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This book represents a detailed and systematic account of the basic principles, developments and applications of the theory of nucleation.

The formation of new phases begins with the process of nucleation and is, therefore, a widely spread phenomenon in both nature and technology. Condensation and evaporation, crystal growth, electrodeposition, melt crystallization, growth of thin films for microelectronics, volcano eruption and formation of particulate matter in space are only a few of the processes in which nucleation plays a prominent role.

The book has four parts, which are devoted to the thermodynamics of nucleation, the kinetics of nucleation, the effect of various factors on nucleation and the application of the theory to other processes, which involve nucleation. The first two parts describe in detail the two basic approaches in nucleation theory - the thermodynamic and the kinetic ones. They contain derivations of the basic and most important formulae of the theory and discuss their limitations and possibilities for improvement. The third part deals with some of the factors that can affect nucleation and is a natural continuation of the first two chapters. The last part is devoted to the application of the theory to processes of practical importance such as melt crystallization and polymorphic transformation, crystal growth and growth of thin solid films, size distribution of droplets and crystallites in condensation and crystallization. The book is not just an account of the status quo in nucleation theory - throughout the book there are a number of new results as well as extensions and generalisations of existing ones.

Publisher: Elsevier ScienceReleased: Feb 22, 2000ISBN: 9780080537832Format: book

**Part 1 **

Thermodynamics of nucleation

The physical nature of the phase transitions of first order can be illustrated sufficiently well with the aid of an analysis of the behaviour of the van der Waals (VDW) fluid which is characterized by the following equation of state [**Guggenheim 1957; Landau and Lifshitz 1976] **

Here *P *and *V *are, respectively, the pressure and the volume of the fluid, *M *is the number of molecules (or atoms) in this volume, *T *is the absolute temperature, *k *is the Boltzmann constant, and *a*’ and *b*’ are material constants accounting, respectively, for the molecular interactions and the molecular volume. These two constants can be expressed in terms of the critical pressure *P*cr, volume *V*cr and temperature *T*cr of the VDW fluid by using the relations [**Guggenheim 1957; Landau and Lifshitz 1976] **

For this reason, with the help of the reduced pressure *P*’ – *P/P*cr, volume *V *= *V/V*cr and temperature *T*’ = *T/T*cr**eq. (1.1) passes into the reduced VDW equation **

**(1.3) **

which, according to the law of corresponding states, is universal in the sense that it does not contain explicitly the material constants of the fluid [**Guggenheim 1957; Landau and Lifshitz 1976]. **

Let us now consider the VDW fluid when it is kept at constant temperature *T *and pressure *p*, the respective reduced pressure being *p*’ = *p/P*cr. The fluid will be in *stable *thermodynamic equilibrium (TDE) only when it occupies a volume at which its Gibbs free energy *G *= *F + pV *is minimum. By definition [**Guggenheim 1957], the Helmholtz free energy F is given by F = − P(V) dV so that using eq. (1.3) leads to **

where *G*ref is a reference energy. From the conditions for minimum

it follows that the volume at which the fluid is in stable TDE is the solution of the algebraic equation

**(1.5) **

corresponding to such a portion of the VDW isotherm **(1.3) for which (∂ P’/∂V’)T < 0. If the solution of eq. (1.5) falls in the range of volumes for which (∂P’/∂V’)T > 0, it corresponds to unstable TDE (then G is maximum) and is physically irrelevant. **

**Figure 1.1a shows P’(V’) isotherms of the VDW fluid calculated from eq. (1.3) at a given subcritical temperature (T′ = 0.85, the solid curve) and at the critical temperature (T′ = 1, the dashed curve). The respective G(V’) dependences at three different subcritical pressures (p’ = 0.470, 0.505 and 0.540, the solid curves) and at the critical pressure (p’ = 1, the dashed curve) are drawn in Fig. 1.1b according to eq. (1.4) with an arbitrarily chosen Gref = 2MkTcr. The descending branches of the subcritical P’(V’) isotherm at smaller and larger volumes and the minima of G on the left and on the right correspond to more and less condensed fluid which can be called liquid and gas, respectively. The thermodynamically unstable states of the fluid are limited by the minimum e and the maximum g of the subcritical P’(V’) isotherm. At the critical temperature points e and g merge into a single point c (i.e. the two extrema of the P’(V’) dependence degenerate into a single one), and connecting all points e and g for the subcritical temperatures results in a dome-shaped curve called spinodal (the dotted curve S). The ordinates of points e and g represent the values of the spinodal pressures p’l,s(T’) and p’g,s(T’) of the liquid and the gas, respectively. **

