Introduction to Materials Science and Engineering

Chapter 9: Phase Diagrams

Textbook Chapter 11: Phase Diagrams
 Content

1. Introduction
2. Solubility Limit
3. Phase Diagrams
4. Microstructure Evolution during Cooling
5. Eutectic Systems
6. Fe-C Alloy
Introduction
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?
Introduction
ISSUES TO ADDRESS...

Phase diagram is a graphical illustration of a thermodynamic equilibrium

state of a material system which is defined by the composition, temperature,
and pressure, namely, Gibbs free energy of a system, and illustrates,

(a) The number of phases at equilibrium

(b) The composition of each phases
(c) The amount of each phases

at equilibrium.
 Content

1. Introduction
2. Solubility Limit
3. Phase Diagrams
4. Microstructure Evolution during Cooling
5. Eutectic Systems
6. Fe-C Alloy
 THE SOLUBILITY LIMIT
• Solubility Limit: 100
Solubility

Temperature (ºC)
Max. concentration for which only 80 Limit L
a solution occurs. (liquid)
60 +
L
• Ex: Phase Diagram: 40 (liquid solution S
i.e., syrup) (solid
Water-Sugar System
20 sugar)

Question: What is the

0 20 40 6065 80 100
solubility limit at 20C?

Sugar
Water
C o = Composition (wt% sugar)

Pure

Pure
Answer: 65wt% sugar.
Adapted from Fig. 9.1,
If Co < 65wt% sugar: sugar  syrup Callister 6e.
If Co > 65wt% sugar: syrup + sugar.

• Solubility limit increases with T:

e.g., if T = 100C, solubility limit = 80wt% sugar.
COMPONENTS AND PHASES
• Components:
The elements or compounds which are mixed initially
(e.g., Al and Cu)
• Phases:
The physically and chemically identical material regions
that result (e.g., a and b).

Aluminum-
Copper
Alloy

Adapted from
Fig. 9.0,
Callister 3e.
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(100,70) D(100,90)
1 phase 2 phases
100
L
Temperature (ºC)

• water- 80
(liquid)
sugar
60 +
system L S
(liquid solution (solid
40 i.e., syrup) sugar)
20 A(20,700)
2 phases
Adapted from 0
Fig. 9.1, 0 20 40 60 70 80 100
Callister 6e.
Co=Composition (wt% sugar)
 Content

1. Introduction
2. Solubility Limit
3. Phase Diagrams
4. Microstructure Evolution during Cooling
5. Eutectic Systems
6. Fe-C Alloy
PHASE DIAGRAMS
Gibbs Phase Rule:
• Tell us about phases as function of T, Co, P.
• For this course: P+F=C+2
--binary systems: just 2 components.
--independent variables: T and Co (P = 1 atm is always used).
T(C)
1600 2 phases:
• Phase
Diagram L (liquid)
1500 L (liquid)
for Cu-Ni a (FCC solid solution)
system 1400 3 phase fields:
L
1300 L+a
a
1200 a Adapted from Fig. 9.2(a), Callister 6e.
(Fig. 9.2(a) is adapted from Phase
1100
(FCC solid Diagrams of Binary Nickel Alloys, P.
solution) Nash (Ed.), ASM International,
Materials Park, OH (1991).
1000
0 20 40 60 80 100 wt% Ni
PHASE DIAGRAMS:
# and types of phases
• Rule 1: If we know T and Co, then we know:
--the # and types of phases present.
T(ºC)
• Examples: 1600

