NUCLEATION AND INTERFACE KINETICS HOMOGENEOUS NUCLEATION When a solid forms within its own melt without aid of foreign materials, it is said to nucleate homogeneously. Nucleation in this way requires a large driving force because of the relatively large contribution of surface energy to the total free energy of very small particles. From Eqs. (8-8) and (8-10), the radius r* of a spherical particle which is just stable at an undercooling AT is given by 2oTyV, AH AT (9-1) ‘The particle of radius r* is termed the critical nucleus. Particles larger than this are stable and grow; particles smaller than r* form spontaneously in the liquid metal both above and below the equilibrium melting point. They do so because in this way they increase the entropy of the system. Following Turnbull,” this is seen simply by viewing the liquid as an ideal solution of various size clusters, each containing i atoms or molecules (hereafter termed atoms). Let n equal the number of simple single atoms (= 1) per unit volume and 1; be the number of clusters of i atoms formed from these [> euwsteRs-p-muete! —e FREE ENERGY, AG, ° RaAIUs —= FIGURE 9-1 Free-energy barrier to nucleation, simple atoms. The free-energy change per unit volume of liquid on forming the clusters AG, is then AG, =n, AG, — T AS (9-2) where AG; is the free energy of formation of one cluster of i atoms and AS is the entropy of mixing nj clusters, which for an ideal solution is simply = a8 ——K (min A +nin ) (9-3) Now, at (metastable) equilibrium, 8G,/an; = 0. At this point, let n=, and assume n> n,. Then, Eq. (9-3) becomes nh = ne“ @6tAT) (9-4)and assuming Eq. (9-4) is valid for m; = nf, nf = ne~aouery on ‘The thermodynamic barrier to formation of a critical nucleus AG} decreases rapidly with increasing undercooling AT. Thus ¥, the number of such critical nuclei, is a strong function of undercooling. ‘The greater the number of these critical nuclei, the greater the probability that in a given time one will grow and initiate solidification. We can now derive a rate law for homogeneous nucleation by making two simple assumptions. The first is that the concentration ny of critical nuclei remains that predicted by equilibrium considerations even after nucleation begins. The second is that addition of a single atom to a critical nucleus makes that nucleus supercritical and able to grow rapidly. Then, the rate of formation of nuclei per unit volume J is Tanto. (9-8) where w* is the number of atoms surrounding a critical nucleus and vs is the fre- quency with which atoms jump across the liquid-solid interface. For a spherical nucleus, «* is approximately given by Anr*? y (9-9) The jump of atoms or molecules in the bulk liquid is? (9-10) where 4 is jump distance and D, is liquid diffusion coefficient. The frequency with which each atom strikes the liquid-solid interface is usually taken to be one-sixth its jump frequency in the bulk liquid because it reaches the interface by jumping in only ‘one of six possible directions. Taking 2 ~ a, we arrive at the expression for v,5 By ves ean Substituting Eqs. (9-6) to (9-9) with the foregoing, we arrive finally at the classical expression for homogeneous nucleation in bulk liquids. This equation is essentially equivatent to that derived by Turnbull and Fisher? based on earlier work of nucleation of droplets from the vapor. It is written Di 620° Ty? V2 T= B, P+ exp| — 1620 Ta" ¥e— 12) Bee sarrarir] C1 where the preexponential term B, depends on critical nucleus size and surface energy, and Dry is the liquid diffusion coefficient at the equilibrium melting point Ty. For liquid metals, D,/Dzy ~ 1 and the preexponential B, may be taken as a constant of about 10** (Holloman and Turnbull*),@| é 5 5 gar gear 3 3 3 3 ‘a rs FIGURE 9-2 Characteristic shapes for nucleation rate curves. AT. is the critical undercooling for a sensible nucleation rate. (a) Nonviscous liquids such as metals; (6) viscous nonmetallics including oxides and organic polymers. The nucleation rate is so sensitive to the term within the exponential that changes in B, of several orders of magnitude do not appreciably affect the calculated undercoolings for sensible nucleation, For materials whose liquid diffusivity drops markedly with temperature, e.g., glasses and polymers, the preexponential term D,/Dzy, becomes overriding at lower temperatures. As temperature is lowered from the equilibrium transformation temperature, nucleation rate first increases from zero to a maximum at some given undercooling. Then as the diffusivity D, becomes very small, nucleation rate decreases toward zero again as temperature is further decreased. Figure 9-2 shows schematically the nucleation behavior of a metal as compared with that of a viscous material such as a polymer or oxide glass. Many refinements and modifications of the classical nucleation theory given here have been proposed, but that described above adequately explains most experi- mental results thus far obtained. The most fruitful experimental approach employed to confirm the theory is that of solidification studies on finely divided droplets. Two methods have been employed: microscopical observation of small drops and thermal analysis on aggregates of drops separated by thin films. In qualitative agreement with the prediction of Eq. (9-12), these studies show that a given droplet supercool without nucleating until it reaches a given critical temperature AT. after which nucleation occurs rapidly. The droplet can be held at undercoolings less than AT, for very long times without nucleating. Quantitatively, results of Turnbull and coworkers!’ and of most studies since theirs have shown that for metals the maximum undercooling achieved is about 0.18 of the absolute melting point (Table 9-1). Taking this undercooling as represent- ing the undercooling required for homogeneous nucleation, Turnbull calculated [from Eq. (9-12)] the liquid-solid surface energies o. These surface energies are of the‘Thus, a liquid at temperature either above or below its melting point will have a distribution of solidlike clusters given by Eq. (9-4) at equilibrium. The free energy of formation of each of these clusters AG, is AG AG, =cA+V (9-5) where A is the surface area and V is the volume of the cluster; AG is the thermo- dynamic driving force for solidification as given by Eq. (8-3), and V, is the molar volume. The form of this curve is as drawn in Fig. 9-1. AG, increases to a maximum AG} at r =r", the critical radius; thereafter it decreases rapidly. For a spherical cluster, substituting Eqs. (8-3) and (9-1) in Eq. (9-5) yields AGT ae O° Ty? V2 9-6) AH? AT? sine