Flow rates of polymer solutions through porous disks as a function of solute. II. Thickness and structure of adsorbed polymer films

Abstract The thickness of films of poly(methyl methacrylate) (PMMA), poly(vinyl acetate) (PVAc), and polystyrene (PS) adsorbed on Pyrex glass was studied by measuring the flow rates of polymer solutions and the corresponding pure solvents through sintered filter disks. Adsorption isotherms were in agreement with those reported by other workers and showed saturation adsorption equivalent to 2–8 condensed monolayers of monomer units. Film thicknesses were of the order of magnitude of the free coil diameters in solution and were directly proportional to the intrinsic viscosity of the polymer, except for PS in benzene where the thicknesses leveled off as molecular weight increased. It was concluded that polymers adsorb from solution in monolayers of compressed or interpenetrating coils; that below some critical molecular weight which varies with polymer and solvent, a much larger fraction of the segments lies directly in the interface; that adsorbed films may consist of a dense layer immediately adjacent to the surface and a deep layer of loops extending into the solvent; and that it is the segment—solvent interaction rather than the segment—surface interaction which dominates the conformation of the adsorbed chain.