Molecular Dynamics Investigation of the Relaxation Mechanism of Entangled Polymers after a Large Step Deformation

The chain retraction hypothesis of the tube model for nonlinear polymer rheology has been challenged by the recent small-angle neutron scattering (SANS) experiment (Wang, Z.; Lam, C. N.; Chen, W.-R.; Wang, W.; Liu, J.; Liu, Y.; Porcar, L.; Stanley, C. B.; Zhao, Z.; Hong, K.; Wang, Y., Fingerprinting Molecular Relaxation in Deformed Polymers. Phys. Rev. X 2017, 7, 031003). In this work, we further examine the microscopic relaxation mechanism of entangled polymer melts after a large step uniaxial extension by using large-scale molecular dynamics simulation. We show that the unique structural features associated with the chain retraction mechanism of the tube model are absent in our simulations, in agreement with the previous experimental results. In contrast to SANS experiments, molecular dynamics simulations allow us to accurately and unambiguously determine the evolution of the radius of gyration tensor of a long polymer chain after a large step deformation. Contrary to the prediction of the tube model, our simulations reveal that the radius of gyration in the perpendicular direction to stretching increases monotonically toward its equilibrium value throughout the stress relaxation. These results provide a critical step in improving our understanding of nonlinear rheology of entangled polymers.