Dissipative particle dynamics simulation of the interplay between spinodal decomposition and wetting in thin film binary fluids

The dynamics of phase separation of thin film binary fluids is investigated via dissipative particle dynamics simulation. We consider both cases of symmetric and asymmetric interactions between the walls and the two components. In the case of walls interacting symmetrically with the two fluid components, corresponding to a nonwetting case, relatively fast kinetics is observed when the average domain size is smaller than the slit thickness. A crossover to a slow Lifshitz-Slyozov growth is observed at late times. Faster dynamics is observed when the walls act as a slip boundary condition to the velocity field. In the case of asymmetric interactions, such that the system is in the wetting regime, the interplay between wetting kinetics and spinodal decomposition leads to rich dynamics. The phase separation proceeds through three stages. During the first stage, the dynamics is characterized as surface-directed spinodal decomposition, with growth of both average domain size and thickness of the wetting layers. The domain morphology is three dimensional and bicontinuous during the first stage, with kinetics reminiscent of that in bulk systems is observed. The second stage of the phase separation is characterized by the breakup of the bicontinuous domain morphology into small tubular domains bridging the two wetting layers and depletion of the core of the film from the wetting component. During this stage, domains with diameter smaller than thickness of the film shrink and disappear while those with diameter larger that the film thickness grow. The third stage is characterized by growth induced by the backflow of A-component from the wetting layers to the core of the film, leading to the decay in the thickness of the film and growth of the domains bridging the wetting layers. At even later times of the third stage, when the wetting layers become very depleted in the wetting component, growth becomes mediated by diffusion followed by collision of the tubular domains.