Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International, Materials
Park, OH (1991).
Chapter 9 - 17

Ex: Cooling of a Cu-Ni Alloy

Phase diagram:
Cu-Ni system.

Consider
microstuctural
changes that
accompany the
cooling of a

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

C0 = 35 wt% Ni alloy

L: 35wt%Ni

Cu-Ni
system

A
35
32

B
C

46
43

24

L: 32 wt% Ni

36

120 0

a: 43 wt% Ni

L: 24 wt% Ni
a: 36 wt% Ni

a
(solid)
110 0
20

30

Adapted from Fig. 9.4,

Callister & Rethwisch 8e.

35
C0

40

50

wt% Ni
Chapter 9 - 18

Cored vs Equilibrium Structures

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

Slow rate of cooling:

Equilibrium structure
Uniform Ca:
35 wt% Ni

Fast rate of cooling:

Cored structure
First a to solidify:
46 wt% Ni
Last a to solidify:
< 35 wt% Ni

Chapter 9 - 19

Mechanical Properties: Cu-Ni System

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

400
TS for
pure Ni

300
TS for pure Cu
200
0 20 40
Cu

60 80 100
Ni

Composition, wt% Ni
Adapted from Fig. 9.6(a),
Callister & Rethwisch 8e.

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 & Rethwisch 8e.

Chapter 9 - 20

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, a, b)
a L + a 779C
Limited solubility:
TE 800 8.0
a: mostly Cu
b: mostly Ag
600
TE : No liquid below TE
a+b
400
CE : Composition at
temperature TE
200
Eutectic reaction

20

a(CaE) + b(CbE)

L(CE)
L(71.9 wt% Ag)

cooling
heating

40

L+b b

71.9 91.2

60 CE 80

100

C, wt% Ag
Adapted from Fig. 9.7,
Callister & Rethwisch 8e.

a(8.0 wt% Ag) + b(91.2 wt% Ag)

Chapter 9 -

21

Binary-Eutectic HOT CHOCOLATE

Chapter 9 -

EX 1: Pb-Sn Eutectic System

For a 40 wt% Sn-60 wt% Pb alloy at 150C, determine:
-- the phases present
Answer: a + b
-- the phase compositions
Answer: Ca = 11 wt% Sn
Cb = 99 wt% Sn

-- the relative amount

of each phase
Answer:
S
=
W =
R+S
a
99 - 40
=
99 - 11
Wb = R =
R+S
40 - 11
=
99 - 11

T(C)
300

200

59
= 0.67
88
C0 - Ca
Cb - Ca

29
= 0.33
88

L (liquid)
a

L+ a

100

L+b b

183C

18.3
150

Cb - C0
Cb - Ca

Pb-Sn
system

61.9

97.8

S
a+b

0 11 20
Ca

40
C0

60

80

C, wt% Sn

99100
Cb

Adapted from Fig. 9.8,

Callister & Rethwisch 8e.
Chapter 9 - 23

EX 2: Pb-Sn Eutectic System

For a 40 wt% Sn-60 wt% Pb alloy at 220C, determine:
-- the phases present:
Answer: a + L
-- the phase compositions
Answer: Ca = 17 wt% Sn
CL = 46 wt% Sn

-- the relative amount

of each phase

Pb-Sn
system

T(C)
300

220
200

L (liquid)

L+a
R

L+b b

S
183C

Answer:
CL - C0
46 - 40
=
Wa =
CL - Ca
46 - 17
6
=
= 0.21
29
C0 - Ca
23
=
= 0.79
WL =
CL - Ca
29

100

a+b
0

17 20
Ca

40 46 60
C0 CL

80

C, wt% Sn

Adapted from Fig. 9.8,

Callister & Rethwisch 8e.
Chapter 9 - 24

100

Microstructural Developments
in Eutectic Systems I
For alloys for which
C0 < 2 wt% Sn
Result: at room temperature
-- polycrystalline with grains of
a phase having
composition C0

T(C)
400

L
a

300

200

TE
100

Adapted from Fig. 9.11,

Callister & Rethwisch 8e.

