Chapter 10: Phase Diagrams

ISSUES TO ADDRESS...
When we combine two elements... what is the resulting equilibrium state? In particular, if we specify... -- the composition (e.g., wt% Cu - wt% Ni), and -- the temperature (T ) then... How many phases form? What is the composition of each phase? What is the amount of each phase?

Phase A
Nickel atom Copper atom

Phase B

Chapter 10 - 1

Phase Equilibria: Solubility Limit

Solution solid, liquid, or gas solutions, single phase Mixture more than one phase Adapted from Fig. 10.1,
Callister & Rethwisch 4e.

Solubility Limit:
Temperature (C)

Sugar/Water Phase Diagram

10 0 80 60 40 20 0 Solubility Limit

Maximum concentration for which only a single phase solution exists.

L
(liquid)

Question: What is the

solubility limit for sugar in water at 20C?

L
(liquid solution i.e., syrup)

+ S
(solid sugar)

Answer: 65 wt% sugar.

At 20C, if C < 65 wt% sugar: syrup At 20C, if C > 65 wt% sugar:
syrup + sugar

Water

Chapter 10 - 2

Sugar

20 40 6065 80 100 C = Composition (wt% sugar)

Components and Phases

Components:
The elements or compounds which are present in the alloy
(e.g., Al and Cu)

Phases:
The physically and chemically distinct material regions that form (e.g., a and b).
AluminumCopper Alloy

b (lighter phase)

Adapted from chapteropening photograph, Chapter 9, Callister, Materials Science & Engineering: An Introduction, 3e.

a (darker phase)

Chapter 10 - 3

Effect of Temperature & Composition

Altering T can change # of phases: path A to B. Altering C can change # of phases: path B to D. B (100C,C = 70) D (100C,C = 90)

100
Temperature (C)

1 phase

2 phases

80
60 40 L
(liquid solution
i.e., syrup)

L
(liquid)

watersugar system

+ S
(solid sugar)

20
0
0

A (20C,C = 70)
2 phases

Adapted from Fig. 10.1, Callister & Rethwisch 4e.

20 40 60 70 80 100 C = Composition (wt% sugar)

Chapter 10 - 4

Criteria for Solid Solubility

Simple system (e.g., Ni-Cu solution) Crystal Structure
electroneg

r (nm)

Ni
Cu

FCC
FCC

1.9
1.8

0.1246
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 soluble in one another for all proportions.

Chapter 10 - 5

Phase Diagrams
Indicate phases as a function of T, C, and P. For this course:
- binary systems: just 2 components. - independent variables: T and C (P = 1 atm is almost always used).

T(C)
Phase Diagram for Cu-Ni system
1600 1500

2 phases:

L (liquid)

L (liquid) a (FCC solid solution)

3 different phase fields: L L+a a
Adapted from Fig. 10.3(a), Callister & Rethwisch 4e. (Fig. 10.3(a) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park, OH (1991).

1400
1300 1200 1100 1000 0 20

a (FCC solid solution)

40 60 80

100

wt% Ni

Chapter 10 - 6

Isomorphous Binary Phase Diagram

Phase diagram:
Cu-Ni system.

T(C)
1600
1500 1400 1300 1200 1100 1000 0 20

System is:
-- binary
i.e., 2 components: Cu and Ni.

L (liquid)

Cu-Ni phase diagram

-- isomorphous
i.e., complete solubility of one component in another; a phase field extends from 0 to 100 wt% Ni.

a (FCC solid solution)

40 60 80 100

wt% Ni

Adapted from Fig. 10.3(a), Callister & Rethwisch 4e. (Fig. 10.3(a) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park, OH (1991).

Chapter 10 - 7

Phase Diagrams:
Determination of phase(s) present
Rule 1: If we know T and Co, then we know:
-- which phase(s) is (are) present.

