High-temperature thermal degradation of polyethylene from reactive molecular dynamics

Thermal degradation of polyethylene is studied under extremely high-rate temperature ramp rates from 10$^{14}$ to 10$^{10}$ K/s in isochoric, condensed phases. The molecular evolution and macroscopic state variables are extracted as a function of density from reactive molecular dynamics simulations using the ReaxFF potential. These results are used to parameterize a kinetic rate model for the dissociation and coalescence of hydrocarbons as a function of temperature, temperature ramp rate, and density. The results are contrasted to first-order random-scission macrokinetic models often assumed for pyrolysis of linear polyethylene under ambient conditions. Sandia National Laboratories is a multi program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04- 94AL85000.