Mesoscale Simulation of Polymer Pyrolysis by Coarse-Grained Molecular Dynamics: A Parametric Study.

Abstract

Full comprehension of the pyrolysis of polymer materials is crucial for the design and application of thermal protection systems; however, it involves complex phenomena at different spatial and temporal scales. To bridge the gap between the abundant atomistic simulations and continuum modeling in the literature, we perform a novel mesoscale study of the pyrolysis process using coarse-grained molecular dynamics (CG MD) simulations. Polyethylene (PE) consisting of united atoms including implicit hydrogen is considered a model polymer, and the configurational change of PE in thermal degradation is modeled by applying the bond-breaking phenomenon based on bond energy or bond length criteria. A cook-off simulation is implemented to optimize the heuristic protocol of bond dissociation by comparing the reaction products with a ReaxFF simulation. The aerobic hyperthermal pyrolysis under oxygen bombardment is simulated at a large scale of hundreds of nanometers to observe the intricate phenomena occurring from the surface to the depth inside the material. The intrinsic thermal durability of the model polymer at extreme conditions with and without oxygen environment can be effectively simulated from the proposed mesoscale simulation to predict important thermal degradation properties required for continuum-scale pyrolysis and ablation simulations. This work serves as an initial investigation of polymer pyrolysis at the mesoscale and helps understand the concept at a larger scale.