Examples:

T(C)
1600 B (1250C,35)

A(1100C, 60 wt% Ni): 1500 1 phase: a B (1250C, 35 wt% Ni): 1400 2 phases: L + a
1300 1200
Adapted from Fig. 10.3(a), Callister & Rethwisch 4e. (Fig. 10.3(a) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park, OH (1991).

L (liquid) Cu-Ni phase diagram

a
(FCC solid solution)
A(1100C,60)

1100 1000 0 20 40

60

80

100

wt% Ni

Chapter 10 - 8

Phase Diagrams:
Determination of phase compositions
Rule 2: If we know T and C0, then we can determine:
-- the composition of each phase. Cu-Ni system A L (liquid) B D
30 32 35

Examples:
Consider C0 = 35 wt% Ni At TA = 1320C: Only Liquid (L) present CL = C0 ( = 35 wt% Ni) At TD = 1190C: Only Solid (a) present Ca = C0 ( = 35 wt% Ni) At TB = 1250C: Both a and L present CL = C liquidus ( = 32 wt% Ni) Ca = C solidus ( = 43 wt% Ni)

T(C) TA
1300

tie line

TB
1200 TD 20

a (solid)
4043 50

CL C0

Ca wt% Ni

Adapted from Fig. 10.3(a), Callister & Rethwisch 4e. (Fig. 10.3(a) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park, OH (1991).

Chapter 10 - 9

Phase Diagrams:
Determination of phase weight fractions
Rule 3: If we know T and C0, then can determine:
-- the weight fraction of each phase.

Examples: Consider C0 = 35 wt% Ni

At TA : Only Liquid (L) present WL = 1.00, Wa = 0 At TD : Only Solid ( a) present WL = 0, Wa = 1.00 At TB : Both a and L present

T(C) TA
1300

Cu-Ni system A
tie line

L (liquid)
B R S D
30 32 35

TB
1200 TD

a (solid)
50

WL =

S R +S

43 - 35 = = 0.73 43 - 32

20

CL C 0

4 0 43

Ca wt% Ni

Wa =

R = 0.27 R +S

Adapted from Fig. 10.3(a), Callister & Rethwisch 4e. (Fig. 10.3(a) is adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM International, Materials Park, OH (1991).

Chapter 10 - 10

The Lever Rule

Tie line connects the phases in equilibrium with each other also sometimes called an isotherm
T(C)
tie line 1300

L (liquid)

What fraction of each phase? Think of the tie line as a lever (teeter-totter)
ML Ma

TB
1200

B
a (solid)
R S
50 3 0CL

20

wt% Ni

C0 4 0 Ca

Adapted from Fig. 10.3(b), Callister & Rethwisch 4e.

Ma x S = ML x R
C0 - CL R Wa = = R + S Ca - CL
Chapter 10 - 11

Ca - C0 ML S WL = = = ML + Ma R + S Ca - CL

Ex: Cooling of a Cu-Ni Alloy

Phase diagram:
Cu-Ni system.
T(C)L (liquid)
130 0 L: 35 wt% Ni a: 46 wt% Ni 32 24 120 0 L: 35wt%Ni

Consider microstuctural changes that accompany the cooling of a

A
35

Cu-Ni system
46 43 L: 32 wt% Ni a: 43 wt% Ni L: 24 wt% Ni a: 36 wt% Ni

B C

D E
a (solid)

36

C0 = 35 wt% Ni alloy

110 0 20

30

Adapted from Fig. 10.4, Callister & Rethwisch 4e.

35 C0

40

50

wt% Ni
Chapter 10 - 12

Cored vs Equilibrium Structures

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.

Slow rate of cooling:

Equilibrium structure
Uniform Ca: 35 wt% Ni

Fast rate of cooling:

Cored structure
First a to solidify: 46 wt% Ni Last a to solidify: < 35 wt% Ni

Chapter 10 - 13

Mechanical Properties: Cu-Ni System

Effect of solid solution strengthening on:
-- Tensile strength (TS)
Tensile Strength (MPa)

-- Ductility (%EL)
Elongation (%EL)
60 50 40 30 20 0 20 Cu 40 60 80 100 Ni %EL for pure Cu %EL for pure Ni

400 TS for pure Ni

300

TS for pure Cu
200 0 20 40 Cu 60 80 100 Ni

Composition, wt% Ni
Adapted from Fig. 10.6(a), Callister & Rethwisch 4e.

