Kinetic Traps in Polymer Adsorption. 1. Polystyrene Displaced by Polyisoprene at 12 °C

Sequential adsorption experiments were performed to determine the kinetics of polymer displacement. Protiopolystyrene (PS) and deuterio-cis-polyisoprene (PI) were allowed to adsorb sequentially at 12 °C, from dilute solution in carbon tetrachloride, onto a single surface of oxidized silicon. Whereas the net surface excess equilibrated rapidly, the individual populations of PS and PI equilibrated far more slowly. The adsorption of PI was enthalpically favored, but PS arrived first at the surface, so initially-adsorbed PS was displaced. This displacement was strongly nonexponential in time. When desorption kinetics were fitted to the stretched-exponential function as suggested by theoretical considerations, the power of time, β, increased from β≅0.2 for the PS chains of lowest molecular weight (M_PS) to a limiting value, β≅ 1/2 , for the highest M_PS. The time constant for desorption, τ_off, depended only weakly on M_PS. The minimal molecular weight dependence of τ_off in this PS-PI system contrasts with our findings in the PS-PMMA [poly(methyl methacrylate)] system and is tentatively attributed to the fact that less PI adsorbed at any instant in time, the higher the M_PS. However, the pronounced nonexponential desorption confirms previous experience, as well as expectation based on a simple kinetic model. This gives corroborative evidence that β≅ 1/2 is the limiting value to be expected of simple diffusion-limited desorption.