Spectral properties and shielding behavior of gamma irradiated MoO3-doped silicophosphate glasses

Combined optical and infrared absorption spectra of prepared molybdenum ions in sodium silicophosphate host glasses were investigated before and after gamma irradiation with a dose of 8 Mrad (8×104 Gy). The undoped base sodium silicophosphate glass reveals strong charge transfer ultraviolet absorption but with no visible bands. This strong UV absorption is related to the presence of contaminated trace iron impurities (mainly Fe3+ ions) within the raw materials used for the preparation of this host glass. The MoO3 doped glasses exhibit extra characteristic absorption bands due to the presence of molybdenum ions in three possible valence states, the trivalent, pentavalent and hexavalent forms. Gamma irradiation of the base undoped glass increases the extension of optical absorption within the UV spectrum and produces an extra broad visible band centered at 520 nm. Such radiation-induced spectra are interpreted by assuming the formation of new induced color centers through the absorption of released electrons and formed positive holes during the irradiation process. Also, the possible formation of induced centers through photochemical transformation of some Fe2+ ions to Fe3+ ions by accepting positive holes. The presence of molybdenum ions is assumed to compete with the suggested irradiation reactions by capturing electrons and positive holes during the irradiation process.Infrared absorption spectra of the undoped and MoO3-doped glasses reveal broad IR vibrational bands which are attributed to the presence of combined characteristic vibrational IR modes due to main phosphate and partner silicate groups. The addition of MoO3 (0.5–1.5%) as dopant level causes no changes in the number and position of the main characteristic absorption bands. Gamma irradiation did not cause any marked changes in the IR spectra and the maintainance of the same main IR bands due to the stability of the network containing dual compact two glass-formers units and the presence of molybdenum ions as shielding component. The changes in intensities of some bands are correlated with changes in bond angles and/or bond lengths of some structural units as previously suggested by several authors. E.S.R. data of the MoO3-doped glasses reveal indication of several valence states of molybdenum ions as suggested by optical measurements. The irradiated samples show the change in resonance spectra of high MoO3-doped glasses which can be related to change of some Mo6+ to Mo5+ ions as deduced from optical spectra.