Chapter 11: 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 11 - 1
 Phase Equilibria: Solubility Limit
• Solution – solid, liquid, or gas solutions, single phase
• Mixture – more than one phase Adapted from Fig. 11.1,
Callister & Rethwisch 9e.

Sugar/Water Phase Diagram

• Solubility Limit: 100
Maximum concentration for

Temperature (°C)
Solubility
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 20°C? 20 sugar)

Answer: 65 wt% sugar.

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

Sugar
Water

C = Composition (wt% sugar)

At 20°C, if C > 65 wt% sugar:
syrup + sugar Chapter 11 - 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., α and β).

Aluminum- β (lighter
Copper
phase)
Alloy

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

Chapter 11 - 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 (100°C,C = 70)D (100°C,C = 90)
1 phase 2 phases
100
L
Temperature (°C)

80
(liquid)
water- 60 +
sugar L S
system (liquid solution (solid
40 i.e., syrup) sugar)
20 A (20°C,C = 70)
2 phases
Fig. 11.1, Callister & 0
Rethwisch 9e. 0 20 40 60 70 80 100
C = Composition (wt% sugar)
Chapter 11 - 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 11 - 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 L (liquid)
for Cu-Ni α (FCC solid solution)
system 1400 • 3 different phase fields:
L
1300 L+α
α
1200 α Fig. 11.3(a), Callister & Rethwisch 9e.
(Adapted from Phase Diagrams of Binary

1100
(FCC solid Nickel Alloys, P. Nash, Editor, 1991. Reprinted
by permission of ASM International, Materials
solution) Park, OH.)

1000
0 20 40 60 80 100 wt% Ni
Chapter 11 - 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 α
solubility of one
component in 1100
(FCC solid
another; α phase solution)
field extends from 1000
0 to 100 wt% Ni.
0 20 40 60 80 100 wt% Ni
Fig. 11.3(a), Callister & Rethwisch 9e.
(Adapted from Phase Diagrams of Binary
Nickel Alloys, P. Nash, Editor, 1991. Reprinted
by permission of ASM International, Materials
Park, OH.)

Chapter 11 - 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(1100°C, 60 wt% Ni): L (liquid)
1 phase: α

B (1250ºC,35)
1500
Cu-Ni
B(1250°C, 35 wt% Ni): 1400 phase
2 phases: L + α diagram
1300 α
(FCC solid
1200
Fig. 11.3(a), Callister & Rethwisch 9e.
solution)
(Adapted from Phase Diagrams of Binary
Nickel Alloys, P. Nash, Editor, 1991. Reprinted 1100 A(1100ºC,60)
by permission of ASM International, Materials
Park, OH.)
1000
0 20 40 60 80 100 wt% Ni
Chapter 11 - 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 = 1320°C: 1300 L (liquid)
Only Liquid (L) present B
CL = C0 ( = 35 wt% Ni) TB
α
At TD = 1190°C:
1200 D (solid)
Only Solid (α) present TD
Cα = C0 ( = 35 wt% Ni)
20 3032 35 4043 50
At TB = 1250°C: CL C0 Cα wt% Ni
Both α and L present Fig. 11.3(b), Callister & Rethwisch 9e.
(Adapted from Phase Diagrams of Binary
CL = C liquidus ( = 32 wt% Ni) Nickel Alloys, P. Nash, Editor, 1991. Reprinted
by permission of ASM International, Materials
Cα = C solidus ( = 43 wt% Ni) Park, OH.)

Chapter 11 - 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 ( α ) present TB R S
α
WL = 0, Wα = 1.00
1200 D (solid)
At TB : Both α and L present TD
S 43 - 35
WL =
20 3032 35 40 43 50
= = 0.73 CL C 0 Cα wt% Ni
R +S 43 - 32
Fig. 11.3(b), Callister & Rethwisch 9e.
(Adapted from Phase Diagrams of Binary
R Nickel Alloys, P. Nash, Editor, 1991. Reprinted

Wα = = 0.27 by permission of ASM International, Materials

Park, OH.)
R +S
Chapter 11 - 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 Mα
α
1200 (solid)
R S

20 30CL R S
C0 40 Cα 50
Adapted from Fig. 11.3(b),
wt% Ni Callister & Rethwisch 9e.

