Phase equilibria: solubility limit

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

Sucrose/Water Phase Diagram

• Solubility Limit:
Max concentration for 10 0
which only a single phase Solubility
Limit L
solution occurs. 80

Temperature (°C)
(liquid)
60 L +
(liquid solution S
40
i.e., syrup) (solid
20 sugar)

0 20 40 60 80 100

Sugar
Water

Co =Composition (wt% sugar)

Pure

Pure
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., α and β).

Aluminum- β (lighter
Copper
phase)
Alloy

α (darker

phase)
Adapted from
chapter-opening
photograph,
Chapter 9,
Callister 3e.
2
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)
1600 • 2 phases:
• Phase
L (liquid)
Diagram
for Cu-Ni 1500 L (liquid) α (FCC solid solution)
system
1400 • 3 phase fields:
us L
ui d α
1300 liq + L+ α
L us
lid α
1200 so α
Adapted from Fig. 9.3(a), Callister 7e.
(FCC solid (Fig. 9.3(a) is adapted from Phase
1100 Diagrams of Binary Nickel Alloys, P. Nash
solution) (Ed.), ASM International, Materials Park,
OH (1991).
1000
0 20 40 60 80 100 wt% Ni 3
Phase diagrams

• Rule 1: If we know T and Co, then we know:

--the # and types of phases present.

T(°C)
• Examples: 1600
L (liquid)
1500
us Cu-Ni
u i d
liq phase
1400 s
li du diagram
so
α α
1300 +
L (FCC solid
1200 solution)
Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase 1100
Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
1000
100 wt% Ni
OH, 1991).
0 20 40 60 80
4
Phase diagrams

• Rule 2: If we know T and Co, then we know:

--the composition of each phase.
Cu-Ni
system
T(°C)
• Examples:

u i dus
1300 L (liquid) liq
α
L +
s
o l idu
s
α
α
L + (solid)
1200

20 30 40 50
wt% Ni
Adapted from Fig. 9.3(b), Callister 7e.
(Fig. 9.3(b) is adapted from Phase Diagrams
of Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH, 1991.)

5
Phase diagrams

• Rule 3: If we know T and Co, then we know:

--the amount of each phase (given in wt%).
Cu-Ni
system
• Examples: T(°C)
C o = 35 wt% Ni TA A
tie line idus
At T A : Only Liquid (L)
1300 L (liquid) liqu
α
WL = 100 wt%, W α = 0 L +
B
At T D : Only Solid ( α ) TB l i dus
R S so
α
W L = 0, Wα = 100 wt% α
L + (solid)
At T B : Both α and L 1200 D
TD

20 3032 35 404 3 50
C LC o C α wt% Ni

Adapted from Fig. 9.3(b), Callister 7e.

(Fig. 9.3(b) is adapted from Phase Diagrams of
Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH, 1991.)
6
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 idus Think of it as a lever (teeter-totter)
1300 L (liquid) liqu
α
L + ML Mα
B
TB li dus
so
α
α
L + (solid)
1200
R S R S
20 30C C 40 Cα 50 M " !S = M L !R
L o
wt% Ni Adapted from Fig. 9.3(b),
Callister 7e.

7
Cooling

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

Cu-Ni system.
Cu-Ni
• System is:
1300 α system
A
L+
--binary
L: 35 wt% Ni
i.e., 2 components:
Cu and Ni.
α: 46 wt% Ni
35 B
46
--isomorphous 32 C 43
i.e., complete
solubility of one 24 D L: 32 wt% Ni
36
component in α α: 43 wt% Ni
L+
another; α phase 1200 E
field extends from L: 24 wt% Ni
0 to 100 wt% Ni. α: 36 wt% Ni
α
(solid)
• Consider
Co = 35 wt%Ni. 1100
20 30 35 40 50
Adapted from Fig. 9.4, Co wt% Ni
Callister 7e. 8
 Binary eutectic systems

has a special composition

2 components with a min. melting T.
Cu-Ag
Ex.: Cu-Ag system
T(°C) system
1200
• 3 single phase regions
L (liquid)
(L, α, β ) 1000
• Limited solubility: α L+α L+β β
800 779°C
α : mostly Cu TE 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)
Adapted from Fig. 9.7,
Callister 7e.
9
Binary eutectic systems

• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, find...

--the phases present:
Pb-Sn
T(°C) system

300
L (liquid)
α L+ α
200 183°C L+β β
18.3 61.9 97.8

100
α+β

0 20 60 80 100
C, wt% Sn
Adapted from Fig. 9.8,
Callister 7e.

10
Binary eutectic systems

• For a 40 wt% Sn-60 wt% Pb alloy at 200°C, find...

--the phases present:
Pb-Sn
T(°C) system

300
L (liquid)
L+ α
200
α L+β β
183°C

100
α+β

0 20 60 80 100
C, wt% Sn
Adapted from Fig. 9.8,
Callister 7e.

