Chapter 9: Phase Diagrams

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 A Phase B

Nickel atom
Copper atom
Chapter 9 - 1
 Phase Diagrams:
# and types of phases
• Rule 1: If we know T and Co, then we know:
--the # and types of phases present.
T(°C)
• Examples: 1600
A(1100°C, 60): L (liquid)
1 phase: a 1500

C,35)
Cu-Ni

B (1250°C
B(1250°C, 35): 1400 phase
2 phases: L + a diagram
1300 a
(FCC solid
1200 solution)
Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase 1100 A(1100°C,60)
Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
1000
OH, 1991).
0 20 40 60 80 100 wt% Ni
Chapter 9 - 2
 Phase Diagrams:
composition of phases
• Rule 2: If we know T and Co, then we know:
--the composition of each phase. Cu-Ni
T(°C) system
• Examples:
TA A
Co = 35 wt% Ni tie line
At T A = 1320°C: 1300 L (liquid)

Only Liquid (L) B

CL = Co ( = 35 wt% Ni) TB
a
At T D = 1190°C:
1200 D (solid)
Only Solid ( a) TD
Ca = Co ( = 35 wt% Ni)
20 3032 35 4043 50
At T B = 1250°C: CLCo Ca wt% Ni
Both a and L Adapted from Fig. 9.3(b), Callister 7e.
CL = C liquidus ( = 32 wt% Ni here) (Fig. 9.3(b) is adapted from Phase Diagrams
of Binary Nickel Alloys, P. Nash (Ed.), ASM
Ca = C solidus ( = 43 wt% Ni here) International, Materials Park, OH, 1991.)
Chapter 9 - 3
 Phase Diagrams:
weight fractions of phases
• Rule 3: If we know T and Co, then we know:
--the amount of each phase (given in wt%). Cu-Ni
• Examples: T(°C) system
Co = 35 wt% Ni TA A
tie line
At T A : Only Liquid (L) 1300 L (liquid)
W L = 100 wt%, W a = 0 B
At T D: Only Solid ( a) TB R S
a
W L = 0, Wa = 100 wt%
1200 D (solid)
At T B : Both a and L TD
S 43  35
WL 
20 3032 35 40 43 50
  73 wt % CLCo Ca wt% Ni
R + S 43  32
Adapted from Fig. 9.3(b), Callister 7e.
R (Fig. 9.3(b) is adapted from Phase Diagrams of
Wa  = 27 wt% Binary Nickel Alloys, P. Nash (Ed.), ASM
R +S International, Materials Park, OH, 1991.)

Chapter 9 - 4
 The Lever Rule
• Tie line – connects the phases in equilibrium with
each other - essentially an isotherm
T(°C) How much of each phase?
tie line
Think of it as a lever (teeter-totter)
1300 L (liquid)
ML Ma
B
TB
a
1200 (solid)
R S R S
20 30C C
L o
40 C
a
50
M a S  M L R
wt% Ni Adapted from Fig. 9.3(b),
Callister 7e.

ML S C  C0 R C  CL
WL    a Wa   0
M L  M a R  S C a  CL R  S Ca  CL
Chapter 9 - 5
 Ex: Cooling in a Cu-Ni Binary
• Phase diagram: T(°C) L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
• System is: 130 0 system
A
--binary L: 35 wt% Ni
a: 46 wt% Ni B
i.e., 2 components: 35 46
Cu and Ni. 32 C 43
--isomorphous 24 D
36 L: 32 wt% Ni
i.e., complete a: 43 wt% Ni
solubility of one 120 0 E
L: 24 wt% Ni
component in
another; a phase a: 36 wt% Ni
a
field extends from (solid)
0 to 100 wt% Ni.
• Consider 110 0
Co = 35 wt%Ni. 20 30 35 40 50
Adapted from Fig. 9.4, Co wt% Ni
Callister 7e.
Chapter 9 - 6
 Cored vs Equilibrium Phases
• 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.
• Fast rate of cooling: • Slow rate of cooling:
Cored structure Equilibrium structure
Uniform C a:
First a to solidify:
46 wt% Ni 35 wt% Ni
Last a to solidify:
< 35 wt% Ni

Chapter 9 - 7
 Mechanical Properties: Cu-Ni System
• Effect of solid solution strengthening on:
--Tensile strength (TS) --Ductility (%EL,%AR)

60
Tensile Strength (MPa)

%EL for pure Cu

(%EL)
400 50 %EL for

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

--Peak as a function of Co --Min. as a function of Co

Chapter 9 - 8
 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 779°C L+b b
T 800
a: mostly Cu E 8.0 71.9 91.2
b: mostly Ag 600
• TE : No liquid below TE ab
• CE : Min. melting TE 400

composition 200
0 20 40 60 CE 80 100
• Eutectic transition Co , wt% Ag
L(CE) a(CaE) + b(CbE) Adapted from Fig. 9.7,
Callister 7e.