1500 L (liquid)
Cu-Ni

B(1250,35)
1400 phase
diagram
1300 a
(FCC solid
1200 solution)
Adapted from Fig. 9.2(a), Callister 6e.
(Fig. 9.2(a) is adapted from Phase 1100 A(1100,60)
Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International,
1000
Materials Park, OH, 1991).
0 20 40 60 80 100 wt% Ni
PHASE DIAGRAMS:
composition of phases
• Rule 2: If we know T and Co, then we know:
--the composition of each phase. Cu-Ni
T(ºC) system
• Examples:
TA A
Co = 35wt%Ni tie line
At TA: ? 1300 L (liquid)
Only Liquid (L) B
CL = Co ( = 35wt% Ni) TB
a
At TD: ?
1200 D (solid)
Only Solid (a) TD
Ca = Co ( = 35wt% Ni)
20 3032 35 4043 50
At TB: ? CLCo Ca wt% Ni
Both a and L Adapted from Fig. 9.2(b), Callister 6e.
(Fig. 9.2(b) is adapted from Phase Diagrams
CL = Cliquidus ( = 32wt% Ni here) of Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH, 1991.)
Ca = Csolidus ( = 43wt% Ni here)
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: system
T(ºC)
Co = 38wt%Ni
TA A
At TA: Only Liquid (L) tie line
1300 L (liquid)
WL = 100wt%, Wa = 0 B
At TD: Only Solid (a)
TB
WL = 0, Wa = 100wt% R S
At TB: Both a and L a
1200 D
TD (solid)
What would be WL and Wa?
20 3032 38 4044 50
S 44  38 CL Co Ca
WL  +   50wt % wt% Ni
R S 44  32
R 38  32
Wa  +   50wt %
R S 44  32
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: system
T(ºC)
TA A
tie line
1300 L (liquid)
B
TB
R S
a
1200 D
TD (solid)
What would be WL and Wa?
20 303235 4044 50
S 44  35 CLCo Ca
WL  +   75wt % wt% Ni
R S 44  32
R 35  32
Wa  +   25wt %
R S 44  32
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%).
• Examples:
Cu-Ni system
T(ºC)
TA A
tie line
1300 L (liquid)
B
TB R S
a
What would be WL and Wa? 1200 D
TD (solid)
S 43  35
WL  +   73wt % 20 3032 35 4043 50
R S 43  32 CLCo Ca
wt% Ni
R
Wa  = 27wt% Adapted from Fig. 9.2(b), Callister 6e.

R+S
(Fig. 9.2(b) is adapted from Phase Diagrams
of Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH, 1991.)
THE LEVER RULE: A PROOF
• Sum of weight fractions: WL + Wa  1
• Conservation of mass (Ni): Co  WL CL + WaCa
• Combine above equations:

• A geometric interpretation:
moment equilibrium:
WLR  WaS

1 Wa
solving gives Lever Rule
 Content

1. Introduction
2. Solubility Limit
3. Phase Diagrams
4. Microstructure Evolution during Cooling
5. Eutectic Systems
6. Fe-C Alloy
EX: COOLING IN A Cu-Ni BINARY
• Phase diagram:
Cu-Ni system. T(ºC) L (liquid) L: 35wt%Ni
• System is: Cu-Ni
--binary 1300
system
A
i.e., 2 components: L: 35wt%Ni
a: 46wt%Ni B
Cu and Ni. 35 46
--isomorphous 32 C 43
i.e., complete
24 D L: 32wt%Ni
36
solubility of one
a: 43wt%Ni
component in 1200 E
another; a phase L: 24wt%Ni
field extends from a: 36wt%Ni
a
0 to 100wt% Ni.
(solid)
• Consider
Co = 35wt%Ni. 1100
20 30 35 40 50
Co wt% Ni
What would be the microstructure?
EX: COOLING IN A Cu-Ni BINARY

T(ºC) L (liquid) L: 35wt%Ni

Cu-Ni
1300
system
A
L: 35wt%Ni
a: 46wt%Ni B
35 46
32 C 43

24 D L: 32wt%Ni
36
a: 43wt%Ni
1200 E
L: 24wt%Ni
a: 36wt%Ni
a
(solid)

• Consider 1100
Co = 35wt%Ni. 20 30 35 40 50
Adapted from Fig. 9.3, Co wt% Ni
Callister 6e.
If the alloy (65%Cu-35%Ni) is cooled from A to D at 10oC/sec,
what would be the details inside the solid?

