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 Phase B

Nickel atom
Copper atom

1
 PHASE EQUILIBRIA: SOLUBILITY LIMIT

• Solution – solid, liquid, or gas solutions, single phase

• Mixture – more than one phase Adapted from Fig. 9.1,
Callister & Rethwisch 8e.

Sugar/Water Phase Diagram

• Solubility Limit: 10 0
Maximum concentration for Solubility

Temperature (ºC)
which only a single phase 80 Limit L
solution exists. (liquid)
60 +
L
Question: What is the 40 (liquid solution S
solubility limit for sugar in i.e., syrup) (solid
water at 20ºC? 20 sugar)

Answer: 65 wt% sugar.

0 20 40 6065 80 100
At 20ºC, if C < 65 wt% sugar: syrup

Sugar
Water

C = Composition (wt% sugar)

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

2
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).

Aluminum- b (lighter
Copper
phase)
Alloy

a (darker
Adapted from chapter-
opening photograph,
phase)
Chapter 9, Callister,
Materials Science &
Engineering: An
Introduction, 3e.

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 (100ºC,C = 70) D (100ºC,C = 90)
1 phase 2 phases
100

80 L
Temperature (ºC)

(liquid)
water- 60 +
sugar L S
system (liquid solution (solid
40 i.e., syrup) sugar)
20 A (20ºC,C = 70)
2 phases
Adapted from Fig. 9.1, 0
Callister & Rethwisch 8e. 0 20 40 60 70 80 100
C = Composition (wt% sugar)

4
CRITERIA FOR SOLID SOLUBILITY

Simple 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 soluble in one another for all proportions.

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(ºC)
Phase
1600 • 2 phases:
Diagram L (liquid)
1500
for Cu-Ni L (liquid) a (FCC solid solution)
system 1400 • 3 different phase fields:
L
1300 L+a
a
1200 a Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
1100
(FCC solid Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
solution) Materials Park, OH (1991).
1000
0 20 40 60 80 100 wt% Ni

6
ISOMORPHOUS BINARY PHASE DIAGRAM

• Phase diagram: T(ºC)

Cu-Ni system. 1600

• System is: 1500 L (liquid) Cu-Ni

-- binary phase
i.e., 2 components: 1400
diagram
Cu and Ni.
1300
-- isomorphous
i.e., complete 1200 a
solubility of one
component in 1100
(FCC solid
another; a phase solution)
field extends from 1000
0 to 100 wt% Ni.
0 20 40 60 80 100 wt% Ni
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
Materials Park, OH (1991).

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.
T(ºC)
• Examples: 1600
A(1100ºC, 60 wt% Ni): L (liquid)
1 phase: a

B (1250ºC,35)
1500
Cu-Ni
B (1250ºC, 35 wt% Ni): 1400 phase
2 phases: L + a diagram
1300 a
(FCC solid
1200
Adapted from Fig. 9.3(a), Callister &
solution)
Rethwisch 8e. (Fig. 9.3(a) is adapted from 1100 A(1100ºC,60)
Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
Materials Park, OH (1991). 1000
0 20 40 60 80 100 wt% Ni

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
T(ºC) system
• Examples:
Consider C0 = 35 wt% Ni TA A
tie line
At TA = 1320ºC: 1300 L (liquid)
Only Liquid (L) present B
CL = C0 ( = 35 wt% Ni) TB
a
At TD = 1190ºC:
1200 D (solid)
Only Solid (a) present TD
Ca = C0 ( = 35 wt% Ni)
20 3032 35 4043 50
At TB = 1250ºC: CL C0 Ca wt% Ni
Both a and L present Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
CL = C liquidus ( = 32 wt% Ni) Phase Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International, Materials
Ca = C solidus ( = 43 wt% Ni) Park, OH (1991).

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. Cu-Ni
• Examples: T(ºC) system
Consider C0 = 35 wt% Ni TA A
tie line
At TA : Only Liquid (L) present 1300 L (liquid)
WL = 1.00, Wa = 0 B
At TD : Only Solid ( a) present TB R S
a
WL = 0, Wa = 1.00
1200 D (solid)
At TB : Both a and L present TD
S 43  35
WL    0.73
20 3 032 35
CL C 0
4 0 43
Ca wt% Ni
50
R +S 43  32
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
R
Wa 
Phase Diagrams of Binary Nickel Alloys, P.
= 0.27 Nash (Ed.), ASM International, Materials
R +S Park, OH (1991).

