Thermodynamics of void nucleation in nanoparticles

The nucleation of voids at the initial stage of hollow nanoshell formation is described in terms of the thermodynamics of nucleation in systems of finite size (or small systems) pumped with vacancies by interdiffusion-driven vacancy influx. Crossovers from suppressed nucleation to metastable nucleus formation and then to stable nucleus formation are analysed, describing, in particular, the possibility of significant supersaturations with vacancies of the metallic core. It is shown that at higher temperatures it becomes more favourable to nucleate at once a large single void instead of multiple tiny voids.     

Possibility of a shape phase transition for solidification of tin at scallop-like surfaces of Cu6Sn5

The possibility of solder-spreading transitions in solidification of solder at a rough rigid intermetallic surface is proven theoretically. Depending on the misorientation of scallops on the interface, one can observe a two-dimensional spreading transition over the scallops or a one-dimensional spreading transition along the triple-junction of two intermetallic compound scallops and liquid solder. The extent of undercooling can be determined not only by different interface energies, but by different angles between neighbouring scallops as well.     

Flux-driven nucleation at interfaces during reactive diffusion

Nucleation of intermetallic compounds and of voids at interfaces during reactive diffusion is treated with account of influence of the flux divergence in the nucleation regions of the real space as an additional term for drift in the size space (in Fokker–Planck equation for nucleation). Such approach enables the construction of effective Gibbs nucleation barrier which may (in the broad region of parameters) increase to infinity meaning the full suppression of nucleation, or, by the contrast, decrease assisting the nucleation. The introduced effective nucleation barriers depend on kinetic factors – on the ratio of diffusivities in nucleating and in neighboring phases. Thus, the competition of stable and metastable phases is reconsidered, as well as nucleation of Kirkendall/Frenkel voids at the interfaces.