Evidence of convective constraint release during hole growth in freely standing polystyrene films at low temperatures

Abstract

Hole growth measurements were performed using optical microscopy on freely standing polystyrene films at temperatures that were slightly larger than the bulk value of the glass transition temperature T(bulk)g. For the measured range of temperatures, we have observed a transition from linear growth of the hole radius R during the early stages to exponential growth of R at later times. We have characterized this transition as a function of molecular weight 120 x 10(3) < Mw <2240 x 10(3) , film thickness 61 nm<h<125 nm , and temperature 101 degrees C<T<117 degrees C . The viscosity at the edge of the hole inferred from the long time exponential growth regime exhibits shear thinning due to the large shear strain rates present at the edge of the hole. The R (t) data for all times can be fit very well using an expression that describes exponential hole growth with a time-dependent viscosity that allows for an initial, transient response due to the decay of elastic entanglements. The time scale for the decay of the transient behavior is interpreted in terms of the decay of entanglements by the convective constraint release mechanism of the tube theory of entangled polymer dynamics.