The compensation effect (Meyer–Neldel rule) on [AlO4/h+] and [TiO4/M+] paramagnetic centers in irradiated sedimentary quartz

Abstract

The effect of thermal excitation on paramagnetic defects in natural sedimentary quartz irradiated with different doses of gamma radiation was studied using electron spin resonance (ESR) spectroscopy. We report a variation in the activation energy and the frequency factor for [AlO4/h+]0 and [TiO4/M+]0 paramagnetic defects with the gamma dose, for a dose range investigated between ∼100 Gy and ∼40 000 Gy. Our results indicate that both [AlO4/h+]0 and [TiO4/M+]0 defects are less thermally stable above 1 kGy–2 kGy than below this dose range. The correlation between the two kinetic parameters (activation energy and frequency factor) satisfies the Meyer–Neldel rule. A linear correlation was found between the amplitude of the ESR signals of [AlO4/h+]0 and [TiO4/M+]0 paramagnetic defects corresponding to different doses after the application of thermal treatments in the pulse annealing procedure. We propose a mechanism involving the exchange of the cation, assigned mainly to Li+ here, between the two defects. Under irradiation, the cation is removed from [AlO4/M+]0 (forming [AlO4/h+]0) to [TiO4]− (forming [TiO4/M+]0), while under heating, the reverse mechanism takes place. The migration energy of the cation from one defect to another was found to be about 51 meV, corresponding to a temperature of about 325 °C.