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 A Phase B

Nickel atom
Copper atom
Chapter 9 - 1

Phase Equilibria: Solubility Limit

• Introduction
– Solutions – solid solutions, solute atoms dissolve in the
solvent to form a solid solution – a single phase
– Mixtures – more than one phase
• Solubility Limit:
Max concentration for
which only a single phase
solution occurs.

Question: What is the

solubility limit at 20°C?

The solubility of sugar in a sugar-water syrup

Answer: 65 wt% sugar.
If Co < 65 wt% sugar at 20°C : syrup
If Co > 65 wt% sugar at 20°C : syrup + sugar. Chapter 9 - 2

1
Components and Phases

• Components:
The elements or compounds which are present in the mixture
(e.g., Al and Cu)
• Phases:
A homogeneous portion of a system that has uniform physical
and chemical characteristics (e.g., a and b).

b (lighter
phase)

a (darker
phase)

Aluminum-Copper Alloy Chapter 9 - 3

Effect of T & Composition (Co)

.
• Changing T can change number of phases: path A to B
• Changing Co can change number of phases: path B to D.

B (100°C,70) D (100°C,90)
1 phase 2 phases
100
Temperature (°C)

80 L
(liquid)
water- 60 +
sugar L S
(liquid solution (solid
system 40 i.e., syrup) sugar)
A (20°C,70)
20 2 phases

00 20 40 60 70 80 100
Co =Composition (wt% sugar)
Chapter 9 - 4

2
 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 - 5

Binary Phase Diagrams

• Indicate phases as function of T, Co, and P (pressure).
• For this course:
- binary systems: just 2 components.
- independent variables: T and Co (P = 1 atmosphere is almost
always used).
T(°C)
1600 • 2 phases:
L (liquid)
1500 L (liquid)
a (FCC solid solution)
1400 • 3 phase fields:
s L
uid u a
1300 li q +
L lidus L+a
1200 so a a

1100 (FCC solid solution)

1000
0 20 40 60 80 100 (wt% Ni)
• Phase Diagram for Cu-Ni system Chapter 9 - 6

3
 Phase Diagrams: numbers and types of phases

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

-- the numbers and type of phases present.

T(°C)
• Examples: 1600
A (1100°C, 60): L (liquid)

B (1250°C,35)
1 phase: a 1500
s Cu-Ni
id u
B(1250°C, 35): 1400 il qu us phase
lid diagram
2 phases: L + a so
1300 +a a
L (FCC solid
1200 solution)
1100 A(1100°C,60)

1000
0 20 40 60 80 100 wt% Ni
Chapter 9 - 7

Phase Diagrams: composition of phases

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

-- the composition of each phase.

• Examples: A

C0 = 35 wt% Ni
At T A = 1320°C:
Only Liquid (L)
CL = Co ( = 35 wt% Ni)
At T D = 1160°C:
Only Solid ( a)
D
Ca = Co ( = 35 wt% Ni)
At T B = 1250°C:
Both a and L
CL = C liquidus ( = 32 wt% Ni here)
Ca = C solidus ( = 43 wt% Ni here)
Chapter 9 - 8

4
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%).

T(°C)
• Examples (9.1 p263):
TA A
C o = 35 wt% Ni tie line s
idu
L (liquid) liqu
At T A : Only Liquid (L) 1300
a
W L = 100 wt%, W a = 0 B L+
s
At T D: Only Solid ( a) TB i du
R S s ol
W L = 0, W a = 100 wt% a a
At T B : Both a and L 1200 L+ D
(solid)
TD
S 43 - 35
WL = = = 73 wt %
R + S 43 - 32 20 3 032 35 4043 50
C LC o C a wt% Ni
R
Wa = = 27 wt% Cu-Ni system
R +S
Chapter 9 - 9

The Lever Rule

• Tie line – connects the phases in equilibrium with each
other - essentially an isotherm

How much of each phase?

T(°C) -- Think of it as a lever (teeter-totter)
tie line dus
i
1300 L (liquid) liqu
a
B L+ s
ML Ma
TB i du
s ol
a a
1200 L+ (solid)
R S R S
20 30C C 40 C 50
L o a Ma S =ML R
wt% Ni Adapted from Fig. 9.3(b),
Callister 7e.

ML S C - C0 R C - CL
WL = = = a Wa = = 0
M L + M a R + S C a - CL R + S C a - CL
Chapter 9 - 10

5
Equilibrium Cooling in a Cu-Ni Binary System

• Phase diagram:
Cu-Ni system.
• System is:
--binary
i.e., 2 components:
Cu and Ni.
--isomorphous
i.e., complete
solubility of one
component in
another; a phase
field extends from
0 to 100 wt% Ni.
• Consider
Co = 35 wt%Ni.

