Al
2O
3-CaO-Cr
2O
3 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
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Al
2O
3-CaO-Cr
2O
3 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 Cr
2O
3, (Al
1−xCr
x)
2O
3 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 (Al
2O
3-CaO-Cr
2O
3-O
2 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 Cr
2O
3, the stability of (Al
1−xCr
x)
2O
3 against CAC was much higher, which improved gradually with the concentration of Al
2O
3 in (Al
1−xCr
x)
2O
3. The substitution of Cr
2O
3 with (Al
1−xCr
x)
2O
3 in the Al
2O
3-CaO-Cr
2O
3 castables could completely inhibit the formation of Cr(VI) compound CaCrO
4 at 500–1100 °C and could drastically suppress Ca
4Al
6CrO
16 generation at 900 to 1300 °C. The Cr(VI) reduction amounting up to 98.1% could be achieved by replacing Cr
2O
3 with (Al
1−xCr
x)
2O
3 solid solution. However, in situ stabilized Cr(III) phases as a mixture of (Al
1−xCr
x)
2O
3 and Ca(Al
12−xCr
x)O
19 solid solution hardly reveal any reoxidation. Moreover, the CA
6 was much more stable than CA and CA
2, and it did not participate in any chemical reaction with (Al
1−xCr
x)
2O
3 solid solution.
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