In this work the synthesis of hercynite from Fe2O3 and Al2O3 powders was carried out by arc-melting method under the protective argon atmosphere. The obtained material was characterized with the use of powder X-ray diffractometry (XRD) and Mössbauer spectroscopy (MS). A Mössbauer effect in hercynite obtained by the arc-melting method indicated the cations distribution in the spinel structure among the tetrahedral and octahedral interstices. The presence of Fe2+ ions was detected in both tetrahedral and octahedral sites while Fe3+ ions occupied only the octahedral interstices. The approximate formula of the obtained iron-aluminate spinel was as follows (Fe2+0.77Al3+0.23) (Fe3+0.07Fe2+0.05Al0.88)2O4.
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.