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 A Phase B

Nickel atom
Copper atom Chapter 9 - 1
 Phase Equilibria: Solubility Limit
Solution solid, liquid, or gas solutions, single phase
Mixture more than one phase Adapted from Fig. 9.1,
Callister & Rethwisch 8e.

Sugar/Water Phase Diagram

Solubility Limit: 100
Maximum concentration for Solubility

Temperature (C)
which only a single phase 80 Limit L
solution exists. (liquid)
60 +
L
Question: What is the 40 (liquid solution S
solubility limit for sugar in i.e., syrup) (solid
water at 20C? 20 sugar)

Answer: 65 wt% sugar.

0 20 40 6065 80 100
At 20C, if C < 65 wt% sugar: syrup

Sugar
Water

C = Composition (wt% sugar)

At 20C, if C > 65 wt% sugar:
syrup + sugar Chapter 9 - 2
 Components and Phases
Components:
The elements or compounds which are present in the alloy
(e.g., Al and Cu)
Phases:
The physically and chemically distinct material regions
that form (e.g., a and b).

Aluminum- b (lighter
Copper
phase)
Alloy

a (darker
Adapted from chapter-
opening photograph,
phase)
Chapter 9, Callister,
Materials Science &
Engineering: An
Introduction, 3e.

Chapter 9 - 3
 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 2 phases
100

80 L
Temperature (C)

(liquid)
water- 60 +
sugar L S
system (liquid solution (solid
40 i.e., syrup) sugar)
20 A (20C,C = 70)
2 phases
Adapted from Fig. 9.1, 0
Callister & Rethwisch 8e. 0 20 40 60 70 80 100
C = Composition (wt% sugar)
Chapter 9 - 4
 Criteria for Solid Solubility

Simple system (e.g., Ni-Cu solution)

Crystal electroneg r (nm)

Structure
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 - 5
 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
1600 2 phases:
Diagram L (liquid)
1500
for Cu-Ni L (liquid) a (FCC solid solution)
system 1400 3 different phase fields:
L
1300 L+a
a
1200 a Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
1100
(FCC solid Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
solution) Materials Park, OH (1991).
1000
0 20 40 60 80 100 wt% Ni Chapter 9 - 6
 Isomorphous Binary Phase Diagram
Phase diagram: T(C)
Cu-Ni system. 1600

System is: 1500 L (liquid) Cu-Ni

-- binary phase
i.e., 2 components: 1400
diagram
Cu and Ni.
1300
-- isomorphous
i.e., complete 1200 a
solubility of one
component in 1100
(FCC solid
another; a phase solution)
field extends from 1000
0 to 100 wt% Ni.
0 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 - 7
 Phase Diagrams:
Determination of phase(s) present
Rule 1: If we know T and Co, then we know:
-- which phase(s) is (are) present.
T(C)
Examples: 1600
A(1100C, 60 wt% Ni): L (liquid)
1 phase: a

B (1250C,35)
1500
Cu-Ni
B(1250C, 35 wt% Ni): 1400 phase
2 phases: L + a diagram
1300 a
(FCC solid
1200
Adapted from Fig. 9.3(a), Callister &
solution)
Rethwisch 8e. (Fig. 9.3(a) is adapted from 1100 A(1100C,60)
Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
Materials Park, OH (1991). 1000
0 20 40 60 80 100 wt% Ni
Chapter 9 - 8
 Phase Diagrams:
Determination of phase compositions
Rule 2: If we know T and C0, then we can determine:
-- the composition of each phase. Cu-Ni
T(C) system
Examples:
TA A
Consider C0 = 35 wt% Ni tie line
At TA = 1320C: 1300 L (liquid)
Only Liquid (L) present B
CL = C0 ( = 35 wt% Ni) TB
a
At TD = 1190C:
1200 D (solid)
Only Solid (a) present TD
Ca = C0 ( = 35 wt% Ni)
20 3032 35 4043 50
At TB = 1250C: CL C0 Ca wt% Ni
Both a and L present Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
CL = C liquidus ( = 32 wt% Ni) Phase Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International, Materials
Ca = C solidus ( = 43 wt% Ni) Park, OH (1991).

