Heterogeneous nucleation on rough surfaces: Generalized Gibbs' approach

Heterogeneous nucleation (condensation) of liquid droplets from vapor (gas) on a defective solid surface is considered. The vapor is described by the van der Waals equation of state. The dependence of nucleating droplet parameters on droplet size is accounted for within the generalized Gibbs approach. As a surface defect, a conic void is taken. This choice allows us to simplify the analysis and at the same time to follow the main aspects of the influence of the surface roughness on the nucleation process. Similar to condensation on ideal planar surfaces, the contact angle and catalytic factor for heterogeneous nucleation on a rough surface depend on the degree of vapor overcooling. In the case of droplet formation on a hydrophilic surface of a conic void, the nucleation rate considerably increases in comparison with the condensation on a planar interface. In fact, the presence of a defect on the hydrophilic surface leads to a considerable shift of the spinodal towards lower supersaturation in comparison with heterogeneous nucleation on a planar interface. With the decrease in the void cone angle, the heterogeneous spinodal approaches the binodal, and the region of metastability is diminished at the expense of the instability region.