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Thermoreversible associating polymer networks. I. Interplay of thermodynamics, chemical kinetics, and polymer physics

2009/08/31 by Robert S. Hoy, Glenn H. Fredrickson
Chemistry · Engineering · Materials Science · Physics and Astronomy · #Chemistry #Classical mechanics #Kinetics #Material Dynamics and Properties #Materials science #Organic chemistry #Phase Equilibria and Thermodynamics #Physics #Polymer #Polymer composites and self-healing #Polymer physics #Polymer science #Statistical physics #Thermodynamics #cond-mat.mtrl-sci #cond-mat.soft

paper · pdf · doi:10.1063/1.3268777

Many minor revisions; accepted for publication in JCP

arxiv created 2009/11/06 · openalex publication_date 2009/12/10 · arxiv updated 2015/05/13 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

Hybrid molecular dynamics/Monte Carlo simulations are used to study melts of unentangled, thermoreversibly associating supramolecular polymers. In this first of a series of papers, we describe and validate a model that is effective in separating the effects of thermodynamics and chemical kinetics on the dynamics and mechanics of these systems, and is extensible to arbitrarily nonequilibrium situations and nonlinear mechanical properties. We examine the model's quiescent (and heterogeneous) dynamics, nonequilibrium chemical dynamics, and mechanical properties. Many of our results may be understood in terms of the crossover from diffusion-limited to kinetically limited sticky bond recombination, which both influences and is influenced by polymer physics, i.e., the connectivity of the parent chains.

Citations