Analysis of elongational flow of star polymers

Abstract

Star polymers with three arms are the simplest example of branched polymers. Elongational rheology data of three well-characterized monodisperse polystyrene melts, a symmetric star, an asymmetric star, and a linear polymer with the same span molecular weight of 180 kg/mol reported by Huang et al. (Macromolecules 49:6694−6699, 2016) are analyzed by the enhanced relaxation of stretch (ERS) model (Wagner and Narimissa, J Rheol 65:1413–1421, 2021). All three melts show the same elongational stress growth coefficient and the same steady-state elongational viscosity in fast extensional flows when the stretch-related Weissenberg number {Wi}_R=dot{varepsilon}{tau}_R>1. Excellent agreement between experimental data of elongational stress growth coefficient and model predictions is obtained, based exclusively on the linear-viscoelastic characterization of the polymer systems. Stress relaxation following steady elongational flow depends on the presence of the branch point and the length of the arm, and a new process regarding relaxation of the orientation of the stars is identified.