High-Temperature Chemical Stability of Cr(III) Oxide Refractories in the Presence of Calcium Aluminate Cement

Al₂O₃-CaO-Cr₂O₃ castables are used in various furnaces due to excellent corrosion resistance and sufficient early strength, but toxic Cr(VI) generation during service remains a concern. Here, we investigated the relative reactivity of analogous Cr(III) phases such as Cr₂O₃, (Al_1−xCr_x)₂O₃ and in situ Cr(III) solid solution with the calcium aluminate cement under an oxidizing atmosphere at various temperatures. The aim is to comprehend the relative Cr(VI) generation in the low-cement castables (Al₂O₃-CaO-Cr₂O₃-O₂ system) and achieve an environment-friendly application. The solid-state reactions and Cr(VI) formation were investigated using powder XRD, SEM, and leaching tests. Compared to Cr₂O₃, the stability of (Al_1−xCr_x)₂O₃ against CAC was much higher, which improved gradually with the concentration of Al₂O₃ in (Al_1−xCr_x)₂O₃. The substitution of Cr₂O₃ with (Al_1−xCr_x)₂O₃ in the Al₂O₃-CaO-Cr₂O₃ castables could completely inhibit the formation of Cr(VI) compound CaCrO₄ at 500–1100 °C and could drastically suppress Ca₄Al₆CrO₁₆ generation at 900 to 1300 °C. The Cr(VI) reduction amounting up to 98.1% could be achieved by replacing Cr₂O₃ with (Al_1−xCr_x)₂O₃ solid solution. However, in situ stabilized Cr(III) phases as a mixture of (Al_1−xCr_x)₂O₃ and Ca(Al_12−xCr_x)O₁₉ solid solution hardly reveal any reoxidation. Moreover, the CA₆ was much more stable than CA and CA₂, and it did not participate in any chemical reaction with (Al_1−xCr_x)₂O₃ solid solution.