Thermal Evolutions to Glass-Ceramics Bearing Calcium Tungstate Crystals in Borate Glasses Doped with Photoluminescent Eu³⁺ Ions

Thermal evolutions of calcium-tungstate-borate glasses were investigated for the development of luminescent glass-ceramics by using Eu³⁺ dopant in a borate glass matrix with calcium tungstate, which was expected to have a combined character of glass and ceramics. This study revealed that single-phase precipitation of CaWO₄ crystals in borate glass matrix was possible by heat-treatment at a temperature higher than glass transition temperature T_g for (100-x) (33CaO-67B₂O₃)-xCa₃WO₆ (x = 8-15 mol%). Additionally, the crystallization of CaWO₄ was found by Raman spectroscopy due to the formation of W=O double bondings of WO₄ tetrahedra in the pristine glass despite starting with the higher calcium content of Ca₃WO₆. Eu³⁺ ions were excluded from the CaWO₄ crystals and positioned in the borate glass phase as a stable site for them, which provided local environments in higher symmetry around Eu³⁺ ions.