Viscoelastic dynamics of polymer thin films and surfaces.

The strain relaxation behavior in a viscoelastic material, such as a polymer melt, may be strongly affected by the proximity of a free surface or mobile interface. In this paper, the viscoelastic surface modes of the material are discussed with respect to their possible influence on the freezing temperature and dewetting morphology of thin polymer films. In particular, the mode spectrum is connected with mode coupling theory assuming memory effects in the melt. Based on the idea that the polymer freezes due to these memory effects, surface melting is predicted. As a consequence, the substantial shift of the glass transition temperature of thin polymer films with respect to the bulk is naturally explanied. The experimental findings of several independent groups can be accounted for quantitatively, with the elastic modulus at the glass transition temperature as the only fitting parameter. Finally, a simple model is put forward which accounts for the occurrence of certain generic dewetting morphologies in thin liquid polymer films. It demonstrates that by taking into account the viscoelastic properties of the film, a morphological phase diagram may be derived which describes the observed structures of dewetting fronts. It is demonstrated that dewetting morphologies may also serve to determine nanoscale rheological properties of liquids.