Flow-induced crystallization of polylactides

Abstract

In this work, the flow-induced crystallization of two polylactides (PLAs) with different microstructures (different l-lactic acid contents) is studied using simple shear, uniaxial extension and capillary flow experiments. In a simple shear and capillary flow, an increase in shear rate and a decrease in temperature were found to enhance the crystallization kinetics particularly for Weissenberg numbers (based on the reptation relaxation time, Wi) greater than 1 (strong flow causing chain stretching). On the other hand, in a uniaxial extensional flow, once a critical Hencky strain is achieved, crystallization starts independently of strain rate and temperature. The amount of mechanical work per unit volume imposed/dissipated onto the polymers during flow to initialize crystallization was also calculated in the simple shear, capillary, and extensional flow. The critical mechanical work for the onset of flow-induced crystallization was found to be independent of temperature and degree of molecular chain stretch (Wi) as Wi becomes greater than 1. The critical mechanical work for the onset of flow-induced crystallization in an extensional flow was found to be much smaller than that in a shear flow. The PLA sample with higher content of PLLA showed slightly higher zero-shear viscosity and a smaller thermodynamic barrier for the onset of crystallization. Finally, the degree of crystallinity increases linearly from 0% at the start of the flow-induced crystallization region and reaches a plateau at Wi equals to around 1.