**Fig. 1.1 **Dependence of (a) the reduced pressure and (b) the Gibbs free energy of VDW fluid on the reduced volume of the fluid: solid curves – **eqs (1.3) and (1.4) at p’ = 0.470, 0.505, 0.540 (as indicated) and T’ = 0.85; dashed curves – eqs (1.3) and (1.4) at p’ = 1 and T = 1. Nucleation-mediated first-order phase transition occurs only for P’, V’ values corresponding to the shaded area between the binodal and spinodal (the dotted curves B and S, respectively). The equality of the hatched areas ‘bdef’ and ‘fghi’ defines the position of the dot-dashed line ‘bfi’ of gas/liquid coexistence. **

As seen from **Fig. 1.1a, for values of p’ between the spinodal pressures p’l,s(T’) and p’g,s(T’) eq. (1.5) has three solutions, two of which are physically interesting (points a and h, b and i, d and j), since they correspond to a liquid or a gas in stable TDE. The minima of G for the liquid and the gas state, however, are equally deep (see curve 0.505 in Fig. 1.1b) only at a certain pressure pe(T), the respective reduced pressure being p’e = pe/Pcr. That is why, at p = pe the liquid and the gas can coexist as separate phases if they are in contact with each other. The liquid and the gas are then in phase equilibrium, and pe is the equilibrium (more precisely, the phase-equilibrium) pressure of the fluid. The reduced phase-equilibrium volumes V’l,e (T′) of the liquid and V’g,e (T′) of the gas are those solutions of eq. (1.5) at p’ = p’e that correspond to points b and i in Fig. 1.1a, and connecting all these points for the subcritical temperatures results in another dome-shaped curve called binodal (the dotted curve B). **

In the general case when *p*’ ≠ *p*’e, but satisfies the condition *p*’l,s < *p*’ < *p*’g,s, the two states of the fluid in stable TDE (see points a and h and points d and j in **Fig. 1.1a, which represent graphically the respective two solutions of eq. (1.5)) correspond to the two minima of G which, however, are of different depth (Fig. 1.1b). This means that while in the state of the deeper minimum the fluid is in truly stable TDE; in the other state it is only in metastable TDE. The corresponding transition from metastable to truly stable thermodynamic state is known as phase transition of first order, and the usual process by which this transition begins is nucleation of the new phase within the old (or the parent) phase. Since the metastable states of the VDW fluid are in the region between the binodal and the spinodal (the shaded area between curves B and S in Fig. 1.1a), clearly, it is meaningful to speak of a first-order phase transition and, hence, of nucleation only when the p′, V’ and T′ values correspond to this region. **

For the sake of completeness, we must note the well-known thermodynamic definition of the first-order phase transitions according to which at the point of phase equilibrium the chemical potentials of the old and the new phases are equal, but their derivatives of first order are not [**Ehrenfest 1933]. Figure 1.2 depicts the pressure dependence of the chemical potential μ ≡ G/M of the VDW fluid and its derivative (∂μ/∂p’)T’ calculated at T = 1 (the dashed curves) and T’ = 0.85 (the solid curves) from eq. (1.4) with the help of (1.3) and the already used Gref = 2MkTcr. Indeed, it is seen that when T’ = 0.85, the conditions for first-order phase transition are fulfilled at p’ = p’e = 0.505 (μg and μ1 are the chemical potentials of the gas and the liquid, respectively): **

