Thermal,Structural, and Crystallization Properties of New Tantalum Alkali‐Germanate Glasses

In this work, new glass compositions were prepared in the ternary system GeO₂–K₂O–Ta₂O₅. Potassium oxide was added to reach the complete melt of the starting mixture and two composition series were investigated: the first one with a constant K₂O molar content of 10% in the ternary system (90–x)GeO₂–10K₂O–xTa₂O₅ and the second one with the same molar content of K₂O and Ta₂O₅ in the ternary system (100–2x)GeO₂–xK₂O–xTa₂O₅. Homogeneous and transparent glasses could be obtained between x = 0 and 20. X‐ray diffraction analyzes of samples with x = 25 identified orthorhombic Ta₂O₅ in the first series and an isostructure of K_3.8Ge₃Nb₅O_20.4 in the second series where it is assumed that Ta⁵⁺ ions are inserted in the Nb⁵⁺ sites. As one of our goal with these materials is related with the preparation of glass‐ceramics containing Ta₂O₅ nanocrystals, the first series has been selected for further characterizations. An increase in glass‐transition temperatures with increasing Ta₂O₅ content as well as an increase of the thermal stability from x = 0 to 10 has been identified by differential scanning calorimetry. For higher contents, crystallization events were identified. Fourier transform infrared and Raman spectroscopic characterizations allowed to point out the intermediary behavior of Ta₂O₅ in the vitreous network where TaO₆ octahedra are inserted inside the germanate network with TaO₆ clusters identified at higher Ta₂O₅ contents. Heat‐treated samples with high tantalum contents (x = 15 and 20) exhibit preferential precipitation of orthorhombic Ta₂O₅ with nanometric size, suggesting the possibility of obtaining transparent glass‐ceramics for optical applications.