Crystallization of niobium germanosilicate glasses

Niobium germanosilicate glasses are potential candidates for the fabrication of transparent glass ceramics with interesting non-linear optical properties. A series of glasses in the (Ge,Si)O2–Nb2O5–K2O system were prepared by melting and casting and their characteristic temperatures were determined by differential thermal analysis. Progressive replacement of GeO2 by SiO2 improved the thermal stability of the glasses. Depending on the composition and the crystallization heat-treatment, different nanocrystalline phases—KNbSi2O7, K3Nb3Si2O13 and K3.8Nb5Ge3O20.4 could be obtained. The identification and characterization of these phases were performed by X-ray diffraction and Raman spectroscopy. The 40 GeO2–10 SiO2–25 Nb2O5–25 K2O (mol%) composition presented the higher ability for volume crystallization and its nucleation temperature was determined by the Marottaʹs method. An activation energy for crystal growth of ∼529 kJ/mol and a nucleation rate of 9.7×1018 m−3 s−1 was obtained, for this composition. Transparent glass ceramics with a crystalline volume fraction of ∼57% were obtained after a 2 h heat-treatment at the nucleation temperature, with crystallite sizes of ∼20 nm as determined by transmission electron microscopy.