Composition, wt% Ni

Adapted from Fig. 10.6(b), Callister & Rethwisch 4e.

Chapter 10 - 14

Binary-Eutectic Systems
2 components has a special composition with a min. melting T.

Ex.: Cu-Ag system

T(C)
1200

Cu-Ag system

3 single phase regions L (liquid) 1000 (L, a, b) a L + a 779C Limited solubility: TE 800 8.0 a: mostly Cu b: mostly Ag 600 TE : No liquid below TE a+b 400 CE : Composition at temperature TE 200 Eutectic reaction
0 20 40

71.9 91.2

L +b b

60 CE 80

100

L(CE)

a(CaE) + b(CbE)
cooling
heating

C , wt% Ag
Adapted from Fig. 10.7, Callister & Rethwisch 4e.

L(71.9 wt% Ag)

a(8.0 wt% Ag) + b(91.2 wt% Ag) Chapter 10 - 15

EX 1: Pb-Sn Eutectic System

For a 40 wt% Sn-60 wt% Pb alloy at 150C, determine:
-- the phases present Answer: a + b -- the phase compositions
Answer: Ca = 11 wt% Sn Cb = 99 wt% Sn

T(C)
300

Pb-Sn system

L (liquid) a
L+ a
18.3
183C

-- the relative amount of each phase

Answer: Cb - C0 S = Wa = R+S Cb - Ca 99 - 40 99 - 11 Wb = R = R+ S 40 - 11 = 99 - 11 =

200 150 100

L +b b
97.8

61.9

S
a+b

59 = 0.67 88 C0 - Ca Cb - Ca 29 = 0.33 88

0 11 20 Ca

40 C0

60

80

C, wt% Sn

99100 Cb

Adapted from Fig. 10.8, Callister & Rethwisch 4e.

Chapter 10 - 16

EX 2: Pb-Sn Eutectic System

For a 40 wt% Sn-60 wt% Pb alloy at 220C, determine:
-- the phases present: Answer: a + L -- the phase compositions
Answer: Ca = 17 wt% Sn CL = 46 wt% Sn

T(C)
300 220 200

Pb-Sn system

-- the relative amount of each phase

Answer: CL - C0 46 - 40 = Wa = CL - Ca 46 - 17 6 = = 0.21 29 C0 - Ca 23 = = 0.79 WL = CL - Ca 29

L+ a
R

L (liquid)
S
183C

L +b b

100

a+b
0 17 20 Ca 40 46 60 C0 CL 80 100

C, wt% Sn
Chapter 10 - 17

Adapted from Fig. 10.8, Callister & Rethwisch 4e.

Microstructural Developments in Eutectic Systems I

For alloys for which C0 < 2 wt% Sn Result: at room temperature
-- polycrystalline with grains of a phase having composition C0
T(C)
400 L a 300 L: C0 wt% Sn

L a
a: C0 wt% Sn

L+ a (Pb-Sn System)

200

TE
100

a+ b

Adapted from Fig. 10.11, Callister & Rethwisch 4e.

0 10 20 30 C0 C , wt% Sn 2 (room T solubility limit)

Chapter 10 - 18

Microstructural Developments in Eutectic Systems II

For alloys for which 400 2 wt% Sn < C0 < 18.3 wt% Sn Result: at temperatures in a + b range 300 -- polycrystalline with a grains and small b-phase particles 200
TE
100

T(C) L L +a a

L: C0 wt% Sn

L a a: C0 wt% Sn

a b

a+ b

Pb-Sn system
30

Adapted from Fig. 10.12, Callister & Rethwisch 4e.

