Chapter 5: 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 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:
10 0
Maximum concentration for Solubility
which only a single phase L

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

Answer: 65 wt% sugar.

0 20 40 60 65 80 100
At 20ºC, if C < 65 wt% sugar: syrup
Water

Sugar
C = Composition (wt% sugar)
At 20ºC, if C > 65 wt% sugar:
syrup + sugar 3
Components
• Components: and Phases
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- phase)
opening photograph,
Chapter 9, Callister,
Materials Science &
Engineering: An
Introduction, 3e.

4
Effect of• Altering
Temperature & Composition
T can change # of phases: path A to B.
• Altering C can change # of phases: path B to D.
B (100ºC,C = 70) D (100ºC,C = 90)
1 phase 2 phases
100

80 L

Temperature (ºC)
(liquid)
water- 60 +
L
sugar S
system 40 (liquid solution (solid
i.e., syrup) sugar)
20 A (20ºC,C = 70)
2 phases

Adapted from Fig. 9.1,

0
Callister & Rethwisch 8e. 0 20 40 60 70 80 100
C = Composition (wt% sugar)
5
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.

6
Phase• Indicate
Diagrams
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(ºC)
Phase
1600 • 2 phases:
L (liquid)
Diagram 1500 L (liquid) a (FCC solid solution)
for Cu-Ni
system 1400 • 3 different phase fields:
L
1300 L+ a
1200 a a
Adapted from Fig. 9.3(a), Callister &
(FCC solid Rethwisch 8e. (Fig. 9.3(a) is adapted from
Phase Diagrams of Binary Nickel Alloys, P.
1100 Nash (Ed.), ASM International, Materials Park,
solution)
OH (1991).
1000
0 20 40 60 80 100 wt% Ni 7
Isomorphous Binary Phase Diagram
• Phase diagram: T(ºC)
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
(FCC solid
component in 1100
another; a phase solution)
field extends from 1000
0 20 40 60 80 100 wt% Ni
0 to 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).
8
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(ºC)
• Examples:
1600
A(1100ºC, 60 wt% Ni): L (liquid)
1 phase: a 1500

B (1250ºC,35)
Cu-Ni
B (1250ºC, 35 wt% Ni): 1400 phase
2 phases: L + a diagram
1300 a
(FCC solid
1200
solution)
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from 1100 A(1100ºC,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

9
Phase Diagrams:
Determination of know
• Rule 2: If we phase compositions
T and C , then we can determine:
0
-- the composition of each phase. Cu-Ni
T(ºC) system
• Examples:
TA A
Consider C0 = 35 wt% Ni tie line
At TA = 1320ºC: 1300 L (liquid)
Only Liquid (L) present B
CL = C0 ( = 35 wt% Ni) TB
a
At TD = 1190ºC:
1200 D (solid)
Only Solid (a) present TD
Ca = C0 ( = 35 wt% Ni)
20 3032 35 40 4 3 50
At TB = 1250ºC: 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 Phase Diagrams
CL = C liquidus ( = 32 wt% Ni) of Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH (1991).
Ca = C solidus ( = 43 wt% Ni)
10
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: system
T(ºC)
Consider C0 = 35 wt% Ni A
TA 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
WL = 0, W a = 1.00 a
1200 D (solid)
At TB : Both a and L present TD

S 43  35 20 3032 35 40 4 3 50
WL   0.73 CL C0 Ca wt% Ni
R + S 43  32
Adapted from Fig. 9.3(a), Callister & Rethwisch
8e. (Fig. 9.3(a) is adapted from Phase Diagrams
R
Wa  = 0.27
of Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH (1991).
R + S
11
The Lever Rule
• Tie line – connects the phases in equilibrium with each
other – also sometimes called an isotherm
T(ºC) 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 Adapted from Fig. 9.3(b),

Callister & Rethwisch 8e. Ma x S  ML x R
ML S C  C0 R C  CL
WL    a Wa   0
ML  Ma R  S Ca  CL R  S Ca  CL
 12
Ex: Cooling of a Cu-Ni
• Phase diagram: T(ºC)
Alloy
L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
• Consider 130 0 system
A
microstuctural L: 35 wt% Ni
changes that a: 46 wt% Ni B
35 46
accompany the 32 C 43
cooling of a
24 D L: 32 wt% Ni
C0 = 35 wt% Ni alloy 36
a: 43 wt% Ni
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.
13
Cored• Cvs
a
Equilibrium
changes as we solidify.
Structures
• 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

14
Mechanical Properties: Cu-Ni System
• Effect of solid solution strengthening on:

-- Tensile strength (TS) -- Ductility (%EL)

60
Tensile Strength (MPa) %EL for pure Cu

Elongation (%EL)
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), Callister Adapted from Fig. 9.6(b), Callister
& Rethwisch 8e. & Rethwisch 8e.