Since the μg and μ1 derivatives are equal to the volumes occupied at *p*’e by a molecule in the gas and in the liquid, respectively [**Guggenheim 1957; Huang 1963], the above inequality means physically that at the point of first-order phase transition the density of the VDW fluid changes abruptly. This is illustrated by the dot-dashed line connecting points i and b in Fig. 1.2b. Figure 1.2 shows also that at T’ = 1 both μ and (∂μ/∂p’)T’ are continuous functions of p’, which reflects mathematically the known fact that at or above the critical temperature occurrence of first-order phase transition is impossible. **

**Fig. 1.2 **Pressure dependence of (a) the chemical potential and (b) the pressure derivative of the chemical potential for VDW fluid at T’ = 0.85 (solid curves) and T’ = 1 (dashed curves) according to **eqs (1.3) and (1.4). The dot-dashed line ‘bi’ illustrates the difference between the volumes occupied by a VDW molecule in the gas and liquid at phase equilibrium. **

Clearly, the equilibrium pressure *p*e is an important thermodynamic characteristic of the fluid, for it determines the direction of the phase transition: while for *p *> *p*e the gas-to-liquid transition takes place (the gas is then metastable (**Fig. 1.1b) and μg > μ1 (Fig. 1.2a)), when p < pe the liquid-to-gas transition occurs (the metastable phase then is the liquid (Fig. 1.1b) and μ1 > μg (Fig. 1.2a)). To find pe we can use the condition for equality of the values of the two minima of G at p’ = p’e, which is equivalent to the condition μg(P’e) = μ1 (P’e). Setting equal the right-hand sides of G from (1.4) at p’e, V’g,e and p’e, V’l,e, we obtain the exact formula **

In view of **(1.3), this equation can be represented in the equivalent form **

which expresses analytically the known Maxwell rule [**Guggenheim 1957; Huang 1963] for the equality of the hatched areas ‘bdef’ and ‘fghi’ on the P’(V’) diagram in Fig. 1.1a. Equation (1.7) is a general thermodynamic relation defining the equilibrium pressure of whatever phase with a given equation of state in the form of P(V) isotherm with VDW loops. **

**Equations (1.6) and (1.7) give p’e implicitly, since V’g,e and V’l,e themselves, being the solutions of (1.5) at p’ = p’e, depend on p’e and T’. However, when T’ is sufficiently less than 1 (i.e. for low enough subcritical temperatures), we have VV’g,e ≈ 8T’/3p’e (the gas is nearly ideal) and V’l,e = constant ≈ 1/2 (the liquid is almost incompressible and its reduced volume is close to 1/2, see Fig. 1.1a). Equation (1.6) then leads to the approximate expression **

In view of **(1.2), this expression can be given the form **

which allows approximate calculation of the phase-equilibrium pressure of the VDW fluid when the material constants *a*’ and *b*’ are known. **Equation (1.9) corresponds to the integrated Clapeyron—Clausius formula for the temperature dependence of the vapour pressure of condensed phases [Glasstone 1956]. **

The above considerations should be sufficient to illustrate the physical nature of the phase transitions of first order. Although the conclusions and the formulae obtained are the result of an analysis of a concrete system, the VDW fluid, most of them are of general validity. Worth remembering is, especially, that (i) first-order phase transition occurs when an old metastable phase transforms into a new truly stable one, (ii) the thermodynamic limit of metastability is at the spinodal point (if this exists) and it is, therefore, meaningless to speak of a first-order phase transition and, hence, nucleation when the values of the parameters used to characterize the state of the old phase are not between the corresponding binodal and spinodal values, and (iii) phase equilibrium or coexistence between the old and the new phases is possible when the corresponding minima of the free energy of these phases are equally deep, i.e. when

**(1.10) **

Here μold,e and μnew,e are, respectively, the chemical potentials of the old and the new phases at phase equilibrium, and μe, the *equilibrium *chemical potential, is the abbreviated notation for either of them.

