Calcite as a Mineralizer and Stabilizer for Low-Cost Zirconia-Mullite-Alumina Composites Synthesized from Siliceous Clay, Alumina and Zirconia

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Fused zirconia-mullite (ZM) and zirconia-alumina (ZA) are expensive aggregates used in refractory formulations to enhance thermal shock tolerance and corrosion resistance, respectively. A cost-effective alternative approach was explored in this work to produce 37.4 wt% ZrO2 containing ZM utilizing conventional reaction sintering of siliceous clay, calcined alumina and monoclinic ZrO2. A series of chemical reactions ensued from 1200 °C, forming low quartz and cristobalite from the clay, in situ ZrSiO4, monoclinic ZrO2, α-Al2O3 and traces of leucite. 1600 °C was required to fully form mullite and monoclinic ZrO2 but it had 26.5% porosity even after firing at 1650 °C for 2 h. It consisted of small equiaxed primary mullite grains secondary mullite rods, and scattered and clustered, round ZrO2 grains. With 1.05% CaO addition, tetragonal ZrO2 formed, but 22.7% porosity remained despite the presence of 13.5% liquid phase having a low viscosity (0.6 Pa.s, from FactSage). With 2.11% CaO, porosity reduced to 10.7% but mullite partly dissolved, forming α-Al2O3 (ZMA aggregate). The added CaO mostly remained in the intergranular glassy phase rather than inside the ZrO2 grains but increased the thickness of the secondary mullite and the ZrO2 grains. Mullite was completely lost with 4.21% CaO doping but favorably formed cubic ZrO2 containing up to 0.26 at% Ca, interlinked α-Al2O3 rods and attained a low porosity of 0.2%. This ZA aggregate is limited to 1550 °C application temperature as excess liquid phase drained out beyond that. 7.37% CaO addition was detrimental as it formed an excessive anorthite-like liquid phase that percolated out at 1550 °C with 5.6% weight loss. Thus, in ZM-based calcium aluminate cement bonded refractory castables, the final CaO content should be restricted to below 2.1% to avoid partial dissolution of mullite.