PHASEDIAGRAMS

Phase achemicallyandstructurallyhomogenousregionofa
material.Regionofuniformphysicalandchemical
characteristics.Phaseboundariesseparatetwodistinctphases.
Asinglephasesystemiscalledhomogeneous.Asystemwithtwo
ormorephasesiscalledheterogeneous.
PhaseDiagram agraphicrepresentationshowingthephaseor
phasespresentforagivencomposition,temperatureand
pressure.
Component thechemicalelementswhichmakeupthealloy.
Solventatoms:primaryatomicspecies.Hostatoms
Solute atoms:theimpurities.Normallytheminorcomponent
SolubilityLimit Maximumconcentrationofsoluteatomsthat
maydissolveinthesolventtoformasolidsolution.Theexcess
ofsoluteformsanotherphaseofdifferentcomposition.
Example:watersugar

PhaseDiagramsofPureSubstances
PredictsthestablephaseasafunctionofPtotal andT.Example:
watercanexistinsolid,liquidandvaporphases,dependingon
theconditionsoftemperatureandpressure.
Characteristicshapepunctuatedbyuniquepoints.
Phaseequilibriumlines
TriplePoint(threedifferentphasesofwaterinequilibrium)
CriticalPoint
Example:
Inthepressuretemperature(PT)phasediagramofwaterthereexists
atriplepointatlowpressure(4.579torr)andlowtemperature
(0.0098oC)wheresolid,liquidandvaporphasesofwatercoexists.
VaporizationLine Liquidandvaporcoexists
FreezingLine Liquidandsolidcoexist.
SublimationLine Solidandvaporcoexist

Phase Anyportionincludingthewholeofasystem,whichisphysically
homogeneouswithinitandboundedbyasurfacesothatitis
mechanicallyseparablefromanyotherportions.

GibbsPhaseRule
Fromthermodynamicconsiderations,J.W.Gibbs(18391903American
physicist UniversityofYale)derivedthefollowingequation:

P+F=C+2
Where
P =numberofphaseswhichcoexistsinagivensystem
F =degreesoffreedom
C =numberofcomponentsinthesystem
2 =onecanvarytemperatureandpressure
F=0 zerodegreesoffreedom.NeitherPorTcanbechange(apoint
invariantpoint)
F=1 onedegreeoffreedom.Onevariable(PorT)canbechanged
independently(aline)
F=2 twodegreesoffreedom.Twovariables(PorT)canbechanged
independently(anarea).

Schematicunaryphasediagram
formagnesium,showingthe
meltingandboilingtemperatures
atoneatmospherepressure.
C=1forpuremagnesium
PointA:
P=1forpureliquidphase
2+C=F+P
2+1=F+1
F=2degreesoffreedom change
pressureandtemperatureinliquid
Phase.
PointB: P=2forliquidandsolid
2+C=F+P
2+1=F+2
F=1degreesoffreedom changepressureortemperature(andthe
othervariableisdependent tostayontheline).

PointX:
P=3(liquid,solidandvaporcoexist)
2+C=F+P
2+1=F+3
F=0degreesoffreedom pressure
andtemperaturearefixedatthe
the singlepointcalledthetriple

point.

Example
ForpuresubstancewherePandTcanbechanged
P+F=C+2=1+2=3
Puresubstanceinatriplepoint,thenC=1(onecomponent)
and
P=3(numberofphasesthatcoexist)
ThevalueofFiszero(zerodegreesoffreedom)thethreephases
coexistinapoint.
ForpuresubstancewherePandTcanbechanged
P+F=1+2=3
Puresubstanceinafreezingline,then
C=1(onecomponent)
andP=2(numberofphasesthat
coexist)
ThevalueofFisone(onedegreeoffreedom)thetwophases(solid
andliquid)coexistinaline.

Solubility: Theamountofonematerialthatwillcompletelydissolvein
asecondmaterialwithoutcreatingasecondphase.
Unlimitedsolubility: Whentheamountofonematerialthatwill
dissolveinasecondmaterialwithoutcreatingasecondphaseis
unlimited.
Limitedsolubility Whenonlyamaximumamountofasolute
materialcanbedissolvedinasolventmaterial.

