Filling and wetting transitions on sinusoidal substrates: a mean-field study of the Landau–Ginzburg model

Abstract

We study the interfacial phenomenology of a fluid in contact with a one-dimensional array of infinitely long grooves of sinusoidal section, characterized by the periodicity length L and amplitude A. The system is modelled by the Landau–Ginzburg–Wilson functional, with fluid-substrate couplings which control the wettability of the substrate. We investigate the filling and wetting phenomena within the mean-field approximation, and compare with the predictions of the macroscopic and interfacial Hamiltonian theories. For large values of L and under bulk coexistence conditions, we observe first-order filling transitions between dry (D) and partially filled (F) interfacial states, and wetting transitions between partially filled F and completely wet (W) interfacial states of the same order as for the flat substrate. Depending on the order of the wetting transition, the transition temperature is either shifted towards lower temperatures for first-order wetting or it coincides with the wetting temperature on the flat substrate for continuous wetting. On the other hand, if the groove height is of order of the correlation length, only wetting transitions between D and W states are observed under bulk coexistence conditions. For this case, the transition temperature shift obeys approximately Wenzel's phenomenological law if the substrate favors first-order wetting, but it remains unshifted for continuous wetting. The borderline between the small and large L regimes correspond to a D − F − W triple point if wetting is first-order, and a D − F critical point for continuous wetting. Beyond bulk coexistence conditions, filling and first-order wetting transitions continue into off-coexistence filling and prewetting lines, which end up at critical points. Our findings show that the macroscopic theory only describes accurately the filling transition close to bulk coexistence and large L, while microscopic structure of the fluid is essential to understand wetting and filling away from bulk coexistence.