Phase Diagrams

• 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?

1
 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.

2
 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 3
 Phase Diagrams:
# and types of phases
• Rule 1: If we know T and Co, then we know:
--the # and types of phases present.
T(°C)
• Examples: 1600
A(1100°C, 60): L (liquid)
1 phase: a

B (1250°C,35)
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
4
 Phase Diagrams:
composition of phases
• Rule 2: If we know T and Co, then we know:
--the composition of each phase. Cu-Ni
T(°C) system
• Examples:
Co = 35 wt% Ni TA A
tie line
At T A = 1320°C: 1300 L (liquid)
Only Liquid (L) B
CL = Co ( = 35 wt% Ni) TB
a
At T D = 1190°C:
1200 D (solid)
Only Solid ( a) 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.
(Fig. 9.3(b) is adapted from Phase Diagrams
CL = C liquidus ( = 32 wt% Ni here) of Binary Nickel Alloys, P. Nash (Ed.), ASM
Ca = C solidus ( = 43 wt% Ni here) International, Materials Park, OH, 1991.)

5
 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%). 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    73 wt %
20 3032 35
CLCo
40 43
Ca wt% Ni
50
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.)

6
 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  M a R  S Ca  CL R  S Ca  CL
7
 Ex: Cooling in a Cu-Ni Binary
• Phase diagram: T(°C) L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
• System is: 130 0 A
system
--binary L: 35 wt% Ni
a: 46 wt% Ni B
i.e., 2 components: 35 46
Cu and Ni. 32 C 43
--isomorphous 24 D36 L: 32 wt% Ni
i.e., complete a: 43 wt% Ni
solubility of one 120 0 E
L: 24 wt% Ni
component in
another; a phase a: 36 wt% Ni
a
field extends from (solid)
0 to 100 wt% Ni.
• Consider 110 0
Co = 35 wt%Ni. 20 30 35 40 50
Adapted from Fig. 9.4, Co wt% Ni
Callister 7e.
8
 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.

--Peak as a function of Co --Min. as a function of Co

9
 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, ) 1000
• Limited solubility: a L + a 779°C L + 
800
a: mostly Cu T E 8.0 71.9 91.2
: mostly Ag 600
• TE : No liquid below TE a
• CE : Min. melting TE 400

composition 200
0 20 40 60 CE 80 100
• Eutectic transition Co , wt% Ag
L(CE) a(CaE) + (CE) Adapted from Fig. 9.7,
Callister 7e.

10
 EX: Pb-Sn Eutectic System (1)
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, find...
--the phases present: a +  Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
Ca = 11 wt% Sn 300
L (liquid)
C = 99 wt% Sn
--the relative amount a L+ a
200 183°C L + 
of each phase: 18.3 61.9 97.8
S C - CO 150
Wa = =  R S
R+S C - Ca 100
a+
99 - 40 59
= = = 67 wt%
99 - 11 88
C - Ca 0 11 20 40 60 80 99100
W = R = O Ca Co C
R+S C - Ca C, wt% Sn
Adapted from Fig. 9.8,
40 - 11 29 Callister 7e.
= = = 33 wt%
99 - 11 88 11
 EX: Pb-Sn Eutectic System (2)
• For a 40 wt% Sn-60 wt% Pb alloy at 200°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 + 
of each phase: 183°C
CL - CO 46 - 40
Wa = = 100
CL - Ca 46 - 17 a+
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.

12
 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+ 
100

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

13
 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 -phase inclusions a

100
a+  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)
14
 Microstructures
in Eutectic Systems: III
• Co = CE
• Result: Eutectic microstructure (lamellar structure)
--alternating layers (lamellae) of a and  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 
TE

100 160 m
a : 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 15
Callister 7e.
 Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister

7e.

