Orientational origin of nonlinear shear rheology in unentangled polymer melts

Abstract

Universal rheological properties of unentangled polymer melts are investigated through the stretch-orientation decomposition of polymer dynamics. By externalizing stretch from the explicit state of each Rouse mode, we construct a constitutive model with orientational kinetics that preserves the Rouse relaxation spectrum. The resulting model yields the observed steady-shear scalings of the shear viscosity and first normal-stress coefficient, predicts a finite second normal-stress coefficient, and approximately reproduces the Cox-Merz and Gleissle-Osaki rules. The derived steady-oscillatory shear correspondence further identifies an elastic contribution, associated with the first normal stress difference, that is absent from the conventional Cox-Merz rule.