ME 330 Engineering Materials

Lecture 10
Solidification and Phase Diagrams

Solidification
Phase Diagram Definitions
Eutectic Phase Diagram
Liquidus/Solidus
Solidification microstructures
Invariant Points
Intermediate compounds
Ternary Phase Diagram

Read Chapter 9
Chapter 9 - 1

Definitions
Alloy metals which are not pure; impurities are added intentionally
Solvent element or compound present in greater amount (host atoms)
Solute element present in minor concentration
Solid solution addition of impurity into metal
solute atoms are added to the host material
crystal structure is maintained
no new structure is formed
atoms are intermixed so composition is uniform
(liquid analogy: mixing of two liquids)
Two types of solid solutions
1. Substitutional solution solute atoms replace or substitute host atoms
2. Interstitial solution impurity atoms fill voids or interstices
Read Section 4.3

Chapter 9 - 2

Terminology

System: For our purposes, alloy under consideration

Fe/C or Pb/Sn

Component: Pure elements of which an alloy is composed

Fe or C, Pb or Sn

Solute: Component of solution being dissolved

Solvent: Component of solution in greatest amount
Solubility: Ability of component to form solution with another
Phase: Portion of system with uniform chemical/physical
characteristics

Sugar + water: Phases have different chemical and

physical compositions
Ice and water: Same chemical, different physical

Equilibrium: State of system where no phase changes occur

Chapter 9 - 3

Chapter 9: Phase Diagrams

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?

Phase B

Phase A
Nickel atom
Copper atom

Chapter 9 - 4

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:

Question: What is the

solubility limit at 20C?

Answer: 65 wt% sugar.

Temperature (C)

Max concentration for

which only a single phase
solution occurs.

10 0
Solubility
Limit

80

L
(liquid)

60

40

(liquid solution
i.e., syrup)

20

+
S
(solid
sugar)

Pure
Water

Pure
Sugar

If Co < 65 wt% sugar: syrup

0
20
40
6065 80
100
If Co > 65 wt% sugar: syrup + sugar.
Co =Composition (wt% sugar)
Chapter 9 - 5

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).
AluminumCopper
Alloy

b (lighter
phase)
a (darker
phase)

Adapted from
chapter-opening
photograph,
Chapter 9,
Callister 3e.
Chapter 9 - 6

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

watersugar
system

Adapted from
Fig. 9.1,
Callister 7e.

Temperature (C)

100

2 phases

80

(liquid)

60

L
(liquid solution

40

i.e., syrup)

+
S
(solid
sugar)

A (20C,70)

20

2 phases

20
40
60 70 80
100
Co =Composition (wt% sugar)
Chapter 9 - 7

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

electroneg

r (nm)

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 - 8

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
Diagram
for Cu-Ni
system

2 phases:

1600
1500

L (liquid)
a (FCC solid solution)

L (liquid)

1400
1300

a
(FCC solid
solution)

1200
1100
1000

20

40

60

80

3 phase fields:
L
L+a
a
Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase
Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
OH (1991).

100

wt% Ni

Chapter 9 - 9

Phase Diagrams:
# and types of phases
Rule 1: If we know T and Co, then we know:
--the # and types of phases present.

A(1100C, 60):
1 phase: a

B (1250C, 35):
2 phases: L + a

1600

L (liquid)
B (1250C,35)

Examples:

T(C)
1500
1400
1300

1200
Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase
Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
OH, 1991).

1100
1000

Cu-Ni
phase
diagram

a
(FCC solid
solution)

A(1100C,60)

20

40

60

80

100

wt% Ni

Chapter 9 - 10

Phase Diagrams:
composition of phases
Rule 2: If we know T and Co, then we know:
--the composition of each phase.

Examples:

T(C)

Cu-Ni
system

A
TA
Co = 35 wt% Ni
tie line
1300 L (liquid)
At T A = 1320C:
Only Liquid (L)
B
TB
CL = Co ( = 35 wt% Ni)
a
At T D = 1190C:
(solid)
1200
D
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
Adapted from Fig. 9.3(b), Callister 7e.
9.3(b) is adapted from Phase Diagrams
CL = C liquidus ( = 32 wt% Ni here) (Fig.
of Binary Nickel Alloys, P. Nash (Ed.), ASM
Ca = C solidus ( = 43 wt% Ni here) International, Materials Park, OH, 1991.)
Chapter 9 - 11

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:
Co = 35 wt% Ni
At T A : Only Liquid (L)
W L = 100 wt%, W a = 0
At T D: Only Solid ( a)
W L = 0, Wa = 100 wt%
At T B : Both a and L

WL
Wa

43 35
S

73 wt %
R + S 43 32

R
= 27 wt%
R +S

Cu-Ni
system

T(C)

TA

tie line

L (liquid)

1300

B
R S

TB
1200

TD
20

3 032 35

CLCo

a
(solid)

4 0 43

50

Ca 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.)
Chapter 9 - 12

The Lever Rule

Tie line connects the phases in equilibrium with
each other - essentially an isotherm
T(C)

How much of each phase?

