Molecular drag–strain coupling in branched polymer melts

Abstract

The “pom-pom” model of McLeish and Larson [J. Rheol. 42, 81–110 (1998)] provides a simple molecular theory for the nonlinear rheology of long chain branched polymer melts. A feature of this model is a maximum stretch for the branched molecules. Sharp transitions were predicted in the extensional viscosity at this maximum stretch. We introduce a simple treatment of the coupling between relaxed and unrelaxed polymer segments at branch points. The branch point is allowed to move in a quadratic localizing potential of unknown strength. Taking account of this effect smoothes the sharp transitions of the model and accounts for the extensional viscosity of “pom-pom” model polymers at their maximum stretch. The result is an improved multimode pom-pom fit for low-density polyethylene rheology. By fitting the nonlinear extensional viscosity, quantitative predictions are made for the nonlinear steady shear viscosity and transient first normal stress difference in shear.