15
Binary-Eutectic Systemshas a special composition
2 components with a min. melting T.
Cu-Ag
T(ºC)
Ex.: Cu-Ag system system
1200
• 3 single phase regions L (liquid)
(L, a, b) 1000
• Limited solubility: a L + a
TE 800 779ºC L +b b
a: mostly Cu 8.0 71.9 91.2
b: mostly Ag 600
• TE : No liquid below TE a  b
• 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) 16
heating
EX 1:• For
Pb-Sn Eutectic
a 40 wt% Sn-60 System
wt% Pb alloy at 150ºC, determine:
-- the phases present Pb-Sn
T(ºC)
Answer: a + b system
-- the phase compositions
300
Answer: Ca = 11 wt% Sn L (liquid)
Cb = 99 wt% Sn
a L+ a
-- the relative amount 200 183ºC L +b b
of each phase 18.3 61.9 97.8
Answer: 150
S Cb - C0 R S
W = = 100
R+S Cb - Ca a + b
a
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C0 - Ca Ca C0 C, wt% Sn Cb
Wb = R =
R+S Cb - Ca Adapted from Fig. 9.8, Callister &
Rethwisch 8e.
40 - 11 29
= = = 0.33 17
99 - 11 88
EX 2:• For
Pb-Sn Eutectic
a 40 wt% Sn-60 System
wt% Pb alloy at 220ºC, determine:
-- the phases present: Pb-Sn
T(ºC)
Answer: a + L system
-- the phase compositions
300
Answer: Ca = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+a
-- the relative amount 220 a
200 R S L +b b
of each phase 183ºC
Answer:
100
CL - C0 46 - 40 a + b
Wa = =
CL - Ca 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 Ca C0 CL C, wt% Sn
29
Adapted from Fig. 9.8, Callister &
C0 - Ca 23 Rethwisch 8e.
WL = = = 0.79
CL - Ca 29
18
Microstructural Developments
in Eutectic Systems I
• For alloys for which T(ºC) L: C0 wt% Sn
C0 < 2 wt% Sn 400
• Result: at room temperature L
a
-- polycrystalline with grains of 300 L
a phase having
composition C0 L+ a
200
a
a: C0 wt% Sn
(Pb-Sn
TE
System)

100
a+ b

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

19
Microstructural Developments
in Eutectic Systems II
L: C0 wt% Sn
• For alloys for which T(ºC)
2 wt% Sn < C0 < 18.3 wt% Sn 400
• Result: L
at temperatures in a + b range L
-- polycrystalline with a grains 300 a
and small b-phase particles L +a
a: C0 wt% Sn
a
200
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)
20
Microstructural Developments
in Eutectic Systems
• For alloy of composition C0 = CE III
• Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of a and b phases.

T(ºC) Micrograph of Pb-Sn

eutectic
L: C0 wt% Sn microstructure
300 L
Pb-Sn L+a
system
a
200 183ºC Lb b
TE

100 160m
ab 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 21
Callister & Rethwisch 8e.
Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister &

Rethwisch 8e.

22
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

T(ºC) • Just above TE :

L: C0 wt% Sn L
a Ca = 18.3 wt% Sn
L
300 L CL = 61.9 wt% Sn
a
Pb-Sn
L+a Wa = S = 0.50
system a R +S
200 R S L+ b WL = (1- W a) = 0.50
TE b
R S
• Just below TE :
100 a+ b C a = 18.3 wt% Sn
primary a C b = 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 W b = 0.27
Adapted from Fig. 9.16,
Callister & Rethwisch 8e. C, wt% Sn 23
Hypoeutectic & Hypereutectic 300
L
Adapted from Fig. 9.8, T(ºC)
a L+a
Callister & Rethwisch 8e. (Fig.
10.8 adapted from Binary
200 L +b b (Pb-Sn
TE
Phase Diagrams, 2nd ed., Vol.
3, T.B. Massalski (Editor-in- a+ b
System)
Chief), ASM International, 100
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, Metallography
a b
and Microstructures, a b
American Society for a a b b
Metals, Materials a b
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)
24
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
25
is a fixed value).
Eutectic, Eutectoid, & Peritectic
• Eutectic - liquid transforms to two solid phases
L cool a + b (For Pb-Sn, 183ºC, 61.9 wt% Sn)
heat
• Eutectoid – one solid phase transforms to two other solid phases
S2 S1+S3
 a + Fe3C (For Fe-C, 727ºC,
intermetallic
0.76 wt%compound
C) -
cementite
cool
heat