10
THE LEVER RULE
Tie line – connects the phases in equilibrium with each
other – also sometimes called an isotherm
T(ºC) What fraction of each phase?
tie line
Think of the tie line as a lever
1300 L (liquid)
(teeter-totter)
B
TB ML Ma
a
1200 (solid)
R S

20 3 0CL 40 50 R S
C0 Ca
wt% Ni Ma x S  ML x R
Adapted from Fig. 9.3(b),
Callister & Rethwisch 8e.

ML S C  C0 R C  CL
WL    a Wa   0
ML  Ma R  S Ca  CL R  S Ca  CL


11
MECHANICAL PROPERTIES: CU-NI
SYSTEM
• Effect of solid solution strengthening on:
-- Tensile strength (TS) -- Ductility (%EL)
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), Adapted from Fig. 9.6(b),
Callister & Rethwisch 8e. Callister & Rethwisch 8e.

12
 BINARY-EUTECTIC SYSTEMS
has a special composition
2 components with a min. melting T.
Cu-Ag
T(ºC) system
Ex.: Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, a, b) 1000
• Limited solubility: a L + a 779ºC 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 : Composition at 400
temperature TE 200
0 20 40 60 CE 80 100
• Eutectic reaction C , wt% Ag
L(CE) a(CaE) + b(CbE) Adapted from Fig. 9.7,
Callister & Rethwisch 8e.
cooling
L(71.9 wt% Ag) a(8.0 wt% Ag)  b(91.2 wt% Ag)

13
heating
EX 1: PB-SN EUTECTIC SYSTEM
• For a 40 wt% Sn-60 wt% Pb alloy at 150ºC, determine:
-- the phases present Pb-Sn
Answer: a + b T(ºC) system
-- the phase compositions
300
Answer: Ca = 11 wt% Sn L (liquid)
Cb = 99 wt% Sn
-- the relative amount a L+ a
200 183ºC L +b b
of each phase 18.3 61.9 97.8
Answer: 150
S Cb - C0 R S
W = 100
a R + S
=
Cb - Ca a+b
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C0 - Ca Ca C0 Cb
Wb = R
= C, wt% Sn
R+ S Cb - Ca Adapted from Fig. 9.8,
Callister & Rethwisch 8e.
40 - 11 29
= = = 0.33

14
99 - 11 88
EX 2: PB-SN EUTECTIC SYSTEM
• For a 40 wt% Sn-60 wt% Pb alloy at 220ºC, determine:
-- the phases present: Pb-Sn
Answer: a + L T(ºC) system
-- the phase compositions
300
Answer: Ca = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+ a
-- the relative amount 220 a
200 R S L +b b
of each phase 183ºC
Answer:
100
Wa =
CL - C0
=
46 - 40 a+b
CL - Ca 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 Ca C0 CL
29 C, wt% Sn
Adapted from Fig. 9.8,
C0 - Ca 23 Callister & Rethwisch 8e.
WL = C - C = 29 = 0.79
L a

15
DEVELOPMENTS
IN EUTECTIC SYSTEMS I

• For alloys for which T(ºC) L: C0 wt% Sn

400
C0 < 2 wt% Sn L
• Result: at room temperature a
300 L
-- polycrystalline with grains of
a phase having L+ a
a
composition C0 200 (Pb-Sn
TE a: C0 wt% Sn
System)

a+ b
100

0 10 20 30
Adapted from Fig. 9.11, C0 C , wt% Sn
Callister & Rethwisch 8e. 2
(room T solubility limit)

16
MICROSTRUCTURAL DEVELOPMENTS
IN EUTECTIC SYSTEMS II

L: C0 wt% Sn
• For alloys for which T(ºC)
400
2 wt% Sn < C0 < 18.3 wt% Sn L
• Result: L
at temperatures in a + b range 300 a
L+a
-- polycrystalline with a grains a: C0 wt% Sn
and small b-phase particles 200 a
TE
a
b
100
a+ b Pb-Sn
system
Adapted from Fig. 9.12, 0 10 20 30
Callister & Rethwisch 8e. 2 C0 C , wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)

17
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.
Micrograph of Pb-Sn
T(ºC) eutectic
L: C0 wt% Sn microstructure
300 L
Pb-Sn
system
L+ a
200
a 183ºC Lb b
TE

100 160 m
ab b: 97.8 wt% Sn
Adapted from Fig. 9.14,
a: 18.3 wt%Sn Callister & Rethwisch 8e.

