1 THERMODYNAMIC

1.1 Nanothermodynamics
Theprogressinthesynthesisandprocessingofmaterialswiththestructuresatthenanometersize hascreatedademandforgreaterscientificunderstandingofthethermodynamicsonnanoscale.The issueofapplicationofthethermodynamicsonnanoscalehasbeencontinuouslyattracted,sincethe nucleationreactionwasdiscoveredintheearly1930s.Forinstance,agoodexampleistherenowned publication of two books with the title Thermodynamics of Small Systems by Hill in early 1960s, andrecently,thethermodynamicsofsmallsystemsisrenamednanothermodynamics. Traditionally,thermodynamicsoflargesystemscomposingmanyparticleshasbeenwelldeveloped. Classicalthermodynamicsdescribesthemostlikelymacroscopicbehavioroflargesystemswiththe changeofmacroscopicparameters.Thereallylargesystemsofastrophysicalobjectsaswellassmall systemscontainingarelativelysmallnumberofconstituents(atthenanometerscale)areexcluded. To generalize the thermodynamics on scale, we need to well understand the unique properties of nanosystems. We have seen previously, that one of the characteristic features of nanosystems is theirhighsurfacetovolumeratio.Asresultsofsurfaceeffectsbecomingincreasinglyimportantwith decreasing size, and then, the Gibbs free energy relatively increases for some thermodynamic equilibrium systems. Therefore, the behavior of such nanoscopic clusters differs significantly from theusualthermodynamiclimit.Uptodate,therearetwokindsoffundamentalapproachestoopen out the thermodynamics on nanoscale based on the microscopic and macroscopic viewpoints, respectively. One would go back to the fundamental theorem of the macroscopic thermodynamics and establish the new formalism of the nanothermodynamics by introducing the new function(s) presentingthesurfaceeffectofnanosystems.Anotheronecoulddirectlymodifytheequationsofthe macroscopicthermodynamicsandestablishthenewmodelofthethermodynamicsonnanoscaleby incorporating the LaplaceYoung or GibbsThomson relation presenting the density fluctuation of nanosystems in the corresponding thermodynamic expressions. The fundamental outlines of these approacheswillbegiveninthefollowingsection.

1.1.1 Hills Theory

In the early 1960s, Hill addressed the subject of the thermodynamics of small systems due to his interest in thermodynamics of polymers and macromolecules. In order to clarify the relationship betweenthemacroscopicthermodynamicsandthenanothermodynamicsofHill,firstofall,goback to the fundamental theorem and recapitulate the foundations of the thermodynamics of macroscopicsystems. Inthecaseoftheequilibriumthermodynamicsofamacroscopicsystem,thefundamentalequation fortheinternalenergy,U,intheabsenceofanexternalfieldisexpressedas

U(S, V, N) = TS - PV + N

(1.1)

WhereSistheentropy(anextensivestatefunction),anditisafunctionoftheextensivevariables(U, V, N) in onecomponent system, T the absolute temperature, P the pressure, V the volume, the chemicalpotential,andNisthenumberofparticles.ThedifferentialformofEq.U(S,V,N)=TSPV

+N (1.1)mayberepresentedas dU = SdT + TdS VdP PdV + Nd + dN

Ontheotherhand,therelationshipsamongU,S,V,N,T,P,andcanbeexpressedas
(1.2)

U N S ,V

(1. 3)

U T = S N ,V U P = V S , N U N S ,V (1.6.5).
SdT + VdP N i d i = 0

1.4)

(1.5)

Eq. 6.3) will change into the following form by employing one of the above three equations

(1.6)

ThisistheGibbsDuhemrelation,andimpliesthatthechangesintheintensivequantities(,T,P) arenotindependent.However,theusualchoice(T,P)ismadeintheliterature,defininganequation ofthestateforthesystem.Inparticular,theGibbsDuhemrelationimpliesthat

V = P T N
and

(1.7)

S = N T P

(1.8)

It is well known that three other functions, besides the internal energy, U, are very useful in applicationstothespecificphysicalsituations. Theenthalpyis

H (S,P,N) = U (S,V,N) + PV
TheHelmholtzfreeenergy

(1.9)

F (T,V,N) = U (S,V,N) TS
AndtheGibbsfreeenergy

(1.10)

G (T,P,N) = U (S,V,N) TS + PV

(1.11)

Eq.H(S,P,N)=U(S,V,N)+PV(1.9)ineq.11,youobtain

G (T,P,N) = H (S,P,N) TS

(1.12)

According to the dependence relationships of these functions (U, H, F, G) and their continuity propertiesintheirappropriatevariables,fourthermodynamicequationscalledtheMaxwellrelations canbeyieldedas

P T = S V V S V T = P S S P

(1. 13)

(1.14)

S P = V T T V
and

(1.15)

V S = T P P T
Ifonecombineseq.dU=SdT+TdSVdPPdV+Nd+dN (1.2)

(1.16)

with

SdT + VdP N i d i = 0

(1.6)wehavethefollowingGibbsgeneralizedrelation

dU = TdS PdV + i dN i
i

(1.17)

i Equation (1.17) applies to a microscopic system only. For example,ifthesystemisasmallonecomponentsphericalaggregatethathasanonnegligiblesurface

dU = TdS PdV + i dN i

i freeenergytermproportionaltoN2/3,equation (1.17) is no longer applicable. This equation can be generalized further to include small systems, by adding anotherterm. Butthisadditionmustbemadeattheensemblelevelratherthanatthesinglesystem level.ThereasonforthisisthatanensembleofBequivalentandnoninteractingsmallsystemsis

dU = TdS PdV + i dN i

itself a macroscopic system, and hence we can use equation (1.17),rewrittenforanensemble,asareliablestartingpoint:

dU = TdS PdV + i dN i
i

dU t = TdS t PdVt + i dN it
i

Ut BU St BS Vt BU

Nit BNi
wheret=total(i.e.,thewholeensembleofsmallsystems).

(1.18)

ThetermweaddtoeqNit BNi

(1.18)isEdB:
(1.19)

dU t = TdS t PdVt + i dN it + EdB

i

WhereE (Ut/B)St,Vt,Nit.Themotivationisthat,forasmallsystem,UtwillalsobeafunctionofB. Eisakindofsystem(ratherthanmolecule)chemicalpotential,calledthesubdivisionpotential.If the systems of the ensemble are macroscopic and are subdivided in order to increase B in eq (1.19)(e.g.,inanextremecase,eachsystemiscutin halftodoubleB),thiswillnothaveanoticeableeffectonUt,St,Vt,NitareallheldconstantasinE ( Ut/ B). That is, surface effects, edge effects, system rotation and translation, etc., are all negligible for macroscopic systems, and hence E is essentially zero: the term E d B in eq.
i

dU t = TdS t PdVt + i dN it + EdB

(1.19) does not contribute appreciably to the equation. But the effects just mentioned are not negligible if an ensemble of small systems is subdividedtoincreaseBineq.(6.19.)ThisisbecausesuchanincreaseinBimpliesadecreaseinV andNi(Visdecreasinginanonlinearmanner(decreasingdensitywithdecreasingsizeNi;Vt,and Nitareheldconstant):unlikemacroscopicsystems,sizeeffectsaresignificantinsmallsystems.Emay beregardedasafunctionofT,P,andthei,aswillbeseenexplicitlybelow.Thus,Eisacomposite
i

dU t = TdS t PdVt + i dN it + EdB

intensivepropertyattheensemblelevel.Equation dU t = TdS t PdVt +

dN
i i

it

+ EdB (1.19)

canbeintegratedfromB=0toB,holdingallsmallsystempropertiesconstant,togive

U t = TS t PVt + i N it + EB
i

(1.20)

Here, new equivalent small systems are added to create the ensemble (subdivision is not used). DivisionbyBthenyields,forasinglesmallsystem,

U = TS PV + i N it + E
i

(1.21)

ThepresenceofEinthisequationisanewfeatureofnanothermodynamics.
i Ifwereturntoeq (1.19), replace dUt by d(BU) = BdU + UdB , and similarly for dSt, dVt, dNit the terms in dB drop out in view of eq

dU t = TdS t PdVt + i dN it + EdB

U = TS PV + i N it + E
i

(1.21).Theremainingequationis(forasinglesmallsystem)
(1.22)

dU = TdS PdV + i dN i
i

Thisisthesameaseq dU = TdS PdV +

dN
i i

(1.17)foramacrosystem:asmallsystemhas

the same energyheatwork relation as in a macrosystem (with the Ni constant) and also the same chemicalpotentialterms.However,eq

dU = TdS PdV + i dN i
i

(1.22)cannotbeintegratedto

giveeq6.21becauseUisnolonger(forasmallsystem)alinearhomogeneousfunctionofS,V,and Ni. Ifwetakedifferentialsineq U = TS PV +

N
i i

it

+E

(1.21) and cancel the terms in eq

dU = TdS PdV + i dN i
i

(1.22),theremainingrelationis
(1.23)

dE = SdT + VdP d i N i
i

Thelefthandsideiszeroinmacroscopicthermodynamics(seeeq.6.6!!).NotethatT,P,andthei areallindependentineq dE = SdT + VdP

d N
i i

(1.23).

