Mechanism of antioxidant interaction on polymer oxidation by thermal and radiation ageing

Seguchi, Tadao*; Tamura, Kiyotoshi; Shimada, Akihiko; Sugimoto, Masaki; Kudo, Hisaaki*

The mechanism of polymer oxidation by radiation and thermal ageing was investigated for the life evaluation of cables installed in radiation environments. The antioxidant as a stabilizer was much effective for thermal oxidation with a small content in polymers, but was not effective for radiation oxidation. The ionizing radiation induced the oxidation to result chain scission even at low temperature, because the free radicals were produced and the antioxidant could not stop the oxidation of radicals with the chain scission. A new mechanism of antioxidant effect for polymer oxidation was proposed. The effect of antioxidant was not the termination of free radicals in polymer chains such as peroxy radicals, but was the depression of initial radical formation in polymer chains by thermal activation. The antioxidant molecule was assumed to delocalize the activated energy in polymer chains by Boltzmann statics (distribution) to result decrease the probability of radical formation at a given temperature. The interaction distance (delocalization area) by one antioxidant molecule was estimated to be 5-10 nm in polymer matrix, though the value would depend on the chemical structure of antioxidant.