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By A. B. Kinzel

IT is with sincere appreciation and a deep sense of responsibility that I accept the honor of delivering the Howe Memorial Lecture. In our time metallurgical research has delved into phenomena ever more complex in character, so that much of this work must be done by organized teams. We, of the Union Carbide and Carbon Research Laboratories and the Electro Metallurgical Co., are truly a team and the lecture which is to follow is due largely to a few of the outstanding members of that team here cited and well known to you in their own right: John Lamont, whose work deserves special recognition, Walter Crafts, William Forgeng, William Binder, Robert Fowler, and David Swan. Thus it is a fitting pleasure to accept this honor for the research institution which I represent. Henry Marion Howe was truly inspirational and his breadth of view was such that he could use either the method of rigid proof or implied mechanism to further the broad understanding. But perhaps his outstanding characteristic was his sound judgment and his ability to weigh observations. The following is replete with observations and judgment as to their implication. We would like to feel that it is the type of dissertation which Howe, himself, would have enjoyed. Chromium carbides in stainless steel have, in a sense, been a key to the progress of the stainless steel industry. Brearley's first stainless steel, containing approximately 0.30 pct C, was successful because it differed from previous Fe-Cr alloys in that the carbides were present in such amount and form as to provide the stainless and cutting properties. Again, the 12 pct Cr die steels with a carbon content of 1.5 pct or more achieved their properties by virtue of the form and distribution of the chromium carbides. In the straight chromium steels with from 12 to 25 pct Cr, chromium carbide amount and distribution are once more the determinants with respect to physical properties and corrosion resistance. In each of the cases just cited the role of the carbide is in essence similar to that of iron carbide in carbon steel and this story is so well known that we need not dwell on it. In the austenitic stainless steels, the chromium carbide plays only a minor positive role with respect to mechanical properties, and for corrosion resistance the objective is to achieve maximum homogeneity. Thus the tendency has been to ever lower the carbon and correlatively the chromium carbide content of the austenitic steels. Today stainless steels with carbon less than 0.03 pct are beginning to find their true place, and this is being aided in major degree by our Company's introduction of a new type of ferrochromium having negligible carbon. The role of carbon in these austenitic steels has long been recognized, and a truly enormous amount of research has been devoted to the subject. Much has been learned about corrosion resistance, but the attack on the problem from the point of view of carbide precipitation and the nature thereof has left much to be understood. Because of its fundamental importance to the future of stainless steels, further study of the mechanism of carbide formation in austenitic steels is of interest. In the 18-8 Cr-Ni steels, which are typical of the austenitic class of steel, carbon is soluble in the aus-tenite to the extent of approximately 0.15 pct at 1832°F (1000°C). The solubility becomes less with decreasing temperature, so that at 1652°F (900°C) the solubility limit is approximately 0.06 pct, at 1472°F (800°C) it is about 0.03 pct, and at 932°F (500°C) it is approximately 0.01 pct. Obviously this is the ideal situation for the classical precipitation phenomenon. It is true that, in a sense, 18-8 austenite resulting from annealing is in a metastable state, and the phenomenon of ferritic precipitation from this austenite should be considered. However, in a so-called fully austenitic 18-8 steel this is secondary with respect to the carbides and can be neglected. A wide variety of chromium carbides is known. Only one chromium carbide, Cr,,C,,, frequently referred to as Cr,C, has been found in unmodified low carbon 18-8 steel. This, fortunately, simplifies the study of the precipitation phenomena. For this study an A.I.S.I. type 304 stainless steel of commercial quality was selected. Analysis showed C 0.07 pct, Mn 0.49 pct, Si 0.33 pct, Ni 9.34 pct, Cr 18.91 pct, and N 0.033 pct. As expected with this composition the steel was homogeneous after annealing except for a few pools of ferrite, which were disregarded in that their location was not coincident with subsequent carbide precipitation areas. On corrosion testing the steel was normal and typical of good commercial quality. Specimens 1/2xlx4 in. were annealed and subjected to precipitation heat treatment for 100 hr at 100" temperature intervals from 1000° to 1500°F and for ten selected intervals ranging from 5 min to 64 hr at 1300°F. These blocks were then cut into small pieces for metallographic studies. The first problem

Jan 1, 1953

By J. Chipman, N. J. Grant, E. C. Roberts

An equilibrium study was made of the distribution of chromium and oxygen between liquid iron, containing less than 1 pct Cr, and simple slags of the CaO(MgO)-Si02-FeO-Cr& type in the temperature range 1526' to 1734OC. The effects of slag oxidation, temperature, and basicity were observed. IN spite of the fact that chromium is one of the most important alloying elements in steel, and exists in almost all steels as a significant residual element, little research has been done to determine its behavior in basic steelmaking processes. Considerably more work has been done under silica-saturated acid slag conditions. Korber and Oelsen,' Herasymenko,' and others have generally agreed that in acid steelmaking practice the chromium in the slag behaved as if it were present as the chrom-ous ion (CrO). Work by Hilty- ir, high chromium slags also indicated that chromium may exist as CrO. In basic slag systems no equilibrium data exist. Based on individual studies of basic open hearth and electric furnace practice, Bardenheuer," Rock-rohr,% nd HauckQ oncluded that: 1—chromium recovery increased with decreasing basicity, and 2— chromium recovery increased with increasing temperature, although the effect was small. In similar studies Yavioskii and Dzemyen' concluded that: 1— slag FeO is the most important variable, 2—the basicity of the slag has no effect on chromium recovery, and 3—slag viscosity is not high even when 20 pct Cr,O, is present. Lapitskii\ oncluded that chromium recovery improved as the basicity of the slag decreased and increased with increasing manganese in the metal. Regarding the effectiveness of CrZ08 as a base or acid in basic slags, both Kristofferseno and Trojer" reported that Cr,08 was an acidic component requiring neutralization as 2CaO-Cr,O,. Experimental Procedure The experimental apparatus and procedure used for the present research were similar in most details to those used by Winkler and Chipman" and were described in detail by them. A magnesia crucible was used, holding 60 to 80 lb of Armco iron which was decarburized with hydrogen to about 0.010 pct C. Since all the metal samples solidified without gas evolution, this carbon level was assumed not to be significant. Synthetic slags made by mixing pure oxides were used throughout the study. Temperatures were measured by means of calibrated W-Mo thermocouples and were checked by Pt-Pt-Rh thermocouples. The range of temperatures covered in this study was from 1526" to 1734°C. The chromium content of the iron was in the range 0.032 to 0.82 pct, although the bulk of the tests showed 0.04 to 0.2 pct. The slags were of the CaO(MgO)-SiO,-FeO-Cr,O, type in which the Cr,O, content was from about 2 to 20 pct, although most of the slags showed from about 2 to 10 pct. The FeO range was from about 10 to 65 pct. CaO and SiO, were in the range of about 5 to 45 pct each, yielding a rather wide range of basicity values. The first 12 heats were made without a sulphur addition, and with only 30 min allowed for slag-metal equilibrium to be reached. In previous research it had been shown that less than 30 min was adequate to achieve equilibrium in slags free of Cr2O8.11,14.15 A study of the present data indicated that some of the tests may not have reached equilibrium in this time; accordingly four additional heats were made in which at least 1 hr was permitted for equilibrium to be reached. For reaching

