Model Polymer Systems Replicate the Experimental Features of the Slow Arrhenius Process
Chun Li, Simone Napolitano
Abstract
We identify the dynamic signatures of the slow Arrhenius process (SAP), which is a relaxation mechanism experimentally observed in polymers and small organic molecules. By applying these criteria to the analysis of the desorption of 1,4-polybutadiene (PB) chains from a series of flat substrates, an archetypal system to investigate interfacial equilibration mechanisms, we verify that molecular dynamics (MD) simulations can reproduce the characteristic features of the SAP. By systematically exploring the role of the different components of the force field, we build up a class of model polymer systems that can be employed to study equilibration mechanisms mediated by the SAP. Our work sheds light on the molecular origin of the SAP and elucidates the role of intramolecular interactions in the relaxation of polymer melts.