SolidSolution:

Solidsolutionstrengthening Increasingthestrengthofa
metallicmaterialviatheformationofasolidsolution.
Dispersionstrengthening Strengthening,typicallyusedin
metallicmaterials,bytheformationofultrafinedispersionsofa
secondphase.
Theeffectsofseveralalloying
elementsontheyieldstrengthof
copper.
Resistancetodislocation
motion(lossinductility)

Microstructure
Thestructureobservedunderamicroscope

AlBrake morethan
onephase

Ironchromiumalloy onephase
(solidsolution)

PhaseEquilibria
Freeenergy:afunctionoftheinternalenergyofasystem
Equilibrium:asystemisatequilibriumifitsfreeenergyisata
minimum
Phaseequilibrium:forasystemwhichhasmorethanonephase
PhaseDiagram isadiagramwithT andCompositionasaxes.They
definethestabilityofthephasesthatcanoccurinanalloysystem
atconstantpressure(P).Theplotsconsistoftemperature(vertical)
axisandcompositional(horizontal)axis.
Constitution:isdescribedby
(a)thephasespresent
(b)thecompositionofeachphase
(c)theweightfractionofeachphase

Isomorphous PhaseDiagrams
Binaryphasediagram Aphasediagramforasystemwithtwo
components(C=2).
Ternaryphasediagram Aphasediagramforasystemwiththree
components(C=3).
Isomorphous phasediagram Aphasediagraminwhichcomponents
displayunlimitedsolidsolubility.
Liquidus temperature Thetemperatureatwhichthefirstsolidbegins
toformduringsolidification.
Solidus temperature Thetemperaturebelowwhichallliquidhas
completelysolidified.
Freezingrange betweentheliquidus andsolidus.

Binaryisomorphous systems
Binaryalloy:Amixtureoftwometalsiscalledabinaryalloyand
constituteatwocomponentsystem.
Eachmetallicelementinanalloyiscalledaseparatecomponent.
[Sometimesacompoundisconsideredacomponent,(e.g.,iron
carbide)]
Isomorphous System:Insomemetallicsystems,thetwoelements
arecompletelysoluble ineachotherinboththeliquidandsolid
states.Inthesesystemsonlyasingletypeofcrystalstructure
existsforallcompositionsofthecomponents(alloy)and
thereforeitiscalledisomorphous system.

Example:BinaryIsomorphous System(Cu Ni)

T<1085oC:Cu&Niare
mutuallysolubleinsolidstate
completesolubility
bothhavethesameFCC
structures,
atomicradiiand
electronegativities arenearly
identical
similarvalences
isomorphous

InterpretationofPhaseDiagrams
Constitution:isdescribedby
(a)thephasespresent
(b)thecompositionofeachphase
(c)theweightfractionofeachphase

(a)PhasesPresent
PointA:atT=1100oC
60wt%Ni 40wt%Cu
Only phaseispresent
PointB:atT=1250oC
35wt%Ni 65wt%Cu
Both &liquidphasesare
presentatequilibrium
(b) Composition of each phase
Singlephase:
PointA:
60wt%Ni 40%Cualloyat1100oC

Twophaseregion:
Tieline:acrossthetwo
phaseregionatthe
temperatureofthealloy
PointB:T=1250oC
CompositionofLiquid
phase:
CL=31.5wt%Ni 68.5%Cu
Compositionof phase:
C=42.5wt%Ni 57.5wt%Cu

(c)Weightfractionofeachphase
Singlephase:100%Ex:PointA:100% phase
Twophaseregion:
Ex:PointB

LEVERRULE
(InverseLeverRule)