T(ºC)
TA A
tie line
1300 L (liquid)
B
TB
a
1200 D (solid)
TD
20 3032 35 4043 50
CLCo Ca wt% Ni
CORED VS EQUILIBRIUM PHASES
• Ca changes as we solidify.
• Cu-Ni case: First a to solidify has Ca = 46wt%Ni.
Last a to solidify has Ca = 35wt%Ni.
• Fast rate of cooling: • Slow rate of cooling:
Cored structure Equilibrium structure
MECHANICAL PROPERTIES:
Cu-Ni System
• Effect of solid solution strengthening on:

--Tensile strength (TS) --Ductility (%EL,%AR)

60
%EL for pure Cu
Tensile Strength (MPa)

Elongation (%EL)
400 50 %EL for

300 ?
TS for pure Cu
TS for
pure Ni 40

30
?
pure Ni

200 20
0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
Composition, wt%Ni Composition, wt%Ni
MECHANICAL PROPERTIES:
Cu-Ni System
• Effect of solid solution strengthening on:
--Tensile strength (TS) --Ductility (%EL,%AR)

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

 Content

1. Introduction
2. Solubility Limit
3. Phase Diagrams
4. Microstructure Evolution during Cooling
5. Eutectic Systems
6. Fe-C Alloy
BINARY-EUTECTIC SYSTEMS
Ex.: Cu-Ag system
Gibbs Phase Rule:
3 single phase regions (L, a, b) P+F=C+2
Limited solubility:
T(ºC)
a: mostly Cu 120 0
b: mostly Ag L (liquid)
1000
a L+a
TE: no liquid below TE T E 800 779ºC L+ b b
CE: minimum melting Temp. 8.0 71.9 91.2
composition 600
a+b
400

200
0 20 40 60 C E 80 100
C o, wt% Ag
EX: Pb-Sn EUTECTIC SYSTEM (1)
• For a 40wt%Sn-60wt%Pb alloy at 150C, find...

--the phases present: T(ºC)

a+b
--the compositions of 300
L (liquid)
the phases:
a L+a
200 183ºC L+b b
18.3 61.9 97.8
150
100 a+b

0 20 40 60 80 100
Co
Co, wt% Sn
EX: Pb-Sn EUTECTIC SYSTEM (2)
• For a 40wt%Sn-60wt%Pb alloy at 150C, find...
--the phases present: a + b
--the compositions of T(ºC)
the phases:
Ca = ? 300
L (liquid)
Cb = ?
--the relative amounts a L+a
200 183ºC L+b b
of each phase: 18.3 61.9 97.8
150
R S
100
Wa = ? wt% a+b
Wb = ? wt%
0 11 20 40 60 80 99100
Co
Co, wt% Sn
EX: Pb-Sn EUTECTIC SYSTEM (2)

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

--the phases present: a + b T(ºC)

--the compositions of
the phases: 300
L (liquid)
Ca = 11wt%Sn
a L+a
Cb = 99wt%Sn 200 183ºC L+b b
--the relative amounts 18.3 61.9 97.8
150
of each phase: R S
100
a+b

0 11 20 40 60 80 99100
Co
Co, wt% Sn
MICROSTRUCTURES
IN EUTECTIC SYSTEMS-I

• Co < 2wt%Sn T(ºC) L: Cowt%Sn

400
• Result: ?
300 L

L+a
a
200
TE (Pb-Sn
System)

100
a+b

0 10 20 30
Co Co, wt% Sn
2
(room T solubility limit)
MICROSTRUCTURES
IN EUTECTIC SYSTEMS-I

