SOLIDIFICATION

Mostmetalsaremeltedandthencastintosemifinished orfinished shape. Solidificationofametalcanbedividedintothefollowingsteps: Formationofastablenucleus Growthofastablenucleus.

(a)Formationofstablenuclei (c)Grainstructure

(b)Growthofcrystals

PolycrystallineMetals
Inmostcases,solidificationbeginsfrom multiple sites, each of which can produceadifferentorientation. Theresultisapolycrystalline material consisting of many small crystals of grains Each grain has the same crystal lattice, but the lattices are misoriented from graintograin

CoolingCurves
Undercooling The temperaturetowhichtheliquid metalmustcoolbelowthe equilibriumfreezing temperaturebeforenucleation occurs. Recalescence Theincreaseintemperatureofanundercooledliquid metalasaresultoftheliberationofheatduringnucleation. Thermalarrest Aplateauonthecoolingcurveduringthe solidificationofamaterialcausedbytheevolutionofthelatentheatof fusionduringsolidification. Totalsolidificationtime Thetimerequiredforthecastingtosolidify completelyafterthecastinghasbeenpoured. Localsolidificationtime Thetimerequiredforaparticularlocation inacastingtosolidifyoncenucleationhasbegun.

SolidificationofPureMetals
Temperatureremains constantwhilegrains grow. Somemetalsundergo allotropic transformationinsolid state. Forexampleoncooling bccironchangesto fcc ironat1400C, whichagaintobcc ironat906C.

Figure8.12(a)Coolingcurveforapuremetal thathasnotbeenwellinoculated.Liquid coolsasspecificheatisremoved(betweens pointsA andB).Undercoolingisthus necessary(betweenpointsB andC).Asthe nucleationbegins(pointC),latentheatof fusionisreleasedcausinganincreaseinthe temperatureoftheliquid.Thisprocessis knownasrecalescence(pointC topointD). Metalcontinuestosolidifyataconstant temperature(Tmelting).AtpointE, solidificationiscomplete.Solidcasting continuestocoolfromthepoint.(b)Cooling curveforawellinoculated,butotherwise puremetal.Noundercoolingisneeded. Recalescenceisnotobserved.Solidification beginsatthemeltingtemperature

Solidificationofan Alloy
Thealloysnormally solidifyinatemperature range

CoolingCurvesare usedtoproducephase diagrams

Drivingforce:solidification

AL AS

ForthereactiontoproceedtotherightGV must benegative.

Writingthefreeenergiesofthesolidandliquidas: GVS =HS TSS GVL =HL TSL GV =H TS Atequilibrium,i.e.Tmelt, thentheGV =0,sowecanestimatethemelting entropyas: S=H/Tmelt = L/Tmelt whereL isthelatentheat(enthalpy)ofmelting. Ignorethedifferenceinspecificheatbetweensolidandliquid, andwe estimatethefreeenergydifferenceas: GV [L T(L/Tmelt)]= LT/Tmelt

Propertiesofmetallicmelts
Nolongrangebutshortrangeorder. Almostasdenseascrystal: oforderof1% Atomshighlymobile:(Tm )~water EntropyofmeltSL>entropyofcrystalSS(disorder,more degreesoffreedom) EnthalpyofmeltHL > enthalpyofcrystalHS(imperfectbinding). GS,GL linearnearTm ..GSL = T Undercooling isneeded:T=Tm T : materialconstant

Sketchofthecourseofthe GibbsfreeenergyGand theenthalpyHofliquid (melt)LandsolidSnear themeltingtemperature Tm.

Observation:SolidificationnotatTm!Undercooling Tisrequireddue tonucleation! Solidification=nucleation+growthofnuclei

NUCLEATION
Thetwomainmechanismsbywhichnucleationofasolidparticles in liquidmetaloccursarehomogeneousnucleationand heterogeneousnucleation.

HomogeneousNucleation
Homogeneousnucleationoccurswhentherearenospecialobjects insideaphasewhichcancausenucleation. Forinstancewhenapureliquidmetalisslowlycooledbelowits equilibriumfreezingtemperaturetoasufficientdegreenumerous homogeneousnucleiarecreatedbyslowmovingatomsbonding togetherinacrystallineform. Considerthefreeenergychangeswhensomeatomsintheliquid collapseandagglomeratetoformasolidofradiusr.