In the preceding Chapter we have seen that when *p*’ ≠ *p*’e (but is limited between *p*’l,s and *p*’g,s), the VDW fluid can be in two states with differently deep minima of *G*. Obviously, the transition from metastable (e.g. gas) to truly stable (e.g. liquid) state occurs because of the necessity for the fluid to occupy a lower—energy state. The same holds true for any other metastable phase and for this reason, in general, the thermodynamic driving force for the first-order phase transition and, hence, for the nucleation process, is the quantity

known as *supersaturation*. Physically, the supersaturation Δμ is the gain in free energy per molecule (or atom) associated with the passage of the phase from the minimum with higher Gibbs free energy *G*old to the minimum with lower Gibbs free energy *G*new (μold and μnew are, respectively, the chemical potentials of the old and the new phases at the corresponding minima).

**Equation (2.1) allows expressing Δμ through experimentally controllable parameters in various particular cases. As an example, let us consider the transition of the VDW fluid from gas (old phase) to liquid (new phase), which occurs at reduced pressure p’ satisfying the condition p’e < p’ < p’g,s (this corresponds to transition from point h to point a in Fig. 1.1). Using eq. (1.4) yields **

Here *V*’g (*p*’ *T*’) and *V*’(*p’, T*’) are, respectively, the reduced volumes of the gas and the liquid, at which *G *has a minimum (i.e. the abscissae of points h and a in **Fig. 1.1). Substitution of Gold and Gnew from above into (2.1) leads to the exact formula **

With the help of **(1.6) this formula can be given the equivalent form **

which shows that Δμ = 0 at *p*’ = *p*’e. Indeed, at phase equilibrium there exists no driving force for first-order phase transition and, hence, for nucleation and then it is said that the old phase is *saturated*. Obviously, nucleation is impossible as well when Δμ < 0: the old phase is then *undersaturated *(its *G *minimum is lower than that of the new phase and μold < μnew).

If *T*’ is kept constant, Δμ can be controlled through the pressure *p*’ or the volume *V*’ of the VDW fluid. In the former case the explicit dependence of Δμ on *p*’ is obtained from **(2.2) or (2.3) upon expressing V’g and V’1 as functions of p’, and V’g,e and V’l,e as functions of p’e by using the equation of state, eq. (1.3), of the VDW fluid. In the latter case eq. (1.3) has again to be used, but for representing p’ and p’e in (2.2) and (2.3) as functions of V’g and V’g,e, respectively. It is worth having an approximate formula for Δμ valid for low enough subcritical temperatures and for pressures sufficiently below the spinodal pressure p’g,s. Under these conditions 3V1, 3V1, V’ ≈ V’l,e ≈ Mv0/Vcr (the liquid is almost incompressible) and V’gP’ ≈ V’g,ep’e (8/3) T′ (the gas is nearly ideal). In view of the relation 3MkTcr = 8PcrVcr, it then follows from (2.3) that, approximately, **

where *v*0 is the molecular volume.

Let us now see how Δμ can be determined in some important cases of nucleation during first-order phase transitions in real systems (see also [**Bohm 1981]). In finding the respective formulae for Δμ we shall use eq. (2.1) and known expressions for the chemical potentials μold and μnew of the old and the new phases. **

In this case the dependence of the chemical potentials of the old phase (vapours) and the new phase (liquid or solid) on the actual pressure *p *of the vapours is given by [**Guggenheim 1957] **

**(2.5) **

**(2.6) **

where *pe*(*T*) is the phase-equilibrium pressure (i.e. the pressure of the saturated vapours of the liquid or the solid), and μe = μold(*p*e) = μnew (*p*e) is the chemical potential of the vapours and of the liquid or the solid at phase equilibrium. The above two expressions hold true provided the vapours behave as ideal gas, and the liquid or the solid is incompressible. Combining **(2.1), (2.5) and (2.6) leads to (e.g. [Toschev 1973a]) **

which in most cases can be approximated sufficiently accurately by [Zettlemoyer 1969]