• Co < 2wt%Sn T(ºC) L: Cowt%Sn

400
• Result: L
--polycrystal of a grains. a
300 L

L+a
a
200
TE a: Cowt%Sn

100
a+b

0 10 20 30
Co Co, wt% Sn
2
(room T solubility limit)
MICROSTRUCTURES
IN EUTECTIC SYSTEMS-II

T(ºC) L: Cowt%Sn
• 2wt%Sn < Co < 18.3wt%Sn
400
• Result:?
L
L
300 a
L+a
a: C owt%Sn
a
200
TE
a
b
100
a+b Pb-Sn
system
0 10 20 30
2 Co Co, wt% Sn
(sol. limit at Troom) 18.3
(sol. limit at TE)
MICROSTRUCTURES
IN EUTECTIC SYSTEMS-II

T(ºC) L: Cowt%Sn
• 2wt%Sn < Co < 18.3wt%Sn
400
• Result:
L
--a polycrystal with fine L
b crystals. 300 a
L+a
a: C owt%Sn
a
200
TE
a
b
100
a+b Pb-Sn
system
0 10 20 30
2 Co Co, wt% Sn
(sol. limit at Troom) 18.3
(sol. limit at TE)
MICROSTRUCTURES
IN EUTECTIC SYSTEMS-III
• Co = CE
• Result: ?
T(ºC)
L: Cowt%Sn
300 L
Pb-Sn
system L+a
200
TE a 183ºC L+b b

100 a+b
b: 97.8wt%Sn
a: 18.3wt%Sn
0
0 20 40 60 80 100
18.3 CE 97.8
61.9 Co, wt% Sn
MICROSTRUCTURES
IN EUTECTIC SYSTEMS-III
• Co = C E
• Result: Eutectic microstructure
--alternating layers of a and b crystals.
T(ºC)
L: Cowt%Sn
300 L
Pb-Sn
system L+a
200
TE a 183ºC L+b b

100 a+b
b: 97.8wt%Sn
a: 18.3wt%Sn
0
0 20 40 60 80 100
18.3 CE 97.8
61.9 Co, wt% Sn
Formation of Eutectic Lamellar Structure
MICROSTRUCTURES
IN EUTECTIC SYSTEMS-IV
• 18.3wt%Sn < Co < 61.9wt%Sn
• Result: a crystals and an eutectic microstructure

L: Cowt%Sn Just above TE:

T(ºC)
Ca = 18.3wt%Sn
L
300 L a CL = 61.9wt%Sn
L+a Wa = S =50wt%
R+S
200 a R S L+b b WL = (1-Wa) =50wt%
TE
R S
Just below TE:
100
a+b Ca = 18.3wt%Sn
Cb = 97.8wt%Sn
0
0 20 40 60 80 100 Wa = S =73wt%
18.3 Co 61.9 97.8 R+S
Co, wt% Sn Wb = 27wt%
MICROSTRUCTURES
IN EUTECTIC SYSTEMS-IV
• 18.3wt%Sn < Co < 61.9wt%Sn
• Result: a crystals and an eutectic microstructure
Just above TE :
T(ºC)
L: Cowt%Sn a L
Ca = 18.3wt%Sn
L
300 L a CL = 61.9wt%Sn
L+a Wa = S =50wt%
R+S
200 a R S L+b b WL = (1-Wa) =50wt%
TE
R S
Just below TE :
100
a+b Ca = 18.3wt%Sn
primary a
eutectic a
Cb = 97.8wt%Sn
0
0 20 40 60 80 100
eutectic b
Wa = S =73wt%
18.3 Co 61.9 97.8 R+S
Co, wt% Sn Wb = 27wt%
HYPOEUTECTIC & HYPEREUTECTIC
T(ºC)
300 L

L+a
200 a L+b (Pb-Sn
TE b
a+b System)
100

Co Co
hypoeutectic hypereutectic
0 Co, wt% Sn
0 20 40 60 80 100

18.3
eutectic 97.8
61.9
hypereutectic: (illustration only)
hypoeutectic: C o =50wt%Sn eutectic: C o =61.9wt%Sn

b
a b
a b b
a a b
a b
160 m m
a
175 m m
eutectic micro-constituent
OTHER EXAMPLES
OTHER EXAMPLES
 Content

