Dewetting of thin polymer films at temperatures close to the glass transition.

We present detailed studies on dewetting of thin polystyrene (PS) films which were deposited onto silicon wafers coated with a polydimethylsiloxane (PDMS) monolayer. Experiments were performed at temperatures close to the glass transition temperature of PS. Several significant deviations from the dewetting behaviour of Newtonian liquids were observed. The length of the PS molecules, and thus the viscosity, turned out to be of minor importance in determining the dewetting velocity, in particular for the later regimes. In stark contrast, the geometry of the drying spot had a striking influence on the dewetting velocity. Initially, dewetting from straight contact lines proceeded faster than the opening of circular holes. At later stages, the process slowed down significantly in both cases. Under the conditions at which our experiments were performed, PS cannot flow like a simple liquid. Thus, the observed dewetting has to be the consequence of plastic deformation induced by capillary forces. Our results indicate that under such conditions the energy dissipation process is strongly affected by geometry, which is not the case for viscous liquids.