AmacrosystemhasonelessdegreeoffreedombecausedE=0.
i Equation (1.23) confirms that E is a function of i, T, P. Note that derivatives of E, a composite intensive property, with respect to intensive variables yield extensivevariables:

dE = SdT + VdP d i N i

E S = T p ,i E V = P T , i E Ni = i
Equations U = TS PV +
(1.24)

T , p , i

N
i i

it

+E

(1.21), dU = TdS PdV +

dN
i i

(1.22)

and

dE = SdT + VdP d i N i
i

(1.23)providethefundamentalsofthegeneralizationofthe

thermodynamicsofGibbstoincludesmallsystems.Althoughconventionalmacrothermodynamicsis byfarthemorewidelyknownsubject,itcanbeviewedasalimitingcaseofnanothermodynamics.In contrasttomacrothermodynamics,thethermodynamicpropertiesofasmallsystemwillusuallybe differentindifferentenvironments.Anexamplewillclarifythisstatement.Consideraratherrigid incompressible linear aggregate of N more or less spherical molecules in an inert constant temperaturebathatT.Nmightbeontheorderof102or103.Theenvironmentalvariableshereare N and T (P can be ignored because of the incompressibility). The aggregate will have a certain amountofentropy,S,associatedwithtranslation,rotation,andthevibrationalmotionofandwithin themoleculesofthechain.Nowsuppose,incontrast,thatthebathincludestheindividualmolecules atchemicalpotentialandthatthesemoleculescangoonandoffthetwoendsoftheaggregate.At equilibrium, there will be a mean number N of molecules in the aggregate. The environmental variableshereareandT.Ifischosensothat N inthe,TcaseisthesameasNintheN,Tcase above,theentropySwillbelargerinthe,TcasebecauseoffluctuationsinNthatarenotpresentin

the N, T case. However, this extra entropy becomes negligible as the aggregate approaches macroscopicsize(byadjusting). It is worth noting that Chamberlin et al. have extended Hills idea by considering the independent thermal fluctuations inside bulk materials. In detail, they adapt Hills theoryto obtain ameanfield modelfortheenergiesandsizedistributionofclustersincondensedmatter.Importantly,themodel provides a common physical basis for many empirical properties, including nonDebye relaxation, nonArrheniusactivation,andnonclassicalcriticalscaling

1.1.2 Tsallis

generalization

of

ordinary

Boltzmann-Gibbs

thermostatics
ThethermodynamictheoryisonthebasisoftheTsallisgeneralizationoftheordinaryBoltzmann Gibbs thermostatistics by relaxing the additive properties of the thermodynamic quantities (the entropy,inparticular)toincludenonextensivityofnanosystems.AsdescribedbyRajagopaletal.[], thenanothermodynamicsdiffersfromHillsapproachbyconsideringthateachofthenanosystems fluctuatesaroundthetemperatureofthereservoir,whilenanosystemsarecoupledtothereservoir. This means that the BoltzmannGibbs distribution has to be averaged over the temperature fluctuationsinducedbythereservoir. Theformalismofnonextensivestatisticalmechanicshasbeendevelopedoverthepast13yearsasa powerful and beautiful generalization of ordinary statistical mechanics. Thermodynamics of metastablephasenucleationonnanoscale(Notfurtherttreatedinthislecture)

1.1.2.1 Classical nucleation thermodynamics

BeforestartingtheanalysisofthethermodynamicsofMPNUR(MetastablePhaseNucleationinthe strongly Unstable Region), we need to look back on some fundamental concepts of the nucleation theory. Actually,thenucleationreferstothekineticprocessesthatinitiatethefirstorderphasetransitionsin nonequilibriumsystems,andthenucleationofanewphaseislargelydeterminedbythenucleation workW.ThequantityisequaltospendingtheGibbsfreeenergyhavingoratleastresemblingthe propertiesofthenewphaseappearanceintheparentphaseofadensityfluctuationandstayingin the labile thermodynamic equilibrium together with the parent phase. With a random acquisition evenofasinglemoleculeofanewphase,thefluctuationmayresultinthespontaneousformationof thecriticalnucleationofthenewphase.Forthisreason,Wistheenergybarrier(criticalenergyof clusterformation,G*)ofthenucleation.Therefore,thenucleationworkplaysanimportantrolein the formation of a new phase. However, it is well known that the initially homogeneous system is also heterogeneous in characterized by the nonuniform density and pressure. Therefore, the determinationofG*isahardproblem.Namely,thecaseabovemakesitimpossibletoderivethe nucleation work only from the method of the thermodynamics of uniformly dense phases. In CNT (ClassicalNucleationTheory),thecriticalnucleusisregardedasaliquiddropwithasharpinterface(a dividingsurface)thatseparatesthenewandparentbulkphases.Matterwithinthedividingsurfaceis treatedasapartofabulkphasewhosechemicalpotentialisthesameasthatoftheparentphase.In theabsenceofknowledgeofthepropertiesofthemicroscopicclustersincludingthesurfacetension,

thebulkthermodynamicpropertieswithseveralapproximationsareusedtoevaluatethenucleation workinthediscussionsbelow. In1878,GibbspublishedhismonumentalworkwiththetitleOntheEquilibriumofHeterogeneous Substances, and his other publications have a special place in thermodynamics of the phases mixture and equilibrium. Concretely, Gibbs extended the science of thermodynamics in a general formtoheterogeneoussystemswithandwithoutchemicalreactions.Especially,heintroducedthe methodofthedividingsurface(DS)andusedittoderiveanexactformulaforG*inthenucleation ofanewphaseinthebulkparentphase.Indetail,withtheaidofanarbitrarilychosensphericalDS, hedividedtheheterogeneoussystemconsistingofthedensityfluctuationandtheparentphaseinto two homogeneous subsystems, which are corresponding to the microscopical and macroscopical subsystems, respectively. The macroscopically large subsystem equals the parent phase with the uniformdensityandpressurebeforethefluctuationformed.Themicroscopicallysmallsubsystemis an imaginary particle (nucleus) replaced a reference new phase with the uniform density and pressure, and surrounded by the large subsystem. The imaginary particle substitutes for the real nucleus of the new phase, which is created by the density fluctuation. As Gibbs described the differencebetweentheimaginaryparticle(globulebyGibbsdefinition)andthedensityfluctuationby thefollowingstatement:Forexample,inapplyingourformulastoamicroscopicglobuleofwaterin steam,bythedensityorpressureoftheinteriormassweshouldunderstandnottheactualdensity orpressureatthecentreoftheglobule,butthedensityofliquidwater(inlargequantities)whichhas thetemperatureandpotentialofthesteam. Therefore,basedontheseapproachesabove,GibbsshowedthatthereversibleworkW(freeenergy ofnucleation),requiredtoformthecriticalnucleusofanewphase,is

G* = A T V ( Pl PV )

(1.25)

WhereAandVaretheareaandvolumeofthespecificsurfaceenergyofaspeciallychosenDS,Plthe pressureofthenewbulkreferencephaseatthesamechemicalpotentialastheparentphase,andPv is the pressure of the parent phase far from the nucleus. T is the surface of tension, called by Gibbs,ofthespecificsurfaceenergyofaspeciallychosenDS,anditiscalledasthesurfacetensionat thepresentday. IntheGibbsanalysis,hefoundoutthattheclassicalLaplaceYoungequationisvalidinhisDS,and governs the pressure of droplets across a curved interface. For a spherical droplet with the critical nucleusradiusr*,theLaplaceYoungequationreads

Pl Pv =

2 T r* Pl Pv =

(1.26)

Further,forthesphericalcriticalnucleus,Gibbsshowedthatwitheq.

