Iron and Steel Division - The Effect of Chromium on the Activity of Sulfur in Liquid Iron

The activity coefficient of sulfur in Cr-Fe-S melts was determined by measuring the values of Ph3Rh,in equilibrium with such melts. The results showed that chromium has a pronounced negative effect on the activity coefficient of sulfur, which up to about 20 pct Cr may be represented by the equation: log f; = - 0.019 pct Cr It was also found that the influence of chromium was not altered by the presence of appreciable amounts of carbon or silicon. The influence of alloying elements on the activity of sulfur in molten iron has been the subject of many investigations; however the effect of one important alloying element, chromium, has not been reported, and the object of the present investigation was to determine its effect on the activity coefficient of sulfur in liquid Fe-Cr-S alloys both in the absence and in the presence of carbon and/or silicon. EXPERIMENTAL PROCEDURE The general method employed consisted of passing mixtures of hydrogen and hydrogen sulfide over the sulfur-containing melt of interest and analyzing the outgoing gas to determine the equilibrium value of which resulted from the reaction shown in Eq. 111. H, (gas) + S (dissolved in melt) = H,S (gas) 111 The activity coefficient of sulfur, fs, was then calculated with Eq. [2] in which K, is the known equilibrium constant of Eq. [I] for dilute solutions of sulfur in iron. Raw materials used in the preparation of the charges included commercial grades of electrolytic iron and chromium and carbon-reduced, acid-treated silicon of 99.9 pct purity. Oxygen in the former presented no problem since it was removed by hydrogen in the normal course of an experiment. Carbon was added in the form of premelted iron-carbon and chromium-carbon master alloys. Sulfur was charged as iron sulfide prepared by first heating powdered iron and sulfur in air in an alumina dish until reaction occurred, and then deoxidizing by melting in a hydrogen atmosphere. Commercially bottled hydrogen and hydrogen sulfide were used after being passed through purification systems containing palladium, "Drierite," and magnesium perchlorate in the case of hydrogen, and "Drierite" alone in the case of hydrogen sulfide. Lamp-grade cylinder argon served as a flushing agent without further purification. Charges weighing from 300 to 500 g were placed in a high-purity alumina crucible of 0250-ml capacity and heated in an argon atmosphere in the induction-heated carbon-tube furnace illustrated in Fig. 1. During heating, a dry hydrogen atmosphere was substituted for argon in order that deoxidation of the charge and flushing out of argon would be accomplished sooner. After the charge melted, a Pt-Pt 10 pct Rh thermocouple contained in an alumina protection tube was immersed in the melt, and the desired melt temperature (usually 1600°C) was established. Higher temperatures up to 1760°C were required for some chromium-rich alloys because of their higher melting points, and in these cases a Pt 6 pct Rh-Pt 30 pct Rh thermocouple was used. The thermocouple output was fed to an automatic controller which provided straight line temperature