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Polycomp Files 2012 06 Ch09 Updated
Polycomp Files 2012 06 Ch09 Updated
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 Chapter 9 - 1
Chapter 9 - 2
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.
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)
Sugar
Water
Temperature (ºC)
80 Limit L
(liquid)
60 +
L
40 (liquid solution S
i.e., syrup) (solid
20 sugar)
0 20 40 60 80 100
Sugar
Water
C = Composition (wt% sugar)
Chapter 9 -
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., and ).
Aluminum- (lighter
Copper
phase)
Alloy
(darker
Adapted from chapter-
opening photograph,
phase)
Chapter 9, Callister,
Materials Science &
Engineering: An
Introduction, 3e.
Chapter 9 - 5
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)
Chapter 9 - 6
Criteria for Solid Solubility
Chapter 9 - 7
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) (FCC solid solution)
system 1400 • 3 different phase fields:
L
1300 L+
1200 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 Chapter 9 - 8
Isomorphous Binary Phase Diagram
• Phase diagram: T(ºC)
Cu-Ni system. 1600
B (1250ºC,35)
1500
Cu-Ni
B(1250ºC, 35 wt% Ni): 1400 phase
2 phases: L + diagram
1300
(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
Chapter 9 - 10
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:
TA A
Consider C0 = 35 wt% Ni tie line
At TA = 1320ºC: 1300 L (liquid)
Only Liquid (L) present B
CL = C0 ( = 35 wt% Ni) TB
At TD = 1190ºC:
1200 D (solid)
Only Solid () present TD
C = C0 ( = 35 wt% Ni)
20 3032 35 4043 50
At TB = 1250ºC: CL C0 C wt% Ni
Both 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
C = C solidus ( = 43 wt% Ni) Park, OH (1991).
Chapter 9 - 11
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, W = 0 B
At TD : Only Solid ( ) present TB R S
WL = 0, W = 1.00
1200 D (solid)
At TB : Both and L present TD
S 43 35
WL
20 3032 35 40 43 50
0.73 CL C0 C wt% Ni
R +S 43 32
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
R
W
Phase Diagrams of Binary Nickel Alloys, P.
= 0.27 Nash (Ed.), ASM International, Materials
R +S Park, OH (1991).
Chapter 9 - 12
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 M
1200 (solid)
R S
20 30CL R S
C0 40 C 50
wt% Ni M x S ML x R
Adapted from Fig. 9.3(b),
Callister & Rethwisch 8e.
ML S C C0 R C CL
WL W 0
M L M R S C CL R S C CL
Chapter 9 - 13
Ex: Cooling of a Cu-Ni Alloy
• Phase diagram: T(ºC) L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
1300 system
• Consider A
L: 35 wt% Ni
microstuctural : 46 wt% Ni B
35 46
changes that 32 C 43
accompany the D
24 36 L: 32 wt% Ni
cooling of a : 43 wt% Ni
C0 = 35 wt% Ni alloy 1200 E
L: 24 wt% Ni
: 36 wt% Ni
(solid)
110 0
20 30 35 40 50
Adapted from Fig. 9.4, C0 wt% Ni
Callister & Rethwisch 8e.
Chapter 9 - 14
Cored vs Equilibrium Structures
• C changes as we solidify.
• Cu-Ni case: First to solidify has C = 46 wt% Ni.
Last to solidify has C = 35 wt% Ni.
• Slow rate of cooling: • Fast rate of cooling:
Equilibrium structure Cored structure
Uniform C:
35 wt% Ni First to solidify:
46 wt% Ni
Last to solidify:
< 35 wt% Ni
Chapter 9 - 15
T(ºC)
1600
L (liquid)
1500
1400
1300
(FCC solid
1200
solution)
1100
1000
0 20 40 60 80 100
Chapter 9 - 16
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.
Chapter 9 - 17
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, , ) 1000
• Limited solubility: L + 779ºC L+
: mostly Cu TE 800 8.0 71.9 91.2
: mostly Ag 600
• TE : No liquid below TE
• CE : Composition at 400
temperature TE 200
0 20 40 60 CE 80 100
• Eutectic reaction C, wt% Ag
L(CE) (CE) + (CE) Adapted from Fig. 9.7,
Callister & Rethwisch 8e.
cooling
L(71.9 wt% Ag) (8.0 wt% Ag) (91.2 wt% Ag)
Chapter 9 - 18
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: + T(ºC) system
-- the phase compositions
300
Answer: C = 11 wt% Sn L (liquid)
C = 99 wt% Sn
-- the relative amount L+
200 183ºC L+
of each phase 18.3 61.9 97.8
Answer: 150
S C - C0 R S
100
W =
R+S
=
C - C +
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C0 - C C C0 C
W = R = C, wt% Sn
R+S C - C Adapted from Fig. 9.8,
Callister & Rethwisch 8e.
40 - 11 29
= = = 0.33 Chapter 9 - 19
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: + L T(ºC) system
-- the phase compositions
300
Answer: C = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+
-- the relative amount 220
200
R S L+
of each phase 183ºC
Answer:
100
W =
CL - C0
=
46 - 40 +
CL - C 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 C C0 CL
29 C, wt% Sn
Adapted from Fig. 9.8,
C0 - C 23 Callister & Rethwisch 8e.
