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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
ORCiD logo [1];  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
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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 Lab. (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; TRN: US1802574
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 122, Issue 16; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

References (26)

Direct-drive inertial confinement fusion: A review journal November 2015
Off-Hugoniot characterization of alternative inertial confinement fusion ablator materials. journal May 2016
Thermogravimetric studies on the thermal decomposition of polyethylene journal April 1996
Detailed mechanistic modeling of high-density polyethylene pyrolysis: Low molecular weight product evolution journal May 2009
Effects of Chain Length on the Rates of C−C Bond Dissociation in Linear Alkanes and Polyethylene † journal May 2007
Assessing the effect of molecular weight on the kinetics of backbone scission reactions in polyethylene using Reactive Molecular Dynamics journal June 2011
Initial Stages of the Pyrolysis of Polyethylene journal November 2015
Simulation of thermal decomposition of a polymer at random scissions of C-C bonds journal September 2012
Statistical model of thermal degradation of linear polymers journal August 2009
Molecular Dynamics Simulation of C–C Bond Scission in Polyethylene and Linear Alkanes: Effects of the Condensed Phase journal March 2014
Study of high density polyethylene (HDPE) pyrolysis with reactive molecular dynamics journal June 2014
Applications of reactive molecular dynamics to the study of the thermal decomposition of polymers and nanoscale structures journal January 2004
A reactive molecular dynamics model of thermal decomposition in polymers: I. Poly(methyl methacrylate) journal January 2003
Population-based models of thermoplastic degradation: Using optimization to determine model parameters journal June 2009
Fast Parallel Algorithms for Short-Range Molecular Dynamics journal March 1995
ReaxFF:  A Reactive Force Field for Hydrocarbons journal October 2001
ReaxFF Reactive Force Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation journal February 2008
First-principles and classical molecular dynamics simulation of shocked polymers journal February 2010
Shock compression of hydrocarbon foam to 200 GPa: Experiments, atomistic simulations, and mesoscale hydrodynamic modeling journal September 2013
Hot spot and temperature analysis of shocked hydrocarbon polymer foams using molecular dynamics simulation journal November 2013
Visualization and analysis of atomistic simulation data with OVITO–the Open Visualization Tool journal December 2009
Pyrolysis of waste high density polyethylene (HDPE) and low density polyethylene (LDPE) plastics and production of epoxy composites with their pyrolysis chars journal November 2017
Aromaticity and degree of aromatic condensation of char journal January 2015
Chemical composition and bioavailability of thermally altered Pinus resinosa (Red pine) wood journal September 2002
Activation energies from bond energies. A modification journal December 1977
Bond Dissociation Energies of Organic Molecules journal April 2003

Figures / Tables (13)

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