2 T r * (1.26),

eq.

G* = A T V ( Pl PV )

(1.25)becomes

G* =

3 T 16 3 ( Pl Pv ) 2

(1.27)

However,thequantityTcouldnotbeobtainedbyexperiment,becauseitdescribessuchasurface animaginaryphysicalobject,i.e.,thenucleuscharacterizedbythesurfaceoftension.Therefore,the dependent relationships of T and pressure, temperature, and composition of the parent phase, respectively,arenotuncovered.Thislimitstheapplicationofthenucleationtheorytovariouscases ofinterest.Ontheotherhand,inordertodescribethethermodynamiccharacterizationofvarious practicalcases,wehavetoapproximateTbyarealphysicalquantity.Clearly,innearlyallnucleation papersthatfollowedGibbsequation,e.g.,oneusedtherealinterfaceenergy0betweenthebulk parent and new phases at the phase equilibrium, i.e., at their coexistence, to replace the surface tensionToftheimaginaryDS.However,toapplythisfamousformulaofGibbs,onehastoknowthe exact interface energy that is related to the radius of dropletsand the droplet reference pressure. Unfortunately, there are tremendous challenges because there is no simple way to extract the interfaceenergyfromtheforcemeasurementsintheory.Agiveninterfaceenergyisafunctionofthe manycoordinatesofthenanoparticles.Lackingtheknowledgeoftheexactinterfaceenergy,thefirst approximationistousetheexperimentalinterfaceenergyofaflatinterface,i.e.,0=.Actually,the surfacestructureofdropletsisdifferentfromthatinthebulk,sothat,strictlyspeaking,theboundary surfacenevercoincideswiththeequimolecularsurface.Nevertheless,theyareusuallyclosetoeach otherandareoftentakenequallyasthephysicalsurfaceofthedroplet.Byassuming0=,onecan obtainthefirstformofthenucleationwork

3 16 G* = 3 ( Pl Pv ) 2

(1.28)

Inprinciple,byadoptingtheapproximation,thevalidityoftheGibbssexpressiononthebasisofthe LaplaceYoung equation should be limited to the sufficiently large nuclei. Interestingly, the applications of the nucleation theorem in the analysis of experimental data in various cases of nucleationimpliedthattheLaplaceYoungequationcouldpredictwellthesizeofthenucleibuiltup oflessthanafewtensofmolecules. Forinstance,Tolbertand Alivisatosdiscussedtheelevationofpressureinthesolidsolidstructural transformationasthecrystallitesizedecreasesinthehighpressuresystemusingtheLaplaceYoung equation.Accordingly,itseemstoberecognizedthattheLaplaceYoungequationcouldbeusedto predictwellthesizeofnucleibuiltupoflessthanafewtensofmolecules.Ontheotherhand,based onthethermodynamicidentity,wehave

l ( Pl ) l ( Pv ) = Vm dP
Pv

Pl

(1.29)

WhereVmisthemolarvolumeofanewphaseand l ( Pl ) and l ( Pv ) arethechemicalpotentialof matter in the new phase at the pressures Pl and Pv. When the critical droplet and the metastable vapourlocatetheconditionoftheunstableequilibrium,onecanobtain

v ( Pv ) = l ( Pl )

(1.30)

Furthermore,ifweapproximatePlbyassumingthatthedropletisincompressible,andassumethat

l ( Pl ) l ( Pv ) = Vm dP
Vmisaconstant.WithEqs. becomes
Pv

Pl

(1.29)and

v ( Pv ) = l ( Pl ) (1.30)

Pl Pv =

v ( Pv ) l ( Pl )
Vm

Vm

(1.31)

Pl Pv =
Eq.

v ( Pv ) l ( Pl )
Vm

3 Vm (1.31)turnsintoEq. G* = 16 (1.28), 3 ( Pl Pv ) 2

one

canobtainthesecondformofthenucleationwork
2 16 3Vm G* = 3 ( ) 2

(1.33)

AsObeidatetal.stated[],theformofthenucleationworkismostusefulifthechemicalpotential difference between a new phase and its parent phase can be obtained. However, the actual performanceisquitecomplicatedduetothelackoftheaccuratepotentialsformostsubstances.In ordertoobtainthe,wehavetoadoptsomenecessaryapproximations.Generally,ifweassume the supersaturated and saturated vapors are the ideal gases and the droplet is an incompressible liquid,thedifferenceofthechemicalpotentialismorecommonlyderivedfromtheapproximate system.Indetail,undertheaboveassumptions,wehave

Pl = Pev

(1.34)

P = Pev (1.34),eq. WherePevistheequilibriumvaporpressure.Witheq. l

(1.29)becomes

l ( Pl ) l ( Pv ) = Vm dP
Pv

Pl

l ( Pv ) = v ( Pev ) + Vm ( Pv Pev )

(1.35)

Whenthenewbulkphaseandtheparentphaseareinthestateofthermodynamicequilibrium,one canobtain

l ( Pev ) = v ( Pev )
Undertheidealvaporcondition,wecaneasilyobtain

(1.36)

v ( Pv ) v ( Pev ) = kT ln

Pv Pev

(1.37)

WherekistheBoltzmannconstant,Ttheabsolutetemperature,andPvistheactualpressure.And finallythethirdformofthenucleationwork

G* =

16 3

3Vm2
P kT ln v P ev

(1.38)

Applyingthefirsttwoformsofthenucleationworkrequirestheknowledgeofthedropletreference pressureorchemicalpotential.Usually,thisinformationisunavailable,andtheexperimentalresults are, instead, compared with the rates predicted using the third form, because the supersaturation ratioisreadilydeterminedfromtheexperimentaldata.Naturally,thesizeofthecriticalnucleation, thecriticalenergy,thephasetransitionprobability,andthenucleationratewouldbeobtainedbythe determinednucleationwork. Insummary,fromthepointofCNTabove,onecanseethatthereisanimportantapproximation,i.e., assuring T = 0 = . Namely, the surface tension (T) of a specially chosen DS, the real interface energy(0)betweenthebulkparentandnewphasesatthephaseequilibrium,andtheexperimental interface energy of a flat interface () are approximated to equal. Furthermore, CNT indicates that theLaplaceYoungequationseemstobecapableofpredictingwellthesizeofnucleibuiltupofless thanafewtensofmolecules.However,ontheotherhand,itiswellknownthattheCNTdescribes thatastablenewphaseformsfromametastableparentphase.

1.1.2.2 Thermodynamics of metastable phase nucleation in unstable reactions of thermodynamic equilibrium phase diagram
MPNUR, such as CVD (Chemical Vapor Deposition) diamond, CVD cBN, HSRC (Hydrothermal SynthesisandtheReductionofCarbide)diamond,andcBN(cubicboronnitride)nucleation,seems to be impossible from the standpoint of thermodynamics, because the nucleation happens in the strongly unstable region of the metastable structural state in terms of the thermodynamic equilibriumphasediagram,andviolatesthesecondlawofthermodynamics.Forthisissue,asHwang and Yoon stated regarding CVD diamond [], Something must be wrong either in interpreting the experimentalobservationorinapplyingthermodynamics.Infact,intheearly1965s,Garviepointed out that MPNUR likely arises out of the capillary pressure built up in the nuclei. Namely, the nanosizeinduced additional pressure could be so large that the highpressure metastable phase tendstobecomemorestablethanthelowpressurestablephase,asshowninFigure11.

