Spectroscopic and Surface Crystallization Characterizations of Yttrium-Doped Phosphate Glasses

The composition, structure, and thermal behaviors of yttrium-containing phosphate glasses were studied in this work, and the glass-ceramics were prepared via the two-step crystallization method. The XRD and SEM-EDS results show the forming range of the phosphate glass system and the formation of YPO4 (xenotime) due to the addition of excessive Y2O3. The spectroscopic characterization of these glasses presented shifts of the infrared and Raman bands, demonstrating the depolymerization of the glass network and the formation of novel P–O–Y bonds, and the deconvoluted Raman spectra also exhibited the occurrence of the disproportionation reaction in the glass melting process. The content of non-bridging oxygen (NBOs) from the UV–vis spectra first increased and then decreased with increasing Y2O3. The thermal behaviors show that the Y2O3 reduced the crystallization peak temperature and the thermal stability of the glasses. The crystalline behaviors of the phosphate glass matrix were investigated at different crystallization times of 2–10 h, and a transformation of the crystallization mechanism from surface to volume crystallization was found. The yttrium phosphate glass-ceramics crystallized for 10 h exhibited transformation of the main crystalline phases with increasing Y2O3, and the grain-oriented crystalline surface became irregular.

The chemistry of melting oxynitride phosphate glasses

Oxide glasses are the most commonly studied non-crystalline materials in Science and Technology, though compositions where part of the oxygen is replaced by other anions, e.g. fluoride, sulfide or nitride, have given rise to a good number of works and several key applications, from optics to ionic conductors. Oxynitride silicate or phosphate glasses stand out among all others because of their higher chemical and mechanical stability and their research continues particularly focused onto the development of solid electrolytes. In phosphate glasses, the easiest way of introducing nitrogen is by the remelting of the parent glass under a flow of ammonia, a method that allows the homogeneous nitridation of the bulk glass and which is governed by diffusion through the liquid-gas reaction between NH3 and the PO4 chemical groupings. After nitridation, two new structural units appear, the PO3N and PO2N2 ones, where nitrogen atoms can be bonded to either two or three neighboring phosphorus, thus increasing the bonding density of the glass network and resulting in a quantitative improvement of their properties. This short review will gather all important aspects of the synthesis of oxynitride phosphate glasses with emphasis on the influence of chemical composition and structure.