, Volume 40, Issue 17, pp 4571-4577

The ZrO2-TiO2 phase diagram

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Abstract

The ZrO2-TiO2 phase diagram was determined experimentally between 800 and 1200°C, 1 atm, extending our knowledge of this system to temperatures previously inaccessible for equilibrium experiments due to sluggish kinetics. The crystallization of the ordered (Zr,Ti)2O4 phase from the oxides was facilitated by the addition of flux (CuO or Li2MoO4/MoO3), and seeds. Two ordered (Zr,Ti)2O4 phases with different compositions were identified, and their phase relationships with TiO2 and ZrO2 solid solutions investigated. Structure data, superstructure reflections and composition were used to locate the ordering phase transition of (Zr,Ti)2O4 in equilibrium with ZrO2 and TiO2. At the onset of ordering between 1130 and 1080°C, (Zr,Ti)2O4 is of composition XTi = 0.495 ± 0.02, and displays a dramatic change in b-dimension. At 1060°C and below, the composition of (Zr,Ti)2O4 is significantly more Ti-rich and dependent on temperature, ranging from XTi = 0.576 at 1060°C to 0.658 at 800°C. This variability in composition of the ordered phase contrasts with previous studies that suggested the composition to be constant at either XTi = 0.667 [ZrTi2O6] or 0.583 [Zr5Ti7O24]. When grown at low temperatures and with lithium molybdate, the crystals of ordered (Zr,Ti)2O4 are acicular to needle shape, and develop distinct square cross-sections and end facets.