Flow induced polymer chain extension and its relation to fibrous crystallization

Abstract

This work examines the effect that appreciable molecular extension has on the crystallization of long chain molecules. Elementary theoretical considerations presented indicate that to achieve high molecular extensions in solution a longitudinal velocity gradient of strain rate about 103s-1 is required. A method of generating such a velocity gradient, involving flow between opposed jets, is reported and the nature of this flow pattern is examined and quantitatively analysed. The behaviour of polyethylene-xylene solutions in the flow field is presented, notably birefringence observations and measurements indicate that a high degree of molecular alinement can be achieved in specific localized areas of the flow field; also concentration effects are observed which are discussed in terms of entanglement concepts. The effect chain alinement has on crystallization is examined in detail, in particular the ‘shish kebab ’ morphology of the crystals so produced is examined in relation to the hydrodynamic conditions in which they were grown.