Module 7

Solidification of pure metal

Lecture 7
Solidification of pure metal

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Keywords:CoolingCurve,PhaseRule,ConceptofFreeEnergy,Entropy,SurfaceEnergy(grain
boundary)&UnderCooling,Nucleation&Growth,Homogeneous&HeterogeneousNucleation,
DirectionalSolidification

Introduction
Puremetalsinitssolidstatehavelowstrengthandgoodductility.Itcanbeformedintoanyshape.It
canberolleddowntothinsheet(Aluminiumfoil)ordrawnintoextremelyfinewires(copperwires
usedaselectricalconductors).Itiscrystallinebutitisnotsoapparentfromitsexternalshapeasin
the cases of several inorganic solids. The distance between atoms is of the order of 0.1nm. It can
diffract Xrays having wavelength of similar order. Its crystal structure can be determined from
diffractionpatterns.Onheatingitmeltsatafixedtemperature.Thisisassociatedwiththelossofits
crystallinenature.Oncoolingitbecomessolidagain.Thismodulegivesanoverviewoftheprocess
of solidification and answers some of the questions listed here. What are the factors that would
determine its final structure? Does the transformation take place at its melting point during
solidification?Whatistheroleplayedbysupercoolingorundercooling?

Coolingcurve
The best way to monitor the process of solidification is to measure its temperature by a
thermocouple. Figure 1 gives a plot of temperature (T) as a function of time (t). It shows that
temperature keeps dropping continuously till it reaches a temperature when cooling stops till the
liquidgetstransformedtotallyintosolid.Thereaftertemperaturekeepsdroppingagain.

L+S
Tm

Fig 1: Shows cooling curve of pure metal as it cools from

liquid state. Gibbs phase rule gives a simple relationship
betweennumbersofphases(P),numberofcomponent(C),
anddegreeoffreedom(F)foragivensystem.Thisisstated
asP+F=C+2.NotethatC=1sinceitisapuremetal&P=1
since there is only one phase above Tm (melting point).
ThereforeF=2.Itmeansthisstatecanhave2controllable
variables.Thesearetemperatureandpressure.

Gibbsphaserule(P+F=C+2)

The degree of freedom that determines the number of control parameters (like temperature,
volume, pressure, composition) for any closed system follows Gibbs phase rule as stated in the
caption of fig1. Above the melting point this is equal to 2. Clearly these variables here are the
temperature and pressure. The cooling curve given above has been obtained at atmospheric
pressure which is of course fixed. Therefore what the phase rule tells us is that the liquid state is
stableoverarangeoftemperature.Inotherwordstodefinethestateofliquidapartfrompressure
youneedtodefineanothervariablethatistemperature.Letusapplythistothestatewhereboth
liquidandsolidcancoexist.HereP=2andC=1.FromphaseruleF=1.Thisstatecanhaveonlyone
variable which in this case is pressure. This means in the case of a pure metal liquid & solid can
coexist only at a definite temperature which happens to be its melting point. As long as the
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solidification process continues both liquid and solid must coexist. Therefore temperature has to
remainconstant.Inotherwordsatagivenpressureallpuremetalsorsubstancemeltsorsolidifies
atafixedtemperaturecalledmeltingpoint.Thishowevercanvarywithpressure.

Phasediagramofpuremetal
Phasediagramofapuremetalorasubstanceisagraphicalrepresentationofthedomaininwhicha
givenstateisstable.Forexampleitgivestherangeoftemperatureandpressureoverwhichitexists
assolid(S),liquid(L)orgasG).Figure2givesatypicalphasediagramofapuremetal.

Melting
point
S

1
G

Fig 2: A schematic phase diagram of a pure metal indicating

the pressure temperature domainwhereit can existassolid,
liquidorgas.Thelineindicatesboundarybetweentwophases.
Onanypointonthelinetwophasesareequallystable.There
isapointwherethreelinesmeet.Thisisacriticalpoint(triple
point)wherethreephasescancoexist.Applyphaserule.This
Boiling
gives F=0 meaning that it has no degree of freedom. Three
point
phasescancoexistonlyatafixedtemperature&pressure.For
waterthetriplepointisat0.006atmosphere0.01C.

Thecaptionoffig2describesthemainfeaturesofthephasediagram.Ithasahorizontallinedrawn
at1atmospherepressure.ItintersectstheS/LboundaryatitsmeltingpointandL/Gboundaryatits
boiling point. The slopes of these lines are positive indicating that both melting and boiling points
increasewithincreasingpressure.