Chapter 9 - 9
 Phase Diagrams:
Determination of phase weight fractions
Rule 3: If we know T and C0, then can determine:
-- the weight fraction of each phase. Cu-Ni
Examples: T(C) system
Consider C0 = 35 wt% Ni TA A
tie line
At TA : Only Liquid (L) present 1300 L (liquid)
WL = 1.00, Wa = 0 B
At TD : Only Solid ( a) present TB R S
a
WL = 0, Wa = 1.00
1200 D (solid)
At TB : Both a and L present TD
S 43 35
WL
20 3032 35 40 43 50
0.73 CL C 0 Ca wt% Ni
R +S 43 32
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
R
Wa
Phase Diagrams of Binary Nickel Alloys, P.
= 0.27 Nash (Ed.), ASM International, Materials
R +S Park, OH (1991).

Chapter 9 - 10
 The Lever Rule
Tie line connects the phases in equilibrium with
each other also sometimes called an isotherm
T(C) What fraction of each phase?
tie line
Think of the tie line as a lever
1300 L (liquid)
(teeter-totter)
B
TB ML Ma
a
1200 (solid)
R S

20 30CL R S
C0 40 Ca 50

wt% Ni Ma x S ML x R
Adapted from Fig. 9.3(b),
Callister & Rethwisch 8e.

ML S C C0 R C CL
WL a Wa 0
ML M a R S Ca CL R S Ca CL
Chapter 9 - 11
 Ex: Cooling of a Cu-Ni Alloy
Phase diagram: T(C) L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
system
Consider 130 0 A
L: 35 wt% Ni
microstuctural a: 46 wt% Ni B
35 46
changes that 32 C 43
accompany the D
24 36 L: 32 wt% Ni
cooling of a a: 43 wt% Ni
C0 = 35 wt% Ni alloy 120 0 E
L: 24 wt% Ni
a: 36 wt% Ni
a
(solid)

110 0
20 30 35 40 50
Adapted from Fig. 9.4, C0 wt% Ni
Callister & Rethwisch 8e.
Chapter 9 - 12
 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: Fast rate of cooling:
Equilibrium structure Cored structure
Uniform Ca:
35 wt% Ni First a to solidify:
46 wt% Ni
Last a to solidify:
< 35 wt% Ni

Chapter 9 - 13
 Mechanical Properties: Cu-Ni System
Effect of solid solution strengthening on:
-- Tensile strength (TS) -- Ductility (%EL)
Tensile Strength (MPa)

60

Elongation (%EL)
%EL for pure Cu
400 50 %EL for
TS for pure Ni
pure Ni 40
300
TS for pure Cu 30
200 20
0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
Composition, wt% Ni Composition, wt% Ni
Adapted from Fig. 9.6(a), Adapted from Fig. 9.6(b),
Callister & Rethwisch 8e. Callister & Rethwisch 8e.