16
 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
L+ a Wa = S = 50 wt%
system R+S
200
a R S L+  WL = (1- Wa) = 50 wt%
TE R S
• Just below TE :
100 a+ Ca = 18.3 wt% Sn
primary a C = 97.8 wt% Sn
eutectic a
eutectic  Wa = S = 73 wt%
0 20 40 60 80 100 R+S
18.3 61.9 97.8 W = 27 wt%
Adapted from Fig. 9.16,
Callister 7e. Co, wt% Sn 17
 Hypoeutectic & Hypereutectic
300
L
T(°C)
L+ a
Adapted from Fig. 9.8,
Callister 7e. (Fig. 9.8 a L+ 
adapted from Binary Phase
200
TE
(Pb-Sn
Diagrams, 2nd ed., Vol. 3, System)
T.B. Massalski (Editor-in- a+
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 
Metallography and a 
Microstructures, a a  
American Society for a 
Metals, Materials
Park, OH, 1985.) a 
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)
18
 Eutectoid
• Eutectic - liquid in equilibrium with two solids
L cool a + 
heat

• Eutectoid - solid phase in equation with two solid

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

19
 Iron-Carbon (Fe-C) Phase Diagram
• 2 important T(°C)
1600
points d
-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
B 727°C = Teutectoid

R S
600
a+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 Co, wt% C
120 m
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.
20
 Hypoeutectoid Steel
T(°C)
1600
d
1400 L
  (Fe-C
  +L
  1200 1148°C L+Fe3C System)

Fe3C (cementite)
(austenite)
  1000
   + Fe3C Adapted from Figs. 9.24
and 9.29,Callister 7e.
a (Fig. 9.24 adapted from
a  800 r s 727°C Binary Alloy Phase
 a aRS Diagrams, 2nd ed., Vol.
1, T.B. Massalski (Ed.-in-
w a =s /(r +s) 600
w  =(1- wa )
a + Fe3C Chief), ASM International,
Materials Park, OH,
1990.)
400
a 0 1 2 3 4 5 6 6.7
(Fe) Co , wt% C
0.76

C0
pearlite
w pearlite = w 
Hypoeutectoid
w a = S/(R + S) 100 m
steel
w Fe3 =(1- w a )
C
pearlite proeutectoid ferrite
Adapted from Fig. 9.30,Callister 7e. 21
 Hypereutectoid Steel
T(°C)
1600
d
1400 L (Fe-C
  +L System)
 
 
1200 1148°C L+Fe3C

Fe3C (cementite)
(austenite)
  1000
   +Fe3C Adapted from Figs. 9.24
and 9.32,Callister 7e.
Fe3C
 
(Fig. 9.24 adapted from
800 r s Binary Alloy Phase
  a R S
Diagrams, 2nd ed., Vol.
1, T.B. Massalski (Ed.-in-
w Fe3C =r /( r +s) 600
a +Fe3C Chief), ASM International,
Materials Park, OH,
w  =(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 
w a =S/( R +S)
w Fe3C =(1- w a ) 60 mHypereutectoid
steel
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33,Callister 7e. 22
 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)

23
 Phase Equilibria
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
d
Fe 3C Co  Ca 1400 L
 x100 T(°C)
Fe 3C  a CFe3C  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
Fe 3C  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 CFe3C

24
 Chapter 9 – Phase Equilibria
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 d
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

25
 Alloying Steel with More Elements

• Teutectoid changes: • Ceutectoid changes:

Ceutectoid (wt%C)
Ti
T Eutectoid (°C)

Si
Mo W Ni
Cr
Cr Si
Mn
Mn W
Ti Mo
Ni

wt. % of alloying elements wt. % of alloying elements

Adapted from Fig. 9.34,Callister 7e. (Fig. 9.34 Adapted from Fig. 9.35,Callister 7e. (Fig. 9.35
from Edgar C. Bain, Functions of the Alloying from Edgar C. Bain, Functions of the Alloying
Elements in Steel, American Society for Metals, Elements in Steel, American Society for Metals,
1939, p. 127.) 1939, p. 127.)

26
 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.

27