Radiochemical ageing of highly filled EPDM seals as revealed by accelerated ageing and ageing in-service for 21 years

Highly filled EPDM rubber used in cable transit seals in nuclear power plants were exposed to γ radiation at a high dose rate at 23 °C in media with different oxygen partial pressures (1-21.2 kPa). The motivation of this study was threefold: highly filled polymers are replacing halogen-containing polymers and these materials have rendered less attention in the literature; there is a need to find efficient tools to make possible condition monitoring and extrapolation. Several profiling methods were used: IR microscopy, micro-indentation, micro-sample extraction/gravimetry and non-invasive NMR spectroscopy, and three different deterioration processes were identified: polymer oxidation, migration of low molar mass species, and anaerobic changes in the polymer network. IR microscopy, micro-indentation profiling and the portable NMR method confirmed diffusion-limited oxidation in samples irradiated in air. The inner non-oxidized part of the blocks showed a pronounced change in the indenter modulus by migration of primarily glyceryl tristearate - migration was accelerated by the presence of oxygen in the surface layer - and anaerobic changes in the polymer network. For extrapolation or for condition monitoring, it is best to use the data obtained by indenter modulus profiling and to use the correlation between indenter modulus and strain-at-break to quantify the sample status. Non-invasive NMR profiling provided useful data but was less precise than the indenter modulus data to predict the strain-at-break.