Chapter 9 - 14
 Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
Cu-Ag
T(C) system
Ex.: Cu-Ag system 1200
3 single phase regions L (liquid)
(L, a, b) 1000
Limited solubility: a L + a 779C L+b b
a: mostly Cu TE 800 8.0 71.9 91.2
b: mostly Ag 600
TE : No liquid below TE ab
CE : Composition at 400
temperature TE 200
0 20 40 60 CE 80 100
Eutectic reaction C, wt% Ag
L(CE) a(CaE) + b(CbE) Adapted from Fig. 9.7,
Callister & Rethwisch 8e.
cooling
L(71.9 wt% Ag) a(8.0 wt% Ag) b(91.2 wt% Ag)
Chapter 9 - 15
heating
 EX 1: Pb-Sn Eutectic System
For a 40 wt% Sn-60 wt% Pb alloy at 150C, determine:
-- the phases present Pb-Sn
Answer: a + b T(C) system
-- the phase compositions
300
Answer: Ca = 11 wt% Sn L (liquid)
Cb = 99 wt% Sn
-- the relative amount a L+ a
200 183C L+b b
of each phase 18.3 61.9 97.8
Answer: 150
S Cb - C0 R S
100
W =
a R+S
=
Cb - Ca a+b
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C0 - Ca Ca C0 Cb
Wb = R = C, wt% Sn
R+S Cb - Ca Adapted from Fig. 9.8,
Callister & Rethwisch 8e.
40 - 11 29
= = = 0.33 Chapter 9 - 16
99 - 11 88
 EX 2: Pb-Sn Eutectic System
For a 40 wt% Sn-60 wt% Pb alloy at 220C, determine:
-- the phases present: Pb-Sn
Answer: a + L T(C) system
-- the phase compositions
300
Answer: Ca = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+a
-- the relative amount 220
200
a R S L+b b
of each phase 183C
Answer:
100
Wa =
CL - C0
=
46 - 40 a+b
CL - Ca 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 Ca C0 CL
29 C, wt% Sn
Adapted from Fig. 9.8,
C0 - Ca 23 Callister & Rethwisch 8e.
WL = = = 0.79
CL - Ca 29
Chapter 9 - 17
 Microstructural Developments
in Eutectic Systems I

For alloys for which T(C)

400
L: C0 wt% Sn

C0 < 2 wt% Sn L
Result: at room temperature a
300 L
-- polycrystalline with grains of
a phase having L+ a
a
composition C0 200 (Pb-Sn
TE a: C0 wt% Sn
System)

a+ b
100

0 10 20 30
Adapted from Fig. 9.11, C0 C , wt% Sn
Callister & Rethwisch 8e. 2
(room T solubility limit)

Chapter 9 - 18
 Microstructural Developments
in Eutectic Systems II
L: C0 wt% Sn
For alloys for which 400
T(C)
2 wt% Sn < C0 < 18.3 wt% Sn L
Result: L
at temperatures in a + b range 300 a
L+a
-- polycrystalline with a grains a: C0 wt% Sn
and small b-phase particles 200 a
TE
a
b
100
a+ b Pb-Sn
system
Adapted from Fig. 9.12, 0 10 20 30
Callister & Rethwisch 8e. 2 C0 C, wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)
Chapter 9 - 19
 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.
Micrograph of Pb-Sn
T(C) eutectic
L: C0 wt% Sn microstructure
300 L
Pb-Sn
system
L+a
200
a 183C Lb b
TE

100 160 m
ab b: 97.8 wt% Sn
Adapted from Fig. 9.14,
a: 18.3 wt%Sn Callister & Rethwisch 8e.

0 20 40 60 80 100
18.3 CE 97.8
Adapted from Fig. 9.13, 61.9 C, wt% Sn Chapter 9 - 20
Callister & Rethwisch 8e.
 Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister

& Rethwisch 8e.

Chapter 9 - 21
 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
Just above TE :
T(C) L: C0 wt% Sn L
a Ca = 18.3 wt% Sn
L
300 L CL = 61.9 wt% Sn
Pb-Sn a S
L+ a Wa = = 0.50
system R+S
a
b b
200 R S L+ WL = (1- Wa) = 0.50
TE S
R
Just below TE :
100 a+b Ca = 18.3 wt% Sn
primary a Cb = 97.8 wt% Sn
eutectic a
eutectic b Wa = S = 0.73
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wb = 0.27
Adapted from Fig. 9.16,
Callister & Rethwisch 8e. C, wt% Sn Chapter 9 - 22
 Hypoeutectic & Hypereutectic
300
L
T(C)
L+ a
Adapted from Fig. 9.8,
Callister & Rethwisch 8e. a L+b b
(Fig. 10.8 adapted from
200
TE
(Pb-Sn
Binary Phase Diagrams,
2nd ed., Vol. 3, T.B. a+b System)
Massalski (Editor-in-Chief), 100
ASM International,
Materials Park, OH, 1990.)

