This work employed total internal reflectance fluorescence (TIRF) to examine the adsorption kinetics of polyethylene oxide (PEO) on silica from aqueous solution in controlled shearing flow. Studies with PEO, fluorescently labeled such that TIRF tracked the chain number on the surface, exhibited an overshoot in the early stages of adsorption. This overshoot was not seen with other polymers such as polyvinyl alcohol, and hydroxyethyl cellulose, possibly because these other polymers were labeled such that TIRF measured the interfacial mass. Indeed, reflectometry studies of PEO adsorption, sensitive to interfacial mass, showed no overshoot. This suggests that the overshoot results from the selectivity of the surface for high molecular weight populations within a polydisperse sample. Initially short chains adsorb because they diffuse to the surface quickly. At longer times, higher molecular weight chains reach the surface and replace the short chains. This evolution occurs as the mass coverage increases (according to reflectivity) but the number of adsorbed chains, and hence the TIRF signal decrease at long times. A study of the impact of the molecular weight distribution confirmed this hypothesis.

Several complications to the molecular weight selectivity hypothesis, however, arose: First, the same PEO samples which overshot during adsorption on silica showed no overshoot on a polystyrene substrate. This suggested that the ability to overshoot was governed by the substratesegment interactions, even though the molecular weight distribution within the sample determined the overshoot shape. Further, the effect of transport conditions (wall shear rate, bulk polymer concentration) were not completely consistent with the molecular weight competition hypothesis, which was based on surface-solution equilibrium, taking into account transport-limited rates of adsorption. Finally certain runs, where the adsorption process was interrupted by solvent flow and later allowed to proceed, never reached the full coverage seen for uninterrupted runs. Hence, the surface coverage and possibly the chain configurations can depend on the history of the adsorption process, a feature which points to surface relaxations and non-equilibrium structures.