Composite zircon ceramics based on raw materials activated by ammonium bifluoride

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.

Shock-twinned zircon in ejecta from the 45-m-diameter Kamil crater in southern Egypt

ABSTRACT With an age of less than ~5000 yr and a diameter of 45 m, Kamil crater in Egypt is one of the youngest and smallest terrestrial impact craters known to date. Abundant evidence of shock-deformed sandstone has been reported from Kamil crater, including shatter cones, vesicular impact glass, high-pressure polymorphs of silica and car bon, planar deformation features (PDFs) and planar fractures (PFs) in quartz, dissociated zircon, melt veins, and intergranular melt, giving rise to a range of estimated shock pressures from ~20 to ~60 GPa. Here, we investigated shocked zircon from Kamil crater through characterization of microstructures in a centimeter-sized clast of shocked nonporous sandstone ejecta, previously described as containing quartz grains with PDFs and PFs, coesite, stishovite, diamond, and lechatelierite. Orientation analysis by electron backscatter diffraction (EBSD) showed that the quartz arenite consists of damaged detrital quartz grains surrounded by a matrix of either comminuted quartz or intergranular melt. Individual quartz grains are pervasively fractured (abundant PFs and PDFs); apparent isotropic crushing resulted in uniformly and highly dispersed orientation clusters on pole figures. Zircon grains are not abundant; however, four of 19 grains analyzed by EBSD contained {112} deformation twin lamellae, with individual lamellae ranging in length from 1 to 2 µm. Lengths of twin lamellae in Kamil zircon grains are anomalously short compared to those report-ed in shocked zircon from other impact structures, where individual lamellae are tens of micrometers long. Previous empirical studies have suggested that {112} twin lamellae in zircon form at ~20 GPa in non-porous target rocks, a finding supported by their coexistence, in some impactites, with high-pressure phases such as reidite. The only available experimental constraint, by diamond anvil cell, found {112} twins in zircon powder quenched at 20 GPa. The presence of coesite, stishovite, lechatelierite, and shocked quartz with PDFs in the studied sample is consistent with empirically derived pressure estimates of ~20 GPa for {112} twin formation in zircon in the ejecta sample from Kamil crater. Kamil thus represents the smallest and youngest impact structure where shock-twinned zircon has been reported. Given the apparent efficiency of {112} twin formation (21% of grains), shock-twinned zircon is here shown to provide a robust and readily identifiable record of shock deformation in a relatively common mineral at one of the smallest known terrestrial impact craters.

PHASE FORMATION PROCESSES AT LOW-TEMPERATURE FLUORINATION OF ZIRCONIUM SILICATE

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.