(Na, Zr) and (Ca, Zr) Phosphate-Molybdates and Phosphate-Tungstates: I-Synthesis, Sintering and Characterization.

Submicron-grade powders of Na 1-x Zr 2 (PO 4 ) 3-x (XO 4 ) x compounds (hereafter referred to as NZP) and Ca 1-x Zr 2 (PO 4 ) 3-x (XO 4 ) x compounds (hereafter, CZP), X = Mo, W (0 ≤ x ≤ 0.5) were obtained by sol-gel synthesis. The compounds obtained were studied by X-ray diffraction phase analysis and electron microscopy. An increase in the W or Mo contents was shown to result in an increase in the unit cell volume of the NZP and CZP crystal lattices and in a decrease in the coherent scattering region sizes. Thermal expansion behavior at high temperatures of synthesized NZP and CZP compounds has been investigated. The dependencies of the parameters a and c on the heating temperature, as well as the temperature dependence of the crystal lattice unit cell volume V in the range from the room temperature up to 800 °C, were obtained. The dependencies of the average thermal expansion coefficient (α av ) and of the volume coefficient (β) on the W and Mo contents in the compositions of NZP and CZP compounds were studied. Ceramics Na 1-x Zr 2 (PO 4 ) 3-x (XO 4 ) x with relatively high density (more than 97.5%) were produced by spark plasma sintering (SPS). The increase in the W or Mo contents in the ceramics leads to an increase in the relative density of NZP and to a decrease of the optimum sintering temperature. The mean grain size in the NZP ceramics decreases with increasing W or Mo contents. The study of strength characteristics has revealed that the hardness of the NZP ceramics is greater than 5 GPa, and that the minimum fracture toughness factor was 1 MPa·m 1/2 .