• Peritectic - liquid and one solid phase transform to a second solid phase
S1 + L S2

 +L  (For Fe-C, 1493ºC, 0.16 wt% C)

cool
heat

26
Eutectoid & Peritectic Peritectic transformation  + L 

Cu-Zn Phase diagram

Adapted from Fig. 9.21,

Callister & Rethwisch 8e.
Eutectoid transformation  +
27
Iron-Carbon (Fe-C)
• 2 important
Phase Diagram
T(ºC)
points 1600

- Eutectic (A): 1400 L
L   + Fe3C   +L A
1200 1148ºC L+Fe3C
- Eutectoid (B): (austenite)

Fe3C (cementite)
  a + Fe3C 1000  
   +Fe3C
800
a B 727ºC = T eutectoid

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,
28
Callister & Rethwisch 8e.) Callister & Rethwisch 8e.
Hypoeutectoid
T(ºC) Steel
1600

1400 L
  (Fe-C
 +L
  1200 1148ºC L+Fe3C System)
(austenite)

Fe3C (cementite)
  1000
   + Fe3C Adapted from Figs. 9.24 and
9.29,Callister & Rethwisch
a 8e.
a  800 727ºC (Fig. 9.24 adapted from
 a a Binary Alloy Phase
Diagrams, 2nd ed., Vol. 1,
600
a + Fe3C T.B. Massalski (Ed.-in-Chief),
ASM International,
Materials Park, OH, 1990.)
400
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. 29
Hypoeutectoid
T(ºC) Steel1600

1400 L
(Fe-C
a  +L
  1200 1148ºC L+Fe3C System)
a (austenite)
 a

Fe3C (cementite)
1000
 + Fe3C Adapted from Figs. 9.24 and
Wa = s/(r + s) 9.29,Callister & Rethwisch
8e.
800 r s 727ºC
W =(1 - Wa) (Fig. 9.24 adapted from
a R S Binary Alloy Phase
Diagrams, 2nd ed., Vol. 1,
600
a a + Fe3C T.B. Massalski (Ed.-in-Chief),
ASM International,
pearlite Materials Park, OH, 1990.)
400
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
W Fe3C=(1 – Wa’)
pearlite proeutectoid ferrite
Adapted from Fig. 9.30, Callister & Rethwisch 8e. 30
Hypereutectoid
T(ºC) Steel 1600

1400 L (Fe-C
 +L System)
 
 
1200
(austenite)
1148ºC L+Fe3C

Fe3C (cementite)
  1000
   +Fe3C Adapted from Figs. 9.24 and
9.32,Callister & Rethwisch
Fe3C 8e. (Fig. 9.24 adapted from
  800 Binary Alloy Phase
  a Diagrams, 2nd ed., Vol. 1,
T.B. Massalski (Ed.-in-Chief),
600
a +Fe3C 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 m Hypereutectoid
steel
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. 31
Hypereutectoid
T(ºC) Steel1600

1400 L (Fe-C
+L System)
Fe3C 1200

  (austenite)
1148ºC L+Fe3C

Fe3C (cementite)
  1000
 +Fe3C Adapted from Figs. 9.24 and
9.32,Callister & Rethwisch
W =x/(v + x)
8e. (Fig. 9.24 adapted from
800 v x Binary Alloy Phase
WFe3C =(1-W)
a Diagrams, 2nd ed., Vol. 1,
V X T.B. Massalski (Ed.-in-Chief),
600
a +Fe3C ASM International,
pearlite 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 m Hypereutectoid
W Fe C’ =(1 - Wa) steel
3
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. 32
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.

33
Solution to the
a) Using Example Problem
RS tie line just below the eutectoid

Ca = 0.022 wt% C
CFe3C = 6.70 wt% C
b) Using the lever rule with
the tie line shown 1600

1400 L
R C  Ca T(ºC)
WFe 3C   0   +L
R  S CFe 3C  Ca 1200 L+Fe3C

Fe3C (cementite)
1148ºC
(austenite)
0.40  0.022
  0.057 1000
 + Fe3C
6.70  0.022
800 727ºC
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 C
= (100 g)(0.057) = 5.7 g 3

34
 Solution to Example
c) Using the VX tieProblem (cont.)
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(ºC)  +L
Wpearlite   0 
V  X C  Ca 1200 L+Fe3C

Fe3C (cementite)
1148ºC
(austenite)
0.40  0.022 1000
  0.512  + Fe3C
0.76  0.022
800 727ºC
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
35
VMSE: Interactive Phase
Microstructure, phase Diagrams
compositions, and phase fractions respond interactively

Change alloy composition 36

Alloying with Other Elements
• Teutectoid changes: • Ceutectoid changes:

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

37