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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, single phase
Mixtures more than one phase Adapted from Fig. 9.1,
Callister 7e.
Temperature (C)
which only a single phase 80 Limit L
solution occurs. (liquid)
60 +
L
Question: What is the 40 (liquid solution S
solubility limit at 20C? i.e., syrup) (solid
20 sugar)
Answer: 65 wt% sugar.
If Co < 65 wt% sugar: syrup 0 20 40 6065 80 100
If Co > 65 wt% sugar: syrup + sugar.
Sugar
Water
Pure
Pure
Chapter 9 - 2
Components and Phases
Components:
The elements or compounds which are present in the mixture
(e.g., Al and Cu)
Phases:
The physically and chemically distinct material regions
that result (e.g., and ).
Aluminum- (lighter
Copper
phase)
Alloy
(darker
phase)
Adapted from
chapter-opening
photograph,
Chapter 9,
Callister 3e.
A phase maybe defined as a homogeneous portion of a system that has
Chapter 9 - 3
uniform physical and chemical characteristics.
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 (100C,70) D (100C,90)
1 phase 2 phases
100
80 L
Temperature (C)
(liquid)
water- 60 +
sugar L S
system (liquid solution (solid
40 i.e., syrup) sugar)
20 A (20C,70)
2 phases
Adapted from 0
Fig. 9.1, 0 20 40 60 70 80 100
Callister 7e.
Co =Composition (wt% sugar)
Chapter 9 - 4
Phase Equilibrium
Chapter 9 - 5
Unary Systems
Triple point
Chapter 9 - 6
Phase Equilibria
Chapter 9 - 7
Unary Systems
Consider 2 metals:
Cu has melting T = 1085oC
Ni has melting T = 1453oC (at standard P = 1 atm)
T T
liquid
liquid
1453oC
1085oC
solid
solid
Cu Ni Chapter 9 - 8
What happens when Cu and Ni are mixed?
Binary Isomorphous Systems
T T
For a pure
liquid component,
complete melting
L occurs before T
liquid
1453oC increases (sharp
phase transition).
But for
1085oC multicomponent
solid systems, there is
S
solid usually a
coexistence of L
0 100 and S.
Cu wt% Ni Ni Chapter 9 - 9
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 L (liquid)
for Cu-Ni (FCC solid solution)
system 1400 3 phase fields:
i d us L
1300 liq
u
+ us L+
L lid
1200 so
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 Chapter 9 - 10
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(1100C, 60): L (liquid)
1500
B (1250C,35)
1 phase: s Cu-Ni
d u
ui phase
B(1250C, 35): 1400 liq us
li d
2 phases: L + so diagram
1300 +
L (FCC solid
1200 solution)
Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase 1100 A(1100C,60)
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 - 11
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:
TA A
Co = 35 wt% Ni tie line dus
l i q ui
At T A = 1320C: 1300 L (liquid)
L +
Only Liquid (L) B s
T lidu
CL = Co ( = 35 wt% Ni) B s o
At T D = 1190C:
1200 L+ D (solid)
Only Solid ( ) TD
C = Co ( = 35 wt% Ni)
20 3032 35 4043 50
At T B = 1250C: CLCo C wt% Ni
Both 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
C = C solidus ( = 43 wt% Ni here) International, Materials Park, OH, 1991.)
Chapter 9 - 12
Determining phase composition
in 2-phase region:
1. Draw the tie line.
2. Note where the tie line intersects
the liquidus and solidus lines (i.e.
where the tie line crosses the
phase boundaries).
3. Read off the composition at the
boundaries:
Liquid is composed of CL amount
of Ni (31.5 wt% Ni).
Solid is composed of C amount of
Ni (42.5 wt% Ni).
Chapter 9 - 13
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 dus
i
At T A : Only Liquid (L) 1300 L (liquid) l i qu
+
W L = 100 wt%, W = 0 B L
id us
At T D: Only Solid ( ) TB R S s ol
W L = 0, W = 100 wt%
L + (solid)
1200 D
At T B : Both and L TD
S 43 35 20 3032 35 40 43 50
WL = = = 73 wt % CLCo C wt% Ni
R + S 43 32
Adapted from Fig. 9.3(b), Callister 7e.
