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2/26/2013

Lecture #12

Chapter 10
Phase Diagrams Equilibrium
Learning Objectives:
What is a phase?

What is thermodynamic equilibrium?


What three components need to be used (established) to define the
equilibrium?
How to determine the composition and fraction of a phase in a twophase regime (Lever Rule).

Relevant Reading for this Lecture...


Pages 359-387.

What am I? Al-Si alloy

Si

Al

What
am I composed of? How do I predict?
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Alloys and Phases


Components: The elements or compounds which are present
in the alloy (e.g., Ni and Cu; Al and Cu; etc.)

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)

When we combine two (or more) 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...
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

Two Phases of H2O


1 Liquid (water)
1.
2. Solid (ice)

The phases can even be from


the same components
ItsallH2O!
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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

add lots off sugar


g

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)

Phase Equilibria: Solubility Limit


RECALL:

Solution solid, liquid, or gas solutions; single phase


Mixture more than one phase

Question: What is the


solubility limit for sugar in
water at 20C?

Sugar/Water Phase Diagram


100
Temperature (C)

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)

Solubility limit increases with T:


e.g., if T = 100C, solubility limit = 80wt% sugar.

Adapted from Fig. 10.1,


Callister & Rethwisch 4e.

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

Single Component (or Unary) System


Phase Diagram for H2O

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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Multiple Component System


P-T-x Phase Diagram for AA-B

L
(Liquid)

+L

Temperature

+L

Solid

Pressure

Gas

Gas

Composition
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Liquid

Temperature
In condensed materials we
usually fix P = 1 atm.

Types of Phase Diagram


Multiplecomponentphasediagrams: Ternary isotherm
Binary =2components
Ternary =3components
Quaternary =4components
= 4 components
Quinary =5components
Etc.

Binary

Tem
mperature

+L

+L

%B

Weusephasediagramsasmapstoguidedesign
withmaterials.
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Effects of Temperature & Composition (Co)


Altering T can change # of phases:

path A to B.

Altering Co can change # of phases:

path B to D.
Solubility
limit

B (100C,Co = 70)
1 phase

watersugar
system

Adapted from Fig. 9.1,


Callister & Rethwisch 8e.

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)

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RECALL

Criteria for Solid Solubility


Simple system (e.g., Cu-Ni solution)
T(C)
1600
1500

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?

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How to Read a Phase Diagram: CuCu-Ni


Allliquid,1phase
L
(Liquid)

1453C

Liquid+solid,2phases,
likeiceteasaturatedwith
sugar.
+

1085C

Allsolid,1solid
solution.
singlephase,
1

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Whatareweassumingaboutoneofthestatevariables?

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Phase Diagram Definitions


Liquidus: The
solubilitylimit
abovewhich
b
h h
thereisonly
liquidpresent.

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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Binary Phase Diagram Definitions


Themelting
temperatureofa
pure component is
purecomponentis
fixed.

L
(Liquid)

1453C

C1

Inalloysmelting
temperatures
dependon
composition
composition.

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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
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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

A tie line is like a


teeter--totter
teeter
Composition
ofthesolid

WL
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C C0
S

R S C CL

C CL
R
0
R S C CL

Tie Line and Quantitative Calculations

WL

The amount of any phase is the opposite side of the lever


divided by the total length of the lever.
KEEP IN MIND:

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W + WL = 1

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EX 1: Pb-Sn Eutectic System


For a 40 wt% Sn-60 wt% Pb alloy at 150C, determine:
-- the phases present
Answer: +
-- the phase compositions
Answer: C = 11 wt% Sn
C = 99 wt% Sn

-- the relative amount


of each phase
Answer:
C - C0
S
=
W =
R+S
R
S
C - C
99 - 40
99 - 11
W = R =
R+S
40 - 11
=
99 - 11
=

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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

Adapted from Fig. 10.8,


Callister & Rethwisch 4e.
3

29
= 0.33
88

EX 2: Pb-Sn Eutectic System


For a 40 wt% Sn-60 wt% Pb alloy at 220C, determine:
-- the phases present:
Answer: + L
-- the phase compositions

Pb-Sn
system

T(C)

Answer: C = 17 wt% Sn
CL = 46 wt% Sn

300

-- the relative amount


of each phase

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

Adapted from Fig. 10.8,


Callister & Rethwisch 4e.
3

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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.

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