Impact of the prequench state of binary fluid mixtures on surface-directed spinodal decomposition

Using lattice Boltzmann simulations we investigate the impact of the amplitude of concentration fluctuations in binary fluid mixtures prior to demixing when in contact with a surface that is preferentially wet by one of the components. We find a bicontinuous structure near the surface for an initial, prequench state of the mixture close to the critical point where the amplitude of concentration fluctuations is large. In contrast, if the initial state of the mixture is not near the critical point and concentration fluctuations are relatively weak, then the morphology is not bicontinuous but remains layered until the very late stages of coarsening. In both cases, it is the morphology of a depletion layer rich in the nonpreferred component that dictates the growth exponent of the thickness of the fluid layer that is in direct contact with the substrate. In the early stages of demixing, we find a growth exponent consistent with a value of 1/4 for a prequench state away from the critical point, which is different from the usual diffusive scaling exponent of 1/3 that we recover for a prequench state close to the critical point. We attribute this to the structure of a depletion layer that is penetrated by tubes of the preferred fluid, connecting the wetting layer to the bulk fluid even in the early stages if the initial state is characterized by concentration fluctuations that are large in amplitude. Furthermore, we find that in the late stages of demixing the flow through these tubes results in significant in-plane concentration variations near the substrate, leading to dropletlike structures with a concentration lower than the average concentration in the wetting layer. This causes a deceleration in the growth of the wetting layer in the very late stages of the demixing. Irrespective of the prequench state of the mixture, the late stages of the demixing process produce the same growth law for the layer thickness, with a scaling exponent of unity usually associated with the impact of hydrodynamic flow fields.