Molecular-scale simulation of cross-flow migration in polymer melts.

Abstract

The first ever molecular-scale simulation of cross-flow migration effects in dense polymer melts is presented; simulations for both unentangled and entangled chains are presented. At quiescence a small depletion next to the wall for the segmental densities of longer chains is present, a corresponding excess exists about one-half a radii of gyration away from the wall, and uniform values are observed further from the wall. In shear flow the melts exhibit similar behavior as the quiescent case; a constant shear rate across the gap does not induce chain length based migration. In contradistinction, parabolic flow (where gradients in shear rate are present) causes profound migration for both unentangled and entangled melts. Mapping onto polyethylene and calculating stress shows the system is far below the stress required to break chains. Accordingly, our findings are consistent with flow induced migration mechanisms predominating over competing chain degradation mechanisms thus resolving a 40 year old controversy.