0 20 40 60 80 100
18.3 CE 97.8
Adapted from Fig. 9.13, 61.9 C, wt% Sn

18
Callister & Rethwisch 8e.
LAMELLAR EUTECTIC
STRUCTURE

Adapted from Figs. 9.14 & 9.15, Callister

& Rethwisch 8e.

19
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 :
T(ºC) L: C0 wt% Sn a L
L Ca = 18.3 wt% Sn
300 L CL = 61.9 wt% Sn
Pb-Sn a S
L+ a Wa = = 0.50
system R+S
200
a R S L+b b WL = (1- Wa) = 0.50
TE R S
• Just below TE :
100 a+b Ca = 18.3 wt% Sn
primary a Cb = 97.8 wt% Sn
eutectic a
eutectic b Wa = S = 0.73
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wb = 0.27
Adapted from Fig. 9.16,
Callister & Rethwisch 8e. C, wt% Sn

20
HYPOEUTECTIC & HYPEREUTECTIC
300
L
T(ºC)
L+ a
Adapted from Fig. 9.8,
Callister & Rethwisch 8e. a L+b b
(Fig. 10.8 adapted from
200
TE
(Pb-Sn
Binary Phase Diagrams, System)
2nd ed., Vol. 3, T.B. a+b
Massalski (Editor-in-Chief), 100
ASM International,
Materials Park, OH, 1990.)

0 20 40 60 80 100 C, wt% Sn
eutectic
hypoeutectic: C0 = 50 wt% Sn 61.9 hypereutectic: (illustration only)
(Figs. 9.14 and 9.17
from Metals
eutectic: C0 = 61.9 wt% Sn
Handbook, 9th ed.,
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 m 160 m
Adapted from eutectic micro-constituent Adapted from Fig. 9.17,
Fig. 9.17, Callister & Adapted from Fig. 9.14, Callister & Rethwisch 8e.
Rethwisch 8e. Callister & Rethwisch 8e. (Illustration only)

21
INTERMETALLIC COMPOUNDS

Adapted from
Fig. 9.20, Callister &
Rethwisch 8e.

Mg2Pb

Note: intermetallic compound exists as a line on the diagram - not an

area - because of stoichiometry (i.e. composition of a compound

22
is a fixed value).
EUTECTIC, EUTECTOID, & PERITECTIC
Eutectic - liquid transforms to two solid phases
cool
L heat
a+b (For Pb-Sn, 183ºC, 61.9 wt% Sn)

• Eutectoid – one solid phase transforms to two other

solid phases
intermetallic compound
S2 S1+S3 - cementite

 cool a + Fe3C (For Fe-C, 727ºC, 0.76 wt% C)

heat

• Peritectic - liquid and one solid phase transform to a

second solid phase
S1 + L S2
cool
 +L heat  (For Fe-C, 1493ºC, 0.16 wt% C)

23
 EUTECTOID & PERITECTIC
Peritectic transformation  + L 

Cu-Zn Phase diagram

Adapted from Fig. 9.21,

Callister & Rethwisch 8e.
Eutectoid transformation  +

24
IRON-CARBON (FE-C) PHASE DIAGRAM
• 2 important T(ºC)
1600
points 
- Eutectic (A): 1400 L
L   + Fe3C   +L
1200 1148ºC
A L+Fe3C
- Eutectoid (B): (austenite)

Fe3C (cementite)
  a + Fe3C 1000  
   +Fe3C
727ºC = T eutectoid
a
800
B
600
a+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 C, wt% C
120 m
Result: Pearlite = Fe3C (cementite-hard)
alternating layers of
a and Fe3C phases a (ferrite-soft)
(Adapted from Fig. 9.27, Adapted from Fig. 9.24,

