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A thermodynamic model is developed of the free energy of gas-filled voids formed within cavities on solid surfaces covered by a liquid. Capillary effects are assumed to be the only important contributions to the free energy, and expressions are derived for the free energy of the system as a function of the void size, the relative surface free energy densities involved, and the geometry of the cavity. The results of the model are (1) construction of a stability diagram that maps the most stable void configuration versus the wetting properties of the various solid surfaces involved, and (2) rough estimates of the work required to liberate a void of a given size and position. The model can give qualitative insight into the stability of coating defects on uneven surfaces, and also can be used to prescribe possible surface treatments for reducing the work required to remove voids from the system.
Keywords: Interfaces; Wetting; Thermodynamic modeling; Air voids