GibbsFreeEnergy(G)
Gibbsfreeenergy(G)isameasureofthestabilityofaphaseatagiventemperatureandpressure.
Thelowerthefreeenergyhigherisitsstability.Atagiventemperature(T)thisisdefinedintermsof
molarenthalpy(H)andmolarentropy(S)ofaparticularphaseasfollows:
G=HTS(1)
Thiscanbewrittenindifferentialformintermsofpressure(P)&temperature(T),thetwocommon
variablesformosttransformationprocesses,as:
dG=VdPSdT(2)
The equation 2 is valid both for solid and liquid. Let us write these explicitly for the two using
subscriptS(forsolid)&L(forliquid).Figure3givesaschematicplotshowinghowfreeenergyvaries
with temperature for the two phases at 1 atmosphere pressure. The point where the two lines
intersectdenotesthemeltingpointat1atm.
dGL=VLdPSLdTforliquid(3)
3
dGS=VSdPSSdTforliquid(4)

P=constant

Fig3:AsketchshowinghowGvariesasafunctionofTforsolid(S)
G
andliquidphase(L).ThetwointersectatmeltingpointTm.Below
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this temperature solid is stable whereas above Tm liquid is stable.
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At any temperature the difference between the two is the driving

forceforthetransformation.
T
Tm

Atthemeltingpointthefreeenergyofsolidandliquidshouldbethesame.Equatingequation3&4
andsubsequentrearrangementofthetermsonegetsthefollowingexpression:

(5)

Apply this to ice making. When water becomes ice there is an increase in volume and it is
accompaniedbyreleaseofheat.Therefore VLSispositive;whereas HLSisnegative.Consequently
(dP/dT)ortheslopeofthelinedenotingLSequilibriumshouldbenegativesignifyingthatathigher
pressureiceformsatlowertemperature.Thisisexploitedduringiceskating.Icemeltsbecauseits
freezing point drops under pressure that is exerted by the skater. The thin layer of molten ice
(water)thatformsprovidesthelubricantrequiredforskating.

Phasediagramofpureiron
Ironcanexistinmorethanonecrystallineform.Meltingpointofpureironis1539C.Ifitiscooled
fromitsmoltenstateitfirstsolidifiesintheformabccphase.Thisformofironisknownas ferrite.
Asthetemperaturegoesdownat1400Cittransformsfrom phasetofccphase.Thisiscommonly
knownas ironoraustenite.Laterat910Citagaintransformsintobcccrystalknownasferrite( ).
Eachofthesetransformationsisassociatedwithachangeinvolumeandenthalpy.Thecoolingcurve
isthereforeisexpectedtoshowsteps(seefig4)ordiscontinuitiesatthesethreetemperatures.A
step indicates coexistence of two phases. The phase diagram of pure iron is shown in fig 5. This
shows the effect of pressure on the temperatures at which transformation of iron from one
crystallinefromtoanothertakesplace.

L L+
1539
L+

T 1400

L+
910

Fig 4: Cooling curve for pure iron showing three steps

representingfollowingtransformations:

L= at1539C
= at1400C
= at910C

time

The dashed vertical line in figure 5 has been drawn at 1atmospheric pressure. It intersects the
boundaries between alpha and gamma at 910C. Alpha (BCC) gamma (FCC) transformation is
accompaniedbycontraction.Thereforetheslopeofthelineisnegative.Thissuggeststhatathigher
pressure
transformation would take place at a lower temperature. As against this the lines
representing gamma delta or delta liquid have positive slopes. At 1atmosphere pressure gamma
deltatransformationtakesplaceat1400Cwhereasdeltaliquidtransformationtakesplaceat1539C.
Bothoftheseareaccompaniedbyexpansionthereforetheslopesofthetwolinesarepositive.
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1400C
910C

Fig 5: A sketch showing the phase diagram

of pure iron. This gives the stability of ,
L & G phases in various temperature
pressuredomains.

1539C

Realcoolingcurve:super(under)cooling
The cooling curve of a pure metal as shown in fig 1 is indeed an idealization of the solidification
process.Inrealitythetransformationfromliquidtosolidstatebeginsonlyafterithascooledbelow
itsmeltingpoint.Figure6showsasketchofrealcoolingcurve.Oncetheprocessinitiatesthelatent
heatthatisreleasedbythemetalraisesthetemperaturebacktoitsmeltingpoint.Thereafterthe
temperatureremainsconstanttillthesolidificationiscomplete.

