Phase formation in the system ZrxTa1–x(O,N)y has been studied by ammonolysis of Zr-Ta gels, prepared by the sol–gel technique, at temperatures between 700 and 1000 °C. The starting gels and observed phases were characterised by X-ray powder diffraction (XRPD), scanning and transmission electron microscopy (SEM and TEM) and thermogravimetric (TG) analysis. Oxynitride phases of compositions ZrxTa1–xO1 +xN1–x, 0≤x≤1, with the baddeleyite-type structure, were prepared at 800 °C. The unit-cell volume increased linearly from 127.8 Å3 for TaON (x= 0) to 140.9 Å3 for ZrO2(x= 1). The structure was verified for the composition Zr0.4Ta0.6O1.6N0.4(x= 0.4) by a Rietveld refinement (RF= 3.5%) using Cu-Kα1, XRPD data. An orthorhombic oxynitride phase was observed in preparations at 700 °C for 0.26 ≤x≤ 0.90 in ZrxTa1–xO1+xN1–x. Unit-cell parameters and powder X-ray reflection intensities agree with an orthorhombic ZrO2 type structure. According to X-ray data, a cubic solid solution phase with a fluorite related subcell is present in materials prepared at 900 °C for 0.26≤x≤ 0.68. However, electron microdiffraction patterns suggest a metrically monoclinic unit cell with a = 6.1 Å, b= 14.1 Å, c= 7.1 Å and β= 125°. The Ta3N5, type of structure was found to incorporate up to ca. 18 atom% Zr at 900 and 1000 °C.
1994. Vol. 4, 1293-1301 p.