Polyethylene is a model polyolefin, and a widely used material for the manufacture of many products, including cable sheaths. Understanding degradation mechanisms at the atomic scale leading to oxidation during aging is crucial for many long-term applications. The concentrations of radicals derived from oxidation and chain scission during radio-oxidation, as well as their ratio, are important parameters controlling the predominance of chain scission or crosslinking of the polymer. In this work, we propose a cryogenic EPR technique for measuring oxidation- and fragmentation-derived radicals as a less-destructive method for the evaluation of cable insulation aging and performance capability. We investigate the effect of the low-dose and high-dose radiation aging on the formation of free radicals in the polymer matrix that are both unprotected and protected by antioxidants. The stability of radicals after aging is a determinant of macroscopic processes and structural changes during aging. Under the conditions of the higher dose rate, the peroxy radical buildup is lower per dose. Peroxy radical buildup is followed by decay during aging, in accordance with POOH content. Our results allow the prediction of the capability of the antioxidant to protect the XLPE material in the function of dose and time.
Keywords: aging; cable insulation; electron paramagnetic resonance; free radicals; ionizing radiation; oxidative degradation; polymers.