Atomistic simulation of flow-induced crystallization at constant temperature

¹  Department of Chemical Engineering, University of Patras & FORTH-ICE/HT - Patras, GR 26504, Greece, EU
²  Department of Chemical and Biomolecular Engineering, University of Tennessee - Knoxville, TN 37996, USA

Corresponding authors: cbaig@iceht.forth.gr bje@utk.edu

Received: 13 October 2009
Accepted: 25 January 2010

Abstract

Semi-crystalline fibers, such as nylon, orlon, and spectra, play a crucial role in modern society in applications including clothing, medical devices, and aerospace technology. These applications rely on the enhanced properties that are generated in these fibers through the orientation and deformation of the constituent molecules of a molten liquid undergoing flow prior to crystallization; however, the atomistic mechanisms of flow-induced crystallization are not understood, and macroscopic theories that have been developed in the past to describe this behavior are semi-empirical. We present here the results of the first successful simulation of flow-induced crystallization at constant temperature using a nonequilibrium Monte Carlo algorithm for a short-chain polyethylene liquid. A phase transition between the liquid and crystalline phases was observed at a critical flow rate in elongational flow. The simulation results quantitatively matched experimental X-ray diffraction data of the crystalline phase. Examination of the configurational temperature generated under flow confirmed for the first time the hypothesis that flow-induced stresses within the liquid effectively raised the crystallization temperature of the liquid.