Theenergychangesinvolvetwoterms: (a)Thechemicalfreeenergychangeassociatedwiththetransferof atomsfromliquidtosolidstate(Gv); (b)theinterfacialenergy()duetothecreationofnewinterface(liquid solidinterface)! *AssumethatGv isthechangeinfreeenergyperunitvolumeand GT isthetotalFreeenergychange,r istheradiusofthenucleus

4 r 3 GT = G V + 4 r 2 3
r0 = 2 GV

d GT dr

= 4 r02 G V + 8 r0 = 0
r = r0

4 r02 16 3 G T ( r0 ) = = 2 3 3 GV

r0 :criticalradius; *forr <r0 :thegrowthofthedroplet GT the embryosshouldshrinkanddisappear! *forr >r0 :thegrowthofthedroplet GT thenuclei couldsteadilygrow! So,whatwouldmakeaembryogobeyondthecriticalsizeto becomeanuclei?Actuallyitisthelocalfluctuationofdensity!

Theprobabilityforaneventtooccuris: exp GT kT

Thetreatmenttoobtainthefreeenergychangesasafunctionof atomsinsolidisthe sameasprevious: Theenergychangesinvolvetwoterms:(a)thechemicalfreeenergychange associatedwiththetransferofatomsfromliquidstatetothesolidstate(gls) ;(b) theinterfacialenergy()duetothecreationofnewinterface(liquidsolidinterface)!

G n = g ls n + n 2 / 3

Theaboveequationcanbewrittenasafunctionofthenumberof atomsn. is a shape factor that links n to the area of the nuclei.
dGn Q dn 2 2 ls 1 / 3 = g + n c = 0 n c = 3 g sl 3
2

n = nc

G nc = n c2 / 3 3 = 4 3 3 27 g ls
Numberofatomsninasphere

n = 4 r 3 3v l r = (3v l n 4 )

1/ 3

4 r 2 = 4 (3v l n 4 )

2/3

= ( 36 )1 / 3 ( v l ) 2 / 3 n 2 / 3 = ( 36 )1 / 3 ( v l ) 2 / 3

Thenumberofembryosofsizenc is(withNthe numberofatomsintheliquid)

N n = Ne G nc / kT

astreatedbefore,forsmallundercooling, thegls :
hm T g = h Ts = hm T = hm Tm Tm
ls ls ls

G nc

4 T = 27 h
3 3

2 m 2 m

1 A = 2 T T 2

GV =

H f T Tm

2 Tm r0 = H f T

Where: Hf =LatentHeatoffusion T=amountofundercooling atwhichthenucleusform

HeterogeneousNucleation
Heterogeneousnucleationisthenucleationthatoccursinaliquid onthesurfacesofitscontainer,insolubleimpuritiesorother structuralmaterial(catalyst)whichlowerthecriticalfreeenergy requiredtoformastablenucleus.

Liquid

L-S

L-C = S-C + L-S Cos

L-C

S-C

Solid

ro

Catalys t

Heterogeneousnucleationfacilitatedby: similarcrystalstructure(lowmisfitstrain) chemicalaffinity roughsurface(reducedmelt/nucleussurface) Graftingofmeltwithsmallparticles fine grains.

Note: Thecriticalradius,r*het,ofaheterogeneousnucleusismuchlarger thanthecriticalradius,r*hom,ofahomogeneousnucleusofthesame phase. Forthesamecriticalradiustheheterogeneousnucleuscontainsfar feweratoms.

MathematicalConsiderationsforHeterogeneousNucleation
Considerahemisphericalcap. NowwehavethreesurfaceenergiesLS:solidliquid;SC:solid mould/catalyst andLC:mould/catalystliquid

Thesurfaceenergycomponentisgivenby: Total = AreaS L S L + AreaS C S C AreaS C L C

Total = 2r 2 (1 cos ) S L + r 2 (1 cos 2 ) ( S C L C )

Firsttermissurfaceareaaddedatthenewliquidsolidinterface Secondtermrepresentsreplacingcatalyst/liquidsurfacewith solid/catalystsurface Wettingangle comesfromforcebalanceofinterfacialenergies

cos =

( L C S C ) = wetting _ angle
LS

ThechemicalcomponenttoGV
2 4 3 (2 + cos )(1 cos ) GV GV = Volume GV = r 3 4

Gv isthesameasinthehomogeneouscase(thethermodynamic drivingforceforphasechange)

GTotal cos = GTotal

2 4 3 (2 + cos )(1 cos ) GV + 2r 2 (1 cos ) S L + r 2 1 cos 2 ( S C L C ) = r 3 4

