Dynamics and rheology of ring-linear blend semidilute solutions in extensional flow. Part I: Modeling and molecular simulations

Abstract

We use Brownian dynamics (BD) simulations and single molecule experiments to investigate the influence of topological constraints and hydrodynamic interactions on the dynamics and rheology of solutions of ring-linear polymer blends at the overlap concentration. We find agreement between simulation and experiment in which rings in solution blends exhibit large conformational fluctuations. A subpopulation of rings shows extension overshoots in the startup of the flow, and other populations display tumbling and tank-treading at the steady state. Ring polymer fluctuations increase with the blend fraction of linear polymers and are peaked at a ring Weissenberg number WiR≈1.5. On the contrary, linear and ring polymers in pure solutions show a peak in fluctuations at the critical coil-stretch Weissenberg number Wi=0.5. BD simulations show that extension overshoots on the startup of the flow are due to flow-induced intermolecular ring-linear polymer hooks, whereas fluctuations at the steady state are dominated by intermolecular hydrodynamic interactions (HIs). This is supported by simulations of bidisperse linear polymer solution blends, which show similar trends in conformational dynamics between rings and linear polymers with a matched contour length. Compared to BD simulations, single molecule experiments show quantitatively larger fluctuations, which could arise because experiments are performed on higher molecular weight polymers with stronger topological constraints. To this end, we have advanced the understanding of the effects of topological interactions and intermolecular HIs on the dynamics of semidilute ring-linear polymer blend solutions.