25
Callister & Rethwisch 8e.) Callister & Rethwisch 8e.
HYPOEUTECTOID STEEL
T(ºC)
1600

1400 L
  (Fe-C
  +L
  1200 1148ºC L+Fe3C System)

Fe3C (cementite)
(austenite)
  1000
   + Fe3C Adapted from Figs. 9.24
and 9.29,Callister &
a Rethwisch 8e.
a  800 727ºC (Fig. 9.24 adapted from
 a a Binary Alloy Phase
Diagrams, 2nd ed., Vol.
600
a + Fe3C 1, T.B. Massalski (Ed.-in-
Chief), ASM International,
Materials Park, OH,
400 1990.)
a 0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76

pearlite

Hypoeutectoid
100 m
steel

pearlite proeutectoid ferrite

26
Adapted from Fig. 9.30, Callister & Rethwisch 8e.
 HYPOEUTECTOID STEEL
T(ºC)
1600

1400 L
(Fe-C
a   +L
System)
a  1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
 a
1000
 + Fe3C Adapted from Figs. 9.24
Wa = s/(r + s) and 9.29,Callister &
Rethwisch 8e.
W =(1 - Wa) 800 r s 727ºC (Fig. 9.24 adapted from

aRS Binary Alloy Phase

Diagrams, 2nd ed., Vol.
a 600
a + Fe3C 1, T.B. Massalski (Ed.-in-
Chief), ASM International,
pearlite Materials Park, OH,
400 1990.)
0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76

Wpearlite = W
Wa’ = S/(R + S) 100 m
Hypoeutectoid
steel
WFe3C =(1 – Wa’)
pearlite proeutectoid ferrite

27
Adapted from Fig. 9.30, Callister & Rethwisch 8e.
 HYPEREUTECTOID STEEL
T(ºC)
1600

1400 L (Fe-C
  +L System)
 
 
1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
  1000
   +Fe3C Adapted from Figs. 9.24
and 9.32,Callister &
Fe3C Rethwisch 8e. (Fig. 9.24
  800 adapted from Binary Alloy
  a Phase Diagrams, 2nd
ed., Vol. 1, T.B. Massalski
600
a +Fe3C (Ed.-in-Chief), ASM
International, Materials
Park, OH, 1990.)
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
pearlite

60 mHypereutectoid
steel
pearlite proeutectoid Fe3C

28
Adapted from Fig. 9.33, Callister & Rethwisch 8e.
 HYPEREUTECTOID STEEL
T(ºC)
1600

1400 L (Fe-C
 +L System)
Fe3C 
  1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
  1000
 +Fe3C Adapted from Figs. 9.24
and 9.32,Callister &
W =x/(v + x) Rethwisch 8e. (Fig. 9.24
800 v x adapted from Binary Alloy
WFe3C =(1-W)
a V X
Phase Diagrams, 2nd
ed., Vol. 1, T.B. Massalski
600
a +Fe3C (Ed.-in-Chief), ASM
pearlite International, Materials
Park, OH, 1990.)
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
Wpearlite = W
Wa = X/(V + X)
60 mHypereutectoid
WFe3C’ =(1 - Wa) steel
pearlite proeutectoid Fe3C

29
Adapted from Fig. 9.33, Callister & Rethwisch 8e.
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.

30
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 1600

the tie line shown 
1400 L
R C  Ca T(ºC)
WFe 3C   0   +L
R  S CFe 3C  Ca

Fe3C (cementite)
1200 1148ºC L+Fe3C
(austenite)
0.40  0.022
  0.057 1000
 + Fe3C
6.70  0.022
800 727ºC
R S
Amount of Fe3C in 100 g 600 a + Fe3C
= (100 g)WFe3C 400
0 1 2 3 4 5 6 6.7
Ca C0 C , wt% C CFe3C
= (100 g)(0.057) = 5.7 g

31
 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

1400 L
V C  Ca T(ºC)  +L
Wpearlite   0 

Fe3C (cementite)
V  X C  Ca 1200
(austenite)
1148ºC L+Fe3C

0.40  0.022 1000

  0.512  + Fe3C
0.76  0.022
800 727ºC
VX
Amount of pearlite in 100 g 600 a + Fe3C
= (100 g)Wpearlite 400
0 1 2 3 4 5 6 6.7
Ca C0 C C, wt% C
= (100 g)(0.512) = 51.2 g

32
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.

33