Jan 1, 1955

By J. H. Swisher

An experimental study has been made of the possible mechanisms for foam stability in the system CaO-SiO2-Cr2O3, where Cr2O3is the foaming agent. The degree of lowering of surface tension by Cr2O3 was determined at 1600 "C for high -silica melts. Measurements were also made of foam stability under standardized conditions. The results of the two sets of measurements then were correlated by applying the Gibbs and Marangoni theories of film elasticity. It was demonstrated that the Marangoni elasticity effect is probably the largest single contributor to foam stability, although the high uiscosity of' silicate melts makes some contribution in controlling the rate of drainage of liquid from bubble lamellae. ThE tendency of metallurgical slags to foam has frequently been observed during steel-refining operations. In the open-hearth furnace,this tendency is considered undesirable because it slows down the rate of heat transfer from the burners to the molten-metal bath. On the other hand, it is sometimes desirable to have a "foamy" slag in the basic oxygen converter.' A more effective blanket over the steel bath is made by a "foamy" slag, and loss in yield of metal due to splashing is minimized. In addition, a flush slag can be removed more easily in this condition. Since slag-foaming problems in the field have been attacked largely on an empirical basis, it appeared desirable to obtain a better basic understanding of the mechanism of foam stability. The experimental work was directed almost entirely toward the behavior of Cr2O3 as the foaming agent in CaO-SiO,-Cr2O3 melts. In the first stage of the investigation, the degree of lowering of surface tension by Cr2O3 was determined at 1600°C. The second stage consisted of measuring foam stabilities under standardized conditions. The two sets of experimental results then were correlated by applying various theories of foam stability. For convenience in interpreting the surface-tension and foam-stability results reported here, a portion of the CaO-SiO2-Cr2O3 phase diagram2 is reproduced in Fig. 1. EXPERIMENTAL 1) Surface-Tension Measurements. Very little information is available in the literature on the lowering of surface tension of slags by foaming agents. Kozakevitch 3 mentioned that the addition of 1.5 pct Cr2O3 lowered the surface tension of FeO slightly. In another system, some data on the lowering of surface tension of foaming slags by P2O5 were reported by Cooper and Kitchener.4 The technique used for the surface-tension measurements was the maximum bubble-pressure method,' using a single tube immersed to various depths in the melt. This method has been used extensively in high-temperature systems, such as in liquid metals, slags, and glasses.6,7 It has the advantage that the contact angle between the liquid and the tube material need not be known. The equation used for calculating surface-tension values from maximum bubble-pressure measurements is the Schroedinger equatioq5 which can be written as follows:

Jan 1, 1964

By D. A. Dukelow, K. Li, G. C. Smith

Decarburization in the Fe-C system by oxygen top blowing has been studied in laboratory -scale experiments. It is shown that equilibrium models fail to explain or predict either the course of refining or endpoint conditions, giving results which either are incompatible with the chemistry of the system or do not satisfy material balance requirements. Also the path of decarburization was found to vary even for heats made under apparently identica1 conditions. A promising approach to analyzing the decarburization results is to relate oxygen efficiency fm carbon removal to bath carbon content. This relationship for Fe-C heats shows the same range of oxygen efficiencies as is obtained in pilot-plant and commercial heats using hot metal-scrap charges. This implies that oxygen transfer is primarily controlled by the decarburization reaction itself, independent of other refining reactions. Therefore, it should be possible to study separately decarburization and slag-metal reactions. DECARBURIZATION is probably the most important reaction in steelmaking. Not only is it a main reaction in the refining of iron to steel but it also provides the stirring action in the bath necessary for the diffusion processes to proceed at reasonable rates so as to make a steelmaking process practical. Kinetics of decarburization in the open-hearth process has been a subject of investigation for many years.&apos;-B It is generally accepted that at steelmaking temperatures the rate of homogeneous C-0 reaction is extremely high and cannot constitute a rate-controlling step. Diffusion of oxygen through a boundary film in the metal phase has been suggested by arken&apos; as rate-determining. Recently, Larsen and sordah16 concluded from experiments in a laboratory furnace that, with oxygen supplied from air or combustion gases, the rate of "steady-state" carbon boil is controlled essentially by a diffusion process of O2, Co2, or H2O through a film of nitrogen above the slag surface. Displacing this diffusion film by a stream of nearly pure oxygen produced a ten-fold increase in the rate of carbon boil with the rates of slag-metal oxygen transfer, bubble nucle-ation, and other steps all apparently able to keep pace. In the top-blown basic oxygen process, however, the transport of oxygen takes a more direct route. and the state of bath agitation is much more turbulent than in the open-hearth process. In addition, direct contact of the gas with the metal phase provides opportunity for direct oxidation of carbon. It is likely that the rate-limiting factor for the decarburization reaction will be different. However, only a few descriptive discussions of the subject have been reported in the literature.10-l2 Studies of the decarburization kinetics based on plant or pilot-plant data are necessarily complicated and are influenced by other refining reactions which occur simultaneously. In order to investigate the mechanism of decarburization, experiments have been conducted in which carbon-saturated iron melts were top-blown with pure oxygen over a range of conditions. It is hoped that this study will form a foundation on which a more basic understanding of this important reaction may be built. EXPERIMENTS One group of blowing experiments was made in a standard 200-lb induction furnace and another group in a 500-lb induction furnace. The furnaces were modified to the general shape of a basic oxygen furnace by adding a rammed refractory cone section to the regular crucible body. Crucible and cone were of high MgO (95 pct) material. A water-cooled lance, 1/2 in. in diam and threaded at one end to take a nozzle, was used for blowing oxygen. The lance with its water and oxygen lines was supported on a cantilever arrangement so that it could be moved up, down, or sideways. Oxygen of 99.5 pct purity was supplied from a cylinder and metered through a rotameter equipped with pressure and temperature gages. Another pressure gage was located at the top of the lance. A schematic diagram of the assembly is shown in Fig. 1. Before each experiment, a weighed amount of ingot iron, containing 0.02 pct C, < 0.01 pct Si, 0.10 pct Mn, 0.019 pct P, and 0.015 pct S, was charged in the furnace and melted down by induction heating. Graphite was then added to the molten charge until it became saturated. When the temperature of the charge reached the desired level, the lance was lowered to a predetermined height above the bath