Think of it as a lever (teeter-totter)

tie line
1300

L (liquid)
B

TB

a
(solid)

1200

R
20

3 0C C
40 C
a
L o

wt% Ni

WL

Ma

ML

50

M a S M L R

Adapted from Fig. 9.3(b),

Callister 7e.

C C0
ML
S

a
ML Ma R S Ca CL

Wa

C CL
R
0
R S Ca CL
Chapter 9 - 13

Ex: Cooling in a Cu-Ni Binary

Phase diagram:
Cu-Ni system.

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

T(C) L (liquid)
130 0
L: 35 wt% Ni
a: 46 wt% Ni

Consider
Co = 35 wt%Ni.

Cu-Ni
system

A
35
32

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

L: 35wt%Ni

B
C

46
43

24

L: 32 wt% Ni

36

120 0

a: 43 wt% Ni

L: 24 wt% Ni
a: 36 wt% Ni

a
(solid)
110 0
20

30

Adapted from Fig. 9.4,

Callister 7e.

35
Co

40

50

wt% Ni
Chapter 9 - 14

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:

Cored structure

Slow rate of cooling:

Equilibrium structure

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

Uniform C a:
35 wt% Ni

Chapter 9 - 15

Mechanical Properties: Cu-Ni System

Effect of solid solution strengthening on:
--Ductility (%EL,%AR)

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. 9.6(a), Callister 7e.

--Peak as a function of Co

Elongation (%EL)

Tensile Strength (MPa)

--Tensile strength (TS)

60

%EL for pure Cu

%EL for
pure Ni

50

40
30
20
0 20
Cu

40

60

80 100
Ni

Composition, wt% Ni

Adapted from Fig. 9.6(b), Callister 7e.

--Min. as a function of Co
Chapter 9 - 16

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

2 components

Cu-Ag
system

T(C)

Ex.: Cu-Ag system

1200

3 single phase regions

L (liquid)
1000
(L, a, b)
a L + a 779C
Limited solubility:
L +b b
800
T
a: mostly Cu
8.0
71.9 91.2
E
b: mostly Ag
600
TE : No liquid below TE
ab
400
CE : Min. melting TE
composition
200
0

Eutectic transition

L(CE)

a(CaE) + b(CbE)

20

40

60 CE 80

100

Co , wt% Ag
Adapted from Fig. 9.7,
Callister 7e.
Chapter 9 - 17

EX: Pb-Sn Eutectic System (1)

For a 40 wt% Sn-60 wt% Pb alloy at 150C, find...
--the phases present: a + b
T(C)
--compositions of phases:
CO = 40 wt% Sn
Ca = 11 wt% Sn
Cb = 99 wt% Sn

--the relative amount

of each phase:
Wa =

C - CO
S
= b
R+S
Cb - Ca

Pb-Sn
system

300

200

L (liquid)
a

L+ a
18.3

150
100

99 - 40
59
=
= 67 wt%
99 - 11
88
C - Ca
Wb = R = O
Cb - Ca
R+S

L +b b

183C

61.9

97.8

S
a+b

40 - 11
29
=
= 33 wt%
99 - 11
88

0 11 20
Ca

40
Co

60

80

C, wt% Sn

99100
Cb

Adapted from Fig. 9.8,

Callister 7e.
Chapter 9 - 18

EX: Pb-Sn Eutectic System (2)

For a 40 wt% Sn-60 wt% Pb alloy at 200C, find...
--the phases present: a + L
T(C)
--compositions of phases:
CO = 40 wt% Sn
Ca = 17 wt% Sn
CL = 46 wt% Sn

--the relative amount

of each phase:
CL - CO
46 - 40
=
Wa =
CL - Ca
46 - 17
6
=
= 21 wt%
29

Pb-Sn
system

300

220
200

L (liquid)

L+ a
R

L +b b

S
183C

100

CO - Ca
23
=
WL =
= 79 wt%
CL - Ca
29

a+b
0

17 20
Ca

40 46 60
Co CL

80

C, wt% Sn

Adapted from Fig. 9.8,

Callister 7e.
Chapter 9 - 19

100

Microstructures
in Eutectic Systems: I
Co < 2 wt% Sn
Result:
--at extreme ends
--polycrystal of a grains
i.e., only one solid phase.

T(C)

L: Co wt% Sn

400

L
a

300

200

(Pb-Sn
System)

a: Co wt% Sn

TE

a+ b

100

Adapted from Fig. 9.11,

Callister 7e.

