Phase Equilibria: Solubility Limit

Introduction
Solutions solid solutions, single phase
Mixtures more than one phase

Sucrose/Water Phase Diagram

Solubility Limit: 10 0
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 20C? 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

Chapter 9 - 1
 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)

Chapter 9 - 2
 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 (100C,70) D (100C,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 (20C,70)
2 phases
0
0 20 40 60 70 80 100
Co =Composition (wt% sugar)
Chapter 9 - 3
 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.

Chapter 9 - 4
 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 Chapter 9 - 5
 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(1100C, 60): L (liquid)
1 phase: a

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

1000
0 20 40 60 80 100 wt% Ni
Chapter 9 - 6
 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 = 1320C: 1300 L (liquid)

Only Liquid (L) B

CL = Co ( = 35 wt% Ni) TB
a
At T D = 1190C:
1200 D (solid)
Only Solid ( a) TD
Ca = Co ( = 35 wt% Ni)
20 3032 35 4043 50
At T B = 1250C: CLCo Ca wt% Ni
Both a and L
CL = C liquidus ( = 32 wt% Ni here)
Ca = C solidus ( = 43 wt% Ni here)
Chapter 9 - 7
 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 3 032 35 4 0 43 50
R + S 43 32 CLCo Ca wt% Ni

R
Wa = 27 wt%
R +S
Chapter 9 - 8
 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 3 0C 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
Chapter 9 - 9
 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
32 C
Cu and Ni. 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
Chapter 9 - 10
 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 - 11
 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 779C L +b b
800
a: mostly Cu TE 8.0 71.9 91.2
b: mostly Ag 600
TE : No liquid below TE ab
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)
Chapter 9 - 12
 EX: Pb-Sn Eutectic System (1)
For a 40 wt% Sn-60 wt% Pb alloy at 150C, 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 183C L +b b
of each phase: 18.3 61.9 97.8
S C - CO 150
Wa = = b R S
R+S Cb - Ca 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
40 - 11 29
= = = 33 wt%
99 - 11 88 Chapter 9 - 13
 EX: Pb-Sn Eutectic System (2)
For a 40 wt% Sn-60 wt% Pb alloy at 200C, 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
200
a R S L +b b
of each phase: 183C
CL - CO 46 - 40
Wa = = 100
CL - Ca 46 - 17 a+b
6
= = 21 wt%
29 100
0 17 20 40 46 60 80
Ca Co CL
CO - Ca 23 C, wt% Sn
WL = = = 79 wt%
CL - Ca 29

Chapter 9 - 14
 Microstructures
in Eutectic Systems: I

Co < 2 wt% Sn T(C)

400
L: Co wt% Sn

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)

a+ b
100

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

Chapter 9 - 15
 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
a
then a alone 300
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
2 Co Co , wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)
Chapter 9 - 16
 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 183C Lb b
TE

100 160 m
ab b: 97.8 wt% Sn
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 - 17
Callister 7e.
Lamellar Eutectic Structure

Chapter 9 - 18
 Microstructures
in Eutectic Systems: IV
18.3 wt% Sn < Co < 61.9 wt% Sn
Result: a crystals and a eutectic microstructure
L: Co wt% Sn
Just above TE :
T(C) a L
L
Ca = 18.3 wt% Sn
300 a CL = 61.9 wt% Sn
L
Pb-Sn
L+ a Wa = S = 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%
Co, wt% Sn Chapter 9 - 19
Hypoeutectic & Hypereutectic
300
L
T(C)
a L+ a
200 L+b b (Pb-Sn
TE

a+b System)
100

0 20 40 60 80 100 Co, wt% Sn

eutectic
hypoeutectic: Co = 50 wt% Sn 61.9 hypereutectic: (illustration only)

eutectic: Co = 61.9 wt% Sn

a b
a b
a a b b
a b
a b
175 m 160 m
eutectic micro-constituent

Chapter 9 - 20