L
T

G S

T
Tm

P=constant

L
T

Fig6:Asketchshowingrealcoolingcurve.
AlongwiththisGversusTplotofthesolid
and liquid phases have been shown. At a
temperature lower than its melting point
GS<GLsignifyingSismorestablethanL.

Whenasolidformsinapoolofliquidanewsurfaceiscreated(seefig7).Thishasafiniteenergy.It
isseenfromfig6thatGS<GLwhensolidificationbegins.Thisdifferenceinfreeenergyactsasthe
driving force for solidification. Once this is large enough for a stable nucleus of solid to form the
process of solidification begins. Until then unstable nuclei may appear and disappear again and
again.Soonafterastablenucleusformsitkeepsgrowing.Thustheprocessofsolidificationcanbe
visualizedasoneofnucleationandgrowth.

Fig7:Asketchshowingasphericalnucleusofsolidofradiusrformedina
pool of liquid. This has a volume

2r

and surface area 4

. The

creationofanewsurfaceneedsenergy.NotethatGS<GL,GLS<0.This
can help do so. Assuming that surface energy / unit area is and free
energychange/unitvolumeisfvitispossibletoderiveanexpressionfor
thetotalchangeinenergyforsolidification.

Figure 7 shows the sketch of a nucleus of solid in a pool of liquid. From the details given in the
captionthenetenergyoftransformationisgivenbythefollowingexpression.

(6)

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Notethatthevolumefreeenergy(orthedrivingforce)termincreasesasthecubeoftheradiusand
thesurfaceenergytermincreasesasthesquareoftheradius.Theformerisnegativewhereasthe
latterispositive.Atextremelysmallervaluesofrthesurfaceenergytermismoredominantandthe
netenergyispositive.Howeverasrgrowstheenergyislikelytoincreaseandpassthroughapeak.
Thelocationofthepeakcanbeestimatedbyequating

0;

0.

(7)

Thisgivesthecriticalsizeofthenucleus.Notethat fVisnegative.Thereforerchasafinitepositive
value. On substitution of the size of the critical nucleus in the expression forthe total energy one
obtainsthemaximumvalueitcanhave.Thisisgivenby:

rC

fT

(8)

SE = b r2

Fig 8: Sketch showing how surface energy which is

positive,volumeenergyandthetotalenergychangewith
fTmax the size of nucleus. Initially SE contribution far exceeds
VE so that the net energy is positive. However VE
increases faster with increasing size of the nucleus. The
r
total energy passes through a peak. The corresponding
valueofristhecriticalnucleussize.Nucleiwithr<rCare
VE = a r3
called unstable nuclei (embryo) and those with r>rC are
thestablenuclei(embryo)thatcangrowspontaneously.

Fromtheaboveanalysisoftheenergeticofsolidificationthefollowingconclusionscanbedrawn.(i)
Supercoolingisnecessaryforstablenucleiofsolidtoforminapoolofliquid.(ii)Onlynucleihaving
sizegreaterthanacriticalvaluerCcangrowspontaneously.(iii)Higherthesupercoolingloweristhe
size of critical nucleus (iv) Higher the supercooling lower is the nucleation barrier ( fT max). This is
alsocalledtheactivationhill.

Conceptofnucleationandgrowth
Solidification takes place by nucleation and growth. Atoms in a solid or in a liquid are never
stationary. Assume that in a pool of molten metal there is a virtual boundary that separates a
potential stable nucleus (embryo) from the surrounding liquid. Such virtual nuclei infinitesimally
smallinsizemaybeassumedtobepresentintheliquidthatisabouttosolidify.Atomskeeptrying
tocrossthebarrier.Let 0bethenumberofattemptsperunittimemadebyanatomtocrossthe
boundary. The number of successful attempt is given by the Boltzmann statistics. This is
representedmathematicallyasfollows:
6

exp

(9)

NotethatkisBoltzmannconstantandEistheenergyneededbyatomtoovercomethebarrierto
crosstheboundary.Inthiscasethiscorrespondsto fTmax.Howeverthisrepresentsthetotalenergy
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neededbyalltheatomsinaunitvolume(n).ThereforetheenergyneededbyasingleE= fT max/n.
ThisshowsthatwithincreasingEtheprobabilityofformationofstablenucleishoulddecrease.Once
stable nuclei form they would continue to grow. Initially the growth occurs at same rate in all
directionuntilthegrowthishinderedduetoimpingement.Theformationofnewnucleiwithinthe
remainingliquidalsocontinues.Whentheprocessiscompletethesolidisfoundtoconsistofseveral
grains(crystals).Thesizeofthegrainsmaydifferdependingonwhetheritdevelopedfromanucleus
formedrightinthebeginningortowardstheendoftheprocess.Thisisshownpictoriallyinfig9.

