Polyethylene loss of ductility during oxidation: Effect of initial molar mass distribution

This paper reports a study of thermal oxidation induced embrittlement in several polyethylene grades differing mainly by the broadness of the molar mass distribution (ranging for lower than 3 to more than 30). Thermal oxidation was monitored at macromolecular scale (Gel Permeation Chromatography, Differential Scanning Calorimetry) and macroscopic scale (tensile tests). As expected, the samples undergo predominant chain scission and plastic deformation is suppressed below a critical molar mass value (M'C). Even though this latter was previously reported to be independent of the initial weight average molar mass, it is shown here that it depends on initial polydispersity index. Samples were also shown to undergo chemicrystallization, i.e. that segments released by chain scissions migrate into the crystalline phase with a yield increasing with initial polydispersity index. Finally, the main novelty of this work is to evidence that the previously proposed end-of-life criteria at macromolecular level linked to loss of ductility (critical molar mass, crystallization yield) depend on the initial polydispersity index.