Iron and Steel Division - Distribution of Manganese Between Silicate and Aluminate Slags and Carbon-Saturated Iron

Limited experimental data and a critical review of the literature are given to indicate that the true equilibrium distribution of manganese between carbon-saturated iron and blast-furnace type slags has not yet been satisfactorily established as a function of the composition, temperature, and pressure of the system. THE distribution of manganese between carbon-saturated iron and blast-furnace type slags has been studied by a number of investigators.1-7 Generalization of the results of these works indicates that the weight percent distribution ratio, (%Mno)/[%Mn], decreases with increasing temperature and slag basicity, in accord with thermodynamic data and practical observation. However, where comparisons among these studies can be made for similar slag compositions and temperatures, the reported values of the manganese distribution ratio are discordant. The variations are attributed to failure of the experimenters to bring their systems completely to equilibrium with graphite and CO at 1 atm, as judged by departures from silicon equilibrium. Even in the most recent work,5-7 this problem was recognized but the authors made the questionable assumption that equilibrium could prevail for manganese distribution even though other reactions were still in progress. Manganese equilibrium values for three particular slag compositions were required incidental to a kinetic study8 and were determined experimentally. Special pains were taken to approach concurrent equilibrium with respect to silicon. Although the results were not completely definitive, they indicate that the true manganese equilibrium distribution ratios are lower than have heretofore been reported. The data are presented together with a brief commentary on the literature to suggest the need for further work in this area. EXPERIMENTAL METHOD Equilibrium runs were carried out in a stationary, induction-heated graphite crucible closed by a graphite lid and flushed continuously by a slow flow of carbon monoxide at 1 atm pressure. Temperature was controlled manually within ±3 deg C with the aid of immersed thermocouples in mullite tubes protected against slag attack by graphite sleeves. The desired temperature was established by a calibrated Pt vs Pt-10 pct Rh thermocouple and control was then maintained using a more stable W-Mo couple. Runs were made at 1500º and 1575ºC for durations of 7.5 to 10.5 hr. The charges were calculated to yield 400 g of metal and 100 g of slag. The primary slag compositions and designation numbers were as follows: