Zirconium silicate ceramics is widely used in different fields of engineering. One of the most actual problem of zircon ceramics is the requiring of high temperatures for its sintering. Perspective method for activation of silicate materials with the aim of intensification of synthesis and sintering processes is the low-temperature fluoridation with the ammonium hydrofluoride. In accordance with that, processes occurring during the interaction of plasma dissociated zircon and natural zircon with ammonium hydrodifluoride were studied. It was established that plasma dissociated zircon actively interacts with ammonium hydrofluoride in the solid phase. Natural zircon because of its chemical inertness reacts with ammonium hydrofluoride only when latter melts. The main product of fluorinating is ammonium hexafluorosilicate. By-products are ammonium hexafluorozirconate and ammonium heptafluorozirconate. Their quantity increases with the content of ammonium hydrofluoride in mixtures. Kinetic equation of reaction between zircon and ammonium hydrofluoride is k×τ = 1-(1-α)1/n. Activation energy of plasma dissociated zircon and natural zircon fluorinating reactions are 13.9 and 32.7 kJ/mol, respectively. Order of reactions (n) are 2.0 and 1.5, respectively. Thermal treatment of fluorinated materials at 400 °C leads to ammonium hexafluorosilicate sublimation and thermal dissociation of ammonium fluorozirconates to zirconium fluoride and fluorozirconate intermediates. It was established that low-temperature fluoridation of zircon makes possible to regulate chemical composition of minerals. Materials obtained by ammonium hydrofluoride treatment of plasma dissociated and natural zircon can be potentialy used in the functional zircon and zirconia-zircon ceramics technology.
The results of studies of the synthesis processes of baddeleyite-zircon ceramics based on fluorinated plasmadissociated and natural zircon are presented. It was found that to obtain densely sintered ceramics based on fluorinated natural zircon, the introduction of CaO is required to stabilize free ZrO2 in the composition of the ceramics. The introduction of Y2O3 into the composition of ceramics based on plasma-dissociated zircon makes it possible to reduce the sintering temperature from 1600 to 1500 °C. It is difficult to obtain ceramics based on plasmadissociated zircon with a high degree of fluorination due to the formation of an excessive amount of ZrF4.
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