Fig 9: A sketch showing a schematic representation of nucleation and growth of solid nuclei
during solidification from the molten liquid state. Colours denote different orientations of
grains.(a)Initiallytherearefewernuclei.Someofthem havegrown.(b)Showsthatgrowth
ceases along certain directions due to impingement. A few more nuclei have formed. All of
thesecontinuetogrow.(c)Showsastatewhenmostofthespaceisfilledupindicatingthat
theprocessisnearlycomplete.Grainsappeartoberandomlyoriented.
Grainorientation
Theprocessofnucleationdescribedaboveistotallyrandom.Grainsmaynucleateanywhereinthe
melt.Itisalsoknownashomogeneousnucleation.Iftheorientationsofthegrainsarerepresented
in a standard projection by their cube poles these will be located uniformly all over the entire
standardprojection.Suchplotsareknownaspolefigures.

Fig 10: (a) Shows a typical microstructure of pure metal each grain having different orientations.
Sometimesgrainlustredependsonitsorientation.(b)Thisshowsdistributionof<001>polesofall
thegrainsonastandardprojection.Thistypeofdiagramisknownaspolefigure.
Homogeneousversusheterogeneousnucleation
Wehavesofarlookedathomogeneousnucleation.Thisismostlikelytohappenifthemoltenpool
ofmetalhasnofreesurface.Thishoweverisonlyahypotheticalcasewhichmayoccuronlyatthe
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centreofthemouldcontainingthemoltenmetal.Mouldsurfaceprovidesaninterfacewheresolid
may nucleate. When it takes place on a preexisting solid surface the process is known as
heterogeneousnucleation.Thisisillustratedinfig11.Sincethemouldsurfaceprovidesapartofthe
surface energy it would need less driving force (super cooling). Thus by providing such nucleation
sites it is possible to promote solidification. More the number of sites for nucleation finer are the
grains.Thisisoneofthewaysofhavingfinegrainstructureonsolidification.Theprocessisknownas
inoculationwhereverysmallamountofeasilydispersiblefinesolidparticlesareaddedtothemetal
asitispouredintomould.

Fig 11 a) A sketch showing homogeneous

nucleation of a solid spherical ball in a molten
pool of metal in a hypothetical mould without
anyboundary.

Fig 11 b) Sketch showing a case where apart

from an embryo at the centre there are several
nucleieachformedontheinterfacebetweenthe
mouldwallandtheliquidmetal.

Figure 12 illustrates the role played by the respective surface tension (or surface energy; both
represent the same physical parameter) and the contact angle ( ). In this case the mould surface
actsasasubstrateonwhichanembryoofthesolidnucleates.Atthepointofcontacttherearethree
surfaceforces;onebetweenthemouldandtheembryo( ME),thesecondbetweenthemould&the
liquid ( ML) and the third between the embryo & the liquid ( EL). The angle between EL and ME is
known as the contact angle. Invoking the condition of equilibrium between the three forces it is
possibletofindouttheconditionthatwouldpromotenucleation(seethefollowingequation).
cos

Liquidnearthemould
&theembryo

EL

(10)

ML

Embryo

Liquid

EL
ML

Embryo

ME

ME

Mouldsurface
Mouldsurface
Fig12:Asketchillustratingtheroleplayedbythesurfacetensionsbetweenthethreesurfacesthat
comeincontactduringthenucleationofanembryo.(a)Showsthecasewhere <90or ML> ME
and(b)showsthecasewhere >90or ML< ME(seeequation10).
8

Clearlythecondition(a)infig12isthefavourableconditionfornucleation.Inthecase(b)wherethe
contactangle>90isnotfavourablefornucleation.Theselectionofinoculatingagenttogetafine
grain structure after solidification is based on this simple concept. Heterogeneous nucleation is
favourable when is small (approaches 0 or cos =1). The best way to promote this is to select a
substratesothatthefollowingconditionsaresatisfied:
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&

(11)