( L C S C )
LS

2 4 3 (2 + cos )(1 cos ) 2 = r GV + 4r S L 4 3

d GT dr

= 4 r G V + 8 r0 = 0
2 0 r = r0

r0 =

2 GV

rCritical isthesameasthehomogeneouscase,butweonlyneedthecap andhencethenumberofatomsneededforthenucleusisverysmall. S()isafraction.Pluginsomevaluesof andyoudget =90, S()=0.5; =60,S()=0.16; =30,S()=0.013 Thismeansthebarrierfornucleationismuchlessthanthe homogeneouscase

Growthofnuclei Puremetals Crucial:directionofheatflowincludingheatofcrystallization.

(a)Theheatisdissipatedthrough thecrystal,i.e.thegrowingcrystalis colderthanthemelt.Hereasolid bulgeintotheliquidwouldmelt againbecausethetemperaturein thebulgeisaboveTm.Therefore, oneobtainsastableflat solidificationfront(facetted)and globulargrains. (b)Forastronglyundercooled melt theheatofcrystallizationcanalso bedissipatedthroughthemelt. Hereanysolidbulgeleadstoa furtherreductionofthe temperatureinthebulge. Therefore,theflatinterfaceis unstableandbranchedcrystalline projections,socalleddendritesare formed.

a)Heatdissipationthroughcrystal stableS/L interface,globular grains b)Heatdissipationalsothroughmelt unstablefront:Dendrites: growinnearlycrystallographicdirections(duetoanisotropicmobility ofS/L front). Residualmeltbetweendendrites:heatedbyheatofcrystallization slowsolidification

Thermaldendritescanformfromsmallperturbationsatliquid/solid interface: T <0 growthintocolderliquidi.e. x unstableinterfaceasTlargersogreaterG preferredgrowthinfavoredcrystallographicdirections,often <100>inmanymetallicalloys. Metallicalloys:partitioncoefficient Duringthesolidificationofmetallicalloys,solutepartitioning (redistribution)occursandthisisthemoreusualcauseofdendritic growthevenwhenthetemperaturegradientintheliquid T Thepartitioncoefficientkis definedaccordingto

<0

cSL cS k= = cLS cL

Alloys: ConstitutionalUndercooling
Aphasediagramwithlinearsolidus andliquidus lines.Thedistribution coefficientk0 isdefinedascS/cL.Thelackofdiffusioninthesolidand limiteddiffusioninthemeltleadtoanenrichmentofsoluteatomsin themeltattheS/L interface.

TheshapeofcL(x) dependsonthe diffusivityinthemeltandthemagnitude ofconvection,whichismuchmore effectiveinredistributingsoluteatoms thandiffusionexceptneartheS/L interfacewheregradc islarge.Thesolute enrichmentattheS/L interfaceleadstoa reductionintheliquidus temperatureTL. Betweenx=0andx=xL onehasTL(x)< T(x),i.e.thealloyisundercooled.

solid Tm

liquid V Heat flow

StableInterfaceFreezing: Solidificationiscontrolledbytherateatwhichthe latentheatofsolidificationcanbeconductedaway fromtheinterface.=>T isimportant! *heatflowawayfromtheinterface=theheatflow fromtheliquid+thelatentheatgeneratedatthe interface(withavelocityV)!

Tm V Heat flow

dTS dTL KS = KL + Vhm dx dx

K:thermalconductivity,

LimiteddiffusioninSandL pileupofsolute atomsinmeltatS/L interface TL(x)<T(x)near interface(constitutionalundercooling) belowcriticalTgradient instabilityofS/L interface dendritesorcellularstructure Whenheatisconductedawayfromthesolid=>more heatisconductedintotheprotrudingsolid=>growth rateisdecreased=>protrusionwilldisappear! Whenheatisconductedawayfromtheliquid,i.e., solidgrowingintosupercooled liquid=>thenegative temperaturegradientintheliquid=>morenegative =>heatisremovemoreeffectivelyfromthetipofthe protrusion=>protrusiongrows(unstable)=> dendritic growth! Lowaccommodationfactorsurface|| interface=>a stableinterface!

