Molecular degradation of concentrated polystyrene solutions in a fast transient extensional flow

The extensional degradation of concentrated polymer solutions is studied. Extensional flows are prevalent in the polymer processing industry, but their effect on polymer degradation is often overlooked. Previous research into dilute solution extensional degradation proved that this type of flow is much more effective than shear flow in causing chain scission. This research extends these dilute solution studies into the concentrated regime, where intermolecular entanglements are expected to affect chain scission. A concentrated polystyrene solution is degraded in an opposed pistons device. This device cycles the solution across a sharp contraction, imposing a strong extensional flow. The flow field is modeled to determine the extension rate along the centerline, and the degradation is quantified by measuring the zero shear viscosity and the molecular weight distribution. The results show that degradation is more significant compared to dilute solutions. The zero shear viscosity drops 30% after a single pass across the orifice at high strain rates. As in a dilute solution, the extensional flow leads to preferential cleavage of the high molecular weight chains. All chains longer than a measured critical molecular weight are ruptured. Multiple passes across the orifice increase chain scission, although degradation is the most significant in the first pass through the high strain rate region.