Using Mw dependence of surface dynamics of glassy polymers to probe the length scale of free surface mobility

Abstract: We describe a series of surface levelling experiments in glassy polystyrene (PS) of varying molecular weight. The evolution through a mobile surface layer is described by the glassy thin film equation that was introduced and used in a previous work. Excellent agreement with the data is achieved, with surface mobility as the single free parameter. Different molecular-weight dependencies in mobility are then observed above and below the glass transition. The results are discussed in terms of surface-chain anchoring in the bulk matrix, and the length scale for surface mobility.