The presence of a surface preferably attracting one component of a polymer mixture by the long-range van der Waals surface potential while the mixture undergoes phase separation by spinodal decomposition is called long-range surface-directed spinodal decomposition (SDSD). The morphology achieved under SDSD is an enrichment layer(s) close to the wall surface and a droplet-type structure in the bulk. In the current study of the long-range surface-directed polymerization-induced phase separation, the surface-directed spinodal decomposition of a monomer-solvent mixture undergoing self-condensation polymerization was theoretically simulated. The nonlinear Cahn-Hilliard and Flory-Huggins free energy theories were applied to investigate the phase separation phenomenon. The long-range surface potential led to the formation of a wetting layer on the surface. The thickness of the wetting layer was found proportional to time t*1/5 and surface potential parameter h 1 1/5. A larger diffusion coefficient led to the formation of smaller droplets in the bulk and a thinner depletion layer, while it did not affect the thickness of the enrichment layer close to the wall. A temperature gradient imposed in the same direction of long-range surface potential led to the formation of a stripe morphology near the wall, while imposing it in the opposite direction of surface potential led to the formation of large particles at the high-temperature side, the opposite side of the interacting wall.
Keywords: long-range surface potential; polymerization-induced phase separation; surface-directed spinodal decomposition; wetting layer.