**(2.8) **

since usually *v*0*p**kT *and the second summand in **(2.7) is negligible. **

Worth noting is the coincidence of **eqs (2.4) and (2.7). It is not accidental, since these two equations are derived under the same assumptions for the gas and the liquid phases and since in many respects the VDW fluid is an acceptable model for real fluids. That is why, if for the determination of Δμ during condensation of vapours into a liquid it is necessary to account for the effects of gas non-ideality and/or liquid compressibility, instead of (2.7) or (2.8) one can use the full equations (2.2) or (2.3), which allow for these effects in the scope of the VDW model. The vapour non-ideality can be taken into account [Guggenheim 1957] also by replacing the p/pe ratio in the logarithm of eqs (2.7) and (2.8) with the ratio fv/fv,e of the actual and the equilibrium fugacities fv and fv,e of the vapours. **

In condensation of molecular beams onto a substrate the experimentally controllable parameter usually is the impingement rate *I *of molecules (per second per m²) rather than the pressure *p*. As *I *= *p*/(2π*m*0*kT*)¹/², in this case Δμ is given approximately by **(2.8) in the form [Sigsbee 1969; Lewis and Anderson 1978] **

**(2.9) **

where *I*e = *p*e/(2π*m*0*kT*)¹/² is the equilibrium value of the impingement rate, *m*0 and *T *being, respectively, the mass of a molecule and the substrate temperature. This formula is valid when thermal equilibration of the deposited molecules with the substrate takes a sufficiently short time [**Sigsbee 1969]. **

In this case the old phase is the liquid or the solid, and the new phase is the vapour. Accordingly, **eqs (2.5) and (2.6) are to be used in (2.1) with exchanged subscripts ‘old’ and ‘new’. This leads again to Δμ from eq. (2.7), but with changed sign of its r.h.s.: **

*p *being the actual pressure of the liquid in boiling or of the vapour in evaporation or sublimation. When *v*0*p**kT*, Δμ can be approximated by

In this case the old phase is constituted of dissolved molecules which along with a solvent (treated as an inert medium) represent a liquid or solid solution, and the new phase is the liquid or solid condensate of the dissolved molecules. Rather than the pressure, the experimentally controllable parameter usually is the actual solute activity *a*, and the dependence of *p*old on *a *is of the form [**Guggenheim 1957] **

**(2.11) **

where *a*e(*T*) is the equilibrium activity, i.e. the activity at which the solute and the condensate are in phase equilibrium. Since μnew is practically *a*-independent, approximately,

**(2.12) **

Combining the above two expressions with **eq. (2.1) yields [Walton 1969a; Söhnel and Garside 1992] **

**(2.13) **

For sufficiently dilute solutions *a *and *a*e can be replaced, respectively, with the actual and the equilibrium concentrations *C *and *C*e(*T*) of the solute (*C*eis also known as *solubility*) and **(2.13) becomes [Nielsen 1964; Söhnel and Garside 1992] **

**(2.14) **

It is worth noting that **eqs (2.13) and (2.14) cover also the case of decay of solids by ‘condensation’ of atomic vacancies (the old ‘phase’) ‘dissolved’ in them [Hirth and Pound 1963]. This ‘condensation’ leads to the appearance of macroscopic cavities (the new ‘phase’) in the solid. Then a, ae and C, Ce are the actual and the equilibrium activities and concentrations of the vacancies in the solid. **

**Equations (2.13) and (2.14) are applicable when the solute molecules in the solution are not dissociated into ions. In many cases, however, this is not the case and then, according to the condition for chemical equilibrium [Guggenheim 1957; Landau and Lifshitz 1976], **

**(2.15) **

where *vi *is the number of *i*th species in the molecule (*i *= 1, 2, …, *k*), and μ*i *is the chemical potential of the *i*th species in the solution. Using **(2.11) in the form **

leads to the following expression for μold:

Here *ai*, is the actual activity of the *i*th species in the solution, *ai*,e and μ*i*,e are the equilibrium activity and chemical potential of the *i*th species, and

Thus, with the help of **eq. (2.12) and the above expression for μold, it follows from (2.1) that **

