Investigating the Transition between Polymer Melts and Solutions in Nonlinear Elongational Flow

The Doi–Edwards tube model, coupled with relaxation mechanisms, such as reptation, contour length fluctuation, and constraint release, allows us to quantitatively predict the linear viscoelastic properties of entangled polymers. However, for nonlinear elongational flows, large discrepancies between theoretical predictions based on the tube model and experimental results still persist today. This is in particular obvious for the experimentally observed strong qualitative differences in extensional flow of entangled polystyrene (PS) melts and solutions despite having the same number of entanglements and exhibiting the same linear viscoelastic behavior. The cause of this non-universality is often attributed either to a monomeric friction reduction or to an interchain pressure effect. In this work, we investigate the changes in extensional flow behavior going from polymer solutions to the melt state. For this purpose, we measure with a filament stretching rheometer the nonlinear extensional responses of differently long PS chains, both in the melt state and diluted in short-chain matrices of the same polymer at varying concentrations. These concentrations have been chosen sufficiently high, such that the chains stay entangled. This allows us to discuss the influence of concentration and molar mass on the steady-state elongational viscosity to highlight scaling relations. The purpose of the present work is to conduct well-defined experiments to further investigate how the steady extensional viscosity of polymer solutions and blends varies with the concentration and with the molecular weight of the chains.