Crystallization Kinetics of LaF3 Nanocrystals in an Oxyfluoride Glass

Nanocrystallization of LaF3 in a glass of composition 55SiO(2)-20Al(2)O(3)-15Na(2)O-10LaF(3) (mol%) has been achieved by heat treatment above the glass transition temperature. A maximum crystal size of 14 nm has been attained, with the crystalline fraction and crystal size dependent on the time and temperature of thermal treatment. The effect of lanthanum fluoride crystallization is noticeable from the microstructural and compositional changes in the glass matrix, which have been studied using several techniques, including viscosity, dilatometry, X-ray diffraction, and quantitative Rietveld refinement, transmission electron microscopy, and differential scanning calorimetry. The crystallization mechanism is shown to occur via regions of La- and Si-phase separation in the glass, from which the fluoride crystals develop during heat treatment. The interface between the glass matrix and the crystals in the demixed ranges is enriched in network formers, mainly SiO2, creating a viscous barrier, which inhibits further crystal growth and limits the crystal size to the nanometric range.