Chapter 9 - 11

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

Chapter 9 - 12

6
nonequilibrium Cooling in a Cu-Ni Binary System

Schematic representation
of the development of
microstructure during the
nonequilibrium
solidification of a
35wt%Ni-65wt%Cu alloy

Chapter 9 - 13

Mechanical Properties: Cu-Ni System

• Effect of solid solution strengthening on:

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

60
Elongation (%EL)

%EL for pure Cu

400 50 %EL for
TS for pure Ni
pure Ni 40
300
TS for pure Cu 30
200 20
0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
Composition, wt% Ni Composition, wt% Ni
Adapted from Fig. 9.6(a), Callister 7e. Adapted from Fig. 9.6(b), Callister 7e.

Chapter 9 - 14

7
 Binary-Eutectic Systems
has a special composition
2 components with a minimum melting T.

T(°C) Cu-Ag system

Ex.: Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, a,b) 1000
• Limited solubility: a L + a 779°C L+b b
a: mostly Cu TE 800 8.0 71.9 91.2
b: mostly Ag 600
• TE : No liquid below TE a +b
• 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 - 15

Chapter 9 - 16

8
 Questions:
1. Give the names for
the single phases in
the Sn-Bi system
2. To fíll the name for
each phase region
3. The eutectic
temperature and the
eutectic composition
4. Tm for pure Sn and
Bi

The tin-bismuth phase diagram

Composition of the Bi-Sn soldier: 57wt% Bi Chapter 9 - 17

For a 40 wt% Sn-60 wt% Pb alloy at 150ºC, (a) What phases are present, (b) What are the
composition of the phases; (c) Calculate the relative amount of each phase present; (d) The same
questions as in (a-c) if the alloy is at 220ºC Chapter 9 - 18

9
EX: Pb-Sn Eutectic System (1)

• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, 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
200 183°C L+b b
of each phase: 18.3 61.9 97.8
S C - CO 150
Wa =
R+S
= b
Cb - Ca
R S
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 - Ca C, wt% Sn
40 - 11 29
= = = 33 wt%
99 - 11 88 Chapter 9 - 19

EX: Pb-Sn Eutectic System (2)

• For a 40 wt% Sn-60 wt% Pb alloy at 220°C, 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 a
200 R S L+b b
of each phase: 183°C
CL - CO 46 - 40
Wa = = 100
CL - C a 46 - 17 a+b
6
= = 21 wt%
29 100
0 17 20 40 46 60 80
Ca Co CL
CO - C a 23 C, wt% Sn
WL = = = 79 wt%
CL - C a 29

Chapter 9 - 20

10
Microstructures in Eutectic Systems: I

• Co < 2 wt% Sn T(°C) L: Co wt% Sn

400
• 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)

100
a+b

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

Chapter 9 - 21

Microstructures in Eutectic Systems: II

L: Co wt% Sn
• 2 wt% Sn < Co < 18.3 wt% Sn 400T(°C)
• Result: L
ƒ Initially liquid + a L
300
ƒ then a alone a
L+a
ƒ finally two phases a: Co wt% Sn
a
¾ a polycrystal 200
TE
¾ 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 - 22

11
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 183°C L +b b
TE

100 160 mm
a +b b: 97.8 wt% Sn
Adapted from Fig. 9.14, Callister 7e.
a: 18.3 wt%Sn

0 20 40 60 80 100
18.3 CE 97.8
61.9 C, wt% Sn Chapter 9 - 23

Lamellar Eutectic Structure

The eutectic structure forms in the alternating layers:

fi atomic diffusiom of lead and tin need only occur
over relatively short distances
Chapter 9 - 24

12
 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 S
L+a Wa = = 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%
Adapted from Fig. 9.16,
Callister 7e. Co, wt% Sn Chapter 9 - 25

Hypoeutectic & Hypereutectic

300
L
Adapted from Fig. 9.8, T(°C)
Callister 7e. (Fig. 9.8 a L+ a
adapted from Binary Phase
200 L+b b (Pb-Sn
TE
Diagrams, 2nd ed., Vol. 3, System)
T.B. Massalski (Editor-in- a+b
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
Vol. 9,
a b
Metallography and a b
Microstructures, a a b b
American Society for a b
Metals, Materials
Park, OH, 1985.) a b
175 mm 160 mm
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)
Chapter 9 - 26

13
Intermetallic Compounds
1. Give the name
for each phase
field
2. To point out
the eutectic
reactions in the
Mg-Pb system,
give the
temperature TE
and the
composion CE for
each reaction.

