Molecular simulation of flow-enhanced nucleation of polyethylene crystallites in biaxial flows

Abstract

Flow-enhanced nucleation (FEN) of n-pentacontahectane (C150) under biaxial extensional flows of varying strain rate ratios is studied using nonequilibrium molecular dynamics simulation. The nucleation rates thus calculated are used to test previously published FEN models based on invariants of the conformation tensor of Kuhn segments and the extra stress tensor. Models based on the conformation tensor provide a more accurate description of FEN observed in biaxial flow simulations than those based on the extra stress tensor. In addition, the formation of nematic domains previously reported to be stabilized by shear or extensional flow is absent in equibiaxial flows. However, such domains do form in non-equibiaxial flows, and nucleation occurs in these domains preferentially. The shape and orientation of nuclei formed under biaxial flows of various strengths and strain rate ratios are also reported.