Iron and Steel Division - Equilibrium Between Titanium in Liquid Iron and Titanium Oxides

The amounts of oxygen in liquid iron-titanium alloys up to 50 pct Ti were measured and the oxide phases in equilibrium with these alloys were determined by using TiO² crucibles. A minimum of about 0.003 pct 0 occurs at less than 1 pct Ti. The various liquid and solid oxide phases can be arranged on a ternary isotherm. THREE characteristics of titanium contribute to the interesting aspects of its reaction with oxygen in liquid iron: 1—It forms a number of stable oxides. 2—All oxides have large negative free energies of formation. 3—The pure metal exhibits high solubility for oxygen. In addition, the use of titanium as a stabilizing and strengthening element in alloys suggests a need for investigation of its reactions in amounts greater than those normally required for deoxidation. These higher compositions are also of interest because they occur during the addition of ferroalloys and produce deoxidation products before dilution is achieved. Titanium Deoxidation in the Literature While the use of titanium as an alloying element and deoxidizer has been common for several decades, the first detailed study of its deoxidizing characteristics was carried out by Wentrup and Hieber' in 1939. These authors determined the extent of deoxidation possible with titanium and identified, by microscopic examination, the products formed. They found that titanium in excess of 0.2 pct did not reduce the oxygen content of iron below 0.004 pct at 1600°C. They identified the spinel FeO-TiO² at low titanium concentrations and Ti2O³ in melts containing more than 0.2 pct Ti. A portion of the area surveyed by Wentrup and Hieber has been investigated recently by Evans and Sloman² using X-ray diffraction for inclusion identification. They concurred in general with the findings of Wentrup and Hieber, but reported the existence of Ti³O5 as a deoxidation product in the range near 0.1 pct Ti. Comstock, Urban, and Cohen³ discussed the deoxidation of iron with titanium, correlating the data of Wentrup and Hieber with free-energy data for the titanium oxides. Scatter at high titanium values was considered attributable either to the formation of an oxide exhibiting high solubility in liquid iron or to the entrainment of solid oxide particles leading to high apparent solubility. Chipman' has calculated the deoxidation curves for titanium based on free-energy data for titanium oxides. These calculations (Fig. 1) and those of Comstock, Urban, and Cohen involve assumptions as to the activity coefficients of oxygen and titanium in liquid iron, since such data have not been determined. Investigation of the deoxidizing characteristics of chromium" and vanadium0 have shown that these elements decrease the activity coefficient of oxygen in liquid iron, leading to a tendency toward relatively high oxygen values and experimental scatter in highly alloyed melts. Experimental This investigation involved two major objectives: 1—determination of the composition of the oxide phases in equilibrium with liquid Fe-Ti alloys, and 2—establishing the pattern of oxygen solubility in liquid Fe-Ti alloys at titanium concentrations in excess of that required for attainment of minimum oxygen content. Raw Materials Ingot iron was used having the following composition: 0.02 pct C, 0.017 pct Mn, 0.01 pct Si, 0.02 pct S, 0.006 pct P, and 0.03 pct 0. The titanium used