Impact of Interaction Strength and Surface Heterogeneity on the Dynamics of Adsorbed Polymers

We present molecular dynamics simulations of bead-and-spring polymer chains on chemically heterogeneous, energetically disordered surfaces at near-monolayer coverages. The surfaces consist of random mixtures of weakly (W) and strongly (S) attractive sites. We explore systematically the effect of surface composition on the diffusive dynamics of the chains. The polymer diffusion coefficients have a near-Arrhenius temperature dependence, with activation energies which have a nonmonotonic dependence on the fraction of S sites. In other words, we see a nonmonotonic dependence of the interfacial polymer dynamics on its affinity with the surface, when the latter involves some heterogeneity. The maximum activation energy belongs to the surface containing 75% S and 25% W sites, which combines near-maximum average polymer-surface interactions with near-maximum spread or disorder in these interactions. Our results have interesting implications for polymer adhesion and friction and structure-property relationships in polymer nanocomposites.