In the present work an attempt is made to build a rigorous theoretical model for the constraint release mechanism found to play an important role in the dynamics of polymer melts. Our goal is a formalism free of adjustable parameters and ''ad-hoc'' assumptions which are inherent to existing theories for constraint release. Our model is capable to describe both thermal and convective constraint release. These processes have the same effect on chains and accordingly can be unified in a single framework. Since polymer chains in the bulk and in the near-wall layer may experience different types of constraint release, the latter case is studied separately. This topic is closely related to the long-standing problem of polymer melt flow instabilities encountered during extrusion. Nowadays it is believed that constraint release plays a crucial role in the dynamics of tethered chains preventing them from being squeezed against the wall. The resulting non-monotonous slip-law is the most probable reason of the so-called spurt instability.
|Publisher||Department of Applied Mathematics, University of Twente|