The influence of niobium on the structure of Nb2O5–ZnO–P2O5 glasses

Abstract

Bulk glasses of the compositional series (A) xNb2O5–(50-x)ZnO–50P2O5 and (B) xNb2O5–50ZnO-(50-x)P2O5 were prepared to investigate possible substitution of cation (Zn2+), series A, and anion (PO3−), series B, with niobium and the effect of this substitution on the structure, density, molar volume, glass transition temperature and coefficient of thermal expansion. The structure was studied by Raman and 31P MAS NMR spectroscopies. The chemical model, based on the idea of chemical compounds as components with the lowest Gibbs energy and therefore the most stable, and on the results of 31P MAS NMR spectroscopy, was proposed for series B. It was found that niobium acts in glasses of series B only as a cation NbO3+, unlike the original idea of forming an anion of NbO−, that is, similarly to series A, where it replaces the cation. This leads to a change in the metaphosphate network of series B to the network that is similar to series A glass. The validity of this idea was verified by experimentally obtained compositional dependencies of molar volume, glass transition temperature and thermal expansion coefficient. Changes observed in thermal measurements indicate the evolution of a more rigid structure and more intensive cross-linking of the phosphate chains with increasing content of niobium.