In this paper, the corrosion mechanism of commercial alumina-spinel refractory was investigated at 1350 and 1450 °C. Disc samples were coated with shells of two different slags containing 4 and 10 wt.% SiO₂. The after-corrosion refractory was investigated in view of changes in its microstructure and phase composition by SEM/EDS and XRD techniques, respectively. At 1350 °C slags slightly infiltrated the microstructure, whereas at 1450 °C slags infiltrated the alumina-spinel refractory causing its significant corrosion. As a result of corrosion, new phases were formed, including calcium dialuminate (Ca₂Al₄O₇), calcium hexaluminate (CaAl₁₂O₁₉), and gehlenite (Ca₂AlSi₂O₇). Formation of calcium aluminate layers in the microstructure of the refractory inhibited further dissolution of alumina aggregates; however, expansive behavior of CaAl₁₂O₁₉ raised the microstructure porosity. The additional SiO₂ in the slag doubled the amount of low melting gehlenite in the matrix, accelerating the corrosion process of alumina-spinel brick at high temperatures.

Chemical resistance of commercial refractory raw materials against Cu slag is critical to consider them as candidates for the production of refractories used in Cu metallurgy. In this study, we show the comparative results for the corrosion resistance of four commercial refractory raw materials—magnesia chromite co-clinkers FMC 45 and FMC 57, PAK, and fused spinel SP AM 70—against aggressive, low-melting PbO-rich Cu slag (Z1) determined by hot-stage microscopy (up to 1450 °C) and pellet test (1100 and 1400 °C). Samples were characterized after the pellet test by XRD, SEM/EDS, and examination of their physicochemical properties to explore the corrosion reactions and then assess comparatively their chemical resistance. Since many works have focused on corrosion resistance of refractory products, the individual refractory raw materials have not been investigated so far. In this work, we show that magnesia chromite co-clinker FMC 45 exhibits the most beneficial properties considering its application in the production of refractories for the Cu industry. Forsterite (Mg₂SiO₄) and güggenite (Cu₂MgO₃) solid solutions constitute corrosion products in FMC 45, and its mixture with slag shows moderate dimensional stability at high temperatures. On the other hand, the fused spinel SP AM 70 is the least resistant to PbO-rich Cu slag (Z1); it starts to sinter at 970 °C, followed by a fast 8%-shrinkage caused by the formation of güggenite solid solution in significant amounts.