A Volume-Corrected Wenzel Model

The Wenzel model, commonly used for predicting the equilibrium contact angle (CA) of drops which penetrate the asperities of a rough surface, does not account for the liquid volume stored in the asperities. Interestingly, many previous experimental and molecular dynamics studies have noted discrepancies between observed CAs and those predicted by the Wenzel model because of this neglected liquid volume. Here, we apply a thermodynamic model to wetting of periodically patterned surfaces to derive a volume-corrected Wenzel equation in the limit of small pattern wavelength (compared to drop size). We show that the corrected equilibrium CA is smaller than that predicted by the Wenzel equation and that the reduction in CA can be significant when the liquid volume within the asperities becomes non-negligible compared to the total droplet volume. In such cases, the corrected CAs agree reasonably well with experimental observations and results of molecular dynamics simulations reported in previous studies.