The effect of TiO(2) on nucleation and crystallization of a Li(2)O-Al(2)O(3)-SiO(2) glass investigated by XANES and STEM

Glass ceramics based on Li(2)O/Al(2)O(3)/SiO(2) are of high economic importance, as they often show very low coefficients of thermal expansion. This enables a number of challenging applications, such as cooktop panels, furnace windows or telescope mirror blanks. Usually, the crystallization of the desired LAS crystal phases within the glasses must be tailored by a careful choice of crystallization schedule and type of nucleation agents to be used. The present work describes the formation of nanocrystalline TiO(2) within an LAS base composition that contains solely TiO(2) as nucleating agent. Using a combination of scanning transmission electron microscopy as well as X-ray absorption spectroscopy, it is found that a mixture of four- and six-fold coordinated Ti(4+) ions exists already within the glass. Heating of the glass to 740 °C immediately changes this ratio towards a high content of six-fold coordinated Ti, which accumulates in liquid-liquid phase-separation droplets. During the course of thermal treatment, these droplets eventually evolve into nanocrystalline TiO(2) precipitations, in which Ti(4+) is six-fold coordinated. Thus, it is shown that the nucleation of nanocrystalline TiO(2) is initiated by a gradual re-arrangement of the Ti ions in the amorphous, glassy matrix, from a four-fold towards a six-fold coordination.