S
WL =
R+S
C Co
WL =
C CL

R
W =
R+S
Co CL
W =
C CL

co c L
35 31.5
= 0.32 or 32%
=
W =
c s c L 42.5 31.5

Example:PointB:
C0=35wt%Ni
C =42.5%,CL=31.5%

c s co
42.5 35
=
= 0.68 or 68%
WL =
c s c L 42.5 31.5

Volumefraction
Foranalloyconsistingof and phases,thevolumefractionofthe phaseis
definedas

v
V =
,
v + v

V + V = 1

v
W =
;
v + v

W =

Then,theweightfractionsare

Where and arethe

volumesof and

v + v

W
W
+

Derivationoftheleverrule
1) Allmaterialmustbeinonephaseortheother:

W + WL = 1

2)Massofacomponentthatispresentinbothphasesequalto
themassofthecomponentinonephase+massofthe
componentinthesecondphase:

W c + WL c L = c o

3)SolutionoftheseequationsgivesustheLeverrule.

co cL
W =
c c L

c c o
WL =
c c L

EquilibriumCooling DevelopmentofMicrostructure
inIsomorphous Alloys
Example:
35wt%Cu65wt%Ni
system Slowcooling
frompointa topointe

a: 1300oC: complete
liquid with 35wt%Cu65wt%Ni
b: ~1260oC: first solid begin
to form
(-46wt%Ni)
c: ~1250oC: -43wt%Ni, L32wt%Ni
d:~1220oC: last liquid to
solidify
e: 35wt%Cu 65wt%Ni
solid phase

Nonequilibrium Cooling Developmentof

MicrostructureinIsomorphous Alloys

Fastcooling
Compositional
changesrequire
diffusion

Diffusion in the solid state is very slow. The new layers that
solidify on top of the existing grains have the equilibrium
composition at that temperature Formation of layered (cored)
grains. Tieline method to determine the composition of the solid
phaseisinvalid.
Thetielinemethodworksfortheliquidphase,wherediffusionis
fast.
Solidus line is shifted to the right (higher Ni contents),
solidificationiscompleteatlowerT,theouterpartofthegrainsare
richerinthelowmeltingcomponent(Cu).
Upon heating grain boundaries will melt first. This can lead to
prematuremechanicalfailure.

Completesolidification
occursatlower
temperatureandhigher
Nickelconcentrationthan
equilibrium
Solidcantfreezefast
enough:solidus line
effectivelyshiftedto
higherNiconcentrations.
Shiftincreaseswithfaster
coolingrates,slower
diffusion

Mechanicalpropertiesofisomorphousalloys
Solidsolutionstrengthening

Themechanicalpropertiesofcopper
nickelalloys.
Copperisstrengthenedbyupto60%
Niandnickelisstrengthenedbyup
to40%Cu.

SolidificationofaSolidSolutionAlloy
Segregation Thepresenceofcompositiondifferencesinamaterial,
oftencausedbyinsufficienttimefordiffusionduringsolidification.

NonEquilibriumSolidification
andSegregation
Coring Chemical
segregationincast
products,alsoknownas
microsegregation or
interdendritic segregation.

Homogenizationheattreatment Theheattreatmentusedtoreduce
themicrosegregation causedduringnonequilibrium solidification.
Macrosegregation Thepresenceofcompositiondifferencesina
materialoverlargedistancescausedbynonequilibrium solidification.

InvariantPointsinBinarySystems
Binaryalloys twocomponentsatambientpressure.Gibbs
rulestatesthat
P+F=2+1=3.
Ifthreephasescoexists(P=3),theycoexistatapoint(zero
degreesoffreedom theinvariantpoint,ataspecific
temperatureandchemicalcomposition
Typesofinvariantpoints:
eutectic,
eutectoid,
peritectic
peritectoid, monotectic etc.