Figure 1-1 : A sketch map of MPNUR mechanism. A region is the metastable structural state of M phase, and B region is the new stable state of M phase by the nanosize-induced additional pressure driving. The inset shown in the sketch map displays the spherical nuclei nucleated on the heterosubstrate. [C.X. Wang, G.W. Yang, Thermodynamics of metastable phase nucleation, Materials Science and Engineering, 2005, p.p. 157-202]

Note that, in the following description, a phase is metastable or stable if it is stable or metastable withouttheeffectofthenanosizeinducedadditionalpressure.Inourtheoreticalapproach,italsois emphasized that the nanosizeinduced additional pressure is reasonably taken into account in the belowanalysis. Generally, the Gibbs free energy is an adaptable measure of the energy of a state in phase transformations among competing phases. At the given thermodynamic condition, both stable and metastable phases can coexist, but only one of the two phases is stable, with the minimal free energy,andtheothermustbemetastableandmaytransformintothestablestate.Thermodynamics ofmeltingandfreezinginsmallparticles

1.1.3 Theory Vanfleet and al. model

Couchman [] developed a thermodynamic framework which Vanfleet and al. [] have modified with Van Der Veens [] ideas to include surface melting. The combination of their ideas results in a thermodynamicmodelthatcanhelpexplainobservedresults.Vanfleetandal.[]basetheirmodelon asphericalparticlesurroundedbyanothermaterial.Thissurroundingmaterialwillbereferredtoas theimbeddingmatrix.Thismatrixcanbeassimpleastheparticlesownvapor,orascomplicatedas acrystallineoramorphoussolid(althoughcertainassumptionswillbemadeshortlyaboutitseffect ontheparticle).Theparticlestemperaturewillbeheldconstant,andwewillexploretheHelmholtz freeenergydifferencebetweentheparticlewhenithasaliquidlayerwithasolidcoreandwhenitis fullysolid.Weassumethatboththesolidandliquidphasesareincompressible.Ourinterestisthe shiftofthemeltingandfreezingpointsduetofinitesizeeffects,sowemustincludeboththesurface energy () and the surface stress (). We will assume that both of these surface quantities are isotropicandindependentofparticlesizeandtemperature.Wewillalsoassumethattheonlyeffect ofthematrixwillbetovarythesurfaceenergiesandsurfacestressesoftheparticle.Therecanbe confusionontheuseofthetermssurfaceenergyandsurfacestress.isthesurfaceenergyandhas units of energy per area. times the area is the energy attributed to the surface; it is the energy requiredtomakenewsurface.Itcanalsobethoughtofastheenergyoftheunsatisfiedbondsonthe surface,butaswewillseelater,italsoincludesthesurfaceinducedorderordisorderinthebulkof thematerial.isthesurfacestressandalsohasunitsofenergyperarea.Thisistheenergyrequired toalteragivensurfacebyelasticallydeformingthatsurface,includingtheenergyofthestretchedor compressedbondswithinthesurface.Thesetwosurfacequantitiesarerelated.,thesurfacestress, isthechangeinthetotalenergyofthesurfacewithasmallchangeinitsarea.

d (A) = + A dA A

(1. 2)

Forthesurfaceofaliquidthemoleculesarefreetomoveandthereforecannotsustainabondstress. Thus,thesecondterminEq. =

d (A) = + A (1.2)iszeroandthesurfacestressisequalto dA A d (A) = + A dA A

(1. 2) can be

thesurfaceenergy.Thefinalsurfacewillbejustliketheoriginalyettherewillbemoreorlessofit. Solidscansustainstresses.Thus,thesecondterminEq. =

significantandisofthesameorderofmagnitudeasthesurfaceenergy.Itmaybeeitherpositiveor negative.Thechoiceofwhichsurface quantitytousedependsuponwhethernewsurfaceisbeing created()oranexistingsurfaceisbeingmodified(). Thefreeenergyofthefullysolidparticleis

Fsolid = (T, P) Ns PsVs + smAs

(1. 3)

is used because the solid matrix surface must be created, and (T, P), a function of the local temperature and pressure, is the chemical potential per particle. With a spherical geometry assumed,thesurfacearea(As)andthevolume(Vs)arejustfunctionsofthenumberofatomsinthe particle(Ns). Here,andfortherestoftheparagraph,asinglesubscriptwillrefertothevolumespecifiedbythe subscript, and a double subscript will refer to the surface specified by the two subscripts. For example,intheaboveequation,thenumberofatomsinthesolidvolumeisNsthesurfaceareaof thesolidvolumeisAsandthesolidmatrixsurfaceenergyissm Thelocalpressure(P)istheexternallyappliedpressure(P0)plustheincreaseinpressureduetothe surface.Theexternalpressure(P0)isallpressuresexceptthosethatarisefromtheparticleitself.The increaseinpressure,usingtheLaplaceYoungequationforasolidorliquidsphereofradiusr,is

P P0 = 2

(1. 4)

Thesurfacestress()isusedbecausethesurfaceisattemptingtocompresstheparticleandchange its area. The chemical potential is analyzed about the bulk melting point (T0) and the externally appliedpressure(P0).Wewillassumethattheexternallyappliedpressureissmallenoughthatthere is no shift in the bulk melting point from standard values. At this reference point, the chemical potentialperparticleisthesameforthesolidandliquidphases.Onlyfirstordertermsarekept,to give

(T , P ) = (T0 , P0 ) +
Thatis

(T T0 ) + ( P P0 ) T P

(1. 5)

(T , P ) = (T0 , P0 ) + s(T T0 ) + ( P P0 )

(1. 6)

Wheresistheentropyperparticleand isthevolumeperparticle.Thepressureduetothesurface can be significant, but because of the assumed incompressibility and small linear expansion coefficient,wecanneglectsecondordertermsinpressure.Thesecondordertermintemperatureis atmostafewpercentofthefirstordertermsandwillalsobeneglected.Thefinalfreeenergyofa crystallineparticleis

 2 Fsolid = (T0 , P0 )N s + s s (T T0 ) N s + s sm r s

2 N s sm + P0 Vs + sm As r s

(1. 7)

Wherethetermsinvolvingthesurfacestresswillcancel. Fortheliquidparticlewiththecrystallinecorewemustsplitthesefreeenergytermsbetweenthe phases. The subscript l will refer to the liquid layer and rl will be the radius of the liquidmatrix surface.Thesubscriptcwillrefertothesolidcorethatissurroundedbytheliquidlayerandrcwillbe itsradius.

Fmixed = Fliquid + Fcore

2 Fliquid = (T0 , P0 )N l + sl (T T0 ) N l + l lm r l 2 N l lm + P0 Vl + lm Al r l

(1. 8)

(1. 9)

2 2 sl Fcore = (T0 , P0 )N c + s s (T T0 ) N c + s lm + r rc l

2 2 sl N c lm + + P0 Vc + sl Ac r rc l
(1. 10)

The volumes ( ) and entropies (s) are labeled for the phase (solid or liquid) to which they apply. Again,surfacestresstermscancel.Thiscancellationofthesurfacestressisaresultoftheassumed incompressibilityofthephases.Anincompressiblematerialcanhavenonetworkdonebychangesin thepressure.Therefore,thechangeinthechemicalpotentialiscounteredbyanothertermtoleave nonetchangeinthefreeenergyduetopressure. Thefreeenergydifferencebetweenthesetwosituationsisnow

F = Fmixed - Fsolid

(1. 11)

F = (T0 , P0 )( N l + N c N s ) (sl N l + s c N c s s N s )(T T0 ) P0 (Vl + Vc Vs ) + lm Al + sl Ac sm As

(1. 12)

The total number of atoms is conserved (Nl + NC Ns) = 0. Entropy terms can be written as the differencebetweentheliquidandsolidentropyperparticleandthenumberofliquidparticles.

T (s l N l + s c N c s s N s )(T T0 ) = T0 (sl s s )N l 1 T 0
Thelatentheat(l0)peratomis(slss)T0

(1. 13)

T F = l 0 1 T 0

N l P0 (Vl + Vc Vs ) + lm Al + sl Ac sm As

(1. 14)

Thereisabulktermduetothetemperaturedifferencefromthebulkvalue,avolumechangeterm, andsurfacetermsthatareproportionaltothesurfaceareas.Fromgeometricalconsiderationsgiven below,thePVtermscanberewrittenasafunctionofNl.

