Binary fluid with attractions near a planar wall

It is well known that a mixture of big and small hard spheres next to a planar wall will exhibit segregation based on their size difference. The larger spheres will tend to locate next to the substrate because the overall system entropy loss per unit area is less. In the present study we determine the role of attraction between the small particles and the wall to displace the larger particles. Both fluids density-functional theory and discontinuous molecular dynamics simulations demonstrate that at a certain attractive potential, which is on the order of the thermal energy, the large particles can indeed be dislodged from the surface layer so the small particles are now the major surface component. Exploration of a range of parameters, including relative sphere size and concentration, as well as attractions between the small spheres in the bulk, shows that the phenomenon is quite robust.