CHAPTER 6: .

PHASE DIAGRAM

1
 Main issues
• When we combine two elements...
what equilibrium state do we get?
• In particular, if we specify...
- a composition (e.g., wt% Cu - wt% Ni),
- 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

Phase Diagrams 2
 Definition and Basic Concept

• Components:
The elements or compounds which are present in the mixture
(e.g., Fe and C)
• System:
A specific body of materials under consideration, it may relate
to the series of possible phase consisting of the same
components (Fe-C system)
• Phases:
The physically and chemically distinct material regions that
result (e.g., a and b)

Phase Diagrams 3
 Microstructure and Phases
• Microstructue:
Subject to direct microscopic observation, using optical or
electron microscopes

b (lighter
Fe-C alloy at phase - pearlite)
0.44% of C
a (darker
phase - Ferrite)
Adapted from
chapter-opening
photograph,
Chapter 9,
Callister 3e.

Phase Diagrams 4
 Microstructure and Phases

Phase Diagrams 5
 Phase Equilibria: Solubility Limit
Introduction
– Solutions – solid solutions, single phase
– Mixtures – more than one phase
Sucrose/Water Phase Diagram
• Solubility Limit: 100
Max concentration for

Temperature (°C)
Solubility
which only a single phase 80 Limit L
solution occurs. (liquid)
60 +
L
Question: What is the 40 (liquid solution S
solubility limit at 20°C? i.e., syrup) (solid
20 sugar)
Answer: 65 wt% sugar.
If Co < 65 wt% sugar: syrup 0 20 40 60
65 80 100
If Co > 65 wt% sugar: syrup + sugar.

Sugar
Water

Co =Composition (wt% sugar)

Pure
Pure

Adapted from Fig. 9.1,

Callister 7e.

Phase Diagrams 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 (100°C,70) D (100°C,90)
1 phase 2 phases
100
L
Temperature (°C)
80
(liquid)
water- 60 +
sugar L S
system (liquid solution (solid
40 i.e., syrup) sugar)
20 A (20°C,70)
2 phases
Adapted from 0
Fig. 9.1, 0 20 40 60 70 80 100
Callister 7e.
Co =Composition (wt% sugar)

Phase Diagrams 7
 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.

Phase Diagrams 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 1600 • 2 phases:
Diagram L (liquid)
1500
for Cu-Ni L (liquid) a (FCC solid solution)
system 1400 • 3 phase fields:
L
1300 L+a
a
1200 a Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase
1100
(FCC solid Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
solution) OH (1991).
1000
0 20 40 60 80 100 wt% Ni
Phase Diagrams 9
 Phase Diagrams: Number and types of phases

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

-the number and types of phases present.

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

B (1250°C,35)
1 phase: a 1500
Cu-Ni
B(1250°C, 35): 1400 phase
2 phases: L + a diagram
1300 a
(FCC solid
1200 solution)
Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase 1100 A(1100°C,60)
Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
OH, 1991). 1000
0 20 40 60 80 100 wt% Ni

Phase Diagrams 10
 Phase Diagrams: phase compositions

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

-the composition of each phase. Cu-Ni
T(°C) system
• Examples:
TA A
Co = 35 wt% Ni tie line
At T A = 1320°C: 1300 L (liquid)

Only Liquid (L) B

CL = Co ( = 35 wt% Ni) T B
a
At T D = 1190°C:
1200 D (solid)
a
Only Solid ( ) TD
Ca = Co ( = 35 wt% Ni)
20 3032 35 4043 50
At T B = 1250°C: CLCo Ca wt% Ni
Both a and L Adapted from Fig. 9.3(b), Callister 7e.
CL = C liquidus ( = 32 wt% Ni here) (Fig. 9.3(b) is adapted from Phase Diagrams
of Binary Nickel Alloys, P. Nash (Ed.), ASM
Ca = C solidus ( = 43 wt% Ni here) International, Materials Park, OH, 1991.)

Phase Diagrams 11
 Phase Diagrams: weight fractions of phase
• Rule 3: If we know T and Co, then we know:
-the amount of each phase (given in wt%). Cu-Ni
• Examples: T(°C) system
Co = 35 wt% Ni TA A
tie line
At T A : Only Liquid (L) 1300 L (liquid)
W L = 100 wt%, W a = 0 B
At T D: Only Solid ( a) TB R S
a
W L = 0, Wa = 100 wt%
1200 D (solid)
At T B : Both a and L TD
S 43  35
WL 
20 3032 35 40 43 50
  73 wt % CLCo Ca wt% Ni
R + S 43  32
Adapted from Fig. 9.3(b), Callister 7e.
R
Wa 
(Fig. 9.3(b) is adapted from Phase Diagrams of
= 27 wt% Binary Nickel Alloys, P. Nash (Ed.), ASM
R +S International, Materials Park, OH, 1991.)