1 1 P0 (Vl + Vc Vs ) = P0 l s

Nl

(1. 15)

Whereisthedensity(atomspervolume)ofthelabeledphase.Thistermissmallcomparedtothe latentheattermandwillbeneglected.Forexample,atatmosphericpressurethisisabout104times thelatentheatterm,unlessthetemperatureisverynearthebulkmeltingpoint. Wewouldliketotakeintoaccounttheorderingordisorderinginducedbythesurface.Vanfleetand al.tooktheircuefromVanDerVeenandtheyderivedacorrectiontothesurfaceenergies,dueto surfaceinduced ordering or disordering. A surface will attempt to propagate its order into the volumeofwhichitformsthesurface.Theorderwillberelatedtoacorrectiontotheenergyforeach unitofvolume.Thiseffectwillbescreenedbyinterveningmaterialandisanalogoustoascreened potential.Usingthescreenedpotentialdecayoftheinteractionwewillwritethattheenergy,dueto thesurface,atadistancerfromanareadAwillbe

r exp dA dE r

(1. 16)

Whereisthescalelengthforthescreening.Thetotalcontribution,atapoint,duetothesurface wouldthenbetheintegraloverthesurfaceoftheabove.ForaflatsurfacethisintegrationgivesC exp(t/),whereCistheconstantofproportionality(unitsofenergyperunitvolume)andtisthe perpendiculardistancefromthesurface. Therefore,foraflatsurface,thetotalcontributionto the energyduetothesurfaceistheintegraloverthevolumeofCexp(t/),plusasurfaceterm.

z z E surface = A * + C1 exp 1 dV + C 2 exp 2 2 1 1 2

dV

(1. 17)

The 1s and 2s designate which side of the surface is the volume to be integrated. If we limit our interesttoathicknesstoneachsideofthesurfaceandintegratewehave

t t E surface = A * + C11 1 exp 1 + C 2 2 1 exp 2 2 1

(1. 18)

For ts much larger than the scale lengths, the energy per unit area due to the surface is

= * + C11 + C 2 2 .Thisistheobservedsurfaceenergythatwefindintheliterature.Thelimitof
tgoingto0gives*,whichwewillcalltheskinenergy.Ifthepresenceofthesurfaceincreasesthe orderforashortdistanceintothebulk,theenergywillbelowered,andCwillbenegative.Increasing the disorder of the material will raise the energy and C will be positive. If we now ask what is the energyperareaduetothesurfaces,fornoninteractingsolidliquidliquidmatrixsurfacesadistance tapart,wherethesolidandmatrixareconsideredinfinite,wehave

* * t t E = lm + sl + C lm l 1 exp + C ml m + C ls l 1 exp + C sl s A l l

(1. 19)

VanDerVeenstatedthattheremustbenodifferencebetweentheenergyofasolidsurface,anda solidsurfacewithaliquidlayer,iftheliquidlayerhaszerothickness.Wewillmakethatassumption but will see shortly that this imposes some conditions under which this model can be applied. Requiring that the above equation give sm in the limit of t = 0 results in

* * sm = lm + sl + C ml m + C sl s .Lettingtnowbelargecomparedtothescalelength,themismatch

betweentheobservedvaluesofthesurfaceenergiesis
* * = sm sl lm = sm lm + sl Clm l C ml m Cls l C sl s = (C lm + C ls ) l (1. 20)

Because the presence of the surface will impose ordering on the liquid, both Clm and Cls will be negativeandthereforeispositive.Weknowthattherearematerialswherethisisnotthecase. When < 0 we cannot impose the constraint that Eq.

* * t t E = lm + sl + C lm l 1 exp + C ml m + C ls l 1 exp + C sl s A l l

(1. 19) give

sm, when t = 0. < 0 is also the nonwetting condition, therefore, a flat liquid layer would be unstableinthatsituation.Thus,forthemoment,wewillconfineourinterestto>0andassume
* * that Eq. = sm sl lm = sm lm + sl C lm l C ml m C ls l C sl s = (C lm + C ls ) l

as

(1.20)holds.Theenergyofthesetwosurfacesseparatedbyathicknesstcannowbewritten

t E = A sm + ( sm + sl + lm )1 exp l
t t exp E = A lm + ( sm lm ) l + sl 1 exp l

(1. 21)

ThislastversionisexactlythecorrectiongivenbyVanDerVeen. To simplify the implementation with spherical geometry, we will make the approximation that the correctionsduetoorderordisorderpropagatingintothesolidormatrixaresmallcomparedtothe contributionsduetotheorderintheliquid.Thisapproximationwillleaveuswithsurfacetermsand thebulkliquidtermswhichwillbewrittenas

C lm l = C ls l = (1 )

(1. 22)

will be between 0 and 1 and will be approximated for the experiment in question. divides between the order imposed on the liquid due to the surface with the matrix and that due to the surfacewiththesolid.Ifthesolidandmatrixwereverysimilar,wewouldexpecttobenearone half.Theotherextremewouldbeaverydissimilarmatrixorvapor,inwhichcasewouldbesmall butnonzero. Even if the matrix has no order to impose on the liquid, the surface itself will impose some order. Therefore,willneverbezero. Goingbacktointegratingoverthesurface,butchangingtoasphericalgeometryweget

E (r )

Rr R exp r

(R + r ) exp

(1. 23)

Ristheradiusofthesurfaceandristheradiusofthepointinquestion.Thetotalenergyduetothe surface will again be found by integrating the above equation over the volume. Using the

approximationmadeabove,wewilllimitourinteresttocorrectionstothebulksurfaceenergiesthat involve.Usingthegeometryofaliquidspherewithasolidcore,theenergyofthesolidliquidand liquidmatrixsurfacesis

E = Alm lm + Asl sl + Glm + G sl

(1. 24)

(rl rc ) (rl + rc ) 2rl + (rc + l ) exp (rl + l ) exp Glm = 4rl l + (rc l ) exp l l l
(1. 25)

(rl rs ) (rl + rs ) 2rc (rl + l ) exp + (rc + l ) exp G sl = 4rc (1 ) l + (rl l ) exp l l l
(1. 26)

ThisismorecomplicatedthanthesimpleformgivenbyVanDerVeen,butittakesintoaccountthe disappearanceofthesolidliquidsurfacescorrectionwhenthesolidcoredisappears. Using the new correction to the solidliquid liquid matrix surface energies results in the following freeenergydifference.

T F = l 0 1 T 0

N l + lm Al + sl Ac sm As + Glm + G sl

(1. 27)

Thiscanbewrittenasafunctionofthenumberofatomsintheliquidlayerbyusingthetotalnumber ofatoms,thesolidandliquiddensities,andtheknowngeometrytoget

3 Ns 3 rs = 4 s 3 N s Nl rc = 4 s
3 rl = 4

(1. 28)

3
1

(1. 29)

N s Nl Nl 3 + l s

(1. 30)

Thethicknessoftheliquidlayer,thevolumes,andtheareasofeachsurfacefollowsnormallyfrom theseradii.


Figure 1-2 : Free energy difference from crystalline state as function of fraction of particles in melted layer. Data are for a lead particle r = 5.0 nm at three different temperatures. (A) T=480 K, (B) T=502 K and (C)T=540 K. [R.R. Vanfleet, J.M. Mochel, Thermodynamics of melting and freezing in small particles, Surface Science, 1995, p.p. 40-50]

Figure12showsthefreeenergydifferenceversus thefraction oftheatomsintheliquidlayerfor threedifferenttemperatures.Thedataareforanr=5nmleadparticleandthetemperaturesareas follows:(A)isT=480K,(B)is502K,and(C)is540K.For(A)and(B),thereisaminimumintheenergy foraliquidlayeroffinitethickness.(B)correspondstothelayerbeingonemonolayerinthickness. Thisminimumarisesfromthepropagationofthesurfaceorderintotheliquid,andcorrespondsto surfacemeltingaspredictedbyVanDerVeenetal.[].(A)and(B)alsoshowanotherlocalminimum with all atoms melted, at the extreme right. This second minima is separated from the surface meltedstatebyanenergybarrier.For(C),allatomsintheliquidstateistheminimumofenergy.For agivenmaterial,boththepresenceortheabsenceoftheseminimaandtheheightofthebarrierare functionsofthesizeoftheparticle,thetemperature,thesurfaceenergies,thescalelength,andthe dividingparameter.

Figure 1-3 : Melting point (M), freezing point (F), and temperature at which there is a monolayer of surface melt (S) for lead, as a function of radius of the particle. G is the region below which a cluster once disordered will remain disordered. Arrows indicate direction of temperature change when transition occurs. [R.R. Vanfleet, J.M. Mochel, Thermodynamics of melting and freezing in small particles, Surface Science, 1995, p.p. 40-50]

We have used bulk parameters in Figure 13 to calculate melting point, freezing point, and temperature where the surface melting is equal to one monolayer in thickness, as functions of particleradiusforlead.Figure13alsoshowstheregionwhereadisorderedparticle,oncecreated, would remain disordered. This is the frozen in region. The arrows indicate the direction of the temperaturechangeforwhichthetransitionwouldbeexpectedtooccur.Thecurveswerecalculated with a simple approach of choosing a particle size and then adjusting the temperature until the meltingpoint,freezingpoint,surfacemeltandfrozenintemperatureswerefound.Allthesepoints werethenstrungtogethertoformthecurvesinFigure13andFigure14.