Chapter 11 - 11
 Ex: Cooling of a Cu-Ni Alloy
• Phase diagram: T(°C)L (liquid) L: 35 wt%Ni
Cu-Ni system. Cu-Ni
system
• Consider 130 0 A
L: 35 wt% Ni
microstuctural α: 46 wt% Ni B
35 46
changes that 32 C 43
accompany the D
24 36 L: 32 wt% Ni
cooling of a α: 43 wt% Ni
C0 = 35 wt% Ni alloy 120 0 E
L: 24 wt% Ni
α: 36 wt% Ni
α
(solid) α: 35 wt% Ni

110 0
20 30 35 40 50
Adapted from Fig. 11.4, C0 wt% Ni
Callister & Rethwisch 9e.
Chapter 11 - 12
 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, α, β) 1000
• Limited solubility: α L + α 779°C L+β β
T 800
α: mostly Cu E 8.0 71.9 91.2
β: mostly Ag 600
• TE : No liquid below TE α+β
• CE : Composition at 400
temperature TE 200
0 20 40 60 CE 80 100
• Eutectic reaction C, wt% Ag
Fig. 11.6, Callister & Rethwisch 9e
L(CE) α(CαE) + β(CβE) [Adapted from Binary Alloy Phase Diagrams, 2nd edition,
Vol. 1, T. B. Massalski (Editor-in-Chief), 1990. Reprinted
by permission of ASM International, Materials Park, OH.].
cooling

heating Chapter 11 - 13
 EX 1: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, determine:
-- the phases present Pb-Sn
Answer: α + β T(°C) system
-- the phase compositions
300
Answer: Cα = 11 wt% Sn L (liquid)
Cβ = 99 wt% Sn
-- the relative amount α L+ α
200 183°C L+β β
of each phase 18.3 61.9 97.8
Answer: 150
S Cβ - C0 R S
Wα = = 100
R+S Cβ - Cα α +β
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C0 - Cα Cα C0 Cβ
Wβ = R = C, wt% Sn
R+S Cβ - Cα Fig. 11.7, Callister & Rethwisch 9e.
[Adapted from Binary Alloy Phase Diagrams,
2nd edition, Vol. 3, T. B. Massalski (Editor-in-
40 - 11 29 Chief), 1990. Reprinted by permission of ASM
= = = 0.33 International, Materials Park, OH.]
99 - 11 88 Chapter 11 - 14
 EX 2: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 220°C, determine:
-- the phases present: Pb-Sn
Answer: α + L T(°C) system
-- the phase compositions
300
Answer: Cα = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+ α
220
-- the relative amount 200 α R S L+ β β
of each phase 183°C
Answer:
100
Wα =
CL - C0
=
46 - 40 α +β
CL - Cα 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 Cα C0 CL
29 C, wt% Sn
Fig. 11.7, Callister & Rethwisch 9e.
C0 - Cα 23 [Adapted from Binary Alloy Phase Diagrams,
WL = = = 0.79 2nd edition, Vol. 3, T. B. Massalski (Editor-in-
CL - Cα 29 Chief), 1990. Reprinted by permission of ASM
International, Materials Park, OH.]
Chapter 11 - 15
 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 α
300 L
-- polycrystalline with grains of
α phase having L+ α
α
composition C0 200 (Pb-Sn
TE α: C0 wt% Sn
System)

100
α+β

0 10 20 30
Fig. 11.10, Callister & C0 C, wt% Sn
Rethwisch 9e. 2
(room T solubility limit)

Chapter 11 - 16
 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 α + β range 300 α
L +α
-- polycrystalline with α grains α: C0 wt% Sn
and small β-phase particles 200 α
TE
α
β
100
α+ β Pb-Sn
system
Fig. 11.11, Callister & 0 10 20 30
Rethwisch 9e. 2 C0 C, wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)
Chapter 11 - 17
 Microstructural Developments
in Eutectic Systems III
• For alloy of composition C0 = CE
• Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of α and β phases.
Micrograph of Pb-Sn
T(°C) eutectic
L: C0 wt% Sn microstructure
300 L
Pb-Sn
system
L+ α
200
α 183°C L+β β
TE

