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Lecture #12
Chapter 10
Phase Diagrams Equilibrium
Learning Objectives:
What is a phase?
Si
Al
What
am I composed of? How do I predict?
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Phase A
Phase B
Solid solution
Intermetallic
Nickel atom
Copper atom
AluminumAl
i
Copper
Alloy
Adapted from chapter-opening
photograph, Chapter 9, Callister,
Materials Science & Engineering:
An Introduction, 3e.
(lighter
phase)
(darker
phase)
Questions to Address...
(components)
then...
1) How many phases form?
2) What is the composition of each phase?
3) What is the amount of each phase?
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What is a Phase?
Aphase isahomogeneousportion ofasystemthat
has uniform physical and chemical characteristics
hasuniformphysicalandchemicalcharacteristics
Aphasedoesnotneedtobecontinuous
You can have many phases
present at the same time
Solubility Limits
Insomesystems,twocomponentscan
mixandmaintainasinglephase:example,
sugar(SOLUTE)+tea(SOLVENT)=SYSTEM
Whenweaddasolutetoasolvent,in
mostsystems,thesolventisableto
dissolvethesolutewhilemaintaininga
singlephase(SOLIDSOLUTION).
Thesolventbecomessaturatedandcan
h
l
b
d d
nolongerdissolveanysoluteatthe
solubilitylimit.
Addingsolutebeyondthesolubilitylimit
yieldstwodifferent phases.
tea
add some sugar
1 phase
tea+
sugar
2 phases
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Composition of Phases
In atwophase region,thephases present inasystemwill have
different compositions thantheaveragecompositionofthe
mixture.
EXAMPLE:Assumethesolubilitylimitforaglassoficedteaat
25oCis4packsofsugar,andyouadded5packs.The
concentrationsofthealloy(tea+sugar),liquid,andsolidare
then:
Alloy :
Co = 5 p sugar, 1 p tea
Liquid :
CL = 4 p sugar, 1 p tea
Solid
CS = 1 p sugar, 0 p tea
(tea + sugar)
(Saturated tea)
(Precipitate)
Solubility Limit:
Maximum concentration for
which only a single phase
solution exists.
Solubility
Limit
80
L
(liquid)
60
40
(liquid solution
i.e., syrup)
20
+
S
(solid
sugar)
Sugar
syrup + sugar
Water
A
Answer:
65 wt% sugar.
0
20
40
6065 80
100
At 20C, if C < 65 wt% sugar: syrup
C = Composition (wt% sugar)
At 20C, if C > 65 wt% sugar:
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Equilibrium
Thermodynamicequilibriumisinlowest energy state at
somespecifiedcombinationoftemperature,pressure,and
composition.
p
Thecharacteristicofthesystemdoesnotchange withtime.
Thesystemisstable.
Metastable:Notinthelowestenergystate,butkinetically
constrained in a higher energy state which does not change
constrainedinahigherenergystatewhichdoesnotchange
forlongperiodoftime(ex.Diamond,carbonwouldlowerits
energyifitweregraphite)
Variableswechangetoadjustequilibrium temperature,
pressure,composition.Theseareourknobsasengineers
STEAM
Gas
Temperature
100C
Liquid
WATER
F1atm= 0
0C
Solid
ICE
1 atm
Pressure(logscale)
Phasediagramsshowuswhichphasesarepresentasafunctionofstatevariables
Pressure (P) Temperature (T) Composition (x or c)
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L
(Liquid)
+L
Temperature
+L
Solid
Pressure
Gas
Gas
Composition
11
Liquid
Temperature
In condensed materials we
usually fix P = 1 atm.
Binary
Tem
mperature
+L
+L
%B
Weusephasediagramsasmapstoguidedesign
withmaterials.
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path A to B.
path B to D.