**(2.16) **

are, respectively, the actual and equilibrium activity products of the solute [**Nielsen 1964; Söhnel and Garside 1992]. **

As seen, **eq. (2.16) is a generalization of eqs (2.13) and (2.14) (for sufficiently dilute solutions Π and Πe are the products of the corresponding concentrations of ith species, Πe being the so-called solubility product). An interesting point concerning eq. (2.16) is that even when the solution is supersaturated with respect to only one of the species in the solution, but is saturated with respect to the others (e.g. a1/a1,e > 1, a2,e/a2,e = a3/a3,e = … = ak/ak,e = 1), there exists a driving force for condensation of the solute, since then Δμ > 0. Moreover, sufficiently high supersaturation of the solution with regard to one (e.g. a1/a1) or more species can create a driving force (Δμ > 0) even if the solution is undersaturated with regard to one (e.g. a2/a2,e < 1) or more of the rest of the species. Detailed considerations concerning Δμ for crystallization from solutions can be found elsewhere [van Leeuwen 1979; van Leeuwen and Blomen 1979; Söhnel and Garside 1992]. **

Analogously to the case of boiling, evaporation or sublimation, the driving force for dissolution is that for condensation of solute, but taken with opposite sign, as now the old and the new phases are reversed. That is why, according to **eqs (2.13), (2.14) and (2.16), for dissolution Δμ is given by **

and, more generally, by

**(2.18) **

In this case the old phase is a melt or a crystal with a given modification, and the new phase is a crystal (which has another modification in polymorphic transformation). The commonly used parameter to control μold experimentally is the temperature rather than the pressure and, for that reason, it is convenient to express Δμ as a function of *T*. Isobarically, from thermodynamics [**Guggenheim 1957], **

**(2.19) **

where *s *is the entropy per molecule (or atom), and *T*e is the absolute phase-equilibrium temperature (the melting point in melt crystallization). Using **(2.19) twice, for μold and μnew, and recalling (2.1) yields [Volmer 1939] **

**(2.20) **

where

Obviously, the main problem in finding Δμ is to know how the entropies *s*old and *s*new of the old and the new phases depend on *T*. In the absence of such a knowledge, following Bohm [1981], it is convenient to use the Taylor expansion

of Δμ from **(2.20) in the vicinity of T = Te where Δse, (dΔs/dT)e and (d²Δs/dT²)eare the values of Δs and its derivatives at T = Te. Recalling the known relationship [Guggenheim 1957] **

between the entropy and the heat capacity (per molecule) *c*p at constant pressure, we can employ it twice (for the old and the new phase) to find that

where Δ*c*p ≡ *c*p,old – *c*p,new, Δ *c*′p = dΔ*c*p/d*T*, and *c*p,old and *c*p,new are the molecular heat capacities of the old and the new phase, respectively. With these expressions for the Δ*s *derivatives, a truncation of the above expansion of Δμ results in

Here

**(2.22) **

is the *undercooling*, Δ*s*e ≡ *s*old(*T*e) – *s*new(*T*e) = λ/*T*e is the difference in the molecular entropies of the old and the new phase at *T *= *T*e, λ is the latent heat (per molecule) of crystallization or polymorphic transformation, Δ*c*p,e ≡ *c*p,old(*T*e) – *c*p,new(*T*e) and Δ*c*′p,e ≡ dΔ*c*p/d*T *at *T *= *T*e.

**Equation (2.21) reduces to the widely used formula [Volmer 1939] **

**(2.23) **

when the undercooling satisfies the condition Δ*T *2*T*eΔ*s*e/Δ*c*p,e = 2λ/Δ*c*p,e, which is usually met in crystallization of metal melts or in polymorphic transformation. For glass-forming, polymer and other more complex melts **eq. (2.23) is not always sufficiently correct, but for them it often suffices to use (2.21) in the simpler form [Bohm 1981] **

This equation is very similar to the one given by Jones and Chadwick [1971]. A number of other Δμ(*T*) dependencies are also known in the literature (see, e.g., [**Hoffman 1958; Gutzow et al. 1985; Toner et al. 1990; Kelton 1991; Gutzow and Schmelzer 1995]). **