0 20 40 60 80 100 C, wt% Sn
eutectic
hypoeutectic: C0 = 50 wt% Sn 61.9 hypereutectic: (illustration only)
(Figs. 9.14 and 9.17
from Metals
eutectic: C0 = 61.9 wt% Sn
Handbook, 9th ed.,
Vol. 9,
a b
Metallography and a b
Microstructures, a a b b
American Society for a b
Metals, Materials
Park, OH, 1985.) a b
175 m 160 m
Adapted from eutectic micro-constituent Adapted from Fig. 9.17,
Fig. 9.17, Callister & Adapted from Fig. 9.14, Callister & Rethwisch 8e.
Rethwisch 8e. Callister & Rethwisch 8e. (Illustration only)
Chapter 9 - 23
 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 - 24
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
S2 S1+S3 - cementite

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
cool
+L heat (For Fe-C, 1493C, 0.16 wt% C)

Chapter 9 - 25
 Eutectoid & Peritectic
Peritectic transformation + L
Cu-Zn Phase diagram

Adapted from Fig. 9.21,

Callister & Rethwisch 8e.
Eutectoid transformation +
Chapter 9 - 26
 Iron-Carbon (Fe-C) Phase Diagram
2 important T(C)
1600
points
- Eutectic (A): 1400 L
L + Fe3C +L
1200 1148C
A L+Fe3C
- Eutectoid (B): (austenite)

Fe3C (cementite)
a + Fe3C 1000
+Fe3C

a
800 727C = T eutectoid
B
600
a+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 C, wt% C
120 m
Result: Pearlite = Fe3C (cementite-hard)
alternating layers of
a and Fe3C phases a (ferrite-soft)
(Adapted from Fig. 9.27, Adapted from Fig. 9.24,
Chapter 9 - 27
Callister & Rethwisch 8e.) Callister & Rethwisch 8e.
 Hypoeutectoid Steel
T(C)
1600

1400 L
(Fe-C
+L
1200 1148C L+Fe3C System)

Fe3C (cementite)
(austenite)
1000
+ Fe3C Adapted from Figs. 9.24
and 9.29,Callister &
a Rethwisch 8e.
a 800 727C (Fig. 9.24 adapted from
a a Binary Alloy Phase
Diagrams, 2nd ed., Vol.
600
a + Fe3C 1, T.B. Massalski (Ed.-in-
Chief), ASM International,
Materials Park, OH,
400 1990.)
a 0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76

pearlite

Hypoeutectoid
100 m
steel

pearlite proeutectoid ferrite

Adapted from Fig. 9.30, Callister & Rethwisch 8e. Chapter 9 - 28
 Hypoeutectoid Steel
T(C)
1600

1400 L
(Fe-C
a +L
System)
a 1200 1148C L+Fe3C

Fe3C (cementite)
(austenite)
a
1000
+ Fe3C Adapted from Figs. 9.24
Wa = s/(r + s) and 9.29,Callister &
Rethwisch 8e.
800 r s 727C
W =(1 - Wa) (Fig. 9.24 adapted from

aRS Binary Alloy Phase

Diagrams, 2nd ed., Vol.
a 600
a + Fe3C 1, T.B. Massalski (Ed.-in-
Chief), ASM International,
pearlite Materials Park, OH,
400 1990.)
0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76

Wpearlite = W
Wa = S/(R + S) 100 m
Hypoeutectoid
steel
WFe3C =(1 Wa)
pearlite proeutectoid ferrite
Adapted from Fig. 9.30, Callister & Rethwisch 8e. Chapter 9 - 29
 Hypereutectoid Steel
T(C)
1600

1400 L (Fe-C
+L System)


1200 1148C L+Fe3C

Fe3C (cementite)
(austenite)
1000
+Fe3C Adapted from Figs. 9.24
and 9.32,Callister &
Fe3C

Rethwisch 8e. (Fig. 9.24
800 adapted from Binary Alloy
a Phase Diagrams, 2nd
ed., Vol. 1, T.B. Massalski
600
a +Fe3C (Ed.-in-Chief), ASM
International, Materials
Park, OH, 1990.)
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
pearlite

