Molecular and Kinetic Models for High-Rate Thermal Degradation of Polyethylene

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...

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Bibliographic Details
Published in:	The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2018-04, Vol.122 (16), p.3962-3970
Main Authors:	Lane, J. Matthew D, Moore, Nathan W
Format:	Article
Language:	eng
Subjects:	INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Online Access:	Get full text
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Summary:	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. The results are contrasted to first-order random-scission macrokinetic models often assumed for pyrolysis of linear polyethylene under ambient conditions.
ISSN:	1089-5639 1520-5215