C0 C , wt% 2 (sol. limit at T room ) 18.3 (sol. limit at TE)

10

20

Sn

Chapter 10 - 19

Microstructural Developments in Eutectic Systems III

For alloy of composition C0 = CE Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of a and b phases.

T(C)
L: C0 wt% Sn

Micrograph of Pb-Sn eutectic microstructure

300

Pb-Sn system
200
TE

L+ a

L
183C

L+b b
160 m
Adapted from Fig. 10.14, Callister & Rethwisch 4e.

100

a+b
0 20 18.3 40

b: 97.8 wt% Sn a: 18.3 wt%Sn

Adapted from Fig. 10.13, Callister & Rethwisch 4e.

60 CE 61.9

80

C, wt% Sn

100 97.8

Chapter 10 - 20

Lamellar Eutectic Structure

Adapted from Figs. 10.14 & 10.15, Callister & Rethwisch 4e.

Chapter 10 - 21

Microstructural Developments in Eutectic Systems IV

For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn Result: a phase particles and a eutectic microconstituent
Just above TE :
Ca = 18.3 wt% Sn CL = 61.9 wt% Sn S = 0.50 = Wa R+S WL = (1- Wa) = 0.50

T(C)
300

L: C0 wt% Sn L

Pb-Sn system
200
TE

L
a
L+ a
R S

a
L+
S

b b

Just below TE :
primary a eutectic a eutectic b

100

a+b

20 18.3

40

60 61.9

80

100 97.8

Adapted from Fig. 10.16, Callister & Rethwisch 4e.

C, wt% Sn

Ca = 18.3 wt% Sn Cb = 97.8 wt% Sn Wa = S = 0.73 R+S Wb = 0.27

Chapter 10 - 22

Hypoeutectic & Hypereutectic

300
Adapted from Fig. 10.8, Callister & Rethwisch 4e. (Fig. 10.8 adapted from Binary Phase Diagrams, 2nd ed., Vol. 3, T.B. Massalski (Editor-in-Chief), ASM International, Materials Park, OH, 1990.)

T(C)
200
TE

L+ a a+b

L+b b

(Pb-Sn System)

100

0
(Figs. 10.14 and 10.17 from Metals Handbook, 9th ed., Vol. 9, Metallography and Microstructures, American Society for Metals, Materials Park, OH, 1985.)

20

40

60
eutectic 61.9

80

100

C, wt% Sn

hypoeutectic: C0 = 50 wt% Sn

hypereutectic: (illustration only)

a a

a a a a
175 m

eutectic: C0 = 61.9 wt% Sn

b b
160 m eutectic micro-constituent
Adapted from Fig. 10.14, Callister & Rethwisch 4e.

b b b b

Adapted from Fig. 10.17, Callister & Rethwisch 4e.

Adapted from Fig. 10.17, Callister & Rethwisch 4e. (Illustration only) Chapter 10 - 23

Intermetallic Compounds
Adapted from Fig. 10.20, Callister & Rethwisch 4e.

Mg2Pb
Note: intermetallic compound exists as a line on the diagram - not an area - because of stoichiometry (i.e. composition of a compound Chapter 10 - 24 is a fixed value).

Eutectic, Eutectoid, & Peritectic

Eutectic - liquid transforms to two solid phases L cool a + b (For Pb-Sn, 183C, 61.9 wt% Sn)
heat

Eutectoid one solid phase transforms to two other solid phases intermetallic compound - cementite S2 S1+S3 cool a + Fe3C (For Fe-C, 727C, 0.76 wt% C)
heat

Peritectic - liquid and one solid phase transform to a second solid phase S1 + L S2 +L
cool heat

(For Fe-C, 1493C, 0.16 wt% C)

Chapter 10 - 25

Eutectoid & Peritectic

Cu-Zn Phase diagram
Peritectic transformation + L

Eutectoid transformation

Adapted from Fig. 10.21, Callister & Rethwisch 4e.

