Structural properties of molybdenum-lead-borate glasses

Abstract

Glasses and glass ceramics in the system xMoO 3·(100 − x)[3B 2O 3·PbO] with 0 ≤ x ≤ 30 mol% have been prepared from melt quenching method and characterized by means of X-ray diffraction, FTIR, UV–VIS and EPR spectroscopy. We have examined and analyzed the effects of systematic molybdenum ions intercalation on lead-borate glasses and glass ceramics with interesting results. The observations present in these mechanisms show the lead ions bonded ionic have a strong affinity towards [BO 3] units containing non-bridging oxygens and [MoO 4] 2− molybdate units. The pronounced affinity towards molybdate anions yields the formation of the PbMoO 4 crystalline phase. Then, the excess of oxygen can be supported into the glass network by the formation of [MoO 6] and [Mo 2O 7] structural units. Pb 2+ ions with 6s 2 configuration show strong absorption in the ultraviolet due to parity allowed s 2–sp transition and yield an absorption band centered at about 310 nm. The changes in the features of the absorption bands centered at about 310 nm can be explained as a consequence of the appearance of additional absorption shoulder due to photoinduced color centers in the glass such as the formation of borate-molybdate and lead-molybdate paramagnetic defect centers in the glasses. The concentration of molybdenum ions influences the shape and width of the EPR signals located at g ∼ 1.86, 1.91 and 5.19. The microenvironment of molybdenum ions in glasses is expected to have mainly sixfold coordination. However, there is a possibility of reduction of a part of molybdenum ions from the Mo 6+ to the Mo 5+ and Mo 4+ to the Mo 3+ states.