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
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 Phase Equilibria: Solubility Limit
Introduction
– Solutions – solid solutions, single phase
– Mixtures – more than one phase

Sucrose/Water Phase Diagram

• Solubility Limit: 100
Max concentration for Solubility

Temperature (°C)
which only a single phase 80 Limit L
solution occurs. (liquid)
60 +
L
Question: What is the 40 (liquid solution S
solubility limit at 20°C? i.e., syrup) (solid
20 sugar)
Answer: 65 wt% sugar.
If Co < 65 wt% sugar: syrup 0 20 40 6065 80 100
If Co > 65 wt% sugar: syrup + sugar.

Sugar
Water

Co =Composition (wt% sugar)

Pure

Pure
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 Components and Phases
• Components:
The elements or compounds which are present in the mixture
(e.g., Al and Cu)
• Phases:
The physically and chemically distinct material regions
that result (e.g., a and b).

Aluminum- b (lighter
Copper
phase)
Alloy

a (darker
phase)

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 Effect of T & Composition (Co)
• Changing T can change # of phases: path A to B.
• Changing Co can change # of phases: path B to D.
B (100°C,70) D (100°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 (20°C,70)
2 phases
0
0 20 40 60 70 80 100
Co =Composition (wt% sugar)
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 Phase Equilibria

Simple solution 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 miscible in all proportions.

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 Phase Diagrams
• Indicate phases as function of T, Co, and P.
• For this course:
-binary systems: just 2 components.
-independent variables: T and Co (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 phase fields:
L
1300 L+a
a
1200 a
1100
(FCC solid
solution)
1000
0 20 40 60 80 100 wt% Ni 6
 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

B (1250°C,35)
1500
Cu-Ni
B(1250°C, 35): 1400 phase
2 phases: L + a diagram
1300 a
(FCC solid
1200 solution)
1100 A(1100°C,60)

1000
0 20 40 60 80 100 wt% Ni
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 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
CL = C liquidus ( = 32 wt% Ni here)
Ca = C solidus ( = 43 wt% Ni here)
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 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  73 wt %
WL 
20 3032 35 40 43 50
R + S 43  32 CLCo Ca wt% Ni

R
Wa  = 27 wt%
R +S
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 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

ML S C  C0 R C  CL
WL    a Wa   0
ML  Ma R  S Ca  CL R  S Ca  CL
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 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 A
system
--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
Co wt% Ni
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 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

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 Mechanical Properties: Cu-Ni System
• Effect of solid solution strengthening on:
--Tensile strength (TS) --Ductility (%EL,%AR)
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), Callister 7e. Adapted from Fig. 9.6(b), Callister 7e.

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

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