Chapter 10 - 26

Ceramic Phase Diagrams

MgO-Al2O3 diagram:

Adapted from Fig. 10.24, Callister & Rethwisch 4e.

Chapter 10 - 27

Iron-Carbon (Fe-C) Phase Diagram

2 important points - Eutectic (A):
L + Fe3C a + Fe3C T(C)
1600

1400 1200 1000 800 600

+Fe3C
727C = T eutectoid

a+Fe3C 0.76
1 2 3 4

120 m

400 0 (Fe)

4.30

6.7

C, wt% C

Result: Pearlite = alternating layers of a and Fe3C phases

(Adapted from Fig. 10.31, Callister & Rethwisch 4e.)

Fe3C (cementite-hard) a (ferrite-soft)

Adapted from Fig. 10.28, Callister & Rethwisch 4e.

Chapter 10 - 28

Fe3C (cementite)

- Eutectoid (B):

+L (austenite)

1148C

L+Fe3C

Hypoeutectoid Steel
T(C)
1600

1400

L Fe3C (cementite)
1148C

a a a

+L 1200 (austenite)
1000 800 600

L+Fe3C

(Fe-C System)
Adapted from Figs. 10.28 and 10.33,Callister & Rethwisch 4e. (Fig. 10.28 adapted from Binary Alloy Phase Diagrams, 2nd ed., Vol. 1, T.B. Massalski (Ed.-inChief), ASM International, Materials Park, OH, 1990.)

+ Fe3C
727C

a
1
0.76

a + Fe3C
2 3 4 5 6

400 0 (Fe)C0
pearlite

6.7

C, wt% C
100 m Hypoeutectoid steel

pearlite

proeutectoid ferrite
Adapted from Fig. 10.34, Callister & Rethwisch 4e. Chapter 10 - 29

Hypoeutectoid Steel
T(C)
1600

1400
a

L Fe3C (cementite)
1148C

+L 1200 (austenite)
1000

L+Fe3C

(Fe-C System)
Adapted from Figs. 10.28 and 10.33,Callister & Rethwisch 4e. (Fig. 10.28 adapted from Binary Alloy Phase Diagrams, 2nd ed., Vol. 1, T.B. Massalski (Ed.-inChief), ASM International, Materials Park, OH, 1990.)

Wa = s/(r + s) 800 r s W =(1 - Wa)

a
pearlite

+ Fe3C
727C

600

aRS
1
0.76

a + Fe3C
2 3 4 5 6

Wpearlite = W

400 0 (Fe)C0

6.7

C, wt% C
100 m Hypoeutectoid steel

Wa = S/(R + S) WFe3C =(1 Wa) pearlite

proeutectoid ferrite
Adapted from Fig. 10.34, Callister & Rethwisch 4e.

Chapter 10 - 30

Hypereutectoid Steel
T(C)
1600

1400

L
1148C

1000 800 600

+Fe3C

Fe3C (cementite)

Fe3C

+L 1200 (austenite)

(Fe-C System) L+Fe3C

a
0.76 1 C0 2 3

a +Fe3C
4 5 6

400 0 (Fe) pearlite

6.7

Adapted from Figs. 10.28 and 10.36,Callister & Rethwisch 4e. (Fig. 10.28 adapted from Binary Alloy Phase Diagrams, 2nd ed., Vol. 1, T.B. Massalski (Ed.-inChief), ASM International, Materials Park, OH, 1990.)

C, wt%C
60 mHypereutectoid steel

pearlite

proeutectoid Fe3C
Chapter 10 - 31

Adapted from Fig. 10.37, Callister & Rethwisch 4e.

