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

Lane, J. Matthew; Moore, Nathan W.

doi:10.1021/acs.jpca.7b11180

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

Journal Article · 31 January 2018 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI: https://doi.org/10.1021/acs.jpca.7b11180 · OSTI ID:1426803

^[1]; Moore, Nathan W. ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

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.

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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

References (26)

First-principles and classical molecular dynamics simulation of shocked polymers Mattsson, Thomas R.; Lane, J. Matthew D.; Cochrane, Kyle R. Physical Review B, Vol. 81, Issue 5 https://doi.org/10.1103/PhysRevB.81.054103	journal	February 2010
Pyrolysis of waste high density polyethylene (HDPE) and low density polyethylene (LDPE) plastics and production of epoxy composites with their pyrolysis chars Sogancioglu, Merve; Yel, Esra; Ahmetli, Gulnare Journal of Cleaner Production, Vol. 165 https://doi.org/10.1016/j.jclepro.2017.07.157	journal	November 2017
Assessing the effect of molecular weight on the kinetics of backbone scission reactions in polyethylene using Reactive Molecular Dynamics Smith, K. D.; Bruns, M.; Stoliarov, S. I. Polymer, Vol. 52, Issue 14 https://doi.org/10.1016/j.polymer.2011.04.035	journal	June 2011
Effects of Chain Length on the Rates of C−C Bond Dissociation in Linear Alkanes and Polyethylene ^† Knyazev, Vadim D. The Journal of Physical Chemistry A, Vol. 111, Issue 19 https://doi.org/10.1021/jp066419e	journal	May 2007
Thermogravimetric studies on the thermal decomposition of polyethylene Conesa, Juan A.; Marcilla, A.; Font, R. Journal of Analytical and Applied Pyrolysis, Vol. 36, Issue 1 https://doi.org/10.1016/0165-2370(95)00917-5	journal	April 1996
Chemical composition and bioavailability of thermally altered Pinus resinosa (Red pine) wood Baldock, Jeffrey A.; Smernik, Ronald J. Organic Geochemistry, Vol. 33, Issue 9 https://doi.org/10.1016/S0146-6380(02)00062-1	journal	September 2002
Applications of reactive molecular dynamics to the study of the thermal decomposition of polymers and nanoscale structures Nyden, Marc R.; Stoliarov, Stanislav I.; Westmoreland, Phillip R. Materials Science and Engineering: A, Vol. 365, Issue 1-2 https://doi.org/10.1016/j.msea.2003.09.060	journal	January 2004
Initial Stages of the Pyrolysis of Polyethylene Popov, Konstantin V.; Knyazev, Vadim D. The Journal of Physical Chemistry A, Vol. 119, Issue 49 https://doi.org/10.1021/acs.jpca.5b07440	journal	November 2015
Statistical model of thermal degradation of linear polymers Koptelov, A. A.; Koptelov, I. A. Polymer Science Series B, Vol. 51, Issue 7-8 https://doi.org/10.1134/S1560090409070161	journal	August 2009
Shock compression of hydrocarbon foam to 200 GPa: Experiments, atomistic simulations, and mesoscale hydrodynamic modeling Root, Seth; Haill, Thomas A.; Lane, J. Matthew D. Journal of Applied Physics, Vol. 114, Issue 10 https://doi.org/10.1063/1.4821109	journal	September 2013
Aromaticity and degree of aromatic condensation of char Wiedemeier, Daniel B.; Abiven, Samuel; Hockaday, William C. Organic Geochemistry, Vol. 78 https://doi.org/10.1016/j.orggeochem.2014.10.002	journal	January 2015
ReaxFF Reactive Force Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation Chenoweth, Kimberly; van Duin, Adri C. T.; Goddard, William A. The Journal of Physical Chemistry A, Vol. 112, Issue 5 https://doi.org/10.1021/jp709896w	journal	February 2008
Visualization and analysis of atomistic simulation data with OVITO–the Open Visualization Tool Stukowski, Alexander Modelling and Simulation in Materials Science and Engineering, Vol. 18, Issue 1 https://doi.org/10.1088/0965-0393/18/1/015012	journal	December 2009
Activation energies from bond energies. A modification Gilliom, Richard D. Journal of the American Chemical Society, Vol. 99, Issue 26 https://doi.org/10.1021/ja00468a004	journal	December 1977
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
Direct-drive inertial confinement fusion: A review Craxton, R. S.; Anderson, K. S.; Boehly, T. R. Physics of Plasmas, Vol. 22, Issue 11 https://doi.org/10.1063/1.4934714	journal	November 2015
Molecular Dynamics Simulation of C–C Bond Scission in Polyethylene and Linear Alkanes: Effects of the Condensed Phase Popov, Konstantin V.; Knyazev, Vadim D. The Journal of Physical Chemistry A, Vol. 118, Issue 12 https://doi.org/10.1021/jp411474u	journal	March 2014
Hot spot and temperature analysis of shocked hydrocarbon polymer foams using molecular dynamics simulation Lane, J. Matthew D.; Grest, Gary S.; Mattsson, Thomas R. Computational Materials Science, Vol. 79 https://doi.org/10.1016/j.commatsci.2013.06.044	journal	November 2013
Study of high density polyethylene (HDPE) pyrolysis with reactive molecular dynamics Liu, Xiaolong; Li, Xiaoxia; Liu, Jian Polymer Degradation and Stability, Vol. 104 https://doi.org/10.1016/j.polymdegradstab.2014.03.022	journal	June 2014
Population-based models of thermoplastic degradation: Using optimization to determine model parameters Bruns, M. C.; Koo, J. H.; Ezekoye, O. A. Polymer Degradation and Stability, Vol. 94, Issue 6 https://doi.org/10.1016/j.polymdegradstab.2009.02.007	journal	June 2009
A reactive molecular dynamics model of thermal decomposition in polymers: I. Poly(methyl methacrylate) Stoliarov, Stanislav I.; Westmoreland, Phillip R.; Nyden, Marc R. Polymer, Vol. 44, Issue 3 https://doi.org/10.1016/S0032-3861(02)00761-9	journal	January 2003
ReaxFF: A Reactive Force Field for Hydrocarbons van Duin, Adri C. T.; Dasgupta, Siddharth; Lorant, Francois The Journal of Physical Chemistry A, Vol. 105, Issue 41 https://doi.org/10.1021/jp004368u	journal	October 2001
Off-Hugoniot characterization of alternative inertial confinement fusion ablator materials. Moore, Alastair S.; Prisbrey, Shon; Baker, Kevin L. Journal of Physics: Conference Series, Vol. 717 https://doi.org/10.1088/1742-6596/717/1/012038	journal	May 2016
Simulation of thermal decomposition of a polymer at random scissions of C-C bonds Koptelov, A. A.; Milekhin, Yu. M.; Baranets, Yu. N. Russian Journal of Physical Chemistry B, Vol. 6, Issue 5 https://doi.org/10.1134/S1990793112050168	journal	September 2012
Bond Dissociation Energies of Organic Molecules Blanksby, Stephen J.; Ellison, G. Barney Accounts of Chemical Research, Vol. 36, Issue 4 https://doi.org/10.1021/ar020230d	journal	April 2003
Detailed mechanistic modeling of high-density polyethylene pyrolysis: Low molecular weight product evolution Levine, Seth E.; Broadbelt, Linda J. Polymer Degradation and Stability, Vol. 94, Issue 5 https://doi.org/10.1016/j.polymdegradstab.2009.01.031	journal	May 2009

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