L+ a

0
Co

10

20

30

Co, wt% Sn

2
(room T solubility limit)

Chapter 9 - 20

Microstructures
in Eutectic Systems: II
L: Co wt% Sn

2 wt% Sn < Co < 18.3 wt% Sn 400T(C)

Result:

Initially liquid + a
then a alone
finally two phases
a polycrystal
fine b-phase inclusions

L
300

L +a
a

200

TE

a: Co wt% Sn

a
b

100

a+ b

Adapted from Fig. 9.12,

Callister 7e.
(sol.

L
a

10

20

Pb-Sn
system
30

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

Sn

Chapter 9 - 21

Microstructures
in Eutectic Systems: III
Co = CE
Result: Eutectic microstructure (lamellar structure)
--alternating layers (lamellae) of a and b crystals.

T(C)
L: Co wt% Sn

300

Pb-Sn
system

200

L+ a

L
Lb b

183C

TE

100

ab
0

20
18.3

Adapted from Fig. 9.13,

Callister 7e.

Micrograph of Pb-Sn
eutectic
microstructure

40

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

60
CE
61.9

80

160 m
Adapted from Fig. 9.14, Callister 7e.

100
97.8

C, wt% Sn

Chapter 9 - 22

Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister

7e.

Chapter 9 - 23

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

T(C)
300

Pb-Sn
system

200

L+ a

TE

L
a

a L

L+b b

primary a
eutectic a
eutectic b

20
18.3

Adapted from Fig. 9.16,

Callister 7e.

40

60
61.9

Ca = 18.3 wt% Sn
CL = 61.9 wt% Sn
Wa = S = 50 wt%
R+S
WL = (1- Wa) = 50 wt%

Just below TE :

a+b

100

Just above TE :

80

Co, wt% Sn

100
97.8

Ca = 18.3 wt% Sn
Cb = 97.8 wt% Sn
Wa = S = 73 wt%
R+S
Wb = 27 wt%
Chapter 9 - 24

Hypoeutectic & Hypereutectic

300

T(C)

Adapted from Fig. 9.8,

Callister 7e. (Fig. 9.8
adapted from Binary Phase
Diagrams, 2nd ed., Vol. 3,
T.B. Massalski (Editor-inChief), ASM International,
Materials Park, OH, 1990.)

200

L+ a
a+b

20

40

hypoeutectic: Co = 50 wt% Sn

a
a

(Pb-Sn
System)

100

0
(Figs. 9.14 and 9.17
from Metals
Handbook, 9th ed.,
Vol. 9,
Metallography and
Microstructures,
American Society for
Metals, Materials
Park, OH, 1985.)

L+b b

TE

60

80

eutectic
61.9

hypereutectic: (illustration only)

b
b

Adapted from
Fig. 9.17, Callister 7e.

Co, wt% Sn

eutectic: Co = 61.9 wt% Sn

a a
175 m

100

b
b b
b

160 m
eutectic micro-constituent
Adapted from Fig. 9.14,
Callister 7e.

Adapted from Fig. 9.17,

Callister 7e. (Illustration
only)
Chapter 9 - 25

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. Chapter 9 - 26

Eutectoid & Peritectic

Eutectic - liquid in equilibrium with two solids
L cool a + b
heat

Eutectoid - solid phase in equation with two solid

phases
intermetallic compound
S2
S1+S3
- cementite
cool a + Fe3C
(727C)
heat

Peritectic - liquid + solid 1 solid 2 (Fig 9.21)

S1 + L
S2
cool
+ L heat
(1493C)

Chapter 9 - 27

Eutectoid & Peritectic

Cu-Zn Phase diagram

Eutectoid transition

Peritectic transition + L

Adapted from
Fig. 9.21, Callister 7e.

Chapter 9 - 28

Iron-Carbon (Fe-C) Phase Diagram

T(C)
1600

1200

a + Fe3C

+L

(austenite)

1000

800
600

120 m

Result: Pearlite =
alternating layers of
a and Fe3C phases
(Adapted from Fig. 9.27, Callister 7e.)

S
+Fe3C
727C = Teutectoid

0.76

L+Fe3C

400
0
(Fe)

1148C

a+Fe3C
4

Fe3C (cementite)

L + Fe3C

-Eutectoid (B):

1400

C eutectoid

2 important
points
-Eutectic (A):

6.7

4.30
Co, wt% C
Fe3C (cementite-hard)
a (ferrite-soft)

Adapted from Fig. 9.24,Callister 7e.

