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.
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