Chromium-Free Binding System for Basic Refractories

"The basic refractories used in non-ferrous industry contain chrome ore for improving the thermal shock resistance, thus reducing the penetration of molten metal and fayalite-type slags into the lining. The current study aims to replace chrome ore with Me4+ ions along with Fe3+ ions in order to form MgO-Al2O3- FeOx-Me4+O2 based complex spinel systems that could perform similar to the complex chromia-bearing spinel in the magnesia-chrome refractories. This system allows for lower temperatures of synthesis and sintering. In our study, compositions with 60% MgO were fired below 1500°C and resulted in complete formation of complex spinel, and open porosity less than 5%. The in-situ formation of the complex spinel from the fine mix of oxides in the MgO-Al2O3-FeOx-Me4+O2 system offers a suitable alternative of binding system to produce basic refractories at lower temperatures and of similar physical and mechanical properties with magnesia-chrome bricks fired above 1750ºC. INTRODUCTIONThe synthesis of magnesium aluminate spinel (MgAl2O4) (Maschio, Fabbri, & Fiori, 1988) or magnesium chromate spinel (MgCr2O4) from their respective oxides is diffusion controlled resulting in a sluggish reaction even at high temperatures. For instance, the diffusion of Mg2+ and Al3+ ions in the intermediate spinel layer during reaction is slower than the diffusion of Mg2+ in corundum and Al3+ in periclase. The interfacial layer of spinel formed during the reaction increases the diffusion path for the spinel forming cations. This accompanied by ~8% volume expansion retards further reaction resulting in incomplete spinel forming reaction during sintering and hence densification during the reaction cannot be achieved. In order to assess sintering studies with fine particulate oxides that would result in a lower diffusion path, a mechanical mixture of the hydroxides of aluminium and magnesium calcined at 1400ºC to 1600ºC for 1 hour does not result in complete spinel formation (Sarkar, Das, & Banerjee, 2003), which indicates that reaction sintering of stoichiometric magnesium aluminate spinel is retarded by initial reaction forming the interfacial spinel layer. The basic bricks used as linings in non-ferrous pyro-metallurgical convertors are manufactured using magnesia and chrome ore, the sintering of which produce spinel solid solution. This solid solution is a mix of both normal and inverse spinel structures that sinters at temperatures in excess of 1800ºC in air."