Solvent mediated interactions between model colloids and interfaces: a microscopic approach

We determine the solvent mediated contribution to the effective potentials for model colloidal or nanoparticles dispersed in a binary solvent that exhibits fluid-fluid phase separation. The interactions between the solvent particles are taken to be purely repulsive point Yukawa pair potentials. Using a simple density functional theory we calculate the density profiles of both solvent species in the presence of the “colloids,” which are treated as external potentials, and determine the solvent mediated (SM) potentials. Specifically, we calculate SM potentials between (i) two colloids, (ii) a colloid and a planar fluid-fluidinterface, and (iii) a colloid and a planar wall with an adsorbed wetting film. We consider three different types of colloidal particles: Colloid A that prefers the bulk solvent phase rich in species 2, colloid C that prefers the solvent phase rich in species 1, and “neutral” colloid B that has no strong preference for either phase, i.e., the free energies to insert the colloid into either of the coexisting bulk phases are almost equal. When a colloid that has a preference for one of the two solvent phases is inserted into the disfavored phase at state points close to coexistence a thick adsorbed “wetting” film of the preferred phase may form around the colloids. The presence of the adsorbed film has a profound influence on the form of the SM potentials. In case (i) reducing the separation between the two colloids of type A leads to a bridging transition whereby the two adsorbed films connect abruptly and form a single fluid bridge. The SM potential is strongly attractive in the bridged configuration. A similar phenomenon occurs in case (iii) whereby the thick adsorbed film on colloid A and that at the planar wall, which prefers the same phase as colloid A, connect as the separation between the colloid and the wall is reduced. In both cases the bridging transition is accompanied, in this mean-field treatment, by a discontinuity of the SM force. On the other hand, for the same wall, and a colloid of type C, the SM potential is strongly repulsive at small separations. For case (ii), inserting a single colloidal particle near the planar fluid-fluidinterface of the solvent, the density profiles of the solvent show that the interface distortion depends strongly on the nature of the colloid-solvent interactions. When the interface disconnects from the colloid there is, once again, a discontinuity in the SM force.