Gamma radiation induced effects on silica and on silica-polymer interfacial interactions in filled polysiloxane rubber

We report in our studies to assess the impact of gamma radiation on silica and on the silica-polymer interface in filled polysiloxane rubber. Electron spin resonance (ESR) and solid-state nuclear magnetic resonance (NMR) studies have been performed on samples exposed to gamma radiation. In an effort to probe directly the effect of gamma radiation on the silica surface, we employed ¹H and ²⁹Si NMR. Our ESR studies show trapped paramagnetic species (positive holes and/or trapped electrons) within the host silica matrix for all samples exposed to gamma radiation. A sample of pure cab-o-sil irradiated to a dose of 50 kGy also shows an ESR signal. Our studies on real-time aged samples (derived from field trials) also show ESR signatures indicative of silica based trapped paramagnetic species. The growth of trapped paramagnetic species as a function of gamma dose was investigated. This shows that the build up of trapped species occurs rapidly at low gamma dose before reaching saturation at about 20-30 kGy. Radiation induced band gap excitation is the likely process leading to the creation of these paramagnetic species which may be trapped in regions of local charge deficit within the silica matrix. Species that are not trapped may take part in silica surface reactions leading to changes in filler-polymer interfacial interactions. NMR studies combined with ammonia modified swell studies have shown increased polymer segmental chain mobility (softening) at low gamma dose indicative of a possible reduction in filler-polymer interfacial interactions. For those samples exposed to high gamma dose, our ammonia modified swell studies suggest increased polymer-filler interactions presumably through silica-polymer crosslinking effects. Our ¹H and ²⁹Si NMR studies on irradiated silica suggest that the silica surface is sensitive to gamma radiation. Our observations are important as they highlight the need to better control the quality (size, purity, etc.) of the silica constituent in filled polymer components used in gamma radiation environments.