1. Introduction
2. Solubility Limit
3. Phase Diagrams
4. Microstructure Evolution during Cooling
5. Eutectic Systems
6. Fe-C Alloy
IRON-CARBON (Fe-C) PHASE DIAGRAM
T(ºC)
1600
Two important points d
-Eutectic (A): 1400 L

L + g + Fe3C g +L
g A
1200 1148ºC L+Fe 3 C
( austenite)
-Eutectoid (B): R S

Fe 3 C (cementite)
g + a + Fe 3C 1000
g +Fe 3 C

800 B
a 727ºC = T eutectoid

R S
600
a +Fe 3 C

400
0 1 2 3 4 5 6 6.7
(Fe) 0.77 4.30 C o , wt% C
IRON-CARBON (Fe-C) PHASE DIAGRAM
T(ºC)
1600
Two important points d
-Eutectic (A): 1400 L
L + g + Fe3C
g g +L
-Eutectoid (B): 1200
A L+Fe 3 C
1148ºC
g + a + Fe 3C ( austenite)
R S

Fe 3 C (cementite)
1000 g g
g g g +Fe 3 C

800 B
a 727ºC = T eutectoid

R S
600
a +Fe 3 C

400
0 1 2 3 4 5 6 6.7
(Fe) 0.77 4.30
C o , wt% C
120 m m
Result: Pearlite = Fe 3 C (cementite-hard)
alternating layers of a (ferrite-soft)
a and Fe3C phases.
Formation of Pearlite Lamellar Structure
HYPOEUTECTOID STEEL
T(ºC)
1600
d
1400 L

g g +L
1200 1148ºC L+Fe 3 C
( austenite)

Fe 3 C (cementite)
1000
g +Fe 3 C

800 r s 727ºC
aR
S
6 00
a +Fe 3 C

4 00
0 Co 1 2 3 4 5 6 6.7
0.77

C o , wt% C
HYPOEUTECTOID STEEL
T(ºC)
1600
d
1400 L

g g g g +L
g g 1200 1148ºC L+Fe 3 C
( austenite)

Fe 3 C (cementite)
g g 1000
g g g +Fe 3 C
a r s
a
g g 800 727ºC
g ag aRS
w a = s/(r+ s) 600 a +Fe 3 C
w g = (1- w a )
400
0 1 2 3 4 5 6 6.7
0.77

Co
a
a pearlite C o , wt% C
a w pearlite = w g
w a = S/( R+ S)
100 m m
w Fe3C = (1- w a )
HYPEREUTECTOID STEEL
T(ºC)
1600
d
1400 L
(Fe-C
g g+L System)
1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
1000
g+Fe3C Adapted from Figs.
9.21 and 9.29,Callister
6e. (Fig. 9.21 adapted
800 r s from Binary Alloy
a R S
Phase Diagrams, 2nd
ed., Vol. 1, T.B.
600
a+Fe3C Massalski (Ed.-in-
Chief), ASM
International, Materials
400 Park, OH, 1990.)
0
0.77

1 Co 2 3 4 5 6 6.7
Co, wt% C
HYPEREUTECTOID STEEL
T(ºC)
1600
d
1400 L
(Fe-C
g g g g+L System)
g g 1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
g g 1000
g g g+Fe3C
Fe 3C
g g 800 r s
g g a R S
wFe3C =r/(r+s)600 a+Fe3C
wg =(1-w Fe3C)
400
0 1 2 3 4 5 6 6.7
0.77

Co
pearlite Co, wt% C
wpearlite = wg
wa =S/(R+S) 60mm Hypereutectoid
wFe3C =(1-w a ) steel
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.