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STRUCTURAL CHANGES IN R2 O-R O -T iO 2 -P 2O5 -R 2O3 - SiO2 GLASS DURING LIQUATION

The mechanism of microliquation in R2O – RO – TiO2 –P 2O5 –R 2O3 – SiO2 glasses is established. In these glasses, after heat treatment drop liquation leads to finely disperse volume sitallization of the crystalline component of the glass undergoing liquation. The formation of secondary spherical nonuniformities about 1 nm in size with drop-like formations intensifies the crystallization of glass after heat-treatment. An important problem in the production of finely disperse volume crystallized glasses is to establish the mechanism and kinetics of the initial stages of phase separation in them. It is known [1] that metastable liquation as an intermediate stage on the way to crystallization is energetically more favorable than stable crystallization, since the fluctuation nature of the micro-nonuniformities has a large effect on the separation of the glass during the precrystallization period [2]. The liquation mechanism of nucleation creates conditions for a uniform sitallized structure with formation of nano- and microsize crystalline phases, which largely determine the physicochemical and operational properties of crystal glass materials. Assuring microheterogeneity of the glasses by means of phase separation, the glass compositions are chosen on the corresponding phase diagrams in the region of existence of metastable liquation. It was established that the silicate systems R2 O–R O –T iO 2 –P 2O5 –R 2O3 – SiO2 are characterized by quite wide regions of liquation. In general, the main reason for liquation in oxide systems is an electrostatic force interaction between the melt ions and the associated striving of the modifier cations and glass-forming cations to create an environment from oxygen anions in accordance with the coordination numbers. In addition, the stronger the field of the modifier cation, the stronger the tendency toward liquation is. It is of special interest to study the particulars of liquation processes in calcium silico-phosphate glasses containing the cations Ti 4+ and Zn 2+ .