100 160 μm
α+β β: 97.8 wt% Sn
Fig. 11.13, Callister & Rethwisch 9e.
α: 18.3 wt%Sn (From Metals Handbook, 9th edition, Vol. 9,
Metallography and Microstructures, 1985.
Reproduced by permission of ASM
International, Materials Park, OH.)
0 20 40 60 80 100
18.3 CE 97.8
Fig. 11.12, Callister & 61.9 C, wt% Sn
Rethwisch 9e. Chapter 11 - 18
 Microstructural Developments
in Eutectic Systems IV
• For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn
• Result: α phase particles and a eutectic microconstituent
• Just above TE :
T(°C) L: C0 wt% Sn αL
L
Cα = 18.3 wt% Sn
300 L α CL = 61.9 wt% Sn
Pb-Sn
L+ α Wα = S = 0.50
system R+S
200
α R S L+β β WL = (1- Wα ) = 0.50
TE S
R
• Just below TE :
100 α+ β Cα = 18.3 wt% Sn
primary α Cβ = 97.8 wt% Sn
eutectic α
eutectic β Wα = S = 0.73
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wβ = 0.27
Fig. 11.15, Callister &
Rethwisch 9e. C, wt% Sn
Chapter 11 - 19
 Hypoeutectic & Hypereutectic
300
L
T(°C)
α L+ α
Fig. 11.7, Callister & Rethwisch
9e. [Adapted from Binary Alloy Phase
200 L+β β (Pb-Sn
TE
Diagrams, 2nd edition, Vol. 3, T. B.
Massalski (Editor-in-Chief), 1990. α+β System)
Reprinted by permission of ASM
International, Materials Park, OH.] 100

0 20 40 60 80 100 C, wt% Sn
eutectic
hypoeutectic: C0 = 50 wt% Sn 61.9 hypereutectic: (illustration only)
(Figs. 11.13 and 11.16 from
Metals Handbook, 9th ed.,
Vol. 9, Metallography and eutectic: C0 = 61.9 wt% Sn
Microstructures, 1985. α β
α
Reproduced by permission
of ASM International, β
Materials Park, OH.) α α β β
α β
α β
175 μm 160 μm
Fig. 11.16, Callister & eutectic micro-constituent Adapted from Fig. 11.16,
Rethwisch 9e. Fig. 11.13, Callister & Callister & Rethwisch 9e.
Rethwisch 9e. (Illustration only)
Chapter 11 - 20
 Eutectic, Eutectoid, & Peritectic
• Eutectic - liquid transforms to two solid phases
L cool α + β (For Pb-Sn, 183°C, 61.9 wt% Sn)
heat

• Eutectoid – one solid phase transforms to two other

solid phases
intermetallic compound
S2 S1+S3 - cementite

γ cool α + Fe3C (For Fe-C, 727°C, 0.76 wt% C)

heat

• Peritectic - liquid and one solid phase transform to a

second solid phase
S1 + L S2
cool
δ +L heat γ (For Fe-C, 1493°C, 0.16 wt% C)

Chapter 11 - 21
 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 (α).
b) The amount of cementite (in grams) that
forms in 100 g of steel.
c) The amounts of pearlite and proeutectoid
ferrite (α) in the 100 g.

Chapter 11 - 22
 Solution to Example Problem
a) Using the RS tie line just below the eutectoid
Cα = 0.022 wt% C
Fig. 11.23, Callister & Rethwisch 9e.
CFe3C = 6.70 wt% C [From Binary Alloy Phase Diagrams, 2nd edition, Vol. 1, T.
B. Massalski (Editor-in-Chief), 1990. Reprinted by
permission of ASM International, Materials Park, OH.]

b) Using the lever rule with 1600

the tie line shown δ
1400 L
T(°C) γ +L
γ

Fe C (cementite)
1200 1148°C L+Fe3C
(austenite)
1000
γ + Fe3C
800 727°C
R S
Amount of Fe3C in 100 g 600 α + Fe3C
= (100 g)WFe3C 400
0 1 2 3 4 5 6 6.7
Cα C0 C , wt% C CFe
3C
= (100 g)(0.057) = 5.7 g
Chapter 11 - 23
 Solution to Example Problem (cont.)
c) Using the VX tie line just above the eutectoid and
realizing that
Fig. 11.23, Callister & Rethwisch 9e.
C0 = 0.40 wt% C [From Binary Alloy Phase Diagrams, 2nd edition, Vol. 1, T.
B. Massalski (Editor-in-Chief), 1990. Reprinted by
Cα = 0.022 wt% C permission of ASM International, Materials Park, OH.]
Cpearlite = Cγ = 0.76 wt% C
1600
δ
1400 L
T(°C) γ +L
γ

Fe C (cementite)
1200 1148°C L+Fe3C
(austenite)
1000
γ + Fe3C
800 727°°C
VX
Amount of pearlite in 100 g 600 α + Fe3C
= (100 g)Wpearlite 400
0 1 2 3 4 5 6 6.7
Cα C0 Cγ C , wt% C
= (100 g)(0.512) = 51.2 g
Chapter 11 - 24
 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 11 - 25
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 11 - 26