Figure 1-4 : Melting point (M), freezing point (F), and temperature at which there is a monolayer of surface melt (S) for platinum, as a function of radius of the particle. G is the region below which a cluster once disordered will remain disordered. Arrows indicate direction of temperature change when transition occurs. [R.R. Vanfleet, J.M. Mochel, Thermodynamics of melting and freezing in small particles, Surface Science, 1995, p.p. 40-50]

Foragivensizeandtemperature,thefreeenergyasafunctionofthenumberofatomsintheliquid layeriscalculated.Thepositionanddepthofthesurfacemeltminimumisfoundandthepositionis comparedtothenumberofatomsinasinglemonolayer.Basedonthiscomparison,thetemperature iseitherraisedorloweredandthecalculationisrepeated.Thisprocessiscontinueduntilthesurface meltingtemperatureisfoundtowithinastepsize.Themelting pointisbaseduponthedifference betweenthesurfacemeltminimumandthemaximumfreeenergy. ThemainfeaturesofFigure13area differencebetween the meltingandfreezingpoints,andthe disappearance of this difference for small enough particles. In the region of differing melting and freezingpoints,thedominantfactorindeterminingthesecriticaltemperaturesistheheightofthe energybarrier.Alowertemperatureisrequiredfortheliquidtosolidtransitiontooccurthanforthe solidtoliquidtransition.Thedifferencebetweenmeltingandfreezingdisappearswhenthebarrier becomes so small that it can be easily overcome in either direction. At this point the absolute

stability becomes the important factor leading to identical melting and freezing points. Another feature of Figure 13, is the lack of surface melting for the smallest particles. This is where the meltingbarrierissurmountablebeforeasurfacemeltlayerwillform.ThelinelabeledGinFigure 13,indicatesthetemperaturebelowwhichaparticleoncedisorderedwouldstaydisordereddueto ahighfreeenergybarrier.

1.2 Phase Diagrams

Inordertodeterminethephasediagramofasmallsystemwhosethermodynamicequilibriumisa metastable one determined in part by the size of the system, isolated particles will be considered. Thetransitionsolidliquidresultsinanequilibriumbetweenthesolidanditsmelt.Further,inviewof the experimental observation that many liquids have a zero contact angle with their solids, this wettingfeatureofthesystemwillbeincorporatedinthemodelbyhavingthesolidincontactwithits melt.Eventhoughtheisolatedparticlewilllikelybecrystallineandhencefaceted,asasimplification, sphericalshapeswillbeassumed.Withtheseinitialassumptionsandconditions,thegeometryofthe systemtobemodeledisanisolatedsolidspheretransformingonheatingtoaspecifictemperature toaliquidlayersurroundingasphericalsolidcore.Theinitialstateoftheparticlebeforemeltingisa solid sphere. Upon melting the solid sphere develops a sheath of liquid which will completely surroundasmallsolidcore.ThiscaseisillustratedinFigure15.

Figure 1-5 : Schematic drawing of isolated particle before melting (complete solid) and after melting (liquid sheath exhibiting zero contact angle with the solid). [W.A. Jesser, G.J. Shiflet, G.L. Allen, J.L. Crawford, Equilibrium phase diagrams of isolated nano-phases, Mat. Res. Innovat, 1999, p.p. 211216]

1.2.1 Governing equations

First, the thermodynamic potential that is a minimum at equilibrium is considered. For an infinite reservoirincontactwithasmall,sphericalparticlethroughawallthatisrigid(nochangeinvolume of the reservoir), diathermal (heat exchanges may occur with the reservoir), and impermeable (no exchangeofmatterbetweenthesystemandreservoir),ithasbeenshown(seeprevioussection)that the Helmholtz potential is minimized at equilibrium. For the more realistic case of an infinite reservoirincontactwiththeparticlethroughawallthatisflexible,diathermal,andimpermeable,the Helmholtz potential is minimized at equilibrium in this case too, provided the reservoir pressure is zero.Accordingly,thermodynamicequationsfortheHelmholtzpotentialwillbeappliedtothemodel ofasphereofsolidisothermallymeltingtoformasphericalshellofliquidsurroundingasolidcore.

TheapproachistoexpressinanalyticalformthedifferenceFinHelmholtzenergybetweenthefinal state,aliquidsheathofthicknesstsurroundingasolidcoreofradiusRs,andtheinitialstate,asolid sphereofradiusR0.Theinitialandfinalstatescanbewrittenintermsofthechemicalpotentialat theactualpressureP,temperatureT,andcompositionXiinthesmallparticleofvolumeVandareaA and the number of atoms in the spherical particle Ni, where the subscript i refers to a particular component, and the surface energies of the solid, liquid, and solidliquid interface are s, l, sl respectively. TheHelmholtzenergyF0oftheinitialstatecanbewritten

F0 = 0 is 0 N is P0sV0s + s A0s
i

(1. 31)

Wherethesubscript0referstotheinitialstateofasolidsphereandthesuperscriptssorlreferto thesolid,orliquidphases.TheHelmholtzenergyforthefinalstateofaliquidsheathofthicknesst surroundingasolidcoreofradiusRscanbewrittenas

F f = il N il P lV l + l A l + is N is P sV s + s A s
i i

(1. 32)

The Helmholtz energy difference between the final and initial states, F is plotted against the compositionandfractionofliquidforconstantmaterialsparametersinordertodeterminewhether andwhereanyminimaexistontheenergysurface.Itwillbeassumedthataregularsolutionmodelis adequatetorepresentthebulkchemicalpotentialsandthatalinearrelationshipexistsbetweenthe surfaceandinterfacialenergiesandcomposition. Usingaregularsolutionapproachonecanincorporateinteractionparameterslfortheliquidands for the solid. These parameters are taken as temperature, pressure and composition independent. ThefinalandsimplifiedexpressionfortheHelmholtzfreeenergydifferenceFcanbewrittenas
l l l l l l s s s s F = N l kT X A ln C A + X B ln C B + X A ln X A + X B ln X B + N s kT X A ln X A + X B ln X B

N 0 A kT ln X 0 A N 0 B kT ln X 0 B + X X N + X X N X 0 A X 0 B N 0
l

+ A
l

[(

)+ A ]
s sl

l A

l B

s A

s B

)
(1. 33)

Where
l l l l s s s s X A ...N A / N l , X B ...N B / N l , X A ...N A / N s , X B ...N B / N s

(1. 34)

With
l l s s N l = N A + N B and N s = N A + N B

(1. 35)

and
l s l s N 0 A ... X A N l + X A N s , N 0 B ... X B N l + X B N s

(1. 36)

Forconvenience C A, B ... s X s / l X l

bulk

representsthebulkcompositionsandactivitycoefficients

forcomponentsAandBrespectivelyforthecaseofthebulkphasediagram. Therelationshipbetweeninteractionparameterandactivitycoefficientis

(1 X i )2 s ,l

= kT ln is ,l

(1. 37)

1.2.2 Mathematical description for nano-phases of Sn-Bi alloys

TofindlocalminimaintheHelmholtzfreeenergydifferencebetweenasphericalsolidparticleanda liquid sheath surrounding a solid core, equation
l l l l l l s s s s F = N l kT X A ln C A + X B ln C B + X A ln X A + X B ln X B + N s kT X A ln X A + X B ln X B l l s s N 0 A kT ln X 0 A N 0 B kT ln X 0 B + l X A X B N l + s X A X B N s X 0 A X 0 B N 0

+ A l s + A s sl

[(

(1.

