Phase Diagrams

ISSUES TO ADDRESS... Phase B

Phase A
• When we combine two elements...
what equilibrium state do we get?
Atoms A
• In particular, if we specify... Atoms B
--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?
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 Reading

– Textbook: Chapter 9 – Phase diagrams

- Section 9.1 Introduction
- Section 9.2 Solubility limit
- Section 9.3 Phases
- Section 9.4 Microstructure
- Section 9.5 Phase equilibria
- Section 9.6 One-component phase diagrams
- Section 9.7 Binary isomorphous systems
- Section 9.8 Interpretation of phase diagrams
- Section 9.9 Development of microstructure in isomorphous alloys
- Section 9.10 Mechanical properties of isomorphous alloys

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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., α and β).
β (lighter
Aluminum- phase)
Copper
Alloy α (darker
phase)
Adapted from
chapter-opening
photograph,
Chapter 9,
Callister 3e.

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 Phase Equilibria: Solubility Limit

Introduction
– Solutions – solid solutions, single phase
Adapted from Fig. 9.1,
– Mixtures – more than one phase Callister 7e.

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
Co =Composition (wt% sugar)
Water
Pure

Pure
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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
Adapted from 0
Fig. 9.1, 0 20 40 60 70 80 100
Callister 7e.
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Co =Composition (wt% sugar) Page 6
 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 L (liquid)
for Cu-Ni α (FCC solid solution)
system 1400 • 3 phase fields:
L
1300 L+α
α
1200 α Adapted from Fig. 9.3(a), Callister 7e.

1100
(FCC solid (Fig. 9.3(a) is adapted from Phase
Diagrams of Binary Nickel Alloys, P. Nash

solution) (Ed.), ASM International, Materials Park,

OH (1991).
1000
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0 20 40 60 80 100 wt% Ni Page 8
 Phase Diagrams: Number 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)

B (1250°C,35)
1 phase: α 1500
Cu-Ni
B(1250°C, 35): 1400 phase
2 phases: L + α diagram
1300 α
(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
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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
α
At T D = 1190°C:
1200 D (solid)
Only Solid ( α) TD
Cα = Co ( = 35 wt% Ni)
20 3032 35 4043 50
At T B = 1250°C: CLCo Cα wt% Ni
Both α 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
Cα = C solidus ( = 43 wt% Ni here) International, Materials Park, OH, 1991.)

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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 α = 0 B
At T D: Only Solid ( α) TB R S
α
W L = 0, Wα = 100 wt%
1200 D (solid)
At T B : Both α and L TD
S 43 − 35 20 3032 35 40 43 50
WL = = = 73 wt % CLCo Cα 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
Wα = = 27 wt% Binary Nickel Alloys, P. Nash (Ed.), ASM
R +S International, Materials Park, OH, 1991.)

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 The Lever Rule
– Tie line – connects the phases in equilibrium with each other - essentially an isotherm

T(°C)
tie line ML S Cα − C0
WL = = =
1300 L (liquid) ML + Mα R + S Cα − CL
B
TB
α R C0 − CL
(solid)
Wα = =
1200 R + S Cα − CL
R S

20 30C C 40 C 50
L o α
Adapted from Fig. 9.3(b),
Callister 7e. wt% Ni
Wα
Volα ρα
Volume Fraction for each phase: Vα = =
Volα + VolL Wα + WL
ρα ρL
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 Question Time 1

Determine which phases are present,

what is the composition of each phase
and the weight percentage that each
phase represents in the material for the
following systems:
a) 50% Cu – 50% Ni at 1050°C
b) 20% Cu – 80% Ni at 1500°C
c) 60% Cu – 40% Ni at 1250°C
d) 20% Cu – 80% Ni at 1400°C
For this last case, calculate the volume
fraction of each phase
Given: ρCu = 8.94 g/cm3 and
ρNi = 8.90 g/cm3

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Microstructure: Cooling in a Cu-Ni Binary

• Phase diagram: T(°C)L (liquid) L: 35wt%Ni

Cu-Ni system. Cu-Ni

1300 system
• System is: A
L: 35 wt% Ni
--binary α: 46 wt% Ni B
35 46
i.e., 2 components: 32 C 43
Cu and Ni.
--isomorphous 24 D L: 32 wt% Ni
36
i.e., complete 1200
α: 43 wt% Ni
solubility of one
E
L: 24 wt% Ni
component in α: 36 wt% Ni
another; α phase α
field extends from (solid)
0 to 100 wt% Ni.
• Consider 110 0
20 30 35 40 50
Co = 35 wt%Ni. Adapted from Fig. 9.4, Co wt% Ni
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 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

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 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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 Binary-Eutectic Systems
Binary = 2 components
Eutectic = has a special composition with a min. melting T.
Cu-Ag
T(°C)
Ex.: Cu-Ag system system
1200
• 3 single phase regions L (liquid)
(L, α, β) 1000
• Limited solubility: α L+ α
T 800 779°C L+β β
α: mostly Cu E 8.0 71.9 91.2
β: mostly Ag 600
• TE : No liquid below TE α + β
• CE : Min. melting TE 400

composition 200
0 20 40 60 CE 80 100
• Eutectic transition Co , wt% Ag
L(CE) α(CαE) + β(CβE)

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 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.

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