Simulation of semidilute polymer solutions in planar extensional flow via conformationally averaged Brownian noise.

Abstract

The dynamics and rheology of semidilute polymer solutions in strong flows are of great practical relevance. Processing applications can in principle be designed utilizing the relationship between nonequilibrium polymer conformations and the material properties of the solution. However, the interplay between concentration, flow, hydrodynamic interactions (HIs), and topological interactions which govern semidilute polymer dynamics is challenging to characterize. Brownian dynamics (BD) simulations are particularly valuable as a way to directly visualize how molecular interactions arise in these systems and are quantitatively comparable to single-molecule experiments. However, such simulations are often computationally intractable and are limited by the need to calculate the correlated Brownian noise via decomposition of the diffusion tensor. Previously, we have introduced an iterative conformational averaging (CA) method for BD simulations which bypasses these limitations by preaveraging the HI and Brownian noise in an iterative procedure. In this work, we generalize the CA method to flowing semidilute solutions by introducing a conformation dependent diffusion tensor and a strain dependent approximation to the conformationally averaged Brownian noise. We find that this approach nearly quantitatively reproduces both transient and steady state polymer dynamics and rheology while achieving an order of magnitude computational acceleration. We then utilize the CA method to investigate the concentration and flow rate dependence of polymer dynamics in planar extensional flows. Our results are consistent with previous experimental and simulation studies and provide a detailed view of broad conformational distributions in the semidilute regime. We observe interconversion between stretched and coiled states at steady state, which we conjecture occur due to the effect of concentration on the conformation dependent polymer drag. Additionally, we observe transient flow-induced intermolecular hooks in the startup of flow which lead to diverse and unique stretching pathways.