• français
    • English
    français
  • Login
Help
View Item 
  •   Home
  • Laboratoire Procédés et Ingénierie en Mécanique et Matériaux (PIMM)
  • View Item
  • Home
  • Laboratoire Procédés et Ingénierie en Mécanique et Matériaux (PIMM)
  • View Item
JavaScript is disabled for your browser. Some features of this site may not work without it.

Elucidating the Role of Alkoxy Radicals in Polyethylene Radio-Oxidation Kinetics

Article dans une revue avec comité de lecture
Author
AHN, Yunho
40012 Service de recherches de métallurgie physique [SRMP]
20287 CEA- Saclay [CEA]
ccROMA, Guido
20287 CEA- Saclay [CEA]
40012 Service de recherches de métallurgie physique [SRMP]
ccCOLIN, Xavier
86289 Laboratoire Procédés et Ingénierie en Mécanique et Matériaux [PIMM]

URI
http://hdl.handle.net/10985/23584
DOI
10.1021/acs.macromol.2c01135
Date
2022-09
Journal
Macromolecules

Abstract

Polyethylene is a widely used polymer and a prototypical polyolefin. Understanding degradation mechanisms at the atomic scale leading to oxidation under the effect of temperature and/or irradiation is crucial for many long-term applications. Here, we focus on a subset of reactions belonging to the generally assumed radio-oxidation reaction scheme and involving alkoxy radicals. We follow a theoretical approach based on density functional theory, in order to assess the role of these species, which are short lived and thus hard to detect experimentally. For every considered reaction, we calculate the reaction enthalpy and the energy barrier, and we evaluate the influence of the local atomic environment, taking advantage of a model surface of a crystalline lamella which mimics the interface between crystalline and amorphous zones. Our results suggest that in certain conditions, the kinetic pathway can bypass the formation of hydroperoxides. The concentrations of alkoxy and peroxy radicals during radio-oxidation and their ratio are important parameters controlling the predominance of chain scission or crosslinking in the polymer. The data presented here constitute part of a database that can be used to set up kinetic simulations based on homogeneous chemical kinetics or Monte Carlo algorithms

Files in this item

Name:
PIMM_M_2022_COLIN.pdf
Size:
3.024Mb
Format:
PDF
Description:
Elucidating the Role of Alkoxy ...
Embargoed until:
2023-03-27
View/Open

Collections

  • Laboratoire Procédés et Ingénierie en Mécanique et Matériaux (PIMM)

Related items

Showing items related by title, author, creator and subject.

  • Atomic scale mechanisms controlling the oxidation of polyethylene: A first principles study 
    Article dans une revue avec comité de lecture
    AHN, Yunho; ROMA, Guido; ccCOLIN, Xavier (2021)
    Understanding the degradation mechanisms of aliphatic polymers by thermal oxidation and radio-oxidation is very important in order to assess their lifetime in a variety of industrial applications. We focus here on polyethylene ...
  • Vieillissement thermique d’un jonc composite carbone/époxy 
    Article dans une revue avec comité de lecture
    SERROR, Maéva; LARCHE, Jean-François; ccCOLIN, Xavier (Lavoisier, 2013)
    Le vieillissement thermique d’un jonc composite carbone/époxy a été étudié dans l’air entre 160 et 220 °C par tomographie X, microscopie optique et flexion trois points. La thermo-oxydation de la matrice affecte une couche ...
  • A general kinetic model for the photothermal oxidation of polypropylene 
    Article dans une revue avec comité de lecture
    FRANÇOIS-HEUDE, Alexandre; DESNOUX, Eric; ccCOLIN, Xavier; ccRICHAUD, Emmanuel (Elsevier, 2015)
    A general kinetic model for the photothermal oxidation of polypropylene has been derived from the basic auto-oxidation mechanistic scheme in which the main sources of radicals are the thermolysis and photolysis of the most ...
  • Méthode de vieillissement accéléré au dioxyde de chlore 
    Article dans une revue avec comité de lecture
    DAUSEINS, J; EL MAZRY, Chaker; MALLET, J; CORREC, Olivier; ccCOLIN, Xavier (ASTEE/EDP Sciences, 2014)
    With the aim to study the long-term behavior of accessories used in the tap domestic water supply system, the Centre scientifique et technique du bâtiment (CSTB) has developed a tool dedicated to accelerated ageing tests ...
  • Thumbnail
    Chain branching detection by Cole–Cole modeling of rheological properties changes during PET mechanical recycling 
    Article dans une revue avec comité de lecture
    NAIT-ALI, K.L.; BERGERET, A; FERRY, L; ccCOLIN, Xavier (Elsevier, 2012)
    The detection of branched chains in thermally degraded thermoplastic polymers is far from simple, especially at a low conversion ratio, mainly because of the low sensitivity of commonly used laboratory analytical techniques. ...

Browse

All SAMCommunities & CollectionsAuthorsIssue DateCenter / InstitutionThis CollectionAuthorsIssue DateCenter / Institution

Newsletter

Latest newsletterPrevious newsletters

Statistics

Most Popular ItemsStatistics by CountryMost Popular Authors

ÉCOLE NATIONALE SUPERIEURE D'ARTS ET METIERS

  • Contact
  • Mentions légales

ÉCOLE NATIONALE SUPERIEURE D'ARTS ET METIERS

  • Contact
  • Mentions légales