Simulating Startup Shear of Entangled Polymer Melts.

Abstract

Start-up shear rheology is a standard experiment used for characterizing polymer flow, and to test various models of polymer dynamics. A rich phenomenology is developed for behavior of entangled monodisperse linear polymers in such tests, documenting shear stress overshoots as a function of shear rates and molecular weights. A tube theory does a reasonable qualitative job at describing these phenomena, although it involves several drastic approximations and the agreement can be fortuitous. Recently, Lu and co-workers published several papers [e.g., Lu ACS Macro Lett. 2014, 3, 569-573] reporting results from molecular dynamics simulations of linear entangled polymers, which contradict both theory and experiment. On the basis of these observations, they made very serious conclusions about the tube theory, which seem to be premature. In this letter, we repeat simulations of Lu et al. and systematically show that neither their simulation results nor their comparison with theory is confirmed.