FiveoftheMostImportantThreePhaseReactions
(InvariantPoints)inBinaryDiagrams

eutectic: Liquid/solidreaction
eutectoid: solid/solidreaction

1150oC:Theinbetweenpointisat
15%B. +L arepresentabovethe
point, ispresentbelow.The
reactionis: +L ,aperitectic
920oC:Thisreactionoccursat40%
B:L1 +L2 amonotectic
750oC:Thisreactionoccursat70%
B:L +,aeutectic
450oC:Thisreactionoccursat20%
B: +,aeutectoid
300oC:Thisreactionoccursat50%
B: + oraperitectoid

EutecticSystems
Thesimplestkindofsystemwithtwosolidphasesiscalleda
eutectic system.
Aeutecticsystemcontainstwosolidphasesatlow
temperature.Thesephasesmayhavedifferentcrystal
structures,orthesamecrystalstructurewithdifferent
latticeparameters.
Examples:
Pb (FCC)andSn (tetragonal) soldersystems
Fe(BCC)andC(graphite hexagonal) castirons
Al(FCC)andSi (diamondcubic) castaluminumalloys
Cu(FCC)andAg(FCC) hightemperaturesolder

Cu/AgEutecticSystem
CopperandSilverarebothFCC,buttheirlatticeparametersand
atomicradiiareverydifferent,sotheyhavelimitedsolubility in
thesolidstate.
Therearetwosolidstablephases and,andathigh
temperaturesthereisaeutecticreaction wherethesolids,
andtheliquidcoexist.

L(CE )
(CE ) + (CE )
Cooling

Heating

Hypoeutecticalloy Analloycompositionbetweenthatoftheleft
handsideendofthetielinedefiningtheeutecticreactionandthe
eutecticcomposition.
Hypereutecticalloys Analloycompositionbetweenthatoftheright
handsideendofthetielinedefiningtheeutecticreactionandthe
eutecticcomposition.

Cu AgSystem
Cu: phase
Ag: phase

Eutecticmeans
easilymelted in
Greek
PointE:invariant
point(eutecticpoint)
BGline:isotherm
line

AB&FG:Solidus line
BC&GH:Solvus line
AE&EF:Liquidus line
BEG:Solidus line,
isothermline
TE:eutecticisotherm

Eutecticisotherm

Invariantor
eutecticpoint

L(CE )

EutecticReaction:
Forcoppersilversystem:

L(71.9 wt % Ag )

Heating

Cooling

Heating

Cooling

(CE ) + (CE )

(8.0 wt % Ag ) + (91.2wt % Ag )

Eutecticorinvariantpoint Liquidandtwosolidphasescoexist
in equilibrium at the eutectic composition CE and the eutectic
temperatureTE.
Eutecticisotherm horizontalsolidus lineatTE.

BinaryEutecticSystem
Eutectic reaction transition from liquid to mixture of two solid
phases, + ateutecticconcentrationCE.
Atmosttwophasescanbe
inequilibrium.Three
phases(L,,)maybein
equilibriumonlyatafew
pointsalongtheeutectic
isotherm.Singlephase
regionsareseparatedby2
phaseregions.

Binary Eutectic System

Compositions and relative amounts of phases are determined
fromthesametielinesandleverrule,asforisomorphousalloys
demonstrate
A
B
C

Example
ForPointC:40wt%Sn60wt%Pballoyat150oC
a) Whatarethephasespresent?
b) Whatarethecompositionsofthephasespresent?
c) Massfraction?
d) Volumefractionat150oC?
KnowingthatthedensitiesofPb andSn are11.23and7.24g/cm3,
respectively

a) AtC, and phases

coexist
b) DrawTieLineat
150oC:
Forphase:
C =10%
10wt%Sn90wt%Pb
Forphase:
C =98%
98wt%Sn2wt%Pb

C C1 98 40
=
= 0.66
W =
C C 98 10

c)Massfraction:

W =

C1 C 40 10
=
= 0.34
C C 98 10

0.66

10.64
=
=
= 0.57
d)volume V =
W
0
.
66
0
.
34
+ W
+
+
fraction:
10
.
64
7.39

V = 1 V = 1 0.57 = 0.43

where

100
=
C Sn C Pb
+

Sn

Pb

100
=
C Sn C Pb
+

Sn

Pb

100
10
90
+
7.24 g .cm 3 11 .23 g .cm 3
100
98
2
+
7.24 g .cm 3 11 .23 g .cm 3

= 10 .64 g .cm 3

= 7.29 g .cm 3

L+

Development of microstructure in
eutectic alloys (I)
Several types of microstructure
formed in slow cooling an different
compositions.
Cooling of liquid lead/tin system at
different compositions.
In this case of lead-rich alloy (0-2
wt% of tin) solidification proceeds in
the same manner as for
isomorphous alloys (e.g. Cu-Ni) that
we discussed earlier.