**Figure 2.1 shows the temperature dependence of Δμ for Li2O · 2SiO2 melt for which Te = 1306 K, Δse = 5.26k and Δcp,e = 1.56k [Kelton 1991]. The circles are the exact values computed by Kelton [1991] with the help of measured Δcp(T) data, and the dashed and solid lines are drawn, respectively, according to eqs (2.23) and (2.24). It is seen that in this case (2.24) describes considerably better than (2.23) the actual dependence of Δμ on ΔT. **

**Fig. 2.1 **Dependence of the supersaturation on the undercooling for Li2O.2SiO2 melt: circles – experimental data [**Kelton 1991]; circular contour – eq. (2.23); solid line – eq. (2.24). **

In this case all equations from case (e) remain in force taking into account that now the old phase is the crystal and the new phase is the melt or the crystal with another modification. This means that everywhere in these equations Δ*s*e, Δ*c*p,e and Δ*c*′p,e have to be taken with opposite sign. Since melting and polymorphic transformation often occur at *T *= *T*e, in many cases the approximation **(2.23) is good enough: **

**(2.25) **

[**Lange and Nagel 1935; Guggenheim 1957] so that rather than by eq. (2.1), Δμ is determined by **

**(2.26) **

on ϕ has the form [**Lange and Nagel 1935; Guggenheim 1957] **

where *z*i is the valency of the solute ions, *e*is practically ϕ-independent, i.e.

using the last two equations in **(2.26) leads to the approximate formula [Volmer 1939; Vetter 1967] **

**(2.27) **

where

**(2.28) **

is the *overvoltage*.

have to be exchanged in **eq. (2.26) and for that reason the supersaturation is again given by eq. (2.27), but with opposite sign of its r.h.s.: **

**(2.29) **

Summarizing, we see that Δμ is determined always by **eq. (2.1) or its appropriate generalization (e.g. eq. (2.26)). The difficulties in the determination of Δμ arise from incomplete knowledge of the exact dependences of μold and μnew on the respective experimentally controllable parameters. It must be emphasized that the correct determination of Δμ in each concrete case is of great importance for the reliable confrontation of theory with experiment. For instance, in the case of melt crystallization the use of different approximate formulae for Δμ can lead to considerable differences in the calculated values of some nucleation parameters [Kelton 1991]. **

Setting the old phase in supersaturated state is a necessary condition for the occurrence of first-order phase transition, but it is not yet a guarantee that such a transition will really take place within a given time interval. The ability of the supersaturated old phase to remain a certain time in the state of metastable TDE is one of the most remarkable features of the phase transitions of first order and is due to the fact that the metastable state is separated from the truly stable one by an energy barrier. Besides, a differently high barrier corresponds to each concrete path along which the transition may proceed and it might be expected that the actual path of the process will be the one requiring the lowest energy expenses. The questions thus arise: what is this path? and what is the height of the respective energy barrier?

A most natural path for the phase transition may seem the one corresponding to the uniform change of the density of the old phase into the density of the new phase. This situation is illustrated in **Fig. 1.1 in the case of VDW fluid. If the old phase is a supersaturated (i.e. metastable) VDW gas under pressure p′ = 0.54 at temperature T′ = 0.85, it occupies a volume corresponding to point h. In order to pass into the stable state of VDW liquid under the same pressure, the gas must diminish its volume up to the volume corresponding to point a. If this is to occur (as assumed) along the path of spatially uniform change of the gas density, the gas volume should decrease and thus cause a variation of the Gibbs free energy G of the fluid in accordance with eq. (1.4) represented by the uppermost curve in Fig. 1.1b. Initially, however, the transition will be impeded by an increase of G. Only on the left of the maximum of G will the transition be spontaneous, since then the volume decrease is accompanied by a lowering of G. For that reason, the difference between the maximum value of G and the value of G at point h is the energy barrier to the phase transition along the path of uniform change of density. Figure 1.1b shows that at the chosen values of p′ and T′ this energy barrier is approximately 0.03MkTcr or, more generally, about MΔμ, since Δμ ≈ 0.03kTcr at p′ = 0.54 (see Fig. 1.2a). This large amount of energy, some 2% of the total kinetic energy (3/2)MkTcrT′ of the VDW gas at T′ = 0.85, must be spent by the system only because all M molecules in it take part in the phase transition. It is clear, therefore, that it is highly improbable for the system to follow the path of spatially uniform change of its density because of the energetically high price of this path. **