33)isplottedasafunctionofcompositionofthesolidcoreandfractionofliquidpresentinthetwo phasestatetherebygeneratinganenergysurface.Thecalculationrequiresanumberoftermstobe specified.Typicallyoneshouldhavedataforthedependenceofinterfaceandsurfaceenergiesasa function of composition and even the interaction parameter used in the regular solution approximation can be limited to a fixed composition range. In this section the calculations for a binary phase diagram of tin and bismuth will be given. The solidus and liquidus lines of the Birich andSnrichsidesofthebulkphasediagramprovidethereferencestateofthebulkphasediagram from which the small particle system of BiSn is calculated. For the Snrich side of the bulk phase diagramtheequationofthesolidusiscloselyapproximatedby
s X Sn = 5.73 10 6 T + 6.62 10 3 T 0.883

(1. 38)

Table 1-1 : Values of parameters employed for the Bi-Sn binary phase diagram. [W.A. Jesser, G.J. Shiflet, G.L. Allen, J.L. Crawford, Equilibrium phase diagrams of isolated nano-phases, Mat. Res. Innovat, 1999, p.p. 211-216]

andthatoftheliquidusby
l X Sn = 1.76 10 6 T 2 + 6.23 10 3 T 1.70

(1. 39)

whilefortheBirichsideofthephasediagramtheequationofthesolidusistakenas
s X Bi = 3.01 10 3 T + 1.639

(1. 40)

andthatoftheliquidusas
l X Bi = 1.204 10 4 T + 0.06559

(1. 41)

Thevaluesoftheparametersusedinequation2maybefoundinTable11. When the above parameters are substituted

F = N kT X ln C A + X ln C B + X ln X + X ln X
l l A l B

l l s s N 0 A kT ln X 0 A N 0 B kT ln X 0 B + l X A X B N l + s X A X B N s X 0 A X 0 B N 0

+ A l s + A s sl

[(

l A

l A

l B

l B

)+ N

s kT X ln X + X ln X B s A s A

into

equation
s B

(1.

33), a F surface versus composition and fraction liquid may be plotted and analyzed for the presenceoflocalminima.AsanillustrativeexampleofatypicalFsurfaceFigure16ispresentedfor abinarybismuthalloywithleadfortwotemperatures.

Figure 1-6 : Helmholtz free energy surface plotted for the case of a binary bismuth alloy as a function of composition and fractional amount of liquid for two temperatures. a) intermediate temperature corresponding to a metastable solid-liquid equilibrium, b) elevated temperature showing a stable equilibrium corresponding to complete liquid. [W.A. Jesser, G.J. Shiflet, G.L. Allen, J.L. Crawford, Equilibrium phase diagrams of isolated nano-phases, Mat. Res. Innovat, 1999, p.p. 211-216]

Here one finds a relative minimum whose location is indicated by the broad dot and an absolute minimumlocatedatthepointwhereonlyliquidexists.Thesetwominimaareseparatedbyasaddle point maximum that prevents the system from jumping this energy barrier. Accordingly, the temperatureofthisplotcorrespondstoametastablesolidliquidequilibrium.Atsignificantlylower temperaturesnolocalminimumexistsandcompletesolidisthestablestate.Atsignificantlyhigher temperatures,againnolocalminimumexistsandthesaddlepointmaximumdisappearssothatthe freeenergysurfaceisonethatcontinuouslydecreasesasonemovestowardthepointofminimum free energy which corresponds to complete liquid. Figure 16 b) represents this latter condition in which the minimum is indicated by the broad dot. There is no progression of the local minimum continuouslytotheconditionofcompleteliquid.Ratherthereisadiscontinuous,abruptshiftofthe minimum from a location away from the point of complete liquid to the point of complete liquid once the saddlepoint maximum disappears. Physically this corresponds to heating the twophase particletoatemperatureatwhichadiscontinuoustransitionoccursfromthestateofaliquidsheath

surroundingasolidcoretothestateofcompleteliquid.Suchanabrupttransitionisexperimentally observedforthisbinaryalloyaswellasforthesolidelementstinandbismuthbothofwhichexhibit nostablesolidliquidequilibrium.

1.2.3 Phase diagram for isolated nano-phases of Sn-Bi alloys

A temperaturecomposition phase diagram for isolated nanospheres of SnBi alloys can be constructedasafunctionofsizeoftheisolatedsphericalparticle.Thisisaccomplishedbytrackingof thepositionofthelocalminimumintheHelmholtzfreeenergysurfaceasafunctionoftemperature forseveralvaluesofradiusoftheinitialsolidsphere.Theresultantphasediagramfortheliquidsolid phaseequilibria,i.e.,thelocationoftheliquidusandsoliduslinesareshowninFigure17forthe case ofasphericalparticle40nmindiameter.

Figure 1-7 : Phase diagram for the binary alloy Sn-Bi. The bulk phase diagram is shown superimposed on the phase diagram for isolated spheres of alloy 40 nm in diameter. The nano-particle phase diagram is the shaded region as given by the thermodynamic calculations and the data points for each of eight compositions as determined from in-situ TEM measurements. [W.A. Jesser, G.J. Shiflet, G.L. Allen, J.L. Crawford, Equilibrium phase diagrams of isolated nano-phases, Mat. Res. Innovat, 1999, p.p. 211-216]

This Figure also includes the phase diagram for bulk SnBi alloys and the experimentally measured liquidus and solidus lines for the isolated spherical particles. The experimental data reported here weremeasuredinsideatransmissionelectronmicroscopemodifiedforultrahighvacuumsothatin situdepositionoftheisolatednanospherescouldbeperformed.Thesenewdatashowthatforthe Snrich side of the phase diagram, the liquidsolid twophase field pinches off to a line thereby indicating no stable equilibrium between the liquid and solid phases in this region. There was no detectablepinchingoffobservedontheBirichsideofthediagram. Inadditiontothepinchingoffofthetwophasefieldnearthecompositionofpuretin,therearetwo othernoteworthyfeaturesinthephasediagram.First,onenoticesthatthereisasubstantialincrease insolubilityforthenanoparticlesascomparedtothatinthebulkalloy.Thesolubilitylimitoftinin bismuthincreasedfrom1.5%(bulk)toabout43%inparticlesofradius20nm.Astrongincreasealso occurredinthetinrichphase.

Second, because the initial melting event is observed to be discontinuous (the liquid sheath forms withaminimumfinitethicknessofabout2nm)andthefinalmeltingeventisalsoadiscontinuous eventwiththeisothermaljumpfromathickliquidsheathsurroundingasolidcoretoacompletely liquid sphere, the location on the phase diagram of the locus of the temperatures at which these discontinuous transitions occur do not represent liquidus and solidus lines that can be used to constructthetielines.Theconventionaltielinesthatdescribemassconservationandareusefulfor leverrulecalculationsextendisothermallybeyondthetwophaseregions.Ifatielineisconstructed betweentheliquidusandsoliduslinesshownonthephasediagram,itsendsdonotcorrespondto either the solid composition or the liquid sheath composition. In order to account for these compositions a longer tie line is required. As the temperature is increased, the tie line changes its length. The two ends of the tie line demark the compositions of the liquid and solid phases and sweepouttwoareasonthephasediagrambothofwhicharedetachedfromthedrawnliquidusand soliduslinesthatdemarktheextentofthetwophasefield.ThisfeatureisshowninFigure18.

Figure 1-8 : Sn-rich segment of a Sn-Bi phase diagram for an isolated sphere of radius 20 nm showing that the areas swept out by the ends of the tie lines are detached from the two-phase region. Note that the two-phase regions and the ends of the tie lines pinch off at about 5% Bi. [W.A. Jesser, G.J. Shiflet, G.L. Allen, J.L. Crawford, Equilibrium phase diagrams of isolated nano-phases, Mat. Res. Innovat, 1999, p.p. 211-216]

Onecanincorporatethesizedependenceofthephasediagrambymakingathreedimensionalplot ofliquidusandsolidustemperaturesasafunctionofbothcompositionandsize.Onecanincorporate a size variable in the phase diagram by recognizing that the Helmholtz free energy depends upon pressurewhichexhibitsadiscontinuityPacrossacurvedsurfaceof

P = 2 / R (liquids)

(1. 42)

Accordinglytheequilibriumlinesshiftapproximatelylinearlywithreciprocalradius. Theaxesofthethreedimensionalphasediagramthenbecometemperature,reciprocalradius,and composition.Figure19showsa3DphasediagramfortheSnBialloysystem.


