Consequences of thermo- and photo-oxidation on end-use properties of pure PE

Thin films of polyethylene have been exposed to thermal and photochemical accelerated agings at different temperatures and different UV intensities. In both cases, mechanical tests performed on aged samples revealed a severe embrittlement of the PE material. However, a multi-scale analysis showed that i) under thermal oxidative conditions, such embrittlement mainly resulted from a reduction of molecular mobility of the amorphous phase due to annealing phenomena, while ii) it was rather associated to a competition between chain scission and cross-linking processes under photo-oxidative conditions. As regards the oxidation mechanisms, it was found that thermo-oxidation is clearly initiated by a bimolecular decomposition of hydroperoxides, while photo-oxidation seems rather initiated by the photolysis of ketones and hydroperoxides. Over a critical threshold of the hydroperoxide concentration, thermolysis of hydroperoxides seems to predominate and even to control the overall photo-oxidation kinetics