60 mHypereutectoid
steel
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. Chapter 9 - 30
 Hypereutectoid Steel
T(C)
1600

1400 L (Fe-C
+L System)
Fe3C
1200 1148C L+Fe3C

Fe3C (cementite)
(austenite)
1000
+Fe3C Adapted from Figs. 9.24
and 9.32,Callister &
W =x/(v + x) Rethwisch 8e. (Fig. 9.24
800 v x adapted from Binary Alloy
WFe3C =(1-W)
a V X
Phase Diagrams, 2nd
ed., Vol. 1, T.B. Massalski
600
a +Fe3C (Ed.-in-Chief), ASM
pearlite International, Materials
Park, OH, 1990.)
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
Wpearlite = W
Wa = X/(V + X)
60 mHypereutectoid
WFe =(1 - Wa) steel
3C
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. Chapter 9 - 31
 Example Problem
For a 99.6 wt% Fe-0.40 wt% C steel at a
temperature just below the eutectoid,
determine the following:
a) The compositions of Fe3C and ferrite (a).
b) The amount of cementite (in grams) that
forms in 100 g of steel.
c) The amounts of pearlite and proeutectoid
ferrite (a) in the 100 g.

Chapter 9 - 32
 Solution to Example Problem
a) Using the RS tie line just below the eutectoid
Ca = 0.022 wt% C
CFe3C = 6.70 wt% C

b) Using the lever rule with 1600

the tie line shown
1400 L
R C Ca T(C)
WFe3C 0 +L
R S CFe3C Ca

Fe C (cementite)
1200 1148C L+Fe3C
(austenite)
0.40 0.022
0.057 1000
+ Fe3C
6.70 0.022
800 727C
R S
Amount of Fe3C in 100 g 600 a + Fe3C
= (100 g)WFe3C 400
0 1 2 3 4 5 6 6.7
Ca C0 C, wt% C CFe
3C
= (100 g)(0.057) = 5.7 g
Chapter 9 - 33
 Solution to Example Problem (cont.)
c) Using the VX tie line just above the eutectoid and
realizing that
C0 = 0.40 wt% C
Ca = 0.022 wt% C
Cpearlite = C = 0.76 wt% C
1600

1400 L
V C Ca T(C) +L
Wpearlite 0

Fe C (cementite)
V X C Ca 1200
(austenite)
1148C L+Fe3C

0.40 0.022 1000

0.512 + Fe3C
0.76 0.022
800 727C
VX
Amount of pearlite in 100 g 600 a + Fe3C
= (100 g)Wpearlite 400
0 1 2 3 4 5 6 6.7
Ca C0 C C, wt% C
= (100 g)(0.512) = 51.2 g
Chapter 9 - 34
 VMSE: Interactive Phase Diagrams
Microstructure, phase compositions, and phase fractions respond interactively

Change alloy composition Chapter 9 - 35

 Alloying with Other Elements

Teutectoid changes: Ceutectoid changes:

Ceutectoid (wt% C)
Ti
T Eutectoid (C)

Si
Mo W Ni
Cr
Cr Si
Mn
Mn W
Ti Mo
Ni

wt. % of alloying elements wt. % of alloying elements

Adapted from Fig. 9.34,Callister & Rethwisch 8e. Adapted from Fig. 9.35,Callister & Rethwisch 8e.
(Fig. 9.34 from Edgar C. Bain, Functions of the (Fig. 9.35 from Edgar C. Bain, Functions of the
Alloying Elements in Steel, American Society for Alloying Elements in Steel, American Society for
Metals, 1939, p. 127.) Metals, 1939, p. 127.)

Chapter 9 - 36
 Summary

Phase diagrams are useful tools to determine:

-- the number and types of phases present,
-- the composition of each phase,
-- and the weight fraction of each phase
given the temperature and composition of the system.
The microstructure of an alloy depends on
-- its composition, and
-- whether or not cooling rate allows for maintenance of
equilibrium.
Important phase diagram phase transformations include
eutectic, eutectoid, and peritectic.

Chapter 9 - 37
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 9 - 38