Jan 1, 1964

By S. Y. Ogawa

The effects of sulfur (up to 0.1 pet) on the deformation and fracture characteristics of iron, in cast form, were studied at strain rates up to 100 pct pcr sec and at temperatures of 1600o to -3300 oF. The effects of oxygen and manganese additions on the behavior of Fe-S alloys were studied under comparable test conditions. Brittle fracture characteristics, evident at all strain rates, resulted from the presence of the liquid iron sulfide phase at grain boundaries. Ductility could be restored in three ways: solution of the sulfide in solid y iron at higher temperatures, spheroid-zzation of the liquid sulfide, and increase. in the melting point ot the sulfide. THE literature shows that most previous studies of deformation and fracture at hot working temperatures have been based on measurements of energy absorption, reduction of height in forging upset tests, torsion tests of bar or wire samples, and so forth,&apos; but that relatively few tension tests have been used at high temperatures and strain rates. The present work was initiated to study the ef- fects of temperature, strain rate, composition, and structure on the deformation and fracture characteristics of iron, utilizing cast specimens tested in tension. As in a previous study,&apos; strain rates up to 100 pct per sec were chosen for the temperature range 1600° to 2400° to provide data which might be useful in the interpretation of the deformation and fracture behavior of steels under hot working conditions. The previous work was with Fe-P solid solution al10ys;2 this work is concerned with Fe-S alloys, and with the effects of oxygen and manganese additions. MATERIALS AND PROCEDURE Cast tes! specimens were employed throughout, since most of the difficulty during hot working occurs in the initial breakdown of the ingot. Alloy Systems. Ten 25 lb. heats containing sulphur were prepared. Of these, three had manganese additions, and two had oxygen additions. The sulfur content varied from 0.023 to 0.10 pct. Manganese contents were intended to be ten to twenty times the sulfur content of the particular alloy. Oxygen, being more difficult to control in small melts, was varied by the amount of solid deoxidizer added, but poor control of the oxygen content was experienced in most instances. Table I shows the chemical analyses of the heats. Melting and Casting. Electrolytic-iron chips were melted by high frequency induction in a prefired, clay-graphite crucible lined with rammed magnesite.

Jan 1, 1962

By John Henderson

Densities of melts 0f the lime-iron oxide-silica system in contact with solid iron have been measured by the maximum bubble pressure method in the temperature range 1250° to 1440°C and the composition range 0 to 40 mol pct lime, 15 to 100 mol pct iron oxide, and 0 to 55 mol pct silica. Densities range from 4.65 g cm 3 for wustite at 1440°C to 2.75 g cm-&apos; at 1350°C for a melt containing 30 mol pct lime, 20 mol pct iron oxide, and 50 mol pct silica. The results are interpreted in terms of a postulate that the melts can be regarded as a random array of oxygen ions in which regions of local order exist to satisfy the coordination requirements 0.f the cations. An understanding of the nature of metallurgical slags is basic to the development of a sound theoretical description of heavy metallurgical extractive and refining processes. Because these liquids are complex, direct measurements of their properties has not thrown much light on their structure. This has led to the approach of measuring the properties of simpler liquids, and building up their complexity until slag compositions are reached. In this way the density of liquid iron silicates was measured in a previous study1 and the present work represents a further stage in this synthesis. EXPERIMENTAL The technique used in the measurement of density was the maximum bubble pressure method. Details of the apparatus and procedure were similar to those previously reported,&apos; with the exception that a constant voltage transformer was used to supply the power input to the furnace and six silicon carbide resistance elements were used in place of the molybdenum winding. With these modifications melt temperature could be maintained within 1 centigrade degree during the course of a run. The silica used to prepare the melts was washed natural quartz ignited at 1000°C; wustite was prepared by air-melting A.R. grade ferric oxide in an iron crucible and lime was prepared by air ignition, at 1000°C, of weighed quantities of A.R. grade calcium carbonate, previously air-dried at 110°C. The finely ground constituents were intimately mixed in a glass ball mill prior to melting. Temperatures quoted are accurate to * 5°C and the standard deviation of the density values, calculated by the method of least squares, ranged from 0.5 to 1.8 pet. However, replicate determinations of density on different melts of the same nominal composition at the same nominal temperature did not vary by more than 1 pct, Table I, and this figure has been taken as an estimate of the accuracy of the density results. The density of carbon tetra-chloride was also measured as a check on the absolute performance of the experimental method. At 20°C a value of 1.593 * 0.002 g cm"3 was obtained; this compares with the literature value2 of 1.595 g cm"3. Results of experiments designed to measure the dependence of the density of lime-iron oxide-silica melts, in contact with solid iron, on composition and temperature are shown in Table I. Because iron sometimes precipitated in the sample during quenching, the Fe203 chemical analyses were only poorly reproducible and should be taken as a guide rather than as absolute values. Fig. 1 shows the data from various sources for the density of liquid iron silicates and Fig. 2 shows isodensity contours at 1410°C for lime-iron oxide-silica melts, calculated by graphical interpolation of smoothed curves drawn through the experimental results, together with the 1400°C results of Adachi and ogino3 and Pope1 and Esin.4 Fig. 3 shows the isothermal variation with composition of the volume of melt per gram ion of oxygen at 1410°C and Fig. 4 shows regions in which the temperature coefficient of this volume is negative, positive, or negligible (<0.005 cm3 deg-I). DISCUSSION a) Disparity Between Reported Density Results. Consider the system iron oxide-silica, the results for which are summarized in Fig. 1. Although there is some difference in the temperatures at which the various densities apply, this difference is not sufficiently large to account for the observed discrepancies. The reliability of the present results for the low-silica region has been confirmed by measurement of the density of liquid wustite by three different techniques. At 1410°C the density measured by a balanced-column method was 4.55 g cm"3, by a combination balanced-column and gas-densitometer method 4.59 g emd3, and by a pycnometer method 4.53 g cm"3. Schenck, Frohberg, and Hoffermann&apos; have also reported a value of 4.55 g cm"3 for the density of liquid wustite at 1400°C. It must be concluded, therefore, that neither Pope1

