Technical Papers and Notes - Institute of Metals Division - Vacuum Melting: Influence of Hydrogen Pretreatment of Crucibles on Oxygen Content of Iron Charges

The effect of hydrogen pretreatment of alumina, magnesia, and zirconia crucibles on reduced oxygen levels in iron charges has been studied. Hydrogen treatment of commercial high-purity magnesia crucibles was observed to produce as high as 70 pct reduction in oxygen content in iron melts. Hydrogen treatment of the commercial high-purity grade zirconia crucibles produced a 25 pct reduction in oxygen levels in iron melts. An average reduction of Knoop hardness of 47 pct was recorded on the iron charges melted in hydrogen-treated crucibles. On the basis of the experiments and the free-energy diagram, it appears that the major source of reducible oxygen to the iron charge is the suboxides and impurity oxides rather than the major oxide of the crucible. Suitable pretreatment of the crucibles to reduce and remove these oxides yields low oxygen levels in iron melted in the crucibles. DURING the last decade, attempts to produce more pure and uniform alloyed metals have brought about the development of many new melting techniques. Notable among these are vacuum-induction melting, inert and consumable-electrode melting, the cold-mold technique, and numerous techniques for removal of impurities by chemical reaction. However great the achievements in this field, metals must still be melted in contact with media of varying reactivity; i.e., gas, ceramic, and slag. Studies have been made to attain an understanding of the reactions that take place during melting, including slag-metal reactions and equilibria, equilibrium of hydrogen and water vapor, and carbon dioxide and carbon monoxide with oxygen in molten iron. These reactions have been treated quite thoroughly. There is one condition, however, that has been widely overlooked, and, to the author's knowledge, only cursive investigation has been made of it. This is the reaction between the ceramic crucible material and the iron charge. In recent years, Hadley and Bianchi' made a series of studies on hydrogen deoxidation of iron in magnesia crucibles. Bianchi2 studied crucible-FeO equilibria in the temperature range 1525°to 1650°C in high vacuum with, however, inconsistent results. Richardson and Jeffes3 in their series of articles on thermodynamic reactions in the making of iron and steel refer to Wentrup and Hieber's4 work on iron and aluminum deoxidation. Their pork included melting iron in alumina crucibles and measuring the aluminum and oxygen content in the iron. Because of the low values obtained, question has arisen of their analytical accuracy.3 Dastur and chipman5 obtained values on hydrogen-oxygen equilibrium in molten iron contained in alumina crucibles similar to those obtained in experiments in the present program. Hochmann6 studied removal of impurities in chromium irons in high vacuum. His results with respect to oxygen level in chromium-iron melted in magnesia crucibles are consistent with results we have obtained.