Spherulitic nucleation and growth rates in a sheared polypropylene melt

Abstract

In common polymer processing operations such as injection molding, film blowing, and fiber spinning, the molten polymer is subjected to intense shear and/or elongational flow fields and crystallizes during or after the application of flow. The semicrystalline morphology that develops in the final product is typically very different from what is observed during quiescent crystallization of the same polymer, and the properties change accordingly. The possibility of controlling the final morphology and the resulting mechanical and functional properties of semicrystalline polymers based on the study of polymer melt crystallization stimulated by flow is highly intriguing. This work starts from the experimental evidence that there exists qualitatively three regimes of crystallization under shear: (a) very low shear rates, in which there is no effect on kinetics; (b) higher shear rates, in which orientational effects enhance just the nucleation and growth rates, and spherulitic crystallization is observed; and (c) high shear rates, in which molecular stretching occurs giving rise to a fibrillar morphology development under very fast kinetics. The first two regimes are explored and analyzed by means of experimental protocols developed on purpose. In particular: - spherulitic nucleation and growth rates under continuous shear rates were carefully measured and related to molecular strain - the condition below which crystallization turns out to be essentially quiescent was evidenced. © 2014 American Institute of Physics.