Directionalsolidification
How the heat is extracted from the molten pool of metal is of considerable importance in
determining the structure of the solid. When liquid metal is poured into a mould (sometime
preheated)theheatflowsfromtheliquidthroughthemouldwalltothesurroundingenvironment.
Heatflowsfromhighertolowertemperature. The rateisproportionaltothermalgradient.Italso
depends on the effective heat transfer coefficient of the entire system consisting of the liquid,
solidifiedlayer,themouldandtheregionsurroundingthemould.Figure13illustratesacasewhere
heat is being extracted in one direction from the liquid metal through solid metal and the mould.
Note that the solid liquid interface is flat in this case. The liquid to solid transformation is
accompaniedbyevolutionofheatattheinterface.Thiscanonlybeextracteddownthetemperature
gradient.Figure14showsasketchwhyanyunevennessislikelytodisappear.

Tm

Fig 13: Sketch showing the direction of heat

flow from the liquid metal through the solid
andthemould.Italsogivesthetemperatureas
a function of distance. The S/L interface is
likely to be flat. The rate at which it moves
would depend on how fast the heat can be
extracted.

Fig14:SketchshowingabulgeintheS/Linterface.
Thearrowdenotesthedirectionofheatflow.This
makesitunstableastheheatflowingintothebulge
wouldmeltitagain.

Summary
Thismoduledescribestheimportantfeaturesofthecoolingcurveofapuremetal.Thereasonfor
theoccurrenceofastephasbeenexplainedbyusingGibbsphaserule.Theequationdescribingthe
effectofpressureonthemeltingpointhasbeenderived.Theimportanceofsupercoolinginonthe
evolution of the structure of metal has been explained. The concepts of nucleation & growth and
directionalsolidificationhavebeenintroduced.
9

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Exercise:
1. Estimatethesizeofcriticalnucleusoftinwhenitissupercooledby20C.Assumenucleation
tobehomogeneous.Theenthalpychangeforsolidificationoftinis0.42GJ/m3.Theliquid/
solidinterfacialenergyis0.055J/m2.Themeltingpointoftinis232C.

2. Ametalundergoesanallotropictransformationatroomtemperatureathighpressureand
at lower temperature at atmospheric pressure. Is the volume change associated with this
transformationpositiveornegative?

3. Bismuthhasadensityof9.8Mg/m3atroomtemperature.Itscoefficientoflinearexpansion
is14.6x106/C.Thedensityofliquidmetalatmeltingpoint (271C)is10.07Mg/m3.Find
our dT/dP and estimate its melting point at 100 atmosphere pressure. Latent heat = 10.9
kJ/mole(atomicweight=209)

4. Deriveanexpressionforcriticalnucleussizeasafunctionoftemperatureandshowwiththe
help of a schematic graph its variation with temperature. Assuming that a stable nucleus
shouldhaveatleast100atomswhichcorrespondtoaround1nmradiusmarktheregionof
homogeneousnucleation.

Answer:
1.

1
.

0.0166 GJ/m3 and Critical nucleus size =

0.42
3.3

2.Theeffectofpressureontransformationtemperatureisgivenby:

.Inthiscaselet

thetransformationberepresentedas

at300K&10atmosphere(say)(P1&T1)

at290K&1atmosphere(say)(P2&T2)

H>0reactionisendothermic&

3. Roomtemperature=25C,volumeincreaseduetotemperaturechange=3 Twhere
is
coefficientoflinearexpansion.Volumeof1gmmassatroomtemperature=1/ 0&volume
ofsolidBiatmeltingpoint=(1/ 0)+3 T.ThereforedensityofsolidBiatmeltingpoint=
.
= 9.7Mg/m3. On melting density increases V < 0.

10

=7.9x107m3.

.
.

25.31

Notethat1bar=100kPa

and100bar=10MPa.Thereforethechangeinmeltingpointat100barpressure=2.53C.

Free energy change / unit volume for solidification =

4. Critical radius =

whereH&Sareenthalpy&entropyterms.Suffixvdenotesperunitvolume.At

melting point (T0) fv = 0. Thus

&

Note that for solidification (it

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releases heat) Hv is negative. Therefore

It shows that r* approaches

infinityasTapproachesT0.AsTapproacheszeror*becomesexceedinglysmallsince Hv>>
.Thisisschematicallyshownasfollows:

Homogeneous

nucleation

1nm

Nohomogeneous
nucleation
Liquid

Homogeneousnucleation
ispossiblebelowa
specifictemperatureTc

Tc

T0

11

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