2016/05/13 by Hong T. Nguyen, Robert S. Hoy
Chemical Engineering · Chemistry · Materials Science · Physics and Astronomy · #Activation energy #Arrhenius equation #Chain (unit) #Chemical physics #Chemistry #Composite material #Computational chemistry #Crystallization #Dynamical heterogeneity #Dynamics (music) #Glass transition #Liquid Crystal Research Advancements #Material Dynamics and Properties #Materials science #Microstructure #Molecular dynamics #Physical chemistry #Physics #Polymer #Rheology #Rheology and Fluid Dynamics Studies #Stiffness #Thermodynamics #cond-mat.soft
paper · pdf · doi:10.1103/physreve.94.052502
11 pages, 7 figures, submitted to J. Chem. Phys
arxiv created 2016/05/13 · openalex publication_date 2016/11/02 · arxiv updated 2016/11/23 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/06
We contrast the dynamics in model unentangled polymer melts of chains of three different stiffnesses: flexible, intermediate, and rodlike. Flexible and rodlike chains, which readily solidify into close-packed crystals (respectively, with randomly oriented and nematically aligned chains), display simple melt dynamics with Arrhenius temperature dependence and a discontinuous change upon solidification. Intermediate-stiffness chains, however, are fragile glass-formers displaying Vogel-Fulcher dynamical arrest, despite the fact that they also possess a nematic-close-packed crystalline ground state. To connect this difference in dynamics to the differing microstructure of the melts, we examine how various measures of structure, including cluster-level metrics recently introduced in studies of colloidal systems, vary with chain stiffness and temperature. No clear static-structural cause of the dynamical arrest is found. However, we find that the intermediate-stiffness chains display qualitatively different dynamical heterogeneity. Specifically, their stringlike motion (cooperative rearrangement) is correlated along chain backbones in a way not found for either flexible or rodlike chains. This activated "crawling" motion is clearly associated with the dynamical arrest observed in these systems, and illustrates one way in which factors controlling the crystallization versus glass formation competition in polymers can depend nonmonotonically on chain stiffness.