Transient Cooperative Processes in Dewetting Polymer Melts

Abstract

We compare the high velocity dewetting behavior, at elevated temperatures, of atactic polystyrene (aPS) and isotactic polystyrene (iPS) films, with the zero shear bulk viscosity (η_{bulk}) of aPS being approximately ten times larger than iPS. As expected, for aPS the apparent viscosity of the films (η_{f}) derived from high-shear dewetting is less than η_{bulk}, displaying a shear thinning behavior. Surprisingly, for iPS films, η_{f} is always larger than η_{bulk}, even at about 50 °C above the melting point, with η_{f}/η_{bulk} following an Arrhenius behavior. The corresponding activation energy of ∼160±10 kJ/mol for iPS films suggests a cooperative motion of segments which are aligned and agglomerated by fast dewetting.