L: C0 wt% Sn

L+ a

a: C0 wt% Sn

(Pb-Sn
System)

a+ b

0
10
20
30
C0
C , wt% Sn
2
(room T solubility limit)
Chapter 9 - 25

Microstructural Developments
in Eutectic Systems II
For alloys for which
400
2 wt% Sn < C0 < 18.3 wt% Sn
Result:
at temperatures in a + b range 300
-- polycrystalline with a grains
and small b-phase particles 200

L: C0 wt% Sn

T(C)
L
L+a
a

TE

a: C0 wt% Sn

a
b

100

Adapted from Fig. 9.12,

Callister & Rethwisch 8e.

L
a

a+ b

10

20

Pb-Sn
system
30

C0
C, wt%
2
(sol. limit at T room )
18.3
(sol. limit at TE)

Sn

Chapter 9 - 26

Microstructural Developments
in Eutectic Systems III
For alloy of composition C0 = CE
Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of a and b phases.

T(C)
L: C0 wt% Sn

300

Pb-Sn
system

200

L+ a

L
L+b b

183C

TE

100

a+b
0

20
18.3

Adapted from Fig. 9.13,

Callister & Rethwisch 8e.

Micrograph of Pb-Sn
eutectic
microstructure

40

b: 97.8 wt% Sn
a: 18.3 wt%Sn

60
CE
61.9

80

160 m
Adapted from Fig. 9.14,
Callister & Rethwisch 8e.

100
97.8

C, wt% Sn

Chapter 9 - 27

Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister

& Rethwisch 8e.

Chapter 9 - 28

Microstructural Developments
in Eutectic Systems IV
For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn
Result: a phase particles and a eutectic microconstituent
L: C0 wt% Sn
L

T(C)
300

Pb-Sn
system

200

L+ a
R

TE

L+

b b

20
18.3

Adapted from Fig. 9.16,

Callister & Rethwisch 8e.

primary a
eutectic a
eutectic b

40

60
61.9

Just above TE :
Ca = 18.3 wt% Sn
CL = 61.9 wt% Sn
S
= 0.50
=
Wa
R+S
WL = (1- Wa) = 0.50

Just below TE :

a+b

100

80

C, wt% Sn

100
97.8

Ca = 18.3 wt% Sn
Cb = 97.8 wt% Sn
Wa = S = 0.73
R+S
Wb = 0.27
Chapter 9 - 29

Hypoeutectic & Hypereutectic

300

T(C)

Adapted from Fig. 9.8,

Callister & Rethwisch 8e.
(Fig. 10.8 adapted from
Binary Phase Diagrams,
2nd ed., Vol. 3, T.B.
Massalski (Editor-in-Chief),
ASM International,
Materials Park, OH, 1990.)

200

L+ a
a+b

20

40

hypoeutectic: C0 = 50 wt% Sn

a
a

(Pb-Sn
System)

100

0
(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+b b

TE

60

80

eutectic
61.9

hypereutectic: (illustration only)

b
b

Adapted from
Fig. 9.17, Callister &
Rethwisch 8e.

C, wt% Sn

eutectic: C0 = 61.9 wt% Sn

a a
175 m

100

b
b b
b

160 m
eutectic micro-constituent
Adapted from Fig. 9.14,
Callister & Rethwisch 8e.

Adapted from Fig. 9.17,

Callister & Rethwisch 8e.
(Illustration only)
Chapter 9 - 30

Intermetallic Compounds
Adapted from
Fig. 9.20, Callister &
Rethwisch 8e.

Mg2Pb
Note: intermetallic compound exists as a line on the diagram - not an
area - because of stoichiometry (i.e. composition of a compound
Chapter 9 - 31
is a fixed value).

Eutectic, Eutectoid, & Peritectic

Eutectic - liquid transforms to two solid phases
L cool a + b
(For Pb-Sn, 183C, 61.9 wt% Sn)
heat

Eutectoid one solid phase transforms to two other

solid phases
intermetallic compound
- cementite
S2
S1+S3
cool a + Fe3C (For Fe-C, 727C, 0.76 wt% C)
heat

Peritectic - liquid and one solid phase transform to a

second solid phase
S1 + L
S2
+L

cool
heat

(For Fe-C, 1493C, 0.16 wt% C)

Chapter 9 - 32

Eutectoid & Peritectic

Peritectic transformation + L

Cu-Zn Phase diagram

Eutectoid transformation

Adapted from Fig. 9.21,

Callister & Rethwisch 8e.

Chapter 9 - 33