A tube based configuration formalism for entangled linear polymers under flow

by Leygue, Adrien

In this thesis, we propose a new microstructural model to describe the rheology of entangled linear polymers. In order to reduce the number of non-linear adjustable parameters, we develop a model capable of predicting both the linear and the non-linear response, using a single set of material parameters. In a first step, a linear differential formulation of the thermal constraint release mechanism is introduced and validated against experimental results for linear polystyrene melts. In a second step, we extend the linear model to the non-linear regime by generalizing the state variables to conformation tensors and accounting for the relevant non-linear relaxation phenomena. The numerical predictions of the resulting model are then compared to experimental data for entangled polymer melts and solutions in different flow regimes. Finally, we show, on a simple reptation model, how the single generator bracket formalism of non-equilibrium thermodynamics can be used for the phenomenological improvement of microstructural constitutive models.