Jan 1, 1964

By William P. Roe, James F. Ellis, W. P. Fishel

This paper reports the distribution of sulphur between iron and titanium in Fe-Ti-S alloys and in Fe-Ti-C-S alloys. The compound TiS was found, which exists as a separate phase at temperatures below 1200°C. Titanium in steels reacts with sulphur in preference to carbon. THE general relationship between sulphides and oxides suggests that titanium should form a sulphide having properties similar to those of titanium oxide. Specifically, titanium should form a sulphide having a high melting point, indicating a stable compound of low solubility in iron. In order for titanium to function as a desulphurizer or sulphur-fixing agent, it must form a stable sulphide. In order for titanium to be useful in steels as a sulphur-fixing agent, it must react with sulphur in preference to carbon; and to prevent red shortness, the sulphide formed must have solubility characteristics such that grain-boundary precipitation of a low melting phase be prevented. The terms desulphurizer and sulphur-fixing agent when used in this paper mean that titanium effectively ties up the sulphur as a stable sulphide of titanium and prevents the formation of FeS. The partition of sulphur between iron and titanium was studied first in a series of Fe-Ti-S alloys with carbon absent, and then in similar alloys with carbon present. It has been established1 a that titanium forms in Fe-Ti-S alloys a sulphide of undetermined composition which can be identified microscopically, and that the titanium-sulphur compound does not respond to sulphur printing. It has been suggested" that titanium acts as a sulphur-fixing agent, although little proof has been given. A report% f The Advisory Committee on Metals and Minerals summarizes the existing knowledge concerning substitutes for manganese in steels. Distribution of Sulphur Between lron and Titanium with Carbon Absent The alloys for this investigation were made by -melting Armco iron, metallic titanium, and iron sulphide in alundum crucibles in an induction furnace. The titanium was added after the other ingredients had melted. In these alloys it is recognized that some TiO, is present, since the melts were made in the air and since no other deoxidizing agent was used; therefore, some of the titanium was not available for union with sulphur. Thirteen ingots were made. Ingots 2 to 8 were cast in baked-sand molds; ingots 12 and 13 were cast in metal molds; and ingot 9 was allowed to cool in the crucible in which it was melted. All ingots were annealed at 900°C for 3 hr and were cooled slowly in the furnace. Subsequent information indicates that this anneal had no effect upon the titanium sulphide particle size, since the sulphide does not go into solution at this temperature. The ingots as-cast were approximately 8 in. long and % in. diam. The compositions of the eight ingots and the results of the partition of sulphur are recorded in Table I. Total titanium and total sulphur were determined by standard gravimetric methods. Sulphur, as iron sulphide, was determined by the evolution method. Boiling HC1 (1:4) liberates the sulphur from iron sulphide, but leaves the titanium sulphide practically undecomposed. A complete separation of titanium sulphide and iron sulphide cannot be made by digesting these compounds in dilute HC1 since titanium sulphide was found to dissolve slowly. The amount of titanium sulphide decomposed will depend upon the time in contact with the acid and upon the particle size of the sulphide. The point

Jan 1, 1952

By C. R. Masson, M. L. Pearce

The nitrogen contents of seven specimens of iron and steel were determined by the three methods. Good agreement won generally observed between the results of the isotope -dilution and Kjeldahl determinations, tltzts establishing the reliability of the isotope -dilutzon technique. For some specimens, the vacuum-fusion values at 1650 °C were lower than the corresponding Kjeldahl values by up to 0.0015 pct absolute. These differences were eliminated for a specimen of "pure" iron by performing the vacuum-fusion analyses at 2100 ° to 2240 °C. The reason for this relatively high temperature required m the vaczium-fusion analyses is discussed. ThE determination of nitrogen in iron and steel has been the subject of numerous investigations and a concise review of the extensive literature in this field has recently appeared.&apos; Two methods of analysis are most commonly employed, the vacuum -fusion and the chemical or Kjeldahl method. Except in special cases where the presence of certain alloying elements may present difficulties, both methods are generally regarded as applicable, although the vacuum-fusion method is more sensitive and is often preferred for samples of very low-nitrogen content. The method of isotope dilution, first employed for the determination of gases in metals by Kirshenbaum and Grosse,2 has recently been applied to the determination of nitrogen in iron and steel.3,4 The method is attractive in that it does not require the quantitative extraction of gas from the metal specimen. Staley and Svec3 modified the standard Kjeldahlpro-cedure by introducing, along with the steel sample, a measured amount of ammonium sulfate enriched in the isotope 15N. The nitrogen content was obtained by measuring the isotopic ratio 15N/14N in the resultant solution. The technique involved the distillation of nitrogen as ammonia from alkaline solution and subsequent oxidation of NH4+ in the distillate to gaseous nitrogen. The results for iron and steel samples of commercial origin were often in reasonable agreement with values quoted by the suppliers, although occasional marked discrepancies were observed, particularly with the results of vacuum-fusion analyses. Preliminary work in this laboratory4 on the determination of nitrogen by isotope-dilution in the gas phase yielded results for three samples which were significantly higher than the values obtained by vacuum-fusion. The present paper describes an extension of this work to a wider variety of samples. Analytical results by the Kjeldahl method are also reported. EXPERIMENTAL The technique employed for the isotope-dilution determinations was similar to that described elsewhere.4 Several minor modifications were made to the apparatus. These included the use of molybdenum instead of platinum-rhodium suspending wires when crucibles were degassed at temperatures above 1600°C. The circulatory system used previously for converting CO to CO2 was replaced by a single chamber, the walls of which were cooled directly in liquid nitrogen. Temperatures were measured with an optical pyrometer which had been recently calibrated and, as in the previous study, were minimum values obtained by sighting on the center bottom of the crucible. Temperatures obtained by sighting on the interior walls were always higher by 100&apos; to 130°C with the design of crucible employed. Flat-bottomed crucibles exhibited an even larger temperature difference. To check the efficiency with which crucibles were degassed in the isotope-dilution apparatus, several experiments were done in the vacuum-fusion apparatus, suitably modified4 for isotope-dilution studies. Faster pumping speeds and higher degassing temperatures were possible, the latter due to the use of a generator with a higher power output (10 Kva at 398 kc per sec). In these experiments the combustion of CO was omitted and a correction4 was made for the contribution of CO to the ion current at m/e 28, used in determining the isotopic ratio R = l5NP4N. This correction did not seriously influence the re-