**Fig. 3.2 **Old phase of *M *molecules before (state 1) and after (state 2) homogeneous formation of a cluster of *n *molecules.

Another conceivable path for the phase transition, which in the light of the aforesaid seems energetically much less expensive, corresponds to a non-uniform change of the density of the old phase into the density of the new one. Suppose that such a change occurs locally as a density fluctuation in a spatial region occupied by a small number of molecules (say, up to a few hundreds). Then, if *n**M *is the characteristic number of molecules in the spatial region of locally changed density, the expectation based on the above considerations (and confirmed by the analysis in **Chapter 4) is that the energy barrier for the phase transition will be of the order of n* Δμ. This is much less than the energy barrier of about MΔμ. for the path corresponding to uniformly changing density and means that, in general, first-order phase transitions are much more likely to occur by local density fluctuations than by uniform change of the density of the old phase as a whole. Numerous everyday observations (recall rains and snowfalls) and experimental investigations lead categorically to the conclusion that this indeed is the path followed in reality by a first-order phase transition: nanoscopical formations with density close to that of the new phase appear randomly in the old phase and the overgrowth of these precursors of the new phase to larger (usually macroscopic) sizes brings to an end the phase transition. For this reason, our next considerations will be devoted solely to phase transitions occurring by local changes in the density of the old phase. The analysis will be focused on the initial or the nucleation stage of the phase transition, during which the precursors of the new phase appear in the system as a result of density fluctuations. Nucleation itself is the process of random generation of those nanoscopically small formations of the new phase that have the ability for irreversible overgrowth to macroscopic sizes. **

Given the path along which the phase transition takes place, we must now turn to the question about the energy barrier (if any) along this path. This question can be answered, however, only upon adopting a concrete approach for describing the tiny precursors of the new phase. Different approaches can be used for such a description, but the two most known of them are the *cluster *approach and the *density-functional *approach. In the cluster approach the nanoscopically small formation of the new phase is considered as a cluster of a certain number *n *of molecules (or atoms) in it (**Fig. 3.1a). The cluster itself is regarded as separated from the old phase by a phase boundary and that makes it possible to say which of all M molecules in the system are still in the old phase and which of them already belong to the new phase. In the density-functional approach the state of the system is described with the aid of the number density ρ (m−3) of the molecules (or the atoms) as a function of the space coordinates (the solid curve in Fig. 3.1b). No phase boundary is assumed to separate the spatial regions with higher and lower density and, for that reason, it is not known whether a given molecule belongs to the old or the new phase. The cluster approach is very perspicuous and has been used already by the pioneers of the nucleation theory [Gibbs 1928; Volmer and Weber 1926; Farkas 1927; Kaischew and Stranski 1934a; Becker and Döring 1935]. It has been extensively developed in numerous studies on nucleation and has led to virtually all basic results known hitherto. The density-functional approach is relatively new and was applied to nucleation first by Cahn and Hilliard [1959]. It is considerably more formal, but is free of some weak points of the cluster approach and, apparently, has the capacity to produce important new results. We shall limit all further considerations entirely in the scope of the cluster approach and will describe the density-functional approach only briefly in Chapter 8. Also, unless especially noted, the considerations will be restricted to one-component nucleation. Results concerning the thermodynamics of multicomponent nucleation can be found elsewhere (e.g. Neumann and Döring [1940]; Reiss [1950]; Sigsbee [1969]; Nishioka and Kusaka [1992]; Wilemski and Wyslouzil **

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