WL = = = 0.79
CL - C 29
Chapter 9 - 20
Microstructural Developments
in Eutectic Systems I
+
100
0 10 20 30
Adapted from Fig. 9.11, C0 C , wt% Sn
Callister & Rethwisch 8e. 2
(room T solubility limit)
Chapter 9 - 21
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 + range 300
L+
-- polycrystalline with grains : C0 wt% Sn
and small -phase particles 200
TE
100
+ 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)
Chapter 9 - 22
Microstructural Developments
in Eutectic Systems III
• For alloy of composition C0 = CE
• Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of and phases.
Micrograph of Pb-Sn
T(ºC) eutectic
L: C0 wt% Sn microstructure
300 L
Pb-Sn
system
L+
200
183ºC L
TE
100 160 m
: 97.8 wt% Sn
Adapted from Fig. 9.14,
: 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 Chapter 9 - 23
Callister & Rethwisch 8e.
Lamellar Eutectic Structure
Chapter 9 - 24
Microstructural Developments
in Eutectic Systems IV
• For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn
• Result: phase particles and a eutectic microconstituent
• Just above TE :
T(ºC) L: C0 wt% Sn L
C = 18.3 wt% Sn
L
300 L CL = 61.9 wt% Sn
Pb-Sn S
L+ W = = 0.50
system R+S
200 R S L+ WL = (1- W) = 0.50
TE S
R
• Just below TE :
100 + C = 18.3 wt% Sn
primary C = 97.8 wt% Sn
eutectic
eutectic W = S = 0.73
0 20 40 60 80 100 R+S
18.3 61.9 97.8 W = 0.27
Adapted from Fig. 9.16,
Callister & Rethwisch 8e. C, wt% Sn Chapter 9 - 25
Hypoeutectic & Hypereutectic
300
L
T(ºC)
L+
Adapted from Fig. 9.8,
Callister & Rethwisch 8e. L+
(Fig. 10.8 adapted from
200
TE
(Pb-Sn
Binary Phase Diagrams,
2nd ed., Vol. 3, T.B. + System)
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,
Metallography and
Microstructures,
American Society for
Metals, Materials
Park, OH, 1985.)
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)
Chapter 9 - 26
Eutectic, Eutectoid, & Peritectic
• Eutectic - liquid transforms to two solid phases
L cool
+ (For Pb-Sn, 183ºC, 61.9 wt% Sn)
heat
Chapter 9 - 27
Eutectoid & Peritectic
Peritectic transformation + L
Cu-Zn Phase diagram
Fe3C (cementite)
+ Fe3C 1000
+Fe3C
800 727ºC = T eutectoid
B
600
+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
and Fe3C phases (ferrite-soft)
(Adapted from Fig. 9.27, Adapted from Fig. 9.24,
Chapter 9 - 29
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 &
Rethwisch 8e.
800 727ºC (Fig. 9.24 adapted from
Binary Alloy Phase
Diagrams, 2nd ed., Vol.
600
+ Fe3C 1, T.B. Massalski (Ed.-in-
Chief), ASM International,
Materials Park, OH,
400
0 1 2 3 4 5 6 6.7 1990.)
(Fe)C0 C, wt% C
0.76
pearlite
Hypoeutectoid
100 m
steel
Fe3C (cementite)
(austenite)
1000
+ Fe3C Adapted from Figs. 9.24
W = s/(r + s) and 9.29,Callister &
Rethwisch 8e.
800 r s 727ºC
W =(1 - W) (Fig. 9.24 adapted from
Wpearlite = W
W’ = S/(R + S) 100 m
Hypoeutectoid
steel
WFe3C =(1 – W’)
pearlite proeutectoid ferrite
Adapted from Fig. 9.30, Callister & Rethwisch 8e. Chapter 9 - 31
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
Phase Diagrams, 2nd
ed., Vol. 1, T.B. Massalski
600
+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
Adapted from Fig. 9.33, Callister & Rethwisch 8e. Chapter 9 - 32
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)
V X
Phase Diagrams, 2nd
ed., Vol. 1, T.B. Massalski
600
+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
W = X/(V + X)
60 mHypereutectoid
WFe =(1 - W) steel
3C’
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. Chapter 9 - 33
Chapter 9 - 34
Chapter 9 - 35
Chapter 9 - 36
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 ().
b) The amount of cementite (in grams) that
forms in 100 g of steel.
c) The amounts of pearlite and proeutectoid
ferrite () in the 100 g.
Chapter 9 - 37
Solution to Example Problem
a) Using the RS tie line just below the eutectoid
C = 0.022 wt% C
CFe3C = 6.70 wt% C
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 + Fe3C
= (100 g)WFe3C 400
0 1 2 3 4 5 6 6.7
C C0 C, wt% C CFe
3C
= (100 g)(0.057) = 5.7 g
Chapter 9 - 38
Solution to Example Problem (cont.)
c) Using the VX tie line just above the eutectoid and
realizing that
C0 = 0.40 wt% C
C = 0.022 wt% C
Cpearlite = C = 0.76 wt% C
1600
1400 L
V C C T(ºC) +L
Wpearlite 0
Fe3C (cementite)
V X C C 1200
(austenite)
1148ºC L+Fe3C
Ceutectoid (wt% C)
Ti
T Eutectoid (ºC)
Si
Mo W Ni
Cr
Cr Si
Mn
Mn W
Ti Mo
Ni
Chapter 9 - 41
Summary
Chapter 9 - 42