Jan 1, 1962

By R. M. Fowler, H. L. Hamner

DURING the last 25 years, there appeared in the literature a number of papers describing equipment and operating techniques for the determination of total oxygen in iron and steel. In the early papers, comparatively little attention was paid to side reactions that occur when iron is saturated with carbon at a high temperature in a high vacuum. As more experience was gained with the new method, the limitations appeared. Metals, with a boiling point lower than iron, distilled out of the crucible, condensed in the cooler part of the furnace, and subsequently reacted with carbon monoxide to form oxides and carbon. Aluminum, manganese, and the alkaline earth metals proved troublesome in this respect. Modifications have been devised to overcome the difficulties due to aluminum and manganese, while the alkaline earth metals are not of too much concern as yet to the steel chemist. The reactions of sulphur have received less attention, although it is generally recognized that some carbon disulphide is probably formed. Liquid air traps have been used in some cases to prevent any carbon disulphide from entering the analytical train. Sulphur was not a particular problem at the Union Carbide and Carbon Research Laboratories until the analysis of the irons of higher than usual sulphur contents became necessary. In order to describe the procedure developed for such irons, it will be necessary to first describe the type of vacuum-fusion equipment employed because the operation of vacuum-fusion equipment is an art to a considerable extent. At the Laboratories, vacuum-fusion equipment has been in daily operation since about 1930. Over the years, the evolution of this apparatus has been governed by the versatility required to analyze a wide variety of materials. Since all types of materials from high purity metals to slags are analyzed and, since seldom more than a few samples of one type are analyzed in succession, the apparatus was designed for accuracy and flexibility rather than for speed. A general view of the equipment is shown in Fig. 1, while Fig. 2 shows the relationship of the various parts. In Fig. 2, A is a vertical double-glazed 24X27/8 in. OD silica tube heated with a 20 kva mercury-arc high frequency generator. The tube is closed with a water-cooled brass head attached with de Khotinsky cement. A turret cap fits on this head and is sealed with a 1/8x3 in. "0" ring. The head contains a sight glass and two 8 in. horizontal glass tubes, for sample storage, cemented in with de Khotinsky cement. B is a four-stage Gaede mercury diffusion pump connected to the water-cooled head with a 11/2 in. copper tube through a flange with an "0" ring. The output of the vacuum pump feeds into an automatic Toepler F pump which compresses the gas sample over mercury in the measuring burettes, G and H. There are bypasses in this line for a McLeod gage C and a Piranni gage D, a manometer E, and for initial pumping out of the system with a Cenco Megavac backing-up pump. The reduction crucible shown in Fig. 3 is machined of Tungar Bulb quality (A.G.K.T.E.-2) graphite. The sample is guided into the crucible with the graphite funnel depicted on this figure. The arrangement of the crucible, radiation screens, etc. in the furnace is as follows: A 1 15/16x61/2 in. Alundum thimble, porosity RA-84, with two 1/8 in. holes near the top and opposite each other which take a pair of special tongs used for lowering it in place, is prepared. A 3/4 in. layer of powdered graphite is placed in this Alundum thimble, and the graphite crucible containing 20 g of ingot iron and 0.5 g of carbon is carefully centered on this bed of graphite powder and graphite powder is packed around it to the top of the graphite cru-

Jan 1, 1953

By G. W. Healy

G. W. Healy (union Carbide Metals 0.)-The author&apos;s paper is a useful contribution to the store of maps of chemical activities of oxides in multi-component slag systems. It is also a good example of the utility of the Gibbs-Schuhmann technique for calculating activities in a system where that of one of the components has been measured. This paper Koh and Caugherty. This plot is reproduced by alor in X-ray Metallography. Because of this nonlinearity, preparation cf suitable standards and/or correction for absorption and enhancement are essential in microanalysis. However, our objection is not the conclusion that Dr. Aaronson has arrived at nor the technique he has used; but only to the foot-note credited to V. Macres. The level of chromium that he was concerned with (less than 3 pet) is so low that the deviation of uncorrected Cr-curve will be negligible. Besides Dr. Aaronson has used chromium intensity from martensite and set it equal the bulk chromium content of the alloy. Using this chromium-intensity as a reference, he has calculated the amount of chromium in the ferrite. This amounts to the same as using an internal standard. Since the chromium content in austenite and ferrite are almost the same, enhancement due to iron in both will be the same and therefore does not need to be corrected. together with the author&apos;s recently published one1 on the CaO-FeO-Fe2O3 system will be most helpful to others learning to apply Schuhmann&apos;s method, which merits a far wider application than it has received to date and should greatly aid our understanding of equilibria between metal and oxide phases. As shown by okcen" its use may even be extended to sections of systems with any number of oxides. I have some questions as to the selection of equilibrium constants made by Dr. Turkdogan. He has chosen one for the formation of Fez03 from FeO and oxygen which gives Fea3 activities 50 pct higher