Solubility
limit
B (100C,Co = 70)
1 phase
watersugar
system
Tempe
erature (C)
100
D (100C,Co = 90)
2 phases
80
60
(liquid)
+
L
(liquid solution
40
(solid
sugar))
i e syrup)
i.e.,
A (20C,Co = 70)
2 phases
20
0
20
40
60 70 80
100
C = Composition (wt% sugar)
13
RECALL
Crystal
Structure
Electroneg
r (nm)
valence
1400
Ni
FCC
1.9
0.1246
+2
1300
Cu
FCC
1.8
0.1278
+2
L (liquid)
(FCC solid
solution)
1200
1100
1000
0
Cu
20
40
60
wt% Ni
80
100
Ni
Both have the same crystal structure (FCC) and valence (+2), and have
similar electronegativities and atomic radii (W. HumeRothery rules)
suggesting high mutual solubility.
Ni and Cu are totally soluble in one another for all proportions.
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Review
(up to this point)
Weusephasediagramstodetermine
which/wherephasesarestableasafunction
hi h/ h
h
t bl
f ti
ofthestatevariables
Whatarevariablestochangephases?Inthe
previous slides what variable have we
previousslides,whatvariablehavewe
assumedisconstant?
15
1453C
Liquid+solid,2phases,
likeiceteasaturatedwith
sugar.
+
1085C
Allsolid,1solid
solution.
singlephase,
1
16
Whatareweassumingaboutoneofthestatevariables?
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L
(Liquid)
1453C
Solidus line
Liquidus line
Solidus: The
solubilitylimit
belowwhich
thereisonly
solidpresent.
1085C
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Composition of Phases
Inasinglephase
region,alloy
composition and
compositionand
phasecomposition
arethesame.
Co =50%Ni
CS,1100oC=50%Ni
CL,1500
1500oC=50%Ni
C 50% Ni
WHATABOUTTHE
2PHASEREGION?
Co
Single
phase
(L)
g
Single
phase
( )
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L
(Liquid)
1453C
C1
Inalloysmelting
temperatures
dependon
composition
composition.
19
Completemelting
ofalloys occurs
over arange of
temperatures.
Melting complete
Melting starts
Solidus line
Liquidus line
C2
+L
Melting complete
Melting starts
1085C
Materials Systems
Whatisthecomposition
fortwophases?
DifferentthanCo!
Co
RECALL:
Sweettea(i.e.,tea+sugar)
isanalogoustoa
materials system!
materialssystem!
Co = 5 p sugar, 1 p tea
Compositionofthe
solid
ld
Composition
oftheliquid
CL = 4 p sugar, 1 p tea
CS = 1 p sugar, 0 p tea
20
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Lever Rule:
Gives you the amounts of each phase
Tieline connectsthephasesinequilibrium.
Itissometimescalledanisotherm.
ML
Compositionof
theliquid
h l
d
Avg.Compositionof
thealloy
M x S ML x R
WL
21
C C0
S
R S C CL
C CL
R
0
R S C CL
WL
22
W + WL = 1
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23
Pb-Sn
system
T(C)
300
L (liquid)
L+
200
18.3
150
61.9
97.8
S
+
100
59
= 0.67
88
C0 - C
C - C
L+
183C
0 11 20
C
60
40
C0
80
C, wt% Sn
99100
C
29
= 0.33
88
Pb-Sn
system
T(C)
Answer: C = 17 wt% Sn
CL = 46 wt% Sn
300
220
200
L (liquid)
L+
R
100
W =
C0 - C
23
=
= 0.79
WL =
CL - C
29
183C
Answer:
CL - C0
46 - 40
=
CL - C
46 - 17
6
=
= 0.21
29
L+
17 20
C
40 46 60
C0 CL
80
100
C, wt% Sn
24
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Summary
Phaseisahomogeneousportionofasystemthathas
uniformphysicalandchemicalcharacteristics
All
Alloycomposition,C
iti
Co,ishowmuchofeachmaterialismixed
i h
h f
h t i li i d
together.
Inasinglephaseregion,compositionofthephase=Co.
Inatwophaseregion,thecompositionofeachphasedoes
notchangewithalloycompositionatfixedtemperature,and
isequaltotheintersectionofthetielinewiththesolubility
l
h
f h
l
h h
l bl
limits.
Inatwophaseregion,theamountofeachphasecanbe
determinedbytheinverseleverrule,dividingtheopposite
sideoftheleverbythelengthofthetieline.
25
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