The radio-thermal oxidation of silane cross-linked polyethylene (Si-XLPE) was studied in air under different γ dose rates (6.0, 8.5, 77.8, and 400 Gy.h −1 ) at different temperatures (21, 47, and 86 °C). The changes in the physico-chemical and mechanical properties of Si-XLPE throughout its exposure were determined by FTIR spectroscopy, differential scanning calorimetry (DSC), swelling measurements, rheometry in rubbery (DMTA) and in molten states, and uniaxial tensile testing. It was found that oxidation leads to the build-up of a wide variety of carbonyl and hydroxyl products (mostly carboxylic acids and hydroperoxides) and an efficient chain scission process that catastrophically reduces the concentration in elastically active chains and the elongation at break from the early periods of exposure. A new analytical model was derived from the current radio-thermal mechanistic scheme without making the usual assumption of thermal stability of hydroperoxides. After an initial period where the oxidation kinetics occurs with a constant rate, this model allows also predicting the auto-acceleration of the oxidation kinetics when the hydroperoxide concentration reaches a critical value of about 1.6 × 10 −1 mol.L −1 . Choosing this critical value as a structural end-of-life criterion allows a more direct assessment of the lifetime of Si-XLPE in the various radio-thermal environments under study, except at the highest temperature (i.e. 86 °C) where the kinetic model can still be noticeably improved.

The radio-thermal ageing of silane-crosslinked polyethylene (Si-XLPE) was studied in air under different γ dose rates (6.0, 8.5, 77.8, and 400 Gy·h−1) at different temperatures (21, 47, and 86 °C). The changes in the physico-chemical and electrical properties of Si-XLPE throughout its exposure were determined using Fourier transform infrared spectroscopy coupled with chemical gas derivatization, hydrostatic weighing, differential scanning calorimetry, dielectric spectroscopy and current measurements under an applied electric field. From a careful analysis of the oxidation products, it was confirmed that ketones are the main oxidation products in Si-XLPE. The analytical kinetic model for radio-thermal oxidation was thus completed with relatively simple structure–property relationships in order to additionally predict the increase in density induced by oxidation, and the adverse changes in two electrical properties of Si-XLPE: the dielectric constant ε′ and volume resistivity R. After having shown the reliability of these new kinetic developments, the lifetime of Si-XLPE was determined using a dielectric end-of-life criterion deduced from a literature compilation on the changes in R with ε′ for common polymers. The corresponding lifetime was found to be at least two times longer than the lifetime previously determined with the conventional end-of-life criterion, i.e., the mechanical type, thus confirming the previous literature studies that had shown that fracture properties degrade faster than electrical properties.