Effect of milling process on the electron spin resonance center formation in pyrex glass by gamma-ray irradiation

Ball-milled Pyrex glass (Coming 7740) was irradiated by gamma-rays to a dose of 30 kGy to investigate the milling effect on the formation of paramagnetic centers with ESR. The formation efficiency of E' centers was increased markedly while that of boron oxygen hole centers (BOHCs) was suppressed by 40%. An annealing experiment showed that the milling process makes BOHCs unstable, which may be the reason for the suppression. Reduction in the ESR intensity, after etching with hydrofluoric acid, clarified that both types of center are concentrated in the near-surface region in different ratios. The milling effect on E' center formation can be explained by the formation of oxygen vacancies in the near-surface region. A similar effect has already been observed in quartz. By contrast, the suppression of BOHC formation in the bulk region needs to be described by a new mechanism. We assume that internal elastic stress induced in the milled grains suppresses BOHC formation. Internal stress in the thermally tempered glass (TTG) was relieved by breaking it to submillimeter size. The observed dependence of the BOHC formation efficiency on grain size allowed us to estimate that the suppression rate per 1 MPa is more than 0.4%, which is consistent with the milling effect assuming a stress of 100 MPa.