Squeezing wetting and nonwetting liquids.

Abstract

We present molecular-dynamics results for the squeezing of octane (C8H18) between two approaching solid elastic walls with different wetting properties. The interaction energy between the octane bead units and the solid walls is varied from a very small value (1 meV), corresponding to a nonwetting surface with a very large contact angle (nearly 180 degrees), to a high value (18.6 meV) corresponding to complete wetting. When at least one of the solid walls is wetted by octane we observe well defined molecular layers develop in the lubricant film when the thickness of the film is of the order of a few atomic diameters. An external squeezing-pressure induces discontinuous, thermally activated changes in the number n of lubricant layers (n-->n-1 layering transitions). With increasing interaction energy between the octane bead units and the solid walls, the transitions from n to n-1 layers occur at higher average pressure. This results from the increasing activation barrier to nucleate the squeeze-out with increasing lubricant-wall binding energy (per unit surface area) in the contact zone. Thus, strongly wetting lubricant fluids are better boundary lubricants than the less wetting ones, and this should result in less wear. We analyze in detail the effect of capillary bridge formation (in the wetting case) and droplets formation (in the nonwetting case) on the forces exerted by the lubricant on the walls. For the latter case small liquid droplets may be trapped at the interface, resulting in a repulsive force between the walls during squeezing, until the solid walls come into direct contact, where the wall-wall interaction may be initially attractive. This effect is made use of in some practical applications, and we give one illustration involving conditioners for hair care application.