solid Tm

liquid V Heat flow

Tm V Heat flow

Dendritic Growth(thermaldendrite): Dendritegrowthoccurswhentheliquidhashighenoughsupercooling. Primarydendrite.Dendritegrowthdirection:highaccommodation factorsurface. Theheatreleasedfromsolidificationcouldraisedthetemperature aroundthedendritewall).=>temperaturegradient(TA> TB),ifthe gradientislargeenough,i.e.heatiseffectivelyremovedfromtheliquid =>Secondarydendrites. Iftheheatisnoteffectivelyremovedfromtheliquid=>temperatureof liquid =>nucleationofasupercooled liquid(recalescence). Intheabsenceofcoolingfromoutside,alargesupercooling isrequired forcompletedendritic freezing.Theamountofsolidthatformsfroma supercooled liquidwithoutheatremovalbythesurroundingis

f S = C p T hm

hm:heatreleasedfromsolidification; CpT:theheatthatcouldbeaccommodatedbytheliquidandsolid; fs:fractionsolidified

FreezinginAlloys:
Consideranisomorphous alloysystematT1. Solidwithcompositiona isinequilibriumwith liquidwithcompositionb.
CS KS Cl
x
Liquidwithcompositionb

b
T1 A

a
CS Cl B

Heatflowdirection

a Initiallysolidificationoccurs=>solidwithlessB atomsis T2 formed=>extraB intheliquidneartheS/L interface (enriched,sayd point)=>theliquidrequireevenlower temperatureT2 tofreezeandthecorrespondingsolidwill freezewithcompositionc =>theprocesscontinuesuntilthe A liquidintheS/L interfacehasthecompositionof fandfreezing temperatureofT3.

T1

b c e

T3

Thesolidwillhavethecompositionofe whichis equaltob.Asteadystateisreached. Twofactorsdeterminetheshapeofthe compositiondistancecurve:(1)freezingrate;(2) diffusivity Noconvectionisconsideredtoredistributethe soluteatomsinliquid;ifconvectionisconsidered =>thesoluteconcentrationattheS/L interface.

d b c a f b a f b a

 Nucleation; Homogeneousnucleation:verypuremetal,substantial undercooling (0.2Tm) Heterogeneousnucleation:nucleationagents(5OCundercooling) Graingrowth Planar:puremetal Dendritic:solidsolution Grainsize dependsonnumberofnucleiandcoolingrate.

SupersaturatedSolutions Iftheliquidisjustatthefreezingpoint,onlyafewmoleculesstick, becausetheyhavecomparativelyhighenergy Astheliquidiscooled,moremoleculescanformintonuclei. Whenthenucleusisbigenough(becauseofundercooling)the supercooled liquidsuddenlychangestoasolid. Metalsoftenexperienceundercooling of50to500degreesC Homogeneousnucleationusuallyonlyoccursinthelab. Impuritiesprovideaseed fornucleation Solidificationcanstartonawall. Itslikecloudseeding,orwatercondensingonthesideofaglass. Addingimpuritiesonpurposeiscalledinoculation Nucleationbegins ChillZone ColumnarZone(a)Theremaybedendritesinthecolumnarzone (b)Grainsgrowinpreferreddirections Equiaxed Zone

ContinuousCastingandIngotCasting

Ingotcasting Theprocessofcastingingots.Thisisdifferentfrom thecontinuouscastingroute. Continuouscasting Aprocesstoconvertmoltenmetaloran alloyintoasemifinishedproductsuchasaslab.

Figure8.21Summaryofstepsintheextractionofsteelsusingironores,cokeand limestone.(Source:www.steel.org.)

Figure8.23Secondaryprocessingstepsinprocessingofsteelandalloys.(Source: www.steel.org.)

Continuouscasting
Predominantprocessforlargescalesteel production(variantssuchasHazlett processfor aluminumalloys). Notethemouldmaybeoscillatedtoimprove surfacequalityandtominimise breakout due tolargeinternalsump. Electromagneticstirringimproves homogenizationandalsorefinesfinalgrainsize.

Figure8.22Verticalcontinuouscasting,usedinproducingmany steelproducts. Liquidmetalcontainedinthetundishpartiallysolidifiesinamold

Rapidsolidification(meltspinning)
Coolingratecanbe104 107 K/s1 andhencecanachieveamorphous (noncrystalline)structuresinmetals(metallicglasses).FeNialloys canbeusedformagneticallysofttransformercoresandalsofor tape recorderheads.

ZoneRefining
TheredistributionofsoluteaheadoftheS/Linterfacecanbeused topurifythemetal.Zonerefining,e.g.ofsilicon,witharepeated sweepinginonedirection,leadingtopurification(elementsfor whichk>1wouldbesweptintheotherdirection).Bymovingthe furnacetoandfro,onecanobtainzoneleveling.