Figure 1-9 : 3-D phase diagram for an isolated tin-bismuth alloy sphere showing the size dependence of the liquidus and solidus lines as well as the eutectic isotherm over the range of reciprocal radius 0 nm1 to 0.05 nm1. Over this size range the eutectic temperature changes from 412 to 320 K and the solubility of Sn in Bi increased from 1.5% to 43%. The dashed lines on the left margin are reference lines parallel to the 1/R axis. The solid lines on the left margin are projections of the melting and eutectic temperatures. The solid lines on the bottom margin are projections of the solubility limits and the eutectic composition. [W.A. Jesser, G.J. Shiflet, G.L. Allen, J.L. Crawford, Equilibrium phase diagrams of isolated nano-phases, Mat. Res. Innovat, 1999, p.p. 211-216]

1.3 Crystal-lattice inhomogeneous state

Innanoparticlesandnanocrystallitiesthefractionofsurface(orinterface)atomsis large. Then, appreciable distinctions between nanoobjects and massive bodies in lattice parameters and the types of atomic structures are plausible. These difference manifest themselves in normal and tangential relaxations of nanoparticles.(54) An atom on the surface hasfewerneighboursthanoneinthevolume,alltheneighboursoftheformerbeinglocated ononesideonly.Thisbreakstheequilibriumoftheinteratomicforcesandgivesrisetoboth thechangeofinteratomicspacing(normalrelaxation)andtensiledeformationswhichsmooth verticlesandedges(tangentialrelaxation). A rough estimate of the average distortion of the interatomic distances a in nanoparticlescausedbysurfacetensionisshownbelow:(55)

a = 2 a r'

(1. 43)

where 2 is the numerical coefficient of the order of 1 (in the case of isotropic spherical particlesitmaybeestimatedas 2/3),isthevolumecompressibilitycoefficient.Accordingto theestimate,thelatticeconstructionisaboutseveraltenthsofapercentattypicalvaluesof parameters~1011m3/J,1J/m2fornanoparticleswithradiusr~10nm. Hereitshouldbementionedthatparametersenteringthisformulaare,inturn,size dependent.Thesurfaceenergyofnanoparticles,forexample,dependsonrasfollows:(56)*

2 a a ' = 1 3 + 4 + ... r r

(1. 44)

wherenumericalcoefficient1011m3/J,1J/m2.Accordingtothisestimatethesurface energy of nanoparticles decreases as r decreases which is intuitively clear, since both the number of bonds formed by the surface atoms and their bond energy are reduced as size decreases.Sizedependentcorrectionsare,inageneralcase,functionsoftemperature.(59)The difference in the lattice parameters of contacting nanoparticles may seriously influence the processofinterparticlesliding. For several decades contradictory experimental results were calling into questioneq.

a = 2 a r'

(1. 43) for the contraction of interatomic spacing. Some of

theseambigiousresultsarecausedbyexperimentalartifactsanddifficulties,whileothersare associated with the complicated spatial distribution of lattice parameter distortions. In the absenceofoxidelayers,(60)absorbedimpurities,etc.,thereisanaverageoverallcontractionin the lattice parameter of a nanoparticle. However, interatomic spacing in the outer part of nanoparticles may be expanded despite the contracted interior.(61) Moreover, the degree of distortion varies with crystallographic as a result of the anisotropy of the volume compressibility coefficient.(62,63) In summary, the experimental and theoretical results show that the average contraction of the lattice parameter in the nanoparticles is inversely proportionaltonanoparticlesradiusr.

1.4 Concentrational inhomogeneity

The spatial distribution of a second component over the bulk of heterogeneous nanoparticlesandnanocrystallitiesmaycontrastwiththatforanalogousmacrocrystals.Anon uniform distortion of the crystal lattice in nanovolumes (see the previous section) and the comparabilityofthewidthofsegregatedlayerss,withtheradiusrmaybothbringaboutan inhomogeneousdistributionofthesecondcomponent. One may estimate the characteristic of a nanoobject when the segregated layer occupieshalfitsvolume.Asimplegeometricalconsiderationgivesthefollowingrelationship:(65)

rs = 5 s

(1. 45)

Where the numerical coefficient 5 is of the order of unity. For spherical nanoparticles (nanocrystallites) it is close to 5. Using s 3a as typical width of the segregated layers the corresponding diameter of nanoparticles (nanocrystallites) is d ~10nm. Thus, under some conditions the multicomponent nanocrystals with grains of the size may be considered massivesegregatedlayers. Ifthemaincontributionofdrivingforceforsegregationisthemismatchinatomicradii ofthematrixandforeignatoms,sandr*smaybeestimatedforaheterophasenanocrystal. The mismatch may be described by the relative difference s = (af / a 1) where af is the effectiveradiusofaforeignatom.Ifthenanocrystallitesinananocompositethecomponents

of which have shear moduli G and G are elastically isotropic and possess nonslipping boundaries,thecharacteristiclengthl*slisasfollows:(65)

s2 a 3 (G G ') l s = 6 a kT

1/ 3

(1. 46)

Where the numerical coefficient 6 3.5, k is the Boltzman constant, and T is temperature. This estimate was obtained by equation kT to the energy of the elastic interaction of the foreign atom with the nonslipping interface. Provided that other driving forces for segregation (heat of mixing, the difference between surface energies of the component)arenegligibleorcanceleachother,whenananocrystallitehasashearmodulusG less than that G of the neighbouring crystallites segregation in that nanocrystallite becomes impossible. So, the concentration of foreign atoms in the vicinity of interfaces diminishes in elasticallysofternanocrystallites. Segregationeffectschangethecompositionoftheinteriorofnanoparticles.Itcanbe (66) shown that the average concentration c of the second component for a twocomponent nanoparticlevarieswithitssize,followingtherelationship:

c = cb + 8 (c s cb )

s r

(1. 47)

wherethenumericalcoefficient83,csandcbareconcentrationsinthesurfacelayer of width s and in bulk of nanoparticles, respectively. If concentrations cs and cb were independent of r over the whole range of sizes, this relationship would be of a general character.Whensizerisnottoosmall,onemayestimatethechangeintheconcentrationof foreignatomsinthesmallerthesizer,thestrongertheconcentrationalinhomogeneitywhich may reach as much as 10%. This conclusion agrees with the numerical simulations of small atomicclusters(67)andexperiments(68)withCuNinanoparticles. Certainconclusionsaboutthecharacteroftheindependenceofsurfaceconcentration csonnanoparticle(nanocrystallite)radiusrcanbedrawnonthebasisofsimplemassbalance considerations. In the limit of small nanoparticles, when all the atoms belong to the surface, the surface composition in an ensemble of nanoparticles would be identical to the average composition in the massive alloy. (69) Such a decrease of the surface segregation has been observedexperimentally. (70)Intheoppositeofverylargeparticlestheywillbehavelikesemi infinitecrystals,andthesurfacecompositionwouldbesimilartothatobtainedinmicroscopic samples. In the intermediate range of sizes, where the number of surface sites is not a negligibly small fraction of the total number of sites available in the particle volume, there existsaregimewheresegregationtothesurfacetendstodecreasethebulkconcentrationof thesegregant. The depletion of the segregated atoms, which would follow from elementary mass balanceconsiderations,maybeimpossibleifthephysicaland/orchemicalpropertiesaresize dependent. For instance, the change in the surface energy (see eq.
2 1 3 a + 4 a + ... '= r r

(1. 44)) may modify the segregation effect. The lattice

contraction(eq.

a = 2 (1. 43)) and the external pressure also affect segregation a r'

phenomena. Intheireffectsonsegregation,applyingexternalpressureandcontractingthecrystal latticeofnanoobjectsaretoacertaindegreeequivalenttothedifferenceintheatomicradii ofthesegregantandmatrixatoms, (71)whichisdescribedbytherelativesizemismatchs.In fact,externalpressurePisconnectedwiththechangeintherelativesizemismatchsbythe simplerelationship(cf.eq.

a = 2 a r' s =

(1.43)):

P ( 1 2 ) 3

(1. 48)

where 1 and 2 are the volume compressibility of the segregant and the solvent, respectively. The hydrostatic stress include by surface tension, approximated as 2 / l, may, thus, change the relative size mismatch by s. According to the wellknown HumeRothery rule(iftherelativesizemismatchexceedsthe15%limit,solidsolubilitywillberestricted (72))a criticalsizel*solshouldexist,abovewhichthesolidsolubilityremainsqualitativelythesame:

sol = 2

( 1 2 ) 0.15 s

(1. 49)

1.5 References
C.X. Wang, G.W. Yang, Thermodynamics of metastable phase nucleation, Materials Science and Engineering,2005,p.p.157202 T.L.Hill,ADifferentApproachtoNanothermodynamics,Nanoletters,2001Vol.1,N5,p.p.273275 C. Beck, Nonadditivity of Tsallis entropies and fluctuations of temperature, Europhysics Letters, 2002,p.p.329333 R.R. Vanfleet, J.M. Mochel, Thermodynamics of melting and freezing in small particles, Surface Science,1995,p.p.4050 W.A. Jesser, G.J. Shiflet, G.L. Allen, J.L. Crawford, Equilibrium phase diagrams of isolated nano phases,Mat.Res.Innovat,1999,p.p.211216