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

Abstract

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.

Authors:
ORCiD logo [1];  [1]
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  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1426803
Report Number(s):
SAND-2018-1785J
Journal ID: ISSN 1089-5639; 660747; TRN: US1802574
Grant/Contract Number:  
AC04-94AL85000; NA0003525
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 122; Journal Issue: 16; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lane, J. Matthew, and Moore, Nathan W. Molecular and Kinetic Models for High-rate Thermal Degradation of Polyethylene. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.7b11180.
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Lane, J. Matthew, & Moore, Nathan W. Molecular and Kinetic Models for High-rate Thermal Degradation of Polyethylene. United States. https://doi.org/10.1021/acs.jpca.7b11180
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Lane, J. Matthew, and Moore, Nathan W. Thu . "Molecular and Kinetic Models for High-rate Thermal Degradation of Polyethylene". United States. https://doi.org/10.1021/acs.jpca.7b11180. https://www.osti.gov/servlets/purl/1426803.
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@article{osti_1426803,
title = {Molecular and Kinetic Models for High-rate Thermal Degradation of Polyethylene},
author = {Lane, J. Matthew and Moore, Nathan W.},
abstractNote = {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.},
doi = {10.1021/acs.jpca.7b11180},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 16,
volume = 122,
place = {United States},
year = {2018},
month = {2}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acs.jpca.7b11180
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Figures / Tables:

Figure 1 Figure 1: Pressure dependence on temperature for 1013 K/s ramps in polyethylene samples of density ranging from 0.3 to 0.96 g/cm3 (full density).
All figures and tables (13 total)
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    Works referencing / citing this record:

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

    • Lane, J. Matthew D.; Leung, Kevin; Thompson, Aidan P.
    • Journal of Physics: Condensed Matter, Vol. 30, Issue 46
    • DOI: 10.1088/1361-648x/aae4af
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      Figures / Tables found in this record:

      Figure 1 (p. 4)figure
      Figure 2 (p. 6)figure
      Figure 3 (p. 7)figure
      Figure 4 (p. 8)figure
      Figure 5 (p. 9)figure
      Figure 6 (p. 10)figure
      Figure 7 (p. 11)figure
      Figure 8 (p. 12)figure
      Table 1 (p. 16)table
      Table 2 (p. 17)table
      Table 3 (p. 18)table
      Figure 9 (p. 20)figure
      Figure 10 (p. 21)figure
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