General solutions for the oxidation kinetics of polymers

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The simplest general kinetic schemes applicable to the oxidation of polymers are presented, discussed and analyzed in terms of the underlying kinetic assumptions. For the classic basic autoxidation scheme (BAS), which involves three bimolecular termination steps and is applicable mainly to unstabilized polymers, typical assumptions used singly or in groups include (1) long kinetic chain length, (2) a specific ratio of the termination rate constants and (3) insensitivity to the oxygen concentration (e.g., domination by a single termination step). Steady-state solutions for the rate of oxidation are given in terms of one, two, three, or four parameters, corresponding respectively to ... continued below

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14 p.

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Gillen, K.T.; Clough, R.L. & Wise, J. August 1, 1996.

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  • Sandia National Laboratories
    Publisher Info: Sandia National Labs., Albuquerque, NM (United States)
    Place of Publication: Albuquerque, New Mexico

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Description

The simplest general kinetic schemes applicable to the oxidation of polymers are presented, discussed and analyzed in terms of the underlying kinetic assumptions. For the classic basic autoxidation scheme (BAS), which involves three bimolecular termination steps and is applicable mainly to unstabilized polymers, typical assumptions used singly or in groups include (1) long kinetic chain length, (2) a specific ratio of the termination rate constants and (3) insensitivity to the oxygen concentration (e.g., domination by a single termination step). Steady-state solutions for the rate of oxidation are given in terms of one, two, three, or four parameters, corresponding respectively to three, two, one, or zero kinetic assumptions. The recently derived four-parameter solution predicts conditions yielding unusual dependencies of the oxidation rate on oxygen concentration and on initiation rate, as well as conditions leading to some unusual diffusion-limited oxidation profile shapes. For stabilized polymers, unimolecular termination schemes are typically more appropriate than bimolecular. Kinetics incorporating unimolecular termination reactions are shown to result in very simple oxidation expressions which have been experimentally verified for both radiation-initiated oxidation of an EPDM and thermoxidative degradation of nitrile and chloroprene elastomers.

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14 p.

Notes

OSTI as DE96011687

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  • 18. annual international conference on advances in the stabilization and degradation of polymers, Luzern (Switzerland), 19-21 Jun 1996

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  • Other: DE96011687
  • Report No.: SAND--96-1480C
  • Report No.: CONF-9606247--1
  • Grant Number: AC04-94AL85000
  • Office of Scientific & Technical Information Report Number: 273806
  • Archival Resource Key: ark:/67531/metadc664095

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  • August 1, 1996

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  • June 29, 2015, 9:42 p.m.

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  • April 14, 2016, 8:58 p.m.

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Gillen, K.T.; Clough, R.L. & Wise, J. General solutions for the oxidation kinetics of polymers, article, August 1, 1996; Albuquerque, New Mexico. (digital.library.unt.edu/ark:/67531/metadc664095/: accessed September 25, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.