Phase Diagrams 12
 The Lever Rule

• Tie line – connects the phases in equilibrium with

each other - essentially an isotherm
T(°C) How much of each phase?
tie line
Think of it as a lever (teeter-totter)
1300 L (liquid)
ML Ma
B
TB
a
1200 (solid)
R S R S
20 30C C
L o
40 C
a
50
M a S  M L R
wt% Ni Adapted from Fig. 9.3(b),
Callister 7e.

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

Phase Diagrams 13
 Binary-Eutectic Systems
has a special composition
2 components
with a min. melting T.
Cu-Ag
T(C) 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
800
a: mostly Cu TE 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
a(CaE) + b(CbE)
Adapted from Fig. 9.7,
L(CE) Callister 7e.

Phase Diagrams 14
 Binary-Eutectic Systems- 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 Cb - CO 150
Wa =
R+S
=
Cb - Ca
R S
100
a+b
99 - 40 59
= = = 67 wt%
99 - 11 88
C O - Ca 0 11 20 40 60 80 99100
Wb = R = Ca Co Cb
R+S C b - Ca C, wt% Sn
Adapted from Fig. 9.8,
40 - 11 29 Callister 7e.
= = = 33 wt%
99 - 11 88
Phase Diagrams 15
 Binary-Eutectic Systems- 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
200
a R S L+b b
of each phase: 183°C
CL - CO 46 - 40
Wa = = 100
CL - Ca 46 - 17 a+b
6
= = 21 wt%
29 100
0 17 20 40 46 60 80
Ca Co CL
CO - Ca 23 C, wt% Sn
WL = = = 79 wt% Adapted from Fig. 9.8,
CL - Ca 29 Callister 7e.

Phase Diagrams 16
 Microstructures in Eutectic Systems: I

• Co < 2 wt% Sn T(C)

400
L: Co wt% Sn

• 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)

a+ b
100

0 10 20 30
Co Co, wt% Sn
Adapted from Fig. 9.11,
Callister 7e. 2
(room T solubility limit)

Phase Diagrams 17
 Microstructures in Eutectic Systems: II

L: Co wt% Sn
• 2 wt% Sn < Co < 18.3 wt% Sn 400T(C)
• Result: L
 Initially liquid + a L
a
 then a alone 300
L +a
 finally two phases a: Co wt% Sn
a
 a polycrystal 200
TE
 fine b-phase inclusions a
b
100
a+ b Pb-Sn
system
0 10 20 30
Adapted from Fig. 9.12, 2 Co Co , wt% Sn
Callister 7e. (sol. limit at T room ) 18.3
(sol. limit at TE)

Phase Diagrams 18
 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 m
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
Adapted from Fig. 9.13, 61.9 C, wt% Sn
Callister 7e.

Phase Diagrams 19
 Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister

7e.

Phase Diagrams 20
 Microstructures in Eutectic Systems: IV
• 18.3 wt% Sn < Co < 61.9 wt% Sn
• Result: a crystals and an 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
L+ a Wa = S = 50 wt%
system R+S
200
a R S L+b b WL = (1- Wa) = 50 wt%
TE S
R

100 a+b
primary a
eutectic a • Just below TE :
eutectic b
Ca = 18.3 wt% Sn
0 20 40 60 80 100
18.3 61.9 97.8 Cb = 97.8 wt% Sn
Adapted from Fig. 9.16,
Callister 7e. Co, wt% Sn Wa = S = 73 wt%
R+S
Wb = 27 wt%
Phase Diagrams 21
 Hypoeutectic & Hypereutectic
300
L
T(°C)
L+ a
Adapted from Fig. 9.8,
Callister 7e. (Fig. 9.8 a L+b b
adapted from Binary Phase
200
TE
(Pb-Sn
Diagrams, 2nd ed., Vol. 3,
T.B. Massalski (Editor-in- a+b System)
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
eutectic: Co = 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 7e. Adapted from Fig. 9.14, Callister 7e. (Illustration
Callister 7e. only)

Phase Diagrams 22
 Eutectoid & Peritectic
• Eutectic - liquid in equilibrium with two solids
cool
L heat a + b

• Eutectoid - solid phase in equation with two solid

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

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

S1 + L S2
cool
 + L heat  (1493ºC)

Phase Diagrams 23
 Eutectoid & Peritectic
Peritectic transition  + L 
Cu-Zn Phase diagram

Adapted from
Fig. 9.21, Callister 7e.
Eutectoid transition  +

Phase Diagrams 24
 Iron-Carbon (Fe-C) Phase Diagram
• 2 important T(°C)
1600
points 
-Eutectic (A): 1400 L
L   + Fe3C   +L
1200 1148°C
A L+Fe3C
-Eutectoid (B): (austenite)

Fe3C (cementite)
R S
  a + Fe3C 1000  
   +Fe3C

a
800 727°C = T
B eutectoid
R S
600
a+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 Co, wt% C
C eutectoid

120 m Fe3C (cementite-hard)

Result: Pearlite = a (ferrite-soft)
alternating layers of
a and Fe3C phases Adapted from Fig. 9.24,Callister 7e.
(Adapted from Fig. 9.27, Callister 7e.)

