Three suitable examples are cubes bounded mainly by facets, octahedra bounded by facets, and truncated octahedra bounded by both and facets. These are crystallographically distinct shapes rather than three arbitrary rounded particle outlines.
At fixed volume the thermodynamic equilibrium shape minimizes , with an edge/corner correction when particles are very small. In the Wulff construction, facet support-plane distances scale as their interfacial free energies. Silver's clean low-index energies, selective adsorption of ligands or ions, solvent chemical potential and possible support contact alter those energies. Crystal twinning and elastic strain can add further costs or stabilize multiply twinned forms. A face with slow attachment kinetics can also survive during growth even when that morphology is not the thermodynamic equilibrium Wulff shape. Homogeneous nucleation describes where nuclei form; it does not guarantee an thermodynamic equilibrium final shape.
Nucleation is the formation of a sufficiently large embryo of the new metallic phase. Producing metal atoms from dissolved precursor can create supersaturation; aggregation lowers bulk free energy but initially creates costly metal-medium interface. In the simplest spherical classical nucleation theory,
where is the metal-medium interfacial free energy and is the bulk driving force per volume. Clusters below the critical size tend to redissolve; larger ones can grow.
In homogeneous nucleation, the critical cluster forms in the solution without a pre-existing interface: the initial products are free particles. In heterogeneous nucleation, a substrate, vessel wall or suspended seed replaces part of that costly new interface. For a spherical cap on a planar substrate,
A wetting substrate therefore lowers the barrier; this assumes the same bulk driving force and isotropic interfacial energies.
Figure 1.
Free and supported particles arise through different nucleation histories
. Original sequential schematics: metal precursor is dispersed in the liquid, a critical embryo forms, and the stable nucleus grows. The lower sequence represents cap nucleation on a fixed substrate. Source. Details.
A final supported particle need not have nucleated heterogeneously: a free particle can nucleate in solution and later adsorb on the support. Conversely, a particle nucleated heterogeneously on a suspended seed can remain freely dispersed as a composite particle. Nucleation location and final support status are different classifications.
Microwave absorption heats the medium and possibly the support, changing reduction, diffusion and supersaturation. Preferential local heating can change the relative rates of the two routes. Microwave irradiation alone does not remove the thermodynamic nucleation barrier or demonstrate a special nonthermal mechanism.