Mg2Pb

Note: intermetallic compound forms a line - not an area - because

stoichiometry (i.e. composition) is exact.
Chapter 9 - 27

Intermetallic Compounds

Mg2Pb

Note: intermetallic compound forms a line - not an area - because

stoichiometry (i.e. composition) is exact.
Chapter 9 - 28

14
 Eutectoid & Peritectic
• Eutectic - liquid in equilibrium with two solids
L fi S1 + S2 L cool a + b
heat

• Eutectoid - solid phase in equation with two solid

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

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

S1 + L S2
cool
d + L heat g (1493ºC)

Chapter 9 - 29

Eutectoid & Peritectic

Peritectic transition g+ L d
Cu-Zn Phase diagram

Adapted from
Fig. 9.21, Callister 7e.
Eutectoid transition d g+ e
Chapter 9 - 30

15
 The copper-zinc phase diagram

Question: Try to find the eutectoid and the peritectic reactions in

the Cu-Zn system Chapter 9 - 31

Microstructural and property changes

in iron-carbon alloys
1. The Iron-iron carbide (Fe-Fe3C) Phase diagram
2. Development of microstructure in Fe-C alloys
3. Phase transformation and TTT diagram

Chapter 9 - 32

16
d-phase
Austenite
Ferrite
Cementite

Pealite
Bainite
Martensite

Eutectic reaction
Eutectoid reaction Fe-Fe3C phase diagram
Maximum solubility Chapter 9 - 33

The Iron-ironcarbide (Fe-Fe3C) Phase diagram

Chapter 9 - 34

17
Iron-Carbon (Fe-C) Phase Diagram

• 2 important points T(°C)

1600
-Eutectic (A): d
L ⇒ g + Fe3C 1400 L
g+L
-Eutectoid (B): 1200
g
1148°C
A L+Fe3C
(austenite)

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

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

Result: Pearlite = Fe3C (cementite-hard)

alternating layers of a (ferrite-soft)
a and Fe3C phases
(Adapted from Fig. 9.27, Callister 7e.) Adapted from Fig. 9.24,Callister 7e.
Chapter 9 - 35

Hypoeutectoid Steel
T(°C)
1600
d
1400 L
g g (Fe-C
g g+L
g g 1200 1148°C L+Fe3C System)
Fe3C (cementite)

(austenite)
g g 1000
g g g + Fe3C
a 800 r s
ag g 727°C
a
g g aRS
w a =s/(r +s) 600
w g =(1- wa )
a + Fe3C
400
a 0 1 2 3 4 5 6 6.7
(Fe) Co , wt% C
0.76

C0
pearlite
w pearlite = w g
Hypoeutectoid
w a =S/(R+S) 100 mm
steel
w Fe3C =(1-w a )
pearlite proeutectoid ferrite
Adapted from Fig. 9.30,Callister 7e. Chapter 9 - 36

18
Hypereutectoid Steel

T(°C)
1600
d
1400 L (Fe-C
g g g+L System)
1200
g
gg 1148°C L+Fe3C

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

(Fe)
pearlite Co , wt%C
w pearlite = w g
w a =S/(R+S)
w Fe3C =(1-w a ) 60 mmHypereutectoid
steel
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33,Callister 7e. Chapter 9 - 37

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 - 38

19
Chapter 9 – Phase Equilibria

Solution: a) composition of Fe3C and ferrite (a)

CO = 0.40 wt% C
Ca = 0.022 wt% C
b) the amount of carbide CFe C = 6.70 wt% C
3
(cementite) in grams that 1600
forms per 100 g of steel d
1400 L
T(°C) g+L
g

Fe3C (cementite)
1200 1148°C L+Fe3C
Fe3C Co - Ca (austenite)
= x100
Fe3C + a CFe3C - Ca 1000
g + Fe3C
0.4 - 0.022 800 727°C
= x 100 = 5.7g
6.7 - 0.022 R S
600 a + Fe3C
400
Fe3C = 5.7 g 0 1 2 3 4 5 6 6.7
Ca CO Co , wt% C CFe
3C
a = 94.3 g
Chapter 9 - 39

Chapter 9 – Phase Equilibria

c. the amount of pearlite and proeutectoid ferrite (a)

note: amount of pearlite = amount of g just above TE

Co = 0.40 wt% C
Ca = 0.022 wt% C 1600
Cpearlite = Cg = 0.76 wt% C d
1400 L
T(°C)
g C -Ca g+L
= o g
Fe3C (cementite)

x 100 = 51.2 g 1200 1148°C L+Fe3C

g+ a Cg -Ca (austenite)
1000
g + Fe3C
800 727°C
RS
pearlite = 51.2 g 600 a + Fe3C
proeutectoid a = 48.8 g 400
0 1 2 3 4 5 6 6.7
Ca C Cg Co , wt% C
O

Chapter 9 - 40

20
 The Gibbs phase rule:
P+F=C+N

P: the number of phases

present
F: the number of degrees of
freedom or the number of
externally controlled variables
(T, P and conposition etc.)
C: the number of components in
the system
N: noncompositional variables
(T and P)

Cu-Ag system
In the a +L phase region: N=1, C=2, P=2, fi F=1
In the a phase region: N=1, C=2, P=1, fi F=2 Chapter 9 - 41

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.

Homework: 9.8, 9.14, 9.24, 9.33,

9.37, 9.38, 9.42, 9.43, p304-307 Chapter 9 - 42

21