Surface phase transitions in athermal mixtures of hard rods and excluded volume polymers investigated using a density functional approach

Using fundamental measures' density functional framework based on Wertheim's first order perturbation theory J. Chem. Phys. 87, 7323 (1987)] we study the surface phase transitions in athermal polymer-needle mixtures, which demix in bulk into the isotropic polymer-rich (rod-poor) and polymer-poor (rod-rich) phases. We find that the polymer-rich (rod-poor) phase wets the hard wall at coexistence and the wetting transition is of first order. In the partial wetting regime we find a sequence of layerings but these transitions are gradually suppressed as the chain length increases. For long enough chains we detect the prewetting line. Rods exhibit pronounced ordering at the wall in the polymer-rich phases. Our results imply that experiments on the (isotropic) wetting transition for colloidal rod-polymer mixtures should be easier to carry out than those for the colloidal rod-sphere mixtures because the wetting transition occurs at lower rod densities. On the other hand, layerings in sphere-needle mixtures may turn out to be difficult to observe experimentally because some of them will be metastable with respect to the freezing transition, whereas the remaining ones are located very close to the binodal.