Chapter 9 - 9
 EX: Pb-Sn Eutectic System (1)
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, find...
--the phases present: a + b Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
Ca = 11 wt% Sn 300
L (liquid)
Cb = 99 wt% Sn
--the relative amount a L+ a
200 183°C L+b b
of each phase: 18.3 61.9 97.8
S C - CO 150
Wa =
R+S
= b
Cb - Ca
R S
100
a+b
99 - 40 59
= = = 67 wt%
99 - 11 88
C - Ca 0 11 20 40 60 80 99100
Wb = R = O Ca Co Cb
R+S Cb - C a C, wt% Sn
Adapted from Fig. 9.8,
40 - 11 29 Callister 7e.
= = = 33 wt%
99 - 11 88 Chapter 9 - 10
 EX: Pb-Sn Eutectic System (2)
• For a 40 wt% Sn-60 wt% Pb alloy at 200°C, find...
--the phases present: a + L Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
Ca = 17 wt% Sn 300
L (liquid)
CL = 46 wt% Sn L+a
--the relative amount 220 a
200 R S L+b b
of each phase: 183°C
CL - C O 46 - 40
Wa = = 100
CL - C a 46 - 17 a+b
6
= = 21 wt%
29 100
0 17 20 40 46 60 80
Ca Co CL
CO - C a 23 C, wt% Sn
WL = = = 79 wt% Adapted from Fig. 9.8,
CL - C a 29 Callister 7e.

Chapter 9 - 11
 Microstructures
in Eutectic Systems: I
• Co < 2 wt% Sn T(°C) L: Co wt% Sn
400
• Result: L
a
--at extreme ends
300 L
--polycrystal of a grains
i.e., only one solid phase. L+ a
200
a
a: Co wt% Sn
(Pb-Sn
TE
System)

100
a+ b

0 10 20 30
Adapted from Fig. 9.11,
Co Co, wt% Sn
Callister 7e. 2
(room T solubility limit)

Chapter 9 - 12
 Microstructures
in Eutectic Systems: II
L: Co wt% Sn
• 2 wt% Sn < Co < 18.3 wt% Sn 400T(°C)
• Result: L
 Initially liquid + a L
300 a
 then a alone
L+a
 finally two phases a: Co wt% Sn
a
 a polycrystal 200
TE
 fine b-phase inclusions a
b
100
a+ b Pb-Sn
system
0 10 20 30
Adapted from Fig. 9.12, 2 Co Co , wt% Sn
Callister 7e. (sol. limit at T room) 18.3
(sol. limit at TE)
Chapter 9 - 13
 Microstructures
in Eutectic Systems: III
• Co = CE
• Result: Eutectic microstructure (lamellar structure)
--alternating layers (lamellae) of a and b crystals.
Micrograph of Pb-Sn
T(°C) eutectic
L: Co wt% Sn microstructure
300 L
Pb-Sn
system
L+a
200
a 183°C Lb b
TE

100 160 m
ab b: 97.8 wt% Sn
Adapted from Fig. 9.14, Callister 7e.
a: 18.3 wt%Sn

0 20 40 60 80 100
18.3 CE 97.8
Adapted from Fig. 9.13, 61.9 C, wt% Sn Chapter 9 - 14
Callister 7e.
 Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister

7e.

Chapter 9 - 15
 Microstructures
in Eutectic Systems: IV
• 18.3 wt% Sn < Co < 61.9 wt% Sn
• Result: a crystals and a eutectic microstructure
• Just above TE :
T(°C) L: Co wt% Sn a L
L
Ca = 18.3 wt% Sn
300 a CL = 61.9 wt% Sn
L
Pb-Sn S
a
L+a Wa = = 50 wt%
system R+S
200
a R S L+b b WL = (1- Wa) = 50 wt%
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 = 73 wt%
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wb = 27 wt%
Adapted from Fig. 9.16,
Callister 7e. Co, wt% Sn Chapter 9 - 16
 Hypoeutectic & Hypereutectic
300
L
Adapted from Fig. 9.8, T(°C)
Callister 7e. (Fig. 9.8 a L+ a
adapted from Binary Phase
200 L+b b (Pb-Sn
TE
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 Co, wt% Sn

eutectic
hypoeutectic: Co = 50 wt% Sn 61.9 hypereutectic: (illustration only)
(Figs. 9.14 and 9.17
from Metals
eutectic: Co = 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 7e. Adapted from Fig. 9.14, Callister 7e. (Illustration
Callister 7e. only)
Chapter 9 - 17
 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 - 18
 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 - 19