Primitive Chain Network Simulations of Entangled Melts of Symmetric and Asymmetric Star Polymers in Uniaxial Elongational Flows

Abstract

Ianniruberto and Marrucci [Macromolecules, 46, 267-275, 2013] developed a theory whereby entangled branched polymers behave like linear ones in fast elongational flows. In order to test such prediction, Huang et al [Macromolecules, 49, 6694-6699, 2016] performed elongational measurements on star polymer melts, indeed revealing that, in fast flows, the elongational viscosity is insensitive to the molecular structure, provided the molecular weight of the "backbone" (spanning the largest end-to-end distance of the molecule) is the same. Inspired by these studies, we here report on results obtained with multi-chain sliplink simulations for symmetric and asymmetric star polymer melts, as well as calculations of the Rouse time of the examined branched structures (not previously determined by Ianniruberto and Marrucci). The simulations semi-quantitatively reproduce the experimental data if the Kuhn-segment orientation-induced reduction of friction (SORF) is accounted for. The observed insensitivity of the nonlinear elongational viscosity to the molecular structure for the same span molar mass may be due to several factors. In the symmetric case, the calculated Rouse time of the star marginally differs from that of the linear molecule, so that possible differences in the observed stress fall within the experimental uncertainty. Secondly, it is possible that flow-induced formation of hooked star pairs (or even larger aggregates) makes the effective Rouse time of the aggregate even closer to that of the linear polymer because the friction center moves towards the branchpoint of the star molecule. In the asymmetric case, it is shown that the stress contributed by the short arms is negligible with respect to that of the long ones. However, such stress reduction is balanced by a dilution effect whereby the unstretched arms reduce SORF as they decrease the Kuhn-segment order parameter of the system. As a result of that dilution, the stress contributed by the backbone is larger. The two effects compensate one another, so that the overall stress is virtually the same of the other architectures.