Approximations of the discrete slip-link model and their effect on nonlinear rheology predictions

Abstract

The discrete slip-link model (DSM) was developed to describe the dynamics of flexible polymer melts. The model is able to predict linear viscoelasticity of monodisperse linear, polydisperse linear, and branched systems. The model also shows good agreement with dielectric relaxation experiments, except for the single data set available for bidisperse linear systems with a small volume fraction of long chains. In this work, both shear and elongational flow predictions obtained using the DSM without parameter adjustment are shown. Model predictions for shear flow agree very well with experimental results. The DSM is able to capture the transient response as well as the steady-state viscosity. However, for elongational flow, agreement is unsatisfactory at large strains. The DSM captures the onset of strain hardening, but after a Hencky strain between 2 and 3, it predicts transient strain softening, whereas experiments show only monotonic growth. We explore a number of assumptions and approximations of the model and their effect on flow predictions. The approximations are related to the neglect of these phenomena, which are expected to be more sensitive in elongational flow: finite extensibility, convective constraint release, and deformation of dangling ends. We indeed find that shear flow predictions are insensitive to these approximations, but elongational flow is affected. However, none of these effects is able to bring prediction in line with experiments. We conclude that the currently accepted view of entanglement dynamics is incomplete.