Phase Diagrams 25
 Iron-Carbon (Fe-C) Phase Diagram: Example

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 (ferrite + cementite) and
proeutectoid ferrite (a)

Phase Diagrams 26
 Iron-Carbon (Fe-C) Phase Diagram: Example
Solution:
a) composition of Fe3C and ferrite (a)
b) the amount of carbide CO = 0.40 wt% C
(cementite) in grams that Ca = 0.022 wt% C
forms per 100 g of steel CFe C = 6.70 wt% C
3
1600

Fe3C Co  Ca 1400 L
 x100 T(°C)
Fe3C  a CFe 3C  Ca   +L

Fe C (cementite)
1200 1148°C L+Fe3C
(austenite)
0.4  0.022
 x 100  5.7g 1000
6.7  0.022  + Fe3C
800 727°C
R S
Fe3C  5.7 g 600 a + Fe3C
a  94 .3 g 400
0 1 2 3 4 5 6 6.7
Ca CO Co , wt% C CFe
3C

Phase Diagrams 27
 Iron-Carbon (Fe-C) Phase Diagram: Example
Solution:
c. the amount of pearlite and proeutectoid ferrite (a)
note: amount of pearlite = amount of  just above TE
Co = 0.40 wt% C
Ca = 0.022 wt% C 1600
Cpearlite = C = 0.76 wt% C 
1400 L
T(°C)
 Co  Ca   +L
 x 100  51.2 g 1200

Fe C (cementite)
1148°C L+Fe3C
  a C  Ca (austenite)
1000
 + 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 CO C Co , wt% C
Phase Diagrams 28
 Phrase Diagram: Formation of compound
R AB c 2a mA + nB = AmBn

L c2 b

Phase Diagrams 29
 Ternary Phase Diagram
C: number of components
Gibbs rule F+P=C+2 F: degree of freedom
P: number of phrases
2: Environmental factors, including temperature
and pressure C
C= 3 (pressure = const)

F=4–P C
1 ≤ P ≤ 4.
 Pmin = 1, completely liquid,
F=4–1=3
 Pmax = 4  F = 0, system is
to be stabilize at E. A, B
and C spontaneously
solidify
E B
A
A%
A B
Phase Diagrams
 Ternary Phase Diagram

Determine
compositions of
M in system

Phase Diagrams
 Ternary Phase Diagram
Determine C
compositions of
a point in system
Draw an arrow from A to D
 A : 100%A, 0%B, 0%C
 D : 0%A, 54%B, 46%C

EF//CB
 A component of all points E
belonging to EF : 35%
D

F A% B
A
Phase Diagrams
 Ternary Phase Diagram
C
Determine
compositions of
apoint in system

I : 25%A, 15%B, 60%C

J : 10%A, 75%B, 15%C
K: 35%A, 25%B, 40%C

A A% B
Phase Diagrams
 Ternary Phase Diagram

Phase Diagrams
 Ternary Phase Diagram

Phase Diagrams
 Ternary Phase Diagram
L: 38% of MgO, 46% of
Al2O3, 16% of SiO2

Solidification of L:
L→b→c→d→4
 At 1850C: Liquid
 At 1670C (b)

Phase Diagrams
 Ternary Phase Diagram
 At 1600C (c) L: 38% of MgO, 46%
Phase components of Al2O3, 16% of SiO2
 Liquid
 Solid: MA and M2S

And:
M2S/MA=MAc’/c’M2S

Phase Diagrams
 Ternary Phase Diagram
 At (4) L: 38% of MgO, 46%
Phase components of Al2O3, 16% of SiO2
 Solid: MA and M2S
 M2A2S5 solid form from the
saturated liquid

Phase Diagrams
 Example

A*

Xét quá trình rắn hóa tại điểm A

a)Xác định sự có mặt và thành phần các pha ở nhiệt độ: 250, 180 và 100C
a) Xác định khối lượng riêng của pha rắn của pha rắn ở nhiệt độ 100C.
Biết Bi = 9.78 g/cm3 và 7.27 g/cm3.

Phase Diagrams 39