Hypereutectoid Steel
T(C)
1600

1400
Fe3C

L
1148C

1000 800

W =x/(v + x) WFe3C =(1-W)

+Fe3C v x X
1 C0 2 3

Fe3C (cementite)

+L 1200 (austenite)

(Fe-C System) L+Fe3C

a V 600
0.76

Wpearlite = W WFe

pearlite 400 0 (Fe)

a +Fe3C
4 5 6

6.7

Adapted from Figs. 10.28 and 10.36,Callister & Rethwisch 4e. (Fig. 10.28 adapted from Binary Alloy Phase Diagrams, 2nd ed., Vol. 1, T.B. Massalski (Ed.-inChief), ASM International, Materials Park, OH, 1990.)

C, wt%C
60 mHypereutectoid steel

Wa = X/(V + X)
3C

=(1 - Wa) pearlite

proeutectoid Fe3C
Chapter 10 - 32

Adapted from Fig. 10.37, Callister & Rethwisch 4e.

Example Problem
For a 99.6 wt% Fe-0.40 wt% C steel at a temperature just below the eutectoid, determine the following: a) The compositions of Fe3C and ferrite (a). b) The amount of cementite (in grams) that forms in 100 g of steel. c) The amounts of pearlite and proeutectoid ferrite (a) in the 100 g.

Chapter 10 - 33

Solution to Example Problem

a) Using the RS tie line just below the eutectoid
Ca = 0.022 wt% C CFe3C = 6.70 wt% C

b) Using the lever rule with the tie line shown

WFe 3C = = R C - Ca = 0 R + S CFe 3C - Ca 0.40 - 0.022 = 0.057 6.70 - 0.022

1600

1200 1000

(austenite)

1148C

L+Fe3C

+ Fe3C
727C

800

Amount of Fe3C in 100 g = (100 g)WFe3C = (100 g)(0.057) = 5.7 g

R
600 400 0 1 2 3

S a + Fe3C
4 5 6

Ca C0

C , wt% C
Chapter 10 - 34

CFe

6.7
3C

Fe C (cementite)

T(C)

1400

+L

Solution to Example Problem (cont.)

c) Using the VX tie line just above the eutectoid and realizing that
C0 = 0.40 wt% C Ca = 0.022 wt% C Cpearlite = C = 0.76 wt% C

1600

1200 1000

(austenite)

1148C

L+Fe3C

0.40 - 0.022 = 0.512 0.76 - 0.022

+ Fe3C VX
727C

800
600 400 0 1

Amount of pearlite in 100 g = (100 g)Wpearlite

a + Fe3C
2 3 4 5 6

= (100 g)(0.512) = 51.2 g

Ca C0 C

6.7

C, wt% C
Chapter 10 - 35

Fe C (cementite)

Wpearlite =

V C - Ca = 0 V + X Cg - Ca

T(C)

1400

+L

VMSE: Interactive Phase Diagrams

Microstructure, phase compositions, and phase fractions respond interactively

Change alloy composition

Chapter 10 - 36

Alloying with Other Elements

Teutectoid changes:
T Eutectoid (C)
Ti Mo Si W Cr Mn Ni

Ceutectoid changes:
Ceutectoid (wt% C)

Ni Cr Si Ti Mo W Mn

wt. % of alloying elements

Adapted from Fig. 10.38,Callister & Rethwisch 4e. (Fig. 10.38 from Edgar C. Bain, Functions of the Alloying Elements in Steel, American Society for Metals, 1939, p. 127.)

wt. % of alloying elements

Adapted from Fig. 10.39,Callister & Rethwisch 4e. (Fig. 10.39 from Edgar C. Bain, Functions of the Alloying Elements in Steel, American Society for Metals, 1939, p. 127.)

Chapter 10 - 37

Summary
Phase diagrams are useful tools to determine:
-- the number and types of phases present, -- the composition of each phase, -- and the weight fraction of each phase

given the temperature and composition of the system.

The microstructure of an alloy depends on

-- its composition, and -- whether or not cooling rate allows for maintenance of equilibrium.

Important phase diagram phase transformations include eutectic, eutectoid, and peritectic.

Chapter 10 - 38

ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 10 - 39