Jan 1, 1963

By W. J. Slatosky

W. 0. Philbrook (Cairiegie Institute of Technologyogv—Mr. Slatosky has presented an interesting and constructive paper that represents another step along the way of converting steelmaking from an art to a science. I am confident that his computer will be practical and successful and that with a very few months of experience it will provide a significantly better degree of control than his record of 65 pct of heats within range obtained with the slide-rule calculator . A paper such as this, with a lot of symbols and condensed mathematics, is difficult to comprehend quickly. Since I have had an opportunity to study it carefully, perhaps my evaluation of its validity and accomplishments will save time for others. Mr. Slatosky has correctly used standard principles of stoichiometry and heat balances, which are available to anybody, but he has also brought to them two original contributions: 1) He has developed from operating data some empirical relations for predicting the final FeO content of the slag (at 0.5 pct C end-point) as a function of slag basicity, lance height, and scrap, ore, and scale in the charge. This improves the accuracy of prediction of temperature or scrap requirement compared with assuming an arbitrary, constant FeO content at the end of each heat. There is no assurance yet that exactly the same relations will hold for other furnaces or practices, but similar correlations can be expected. 2) He has combined calculations that are ordinarily carried out laboriously as a number of individual steps into a single, simple linear equation that can readily be fed into a machine. This involved a tremendous amount of painstaking detail work as well as the imagination to see the possibility and work out the steps. While his particular Eqs. [3] and [6] are valid only for the furnace design, charge weight, and blowing time used at Aliquippa Works, only a few numerical values have to be changed to adapt it for other conditions. In order to arrive at a useable solution, Mr. Slatosky had to make some basic assumptions about the process that are similar to those used by others. He neglected variation in some process variables and assumed an arbitrary average value for waste gas analysis and temperature for want of more exact information at the present time. All of these judgments are clearly stated. In addition, some thermody-namic data presently available are not adequate for the job, notably in relation to heats of formation and sensible heat in slag, and some expedient has to be adopted to get around the difficulty. Other people might prefer slightly different judgments about these details and hence obtain somewhat different numerical solutions. This is not of serious importance, however, because the errors accumulate in the "heat loss" term and are largely self-compensating for a constant heat time. Although the extended Eq. l(a) in Appendix I was set up as a rate equation originally, for convenience in using an analogue computer as stated in the paper, the time dependence was removed by later mathematical manipulations and assumptions about the process. The final result is an integration of element and energy balances from initial to final states; this procedure is as legitimate here as in any other form of heat-balance calculation. The formal handling of stoichiometry and thermochemistry appears to be correct, and it is assumed that any arithmetical errors would have come to light in applying the calculations to furnace practice. Mr. Slatosky&apos;s approach is not necessarily unique, in that other people might start with apparently different equations or prefer another form of final equation for another type of computer. However, he has presented an accomplished result that appears to be a theoretically sound and practically useful way of applying scientific principles and rapid computation for better control of steelmaking. His success will undoubtedly encourage himself and others to improve on the mathematical model and its use as better informatioq becomes available. John F. Elliott (Massachusetts Institute of Teck-t2ology)-The last comment by Mr. Richards that a calculator is quite unnecessary for an L-D operation ?-equi??es a rebuttal. The L-D furnace is a very high capacity process which places a premium on close control. When one is making steel at rates between 100 and 200 tons per hr, one cannot afford the luxury of an extra 5 or 10 min at the end of a heat correcting for an error that should never have been made in the first place. Mr. Slatosky&apos;s paper is a very sound application of the simple principles of stoichiometry and the energy balance. It is a satisfactory and valuable start, but only the start of the development of methods of control for this process. An analysis of the process shows that it should be very suitable to control by a computer. This is especially the case when various grades of steel are to be made. In fact, it would seem that the organizations who are planning new and bigger installations of L-D vessels should consider carefully the advantages that would stem from computer control of a vessel with the operator present to do little more

Jan 1, 1962

By A. U. Seybolt

A. U. Seybolt (General Electric Research Laboratory)— As pointed out in an earlier paper,41 it appears to be very difficult to nucleate Si3N4 in Si-Fe of silicon content up to around 5 pet. Therefore, one observes, as did Pearce, that equilibrations with nitrogen gas yield only nitrogen in solid solution at temperatures above about 700°C, or, as Pearce found, 770°C. Evidently, the free energy of formation of Si3N4 only becomes high enough at -770°C to overcome the reluctance of Si3N4 to nucleate. However, as mentioned in Ref. 41, if some Si3N4 is first formed by a mixture of ammonia and hydrogen, one can then replace this gas mixture by nitrogen gas, and either increase or decrease the amount of Si3N4 present at any temperature by suitable adjustment of nitrogen pressure: that is, to equilibrate with Si3N4. In the equilibration experiments cited in Ref. 41, equilibrium was approached from both sides, and it was found that samples up to 944oC, at least, were in equilibrium with Si3N4. Higher temperatures were not employed, as this would have necessitated a redesign of the apparatus for using nitrogen pressures in excess of 1 atm. To summarize, the results of Pearce&apos;s experiments and those of Ref. 41 cannot be directly compared because two quite different equilibria were studied. Therefore, the statement by Pearce on p. 1398 indicating apparent error in Ref. 41 is unjustified. M. L. Pearce (author&apos;s reply)— There was limited evidence obtained in the current investigation which would indicate that excessive "supercooling" did not occur. A small piece of the same resulting from heat treatment No. 5 in Table III was subsequently held at 800°C for 16 hr in 95 pet N-5 pet H. Isotope-

Jan 1, 1964

By S. K. Tarby, W. O. Philbrook

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:

Jan 1, 1963

By J. E. Stukel, J. Cocubinsky

A CONSIDERABLE amount of information is available on the equilibrium distribution of manganese between slag and metal under oxidizing conditions. These data have increased our knowledge of the manganese reactions in the open hearth, ladle, and ingot mold. In contrast, there is a paucity of data on the slag-metal distribution of manganese under reducing conditions. The purpose of the present investigation was to study the equilibrium distribution of manganese between blast-furnace type slags and iron saturated with carbon. Experimental Method Furnace: The induction furnace used for the experiments is shown in Fig. 1. A 1 in. pipe, attached to the transite cover, was fitted with a window through which the charge could be observed. Material could be introduced into the furnace through a tee and plug without removing the cover. A graph-it cylinder (3 in. ID and 10&apos;/2 in. long), centered within the induction coil, was used as a heating element. During a test, a zircon plug kept the top of the furnace from becoming too hot from heat radiation. At the bottom, a graphite block on the vertical center line of the furnace and extending 1 1/2 in. into the coil, was used as a support for the graphite crucibles containing the melt. The graphite crucibles, machined from regular carbon electrode stock, had a 2% in. OD with 3/16 in. walls and were 5% in. long. The fumes present in the furnace during the early part of a run made optical readings uncertain. A noble metal thermocouple was, therefore, adopted to measure the temperatures. The arrangement used, shown in Fig. 1, allowed the silmanite protection tube to be replaced with a minimum effort. The thermocouple was calibrated against a standard Pt-Pt-Rh thermocouple in a fused quartz protection tube. The latter was inserted in the molten iron by removing the glass window on the cover. The lower couple was found to be very sensitive to temperature changes. To insure accurate temperature readings, the graphite crucibles were made to fit tightly against the silmanite protection tube. Further, to avoid contamination of the thermocouple by carbon, the silmanite tube was changed and the calibration procedure was repeated at frequent intervals. By using this temperature measuring technique, the furnace was easily held within *1O°C of the desired temperature. Because of the small free space in the furnace, no attempt was made to control the atmosphere. It