Chapter 9 - 29

Hypoeutectoid Steel
T(C)
1600

a
a

+L

1200
(austenite)
1000
800

+ Fe3C
r s

727C

aRS

w a =s /(r +s) 600

w = (1- wa )

400
0
(Fe)
pearlite

a + Fe3C
1

C0

w pearlite = w

6.7

100 m

w a = S/(R + S)
w Fe3 =(1- w a )
C

Adapted from Figs. 9.24

and 9.29,Callister 7e.
(Fig. 9.24 adapted from
Binary Alloy Phase
Diagrams, 2nd ed., Vol.
1, T.B. Massalski (Ed.-inChief), ASM International,
Materials Park, OH,
1990.)

Co , wt% C

0.76

L+Fe3C

1148C

(Fe-C
System)

Fe3C (cementite)

1400

pearlite

Hypoeutectoid
steel

proeutectoid ferrite
Adapted from Fig. 9.30,Callister 7e.

Chapter 9 - 30

Hypereutectoid Steel
T(C)
1600

Fe3C

+L

1200
(austenite)

1000

800

w Fe3C =r /( r +s)
w =(1- w Fe3C )

a R
600

400
0
(Fe)
pearlite

L+Fe3C

1148C

+Fe3C

0.76

(Fe-C
System)

S
1 Co

w pearlite = w
w a =S/( R +S)
w Fe3C =(1- w a )

a +Fe3C
2

Fe3C (cementite)

1400

Adapted from Figs. 9.24

and 9.32,Callister 7e.
(Fig. 9.24 adapted from
Binary Alloy Phase
Diagrams, 2nd ed., Vol.
1, T.B. Massalski (Ed.-inChief), ASM International,
Materials Park, OH,
1990.)

6.7

Co , wt%C
60 mHypereutectoid
steel

pearlite

proeutectoid Fe3C
Adapted from Fig. 9.33,Callister 7e.

Chapter 9 - 31

Example: Phase Equilibria

For a 99.6 wt% Fe-0.40 wt% C at a temperature
just below the eutectoid, determine the
following
a) composition of Fe3C and ferrite (a)
b) the amount of carbide (cementite) in grams
that forms per 100 g of steel
c) the amount of pearlite and proeutectoid
ferrite (a)

Chapter 9 - 32

Chapter 9 Phase Equilibria

Solution: a) composition of Fe3C and ferrite (a)
b) the amount of carbide
(cementite) in grams that
forms per 100 g of steel

CO = 0.40 wt% C
Ca = 0.022 wt% C
CFe C = 6.70 wt% C
3

1600

1200

0.4 0.022
x 100 5.7g
6.7 0.022

a 94.3 g

L+Fe3C

1148C

(austenite)

1000

+ Fe3C

800

Fe 3C 5.7 g

+L

Fe C (cementite)

Fe 3C
Co Ca
1400

x100 T(C)
Fe 3C a CFe 3C Ca

727C

S
a + Fe3C

600
400
0

Ca CO

Co , wt% C

6.7

CFe

3C

Chapter 9 - 33

Chapter 9 Phase Equilibria

c. the amount of pearlite and proeutectoid ferrite (a)
note: amount of pearlite = amount of just above TE

1600

1400

T(C)
+L

Co Ca

x 100 51.2 g 1200

(austenite)
a C Ca
1000

+ Fe3C

800

727C

RS

pearlite = 51.2 g
proeutectoid a = 48.8 g

a + Fe3C

600
400
0

L+Fe3C

1148C

Ca CO C

Co , wt% C
Chapter 9 - 34

Fe C (cementite)

Co = 0.40 wt% C
Ca = 0.022 wt% C
Cpearlite = C = 0.76 wt% C

6.7

Alloying Steel with More Elements

Ti

Mo

Si
W

Cr
Mn
Ni

wt. % of alloying elements

Adapted from Fig. 9.34,Callister 7e. (Fig. 9.34
from Edgar C. Bain, Functions of the Alloying
Elements in Steel, American Society for Metals,
1939, p. 127.)

Ceutectoid changes:
Ceutectoid (wt%C)

T Eutectoid (C)

Teutectoid changes:

Ni

Cr
Si
Ti Mo

Mn

wt. % of alloying elements

Adapted from Fig. 9.35,Callister 7e. (Fig. 9.35
from Edgar C. Bain, Functions of the Alloying
Elements in Steel, American Society for Metals,
1939, p. 127.)

Chapter 9 - 35

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.

Chapter 9 - 36

Binary Systems

Two component systems

Isomorphous systems Solid and liquid are completely soluble over
all compositions
Eutectic systems Limited solubility in solid state
Phase diagram has invariant point where a
single phase liquid solidifies to a two phase
solid
Peritectic systems - Invariant point where a liquid and
solid phase solidify into a different solid phase

Eutectoid systems - Invariant point where a solid phase

solidifies into two different solid phases

Compound forming systems - Compounds form rather

than solid solutions
Chapter 9 - 37