R (Fig. 9.3(b) is adapted from Phase Diagrams of
W = = 27 wt% Binary Nickel Alloys, P. Nash (Ed.), ASM
R +S International, Materials Park, OH, 1991.)
Chapter 9 - 14
Lever Rule: Derivation
Since we have only 2 phases:
WL + W = 1 (1)
Sub-in to (2): (1 WL )C + WL C L = Co
C Co Co C L
WL = W =
C C L C C L
Chapter 9 - 15
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 dus
l i qu
i Think of it as a lever (teeter-totter)
1300 L (liquid)
+ M
L ML
B us
TB id
s ol
L + (solid)
1200
R S R S
20 30C C 40 C 50
L o M S = M L R
wt% Ni Adapted from Fig. 9.3(b),
Callister 7e.
ML S C C0 R C CL
WL = = = W = = 0
M L + M R + S C CL R + S C CL
Chapter 9 - 16
Ex: Cooling in a Cu-Ni Binary
Phase diagram: T(C) L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
System is: system
130 0 A
--binary L: 35 wt% Ni L+
i.e., 2 components: : 46 wt% Ni
35 B
46
Cu and Ni. 32 C 43
--isomorphous 24 D
36 L: 32 wt% Ni
i.e., complete : 43 wt% Ni
solubility of one 1200
L + E
L: 24 wt% Ni
component in
another; phase : 36 wt% Ni
field extends from (solid)
0 to 100 wt% Ni.
Consider 1100
Co = 35 wt%Ni. 20 30 35 40 50
Adapted from Fig. 9.4, Co wt% Ni
Callister 7e.
Chapter 9 - 17
Microstructures in Isomorphous Alloys
Microstructures will vary on the cooling rate (i.e. processing conditions)
Chapter 9 - 19
Non-equilibrium cooling
a (T>1260oC): start as
homogeneous liquid solution.
b (T ~ 1260oC): liquidus line
reached. phase begins to nucleate.
C = 46 wt% Ni; CL = 35 wt% Ni
c (T= 1250oC): solids that formed at pt b
remain with same composition (46wt%) and
new solids with 42 wt% Ni form around the
existing solids (Why around them?).
d (T~ 1220oC): solidus line reached. Nearly
complete solidification.
Previously solidified regions maintain original
composition and further solidification occurs at 35
wt% Ni.
Chapter 9 - 20
Cored vs Equilibrium Phases
C changes as we solidify.
Cu-Ni case: First to solidify has C = 46 wt% Ni.
Last to solidify has C = 35 wt% Ni.
Fast rate of cooling: Slow rate of cooling:
Cored structure Equilibrium structure
Uniform C :
First to solidify:
46 wt% Ni 35 wt% Ni
Last to solidify:
< 35 wt% Ni
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 - 22
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, , ) 1000
Limited solubility: L + 779C L+
T 800
: mostly Cu E 8.0 71.9 91.2
: mostly Ag 600
TE : No liquid below TE +
CE : Min. melting TE 400
composition 200
0 20 40 60 CE 80 100
Eutectic transition Co , wt% Ag
L(CE) (CE) + (CE) Adapted from Fig. 9.7,
Callister 7e.
Chapter 9 - 23
Eutectic Point
Eutectic Reaction:
cool
L(CE) (CE) + (CE)
heat
similar to one component (pure) system
except 2 solid phases.
Chapter 9 - 26
Microstructures
in Eutectic Systems: I
Adapted from Fig. 9.11,
Co < 2 wt% Sn T(C) L: Co wt% Sn Callister 7e.
400
L
300 L
1. One component rich
composition. L+
a: start with homogeneous liquid. 200
b: -phase solids with liquid. : Co wt% Sn
(Pb-Sn
TE
Compositions and mass fractions System)
can be found via tie lines and lever 100
rule. +
c: -phase solid solution only.
100 160 m
+ : 97.8 wt% Sn
Adapted from Fig. 9.14, Callister 7e.
: 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 Chapter 9 - 29
Callister 7e.
Lamellar Eutectic Structure
Sn
Pb rich
L
Sn rich
Pb
Adapted from Figs. 9.14 & 9.15, Callister
7e.
In order to achieve large Lamellar structure forms because
homogeneous regions, long relatively short diffusion lengths
Chapter 9 - 30
diffusion lengths are required. are required.