Jan 1, 1955

By J. Chipman, N. J. Grant, R. Rocca

Desulphurization of liquid iron by reducing slags of the electric-furnace type was studied from 65 heats. Variations were made in basicity over a wide range and in FeO up to about 5 pct for their effects on desulphurization. The role of FeO in desulphurization from the blast furnace, to the electric furnace, to the oxidizing conditions of the open hearth is shown to fit a relatively simple pattern of behavior. THE mechanism which controls the desulphurization of molten iron by basic slags has been the object of several investigations. In particular, equilibrium determinations have been made both in the field of basic open-hearth slags, which have a high iron-oxide concentration, and in the field of blast-furnace slags which have a very low iron-oxide concentration. In both cases the desulphurization ratio has been found to increase with increasing basicity of the slags; however, the mechanism of desulphurization differs in the two cases. In basic open-hearth slags desulphurization occurs mainly as a partition of iron sulphide:&apos; FeS * (FeS) and the desulphurization ratio is approximately independent of iron-oxide concentration in the slag. In blast-furnace slags the concentration of iron oxide is very low as a result of the highly reducing conditions in which they are formed. The controlling reaction for desulphurization is then:2,3 FeS + (CaO) <=* (CaS) + (FeO) The slags of the reducing stage in the electric furnace have an iron-oxide concentration which is intermediate between blast-furnace and open-hearth slags. The study of the mechanism of desulphurization for these slags has been the object of this investigation. The importance of low (FeO) in the slag for desulphurization was first verified by Bardenheuer and Geller,& who found that high desulphurization ratios were obtained in highly reduced slags. It was recognized" hat iron oxide in the slag becomes a controlling factor in desulphurization only at FeO concentrations approximately under 5 pct. A recent investigation conducted by Buehl,7 upon the suggestion of one of the authors, confirmed this opinion from the results obtained from a heat conducted in a small arc furnace. In the present investigation, slags of very high basicity, such as often are encountered in the basic electric furnace, could not be studied, but equilibrium data have been obtained for slags in a wide basicity range. The iron-oxide concentration in these slags ranged from 0.08 to 15 pct and was controlled by the addition of silicon to the metal. Other constituents of the slags were mainly CaO, MgO, SiO2, A120,, and CaF,. The experimental technique was essentially the same as that of previous investigations.1 8-lo In an open magnesia-lined induction furnace, 65 lb of Armco ingot iron was melted. An atmosphere of hydrogen was maintained over the melt for 1 hr to bring the carbon content down to approximately 0.010 pct maximum. The bath then was exposed to air for 25 min to remove hydrogen. The electrodes were put in place, and the furnace was operated from this point on in an atmosphere of nitrogen. A synthetic slag was added to which additions of silicon and iron sulphide were made. A rate study conducted at the beginning of this investigation had

Jan 1, 1952

By C. A. Hope, H. B. Wishart

THE number and severity of surface imperfections on rolled slabs, assuming the reception of uniformly good quality heats from the open hearths, depend upon a number of conditions associated with heating and rolling of steel in the primary mills. While there are other elements that have an effect on surface quality, rather than make this paper too lengthy the discussion of mill processing variables will be limited to three factors in order to illustrate their effect on slab surface quality: 1—amount of reduction between ingot and slab, 2—slab finishing temperatures, and 3—influence of roll changes. Measurement of the percentage of surface removed by scarfing on the flat surfaces of the slabs was used for evaluating quality in this study. A study of this nature must be made on slabs that are inspected and conditioned under uniform conditions and standards. In order to be certain that steel of the best possible steelmaking quality was received at the rolling mills, a low carbon deep drawing grade of rimmed steel, made for sheet mill application and manufactured under carefully controlled open hearth practices, was selected. Use of this particular steel thereby reduced the steel quality factor as a possible source of variation. The measure of slab surface quality is the amount of surface removed by scarfing during yard conditioning and is expressed as percentage of surface removal. This percentage was estimated by experienced personnel to uniform standards and it should be noted that these percentage figures are representative only for the grade selected and under the rigid inspection standards to which the slabs were subjected. Surface removal is a matter of concern because the imperfections, if undetected, often are the cause of poor surface quality in the finished product and their removal, by conditioning, add to the total plant costs. The data was collected at various times over a period of six months and, with normal weekly fluctuation in the level of quality, it is to be expected that for any period of sampling there will be some variation in the plotted results. The type of defect that is responsible for most slab conditioning at Gary Steel Works is a light angular surface break. This defect is usually interconnected to form large defective areas and occurs mainly on the bottom half of the slab on both sides. This type of defect is illustrated in Fig. 1, showing a bottom portion of a slab; while a close-up of an area of the same slab where the surface breaks were found is given in Fig. 2. The large dark areas are heat patterns, results of hot stacking and cooling. Independent of these light breaks, but sometimes associated with them, are larger and deeper isolated breaks. However, most of the surface removal occurs from conditioning the large areas of small breaks. There are also occasional scabs of varying degrees of severity but these are relatively infrequent. The slabs are generally free of rolled-in scale. Ingot to Slab Reduction vs Quality Some ten years ago at Gary Steel Works, the minimum slab ingot thickness was 30 in. Subsequent operating and other quality features indicated the desirability of using an ingot of reduced thickness with the result that a series of molds that would produce a 22 in. thick ingot with various widths was adopted as standard. A minimum number of the thicker mold sets are still used. From the standpoint of quality difficulties from pipe and segregation, the smaller ingots are an improvement. From a quality surface viewpoint, the slab product from the thin molds requires approximately twice the surface removal as the slab product from the thick molds. This is shown in Fig. 3 where the percentage of surface removal is plotted against slab product rolled from