11
Microstructures in eutectic systems

• Co < 2 wt% Sn T(°C) L: Co wt% Sn

• Result: 400
--at extreme ends L
--polycrystal of α grains α
i.e., only one solid phase. 300 L

L+ α
α
200 (Pb-Sn
TE α: Co wt% Sn
System)

100
α+β

0 10 20 30
Adapted from Fig. 9.11,
Co Co, wt% Sn
Callister 7e. 2
(room T solubility limit)
12
Microstructures in eutectic systems

• 2 wt% Sn < Co < 18.3 wt% Sn L: Co wt% Sn

T(°C)
• Result: 400
 Initially liquid + α
L
 then α alone L
 finally two phases 300 α
 α polycrystal L+α
 fine β-phase inclusions α: Co wt% Sn
α
200
TE
α
β
100
α+ β
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) 13
Microstructures in eutectic systems

• Co = CE
• Result: Eutectic microstructure (lamellar structure)
--alternating layers (lamellae) of α and β crystals.

Micrograph of Pb-Sn
T(°C) eutectic
L: Co wt% Sn microstructure
300 L
Pb-Sn
system
L+ α
200
α 183°C L+β β
TE

100 160 µm
α+β Adapted from Fig. 9.14, Callister 7e.

0 20 40 60 80 100
CE
Adapted from Fig. 9.13, 61.9 C, wt% Sn 14
Callister 7e.
Microstructures in eutectic systems

• 18.3 wt% Sn < Co < 61.9 wt% Sn

• Result: α crystals and a eutectic microstructure

T(°C) L: Co wt% Sn α L
L
300 α
L
Pb-Sn
L+ α
system
200
α L+ β β
TE

100 α+β
primary α
eutectic α
eutectic β
0 20 40 60 80 100

Adapted from Fig. 9.16,

Callister 7e. Co, wt% Sn 15
Hypoeutectic & hypereutectic

300
L
Adapted from Fig. 9.8, T(°C)
Callister 7e. (Fig. 9.8 α L+ α
adapted from Binary Phase
200 L+β β (Pb-Sn
TE
Diagrams, 2nd ed., Vol. 3,
T.B. Massalski (Editor-in- α+β 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
Handbook, 9th ed., eutectic: Co = 61.9 wt% Sn
α β
Vol. 9,
Metallography and α β
Microstructures, α α β β
American Society for α β
Metals, Materials
Park, OH, 1985.) α β
175 µm 160 µm
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) 16
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.
17
Peritectic & eutectoid

• Cu-Zn Phase diagram

Adapted from
Fig. 9.21, Callister 7e.

18
Fe-C phase diagram

• 2 important T(°C)
points 1600
δ
-Eutectic (A): 1400 L
L ⇒ γ + Fe3C γ +L
1200
γ
1148°C
A L+Fe3C
-Eutectoid (B): (austenite)

Fe3C (cementite)
R S
γ ⇒ α + Fe3C 1000 γ γ
α+ γ γ γ +Fe3C
800
α B 727°C = Teutectoid
γ

R S
600 α+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 Co, wt% C
120 µm
C eutectoid

Result: Pearlite = Fe3C (cementite-hard)

alternating layers of α (ferrite-soft)
α and Fe3C phases
(Adapted from Fig. 9.27, Callister 7e.) Adapted from Fig. 9.24,Callister 7e. 19
Hypoeutectoid steel
T(°C)
1600
δ
1400 L
γ γ γ +L (Fe-C
γ γ γ System)
1200 1148°C L+Fe3C

Fe3C (cementite)
(austenite)
γ γ
1000
γ γ γ + Fe3C Adapted from Figs. 9.24
and 9.29,Callister 7e.
α (Fig. 9.24 adapted from
γ γ 800 r s 727°C Binary Alloy Phase
α
γ αγ αRS Diagrams, 2nd ed., Vol.
1, T.B. Massalski (Ed.-in-
wα =s/(r +s) 600 α + Fe3C Chief), ASM International,
wγ =(1- wα) Materials Park, OH,
1990.)
400
α 0 1 2 3 4 5 6 6.7
(Fe) Co , wt% C
0.76

C0
pearlite
w pearlite = wγ
wα =S/(R+S) 100 µm Hypoeutectoid
steel
w Fe3C =(1-wα)
pearlite proeutectoid ferrite
Adapted from Fig. 9.30,Callister 7e. 20
Hypereutectoid steel
T(°C)
1600
δ
1400 L (Fe-C
γ γ +L System)
γ γ
γ 1200 1148°C L+Fe3C
γ

Fe3C (cementite)
(austenite)
γ γ 1000
γ γ γ +Fe3C Adapted from Figs. 9.24
and 9.32,Callister 7e.
Fe3C (Fig. 9.24 adapted from
γ γ 800 r s Binary Alloy Phase
Diagrams, 2nd ed., Vol.
γ γ α R S 1, T.B. Massalski (Ed.-in-
600 α +Fe3C
w Fe3C =r/(r +s) Chief), ASM International,
Materials Park, OH,
wγ =(1-w Fe3C ) 1990.)
400
0 1 Co 2 3 4 5 6 6.7
0.76

(Fe)
pearlite Co , wt%C
w pearlite = wγ
wα =S/(R+S)
w Fe3C =(1-w α) 60 µmHypereutectoid
steel
pearlite proeutectoid Fe3C
21
Adapted from Fig. 9.33,Callister 7e.