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Title: Molecular and Kinetic Models for High-rate Thermal Degradation of Polyethylene

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Thermal degradation of polyethylene is studied under the extremely high rate temperature ramps expected in laser-driven and X-ray ablation experiments—from 1010 to 1014 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. The enthalpy, dissociation onset temperature, bond evolution, and observed cross-linking are shown to be rate dependent. These results are used to parametrize a kinetic rate model for the decomposition and coalescence of hydrocarbons as a function of temperature, temperature ramp rate, and density. In conclusion, the results are contrasted to first-order random-scission macrokinetic models often assumed for pyrolysis of linear polyethylene under ambient conditions.

Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000; NA0003525
OSTI ID:
1426803
Report Number(s):
SAND--2018-1785J; 660747
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 16 Vol. 122; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Water desorption from rapidly-heated metal oxide surfaces—first principles, molecular dynamics, and the Temkin isotherm journal October 2018

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