TY - JOUR
T1 - Oxidation of crystalline polyethylene
AU - Oluwoye, Ibukun
AU - Altarawneh, Mohammednoor
AU - Gore, Jeff
AU - Dlugogorski, Bogdan Z.
N1 - Funding Information:
This study has been supported by grants of computing time from the National Computational Infrastructure (NCI) and from the Pawsey Supercomputing Centre, Australia as well as funds from Dyno Nobel Asia Pacific and the Australian Research Council (ARC). I.O. thanks Murdoch University for a postgraduate scholarship.
Funding Information:
This study has been supported by grants of computing time from the National Computational Infrastructure (NCI) and from the Pawsey Supercomputing Centre, Australia as well as funds from Dyno Nobel Asia Pacific and the Australian Research Council (ARC). I.O. thanks Murdoch University for a postgraduate scholarship.
Publisher Copyright:
© 2015 The Combustion Institute
PY - 2015/10
Y1 - 2015/10
N2 - Auto-oxidation of polyethylene (PE) is of a common occurrence and could be triggered by several physical and chemical factors. In this study, for the first time, we report a comprehensive theoretical account on the initial oxidation of crystalline PE at low temperatures prior to its melting. We map out potential energy surfaces for large number of reactions, most notably, initial abstraction by O2 molecules, formation of peroxy- and hydroperoxyl adducts, unimolecular eliminations of HO2 and H2O as well as C–C bond fissions. Rate constants have been estimated for all considered reactions over the temperature range of 300–800 K. We have discussed noticeable similarities between the oxidation of PE and that of gas-phase alkanes. Results presented herein provide new insights into the solid-state oxidation of PE and germane crystalline polyolefins/paraffins and pure carbon–hydrogen-type polymers.
AB - Auto-oxidation of polyethylene (PE) is of a common occurrence and could be triggered by several physical and chemical factors. In this study, for the first time, we report a comprehensive theoretical account on the initial oxidation of crystalline PE at low temperatures prior to its melting. We map out potential energy surfaces for large number of reactions, most notably, initial abstraction by O2 molecules, formation of peroxy- and hydroperoxyl adducts, unimolecular eliminations of HO2 and H2O as well as C–C bond fissions. Rate constants have been estimated for all considered reactions over the temperature range of 300–800 K. We have discussed noticeable similarities between the oxidation of PE and that of gas-phase alkanes. Results presented herein provide new insights into the solid-state oxidation of PE and germane crystalline polyolefins/paraffins and pure carbon–hydrogen-type polymers.
KW - Density functional theory
KW - Kinetics and thermochemical parameters
KW - Low-temperature oxidation
KW - Polyethylene
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U2 - 10.1016/j.combustflame.2015.07.007
DO - 10.1016/j.combustflame.2015.07.007
M3 - Article
AN - SCOPUS:84937485330
SN - 0010-2180
VL - 162
SP - 3681
EP - 3690
JO - Combustion and Flame
JF - Combustion and Flame
IS - 10
ER -