Microstructures
in Eutectic Systems: IV
18.3 wt% Sn < Co < 61.9 wt% Sn
Result: crystals and a eutectic microstructure
L: Co wt% Sn
Just above TE :
T(C) L
L
C = 18.3 wt% Sn
300 CL = 61.9 wt% Sn
L
Pb-Sn S
L+ W = = 50 wt%
system R+S
200
R S L+ WL = (1- W) = 50 wt%
TE S
R
Just below TE :
100 + C = 18.3 wt% Sn
primary C = 97.8 wt% Sn
eutectic
eutectic W= 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 Chapter 9 - 31
Hypoeutectic & Hypereutectic
(Pb-Sn Microconstituent: an
System) 300 element of a
L microstructure with
Adapted from Fig. 9.8, T(C)
Callister 7e. (Fig. 9.8 L + identifiable and
adapted from Binary Phase
200 L+
Diagrams, 2nd ed., Vol. 3,
TE characteristic structure (at
T.B. Massalski (Editor-in- + pt. m there are 2
Chief), ASM International, 100
Materials Park, OH, 1990.)
microconstituents: primary
and eutectic structures)
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,
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 7e. Adapted from Fig. 9.14, Callister 7e. (Illustration
Callister 7e. only)
Chapter 9 - 32
Intermediate phases
Terminal solid
solutions: and .
Intermediate solid
solutions: , , and .
Chapter 9 - 33
Intermetallic Compounds
Adapted from
Fig. 9.20, Callister 7e.
Mg2Pb
Chapter 9 - 35
Eutectoid & Peritectic
Peritectic transition + L
Cu-Zn Phase diagram
Adapted from
Fig. 9.21, Callister 7e.
Eutectoid transition +
Chapter 9 - 36
Congruent phase transformation
Chapter 9 - 37
Ceramic phase diagrams
Al2O3-Cr2O3 MgO-Al2O3
Chapter 9 - 38
Gibbs Phase Rule
A criterion for the number of phases that will coexist within a system at equilibrium
Number of non-
Number of compositional variables
phases present P+F=C+N (Temperature & Pressure)
Or
e.g.(for region)
If T is specified to be 800oC, C can be
any where between 0 to ~8 wt% Ag)
Or
C
Chapter 9 - 41
Gibbs Phase Rule
F=3-P=0
Chapter 9 - 42
Concept Check
Question: For a ternary system, three
components are present; temperature is also
a variable. What is the maximum number of
phases that may be present for a ternary
system, assuming that pressure is held
constant?
Chapter 9 - 43
Iron-Carbon Systemstructural material
Ferrite Magnets
TVR Tuscan Speed 6, high-performance sports The world's first bridge made of iron
car with an austempered ductile iron crankshaft. in 1779. The entire structure is
made of cast iron. (near Broseley,
Chapter 9 - 44
UK)
Iron-Carbon System
Steel bridges
Chapter 9 - 46
Iron-Carbon System
Liquid
Liquid
1538
Ferrite (BCC)
Tm 1394
Austenite (FCC)
Solid 912
Ferrite (BCC)
Chapter 9 - 47
Iron-Carbon System
Iron-Iron Carbide Diagram
Chapter 9 - 48
Remarks on Fe-C system
C is an interstitial element in Fe matrix.
C has limited solid solubility in the alpha BCC phase (narrow region close to
pure iron). Max solid solubility of C in alpha iron is 0.022 w% at 727 C.
Austenite phase is not stable below at 727 C. Max solid solubility of C into
austenite is 2.14 w% at 1147C, much larger that that in alpha phase.
Cementite phase (intermetallic, Fe3C) forms over a large region of the Fe-C
phase diagram, but it is a metastable phase (heating above 650 C for years
decomposes this phase into alpha iron and graphite). Cementite is very hard
and brittle.
