Structural relaxation and dynamic heterogeneity in a polymer melt at attractive surfaces

Molecular dynamics simulations of polymer melts at flat and structured surfaces reveal that, for the former, slow dynamics and increased dynamic heterogeneity for an adsorbed polymer is due to densification of the polymer in a surface layer, while, for the latter, the energy topography of the surface plays the dominant role in determining dynamics of interfacial polymer. The dramatic increase in structural relaxation time for polymer melts at the attractive structured surface is largely the result of dynamic heterogeneity induced by the surface and does not resemble dynamics of a bulk melt approaching T(g).