Developmentofmicrostructure
ineutecticalloys(II)
L

+L Atcompositionsbetween
roomtemperaturesolubility

limitandthemaximumsolid
solubilityattheeutectic
+ temperature, phase
nucleatesasthe solid
solubilityisexceededat
solvus line.

Developmentofmicrostructureineutecticalloys(III)
Solidificationattheeutecticcomposition(I)
Nochangesaboveeutectictemperature,TE.AtTE liquidtransforms
to and phases(eutecticreaction).

L +

Developmentofmicrostructureineutecticalloys(IV)
Solidificationattheeutecticcomposition(II)
Compositions of and phases are very different eutectic
reaction involves redistribution of Pb and Sn atoms by atomic
diffusion. Simultaneous formation of and phases results in a
layered(lamellar)microstructure:calledeutecticstructure.
Formationof
eutecticstructurein
leadtinsystem.
Darklayersarelead
reach phase.
Lightlayersarethe
tinreach phase.

Developmentofmicrostructureineutectic
alloys(V)Compositionsotherthaneutecticbut
withintherangeoftheeutecticisotherm
Primary phaseisformedinthe +Lregion,andtheeutectic
structurethatincludeslayersof and phases(calledeutectic and
eutectic phases)isformeduponcrossingtheeutecticisotherm.

+L

Developmentofmicrostructurein
eutecticalloys(VI)
Microconstituent elementof
microstructurehavinga
distinctivestructure.Forcase
describedonpreviouspage,
microstructureconsistsoftwo
microconstituents,primary
phase andtheeutecticstructure.

Although the eutectic structure consists of two phases, it is a

microconstituent withdistinctlamellarstructureandfixedratioof
thetwophases.

Compositionsof and phasesareverydifferent eutectic

reactioninvolvesredistributionofPb andSn atomsbyatomic
diffusion.Simultaneousformationof and phasesresultsina
layered(lamellar)microstructure:calledeutecticstructure.

Formationofeutectic
structureinleadtin
system.
Darklayersarelead
reach phase.
Lightlayersarethetin
reach phase.

Relativeamountsofmicroconstituents?
Eutectic microconstituent forms from liquid
havingeutecticcomposition(61.9wt%Sn)
P
We =
....eutectic
(P + Q )
Treat the eutectic as if it were a separate
phase and apply lever rule to find relative
Q
W =
.... primary
fractionsofprimary phase(18.3wt%Sn)and
(P + Q )
eutecticstructure(61.9wt%Sn):

Terminalsolidsolution:asolid
solutionthatexistsovera
compositionrangeextendingto
eithercompositionextremityof
abinaryphasediagram.

(a)Ahypoeutecticleadtinalloy.(b)Ahypereutecticleadtin
alloy.Thedarkconstituentistheleadrichsolid,thelight
constituentisthetinrichsolid,andthefineplatestructureis
theeutectic(x400).

Theeffectofthechemical
compositionand
strengtheningmechanism
onthetensilestrengthof
leadtinalloys.

Eutecticcoloniesand
interlamellar spacing

EquilibriumDiagramsHavingIntermediatePhasesor
Compounds
Intermediatesolid
solution:

Copper-zinc

and :two
terminalsolid
solution

, , , & are

intermediate
phases

Intermetallic Compounds
Ex:magnesium
leadphase
diagram:
Intermetallic
compound:Mg2Pb
canexistbyitself
onlyattheprecise
compositionof
19wt%Mg
81wt%Pb

EutectoidReaction(InvariantPointEat560oC)
Copperzinc

cooling
heating

Eutectoid reaction

Peritectic Reaction(InvariantPointPat598oC)
Copperzinc

+L

cooling
heating

Peritectic reaction