Chapter 9 - 49
Ferrite (90x) Austenite (x325)
Relatively soft
Density: 7.88g/cm3 Chapter 9 - 50
Classification Scheme of Ferrous Alloys
Iron
Pure ion contains less than 0.008wt% C
Steel
0.008-2.14 wt% C, in practice,<1.0 wt% C
Cast Iron
2.14-6.70 wt% C, in practice, <4.5 wt% C
Chapter 9 - 51
Iron-Carbon (Fe-C) Phase Diagram
Eutectoid cooling: cool
(0.76 wt% C) (0.022 wt% C)
T(C) heat + Fe3C (6.7 wt% C)
2 important
1600
points
-Eutectic (A): 1400 L
L + Fe3C +L
1200 1148C
A L+Fe3C
-Eutectoid (B): (austenite)
Fe3C (cementite)
R S
+ Fe3C 1000
+ +Fe3C
800
B 727C = Teutectoid
R S
600
+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 Co, wt% C
120 m
C eutectoid
colonies
Pearl-microscope picture
(X500)
Mechanically, pearlite has properties intermediate between the
Chapter 9 - 53
soft, ductile ferrite and the hard, brittle cementite.
Hypoeutectoid Steel
T(C)
1600
1400 L
(Fe-C
+L
1200 1148C L+Fe3C System)
Fe3C (cementite)
(austenite)
1000
Adapted from Figs. 9.24
+ Fe3C and 9.29,Callister 7e.
(Fig. 9.24 adapted from
800 r s 727C Binary Alloy Phase
RS Diagrams, 2nd ed., Vol.
1, T.B. Massalski (Ed.-in-
w =s/(r +s) 600
w =(1- w )
+ Fe3C Chief), ASM International,
Materials Park, OH,
1990.)
400
0 1 2 3 4 5 6 6.7
(Fe) Co , wt% C
0.76
C0
pearlite
w pearlite = w
Hypoeutectoid
w =S/(R+S) 100 m
steel
w Fe3C =(1-w )
pearlite proeutectoid ferrite
Adapted from Fig. 9.30,Callister 7e. Chapter 9 - 54
Hypereutectoid Steel
T(C)
1600
1400 L (Fe-C
+L System)
1200
1148C L+Fe3C
Fe3C (cementite)
(austenite)
1000 Adapted from Figs. 9.24
+Fe3C and 9.32,Callister 7e.
Fe3C (Fig. 9.24 adapted from
800 r s Binary Alloy Phase
Diagrams, 2nd ed., Vol.
R S 1, T.B. Massalski (Ed.-in-
600
w Fe3C =r/(r +s) +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 =S/(R+S)
w Fe3C =(1-w ) 60 mHypereutectoid
steel
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33,Callister 7e. Chapter 9 - 55
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 ()
b) the amount of carbide (cementite) in grams
that forms per 100 g of steel
c) the amount of pearlite and proeutectoid
ferrite ()
Chapter 9 - 56
Chapter 9 Phase Equilibria
Solution: a) composition of Fe3C and ferrite ()
b) the amount of carbide CO = 0.40 wt% C
(cementite) in grams that C = 0.022 wt% C
forms per 100 g of steel CFe C = 6.70 wt% C
3
1600
Fe3C Co C 1400 L
= x100 T(C)
Fe3C + CFe3C C +L
Fe3C (cementite)
1200 1148C L+Fe3C
(austenite)
0.4 0.022
= x 100 = 5.7g 1000
6.7 0.022 + Fe3C
800 727C
R S
Fe3C = 5.7 g 600 + Fe3C
= 94.3 g 400
0 1 2 3 4 5 6 6.7
C CO Co , wt% C CFe
3C
Chapter 9 - 57
Chapter 9 Phase Equilibria
c. the amount of pearlite and proeutectoid ferrite ()
note: amount of pearlite = amount of just above TE
Co = 0.40 wt% C
C = 0.022 wt% C 1600
Cpearlite = C = 0.76 wt% C
1400 L
T(C)
Co C +L
Fe3C (cementite)
= x 100 = 51.2 g 1200 1148C L+Fe3C
+ C C (austenite)
1000
+ Fe3C
800 727C
RS
pearlite = 51.2 g 600 + Fe3C
proeutectoid = 48.8 g 400
0 1 2 3 4 5 6 6.7
C C C Co , wt% C
O
Chapter 9 - 58
Effect of alloying elements on Fe-C
phase diagram
Chapter 9 - 59
Alloying Steel with More Elements
C eutectoid (wt%C)
Ti
T Eutectoid (C)
Si
Mo W Ni
Cr
Cr Si
Mn
Mn W
Ti Mo
Ni
Chapter 9 - 60
Summary
Chapter 9 - 61