Slip of polydisperse polymers: Molecular weight distribution above and below the plane of slip

Abstract

When strong slip occurs during the drag flow of highly entangled polybutadienes (PBD) in a sliding plate rheometer equipped with stainless steel parallel plates, a thin film of polymer debris remains on the substrate after the slip. This debris is assumed to be formed by the disentanglement process that occurs in strong slip at a distance of about one molecular size from the plate. In order to evaluate the composition of the debris we collected it with tetrahydrofuran and subjected it to gel permeation chromatography. It was found that the molecular weight distribution (MWD) of the debris is significantly different from that of the bulk. Moreover, in mixtures prepared from long and short PBDs with distinctly different molecular weight distributions, the MWD of the debris was found to be richer in low molecular weight components and leaner in the high molecular weight components compared to the bulk. This information is important since it reveals the compositional difference between the bulk and interfacial layer above and below the plane of slip. The difference in MWD is likely a consequence of the strong slip in which some of long chains are pulled away from the surface-adsorbed chains by the flow leaving a debris lean in the high molecular weight component.