Structural Mechanism for Viscosity of Semiflexible Polymer Melts in Shear Flow.

The viscosities of semiflexible polymers with different chain stiffnesses in shear flow are studied via nonequilibrium molecular dynamics techniques. The simulation reproduces the experimentally observed results, giving a complete picture of viscosity as chain stiffness increases. Analysis of flow-induced changes in chain conformation and local structure indicates two distinct mechanisms behind a variety of viscosity curves. For polymers of small stiffnesses, it is related to flow-induced changes in chain conformation and, for those of large stiffnesses, to flow-induced instabilities of nematic structures. The four-region flow curve is confirmed for polymers of contour length close to persistence length and understood by combining the two structural mechanisms. Thus, these findings clarify the microscopic structures indicated by the macroscopic viscosity.