Jan 1, 1956

By Avnulf Muan, P. V. Riboud

The effect of Cr2O3 on melting relations of iron oxide at oxygen pressures slightly above those prevailing in contact with metallic iron has been determined. Liquidus and solidus temperatures of wüstite are raised by the addition of Cr2O3, from 1385°C for pure iron oxide to 1420°C at the peri-ledie point where wüstite, iron chromite, liquid, and gas coexist in equilibrium under the atmospheric conditions used in the present investigation (CO2/H2 = 1). It has been shown in a previous investigation1 that the liquidus and solidus temperatures of iron oxide are drastically increased by the addition of Cr2O3 under the relatively oxidizing conditions prevailing in air. This is to be expected in view of the easy substitution of cr3+ for Fe3+ in crystalline oxide structures which are stable at high oxygen pressures, as demonstrated for instance by the completeness of the solid solution series Fe2O3-Cr2O3 at high temperatures (>1000°C). The stable phase of iron oxide at oxygen pressures approximating those prevailing when metallic iron is present is wüstite. This phase, although commonly represented by the simplified formula FeO for sake of convenience, in reality has a defect structure in which a part of the iron ions are present as Fe3+. It is to be expected that at least a limited amount of cr3 ions will substitute for Fe in this structure when Cr2O3 is added to wüstite. Depending on the ease of this substitution in comparison with that of cr3 substitution for Fe in iron oxide-Cr2O3 liquids under the same atmos- pheric conditions, the liquidus and solidus temperatures of wüstite may increase or decrease upon addition of Cr2O3. The methods of establishing these melting relations and the results obtained are presented in the following. I) EXPERIMENTAL METHOD 1) General Procedure. The quenching technique was used in this study. Oxide mixtures were heated at chosen constant temperatures in an atmosphere consisting of equal parts of CO2 and H2 until equilibrium was established among gas and condensed phases. The samples were then quenched in mercury to room temperature, and the phases present were determined by microscopic and X-ray investigation. 2) Preparation of the Mixtures. Starting mixtures were prepared by weighing and thoroughly mixing Fe2O3 and Cr2O3, or wüstite and Cr2O3. The Fe2O3 and Cr2O3 used were "Baker Analyzed" reagent grades, whereas wüstite of composition was synthesized by reducing Fe203 at 1325°C in an atmosphere consisting of equal parts of CG andHz. In order to avoid contact with crucibles, the equilibration runs were made with small pellets suspended from thin (-0.004-in.) platinum wires. Mixtures made from FOs and Cr203 were readily pelletized at a pressure of 500 atm in a 9.5-mm die, whereas mixtures made from wüstite and Cr203 when treated identically were too weak for handling. In order to obtain a stronger product, these pellets were sintered by heating for 2 min at -1200°C in the same atmosphere as was subsequently used for the equilibration runs (CG/H2 = 1:1). During the sintering, these pellets were wrapped in thin (0.0004-in.) platinum foil, which was stripped off before the equilibration runs. In order to reduce the time needed for equilibrium to be attained, preliminary equilibration of relatively large pellets of each mixture was carried out at -1200°C for 4 to 12 hr. Smaller pellets

Jan 1, 1964

By J. P. Morris

PREVIOUS investigations1,2 have shown that alloying elements in liquid iron influence the thermodynamic activity of sulphur and thereby affect the partition of sulphur between metal and slag in the desulphurization process. For example, the greater efficiency of desulphurization in the blast furnace as compared to the open hearth can be attributed in part to a higher level of sulphur activity in blast-furnace metal due to the higher concentration of carbon and silicon. In the present investigation, a short study was made of the influence of manganese on the activity of sulphur in liquid iron and iron-carbon alloys. In contrast to carbon and silicon, manganese was found to decrease the activity coefficient of sulphur; and in iron-carbon alloys it counteracts to some extent the influence of carbon. However, at manganese concentrations normally present in the blast furnace or open hearth, the effect of manganese is small. Since manganese sulphide has a limited solubility in iron, manganese can act, under certain conditions as a desulphurizing agent. Considerable data on the manganese-sulphur product in carbon-saturated melts were obtained in the investigation and have been included in this report. The experimental procedure was the same as that used in the earlier investigations on the effect of silicon&apos; and carbon&apos; on sulphur activity. Briefly, the method was as follows: The molten alloy, contained in a graphite or sintered alumina crucible, was brought to equilibrium at a constant temperature with a mixture of hydrogen and hydrogen sulphide of constant composition by bubbling the gas through the metal. Samples of&apos; the melt were taken for analysis at regular intervals by suction through a 2 to 3 mm bore silica tube dipped into the metal. The experiments were run in a graphite spiral resistance furnace with melts weighing 50 to 60 g. The gas bubbling tubes were made of sintered alumina and were 5/16 in. OD, 1/16 in. ID, and 24 in. long. Equilibrium was assumed to have been attained when the sulphur content of the liquid metal reached a constant value. During an experiment there was a rapid loss of manganese from the melt by volatilization. To offset this loss, small additions of manganese were made periodically. The rate of manganese addition needed to maintain a constant manganese concentration was determined in preliminary tests. In all of the experiments, deposits of manganese sulphide formed above the melts in a cooler region of the furnace. Apparently, these deposits resulted from a reaction between manganese vapor and hydrogen sulphide in the gas. To prove that manganese sulphide did not volatilize from the melts to a measurable extent, an experiment was run in which helium was bubbled through liquid iron containing both manganese and sulphur. Although manganese volatilized rapidly in this test, there was no appreciable loss of sulphur. Volatilization of manganese sulphide from a melt would have led to an apparent equilibrium condition in which the sulphur content of the metal was lower than the true equilibrium value. The experimental results are shown in the first seven columns of Table I. The data in the last two columns were obtained from the previous work on the effect of carbon&apos; and show what the results would have been in the absence of manganese but with temperature, gas composition, and carbon content of the metal remaining the same. Comparison of the last four columns show that, in the presence of manganese, the sulphur content of the metal increased at equilibrium and the activity coefficient of sulphur decreased. However, the results show that, for manganese concentrations below 3 pct, the effect of manganese is small. The values for activity coefficient of sulphur given in Table I were calculated from the following relations: S (in liquid metal) + H2 (gas) = H2S (gas) [l] K ph2s/?s X %S X phg = 0.00251 [2] where K is the equilibrium constant for the reaction, PH2S and ph2 are the partial pressures of hydrogen sulphide and hydrogen, respectively, and ?s is the activity coefficient of sulphur. The standard state for sulphur was taken to be a 1 pct solution of sulphur in pure iron. The numerical value for K at 1600°C was determined in the earlier work. For the purpose of showing graphically the results of the tests run at 1600°C, the activity coefficients of sulphur were recalculated so as to correspond to a manganese concentration in the metal of 2 pct in each case. In the calculation it was assumed that the increase in sulphur content of the metal at equilibrium caused by the presence of manganese

Jan 1, 1953

By R. H. Gautschi, F. C. Langenberg

Rare-earth additions were made to laboratory heats of Type 310 stainless to observe their effect on as-cast ingot structure, nitrogen and sulfur contents, and nonmetallic inclusions. Lanthanum had a grain-refining effect in 30-lb ingots, but results with 200-lb ingots were inconsistent. Cerium, lanthanum, and misch metal lowered the sulfur content when the sulfur exceeded 0.015 pct and the rare-earth addition was greater than 0.1 pct. The rare-eardh content in the metal dropped very rapidly within the first few minutes after the addition. The size, shape, and distribution of nonmetallic inclusions was not changed in 30-lb ingots, but changes were noticed in larger ingots. RARE-earth* additions have been made to austenitic Cr-Ni and Cr-Mn steels to improve their hot workability. The high alloy content of these steels often results in a considerable resistance to deformation and inherent hot shortness at rolling temperatures, particularly in larger ingots. Rare earths in the metallic, oxide, or halide form are usually added to the steel in the ladle after deoxidation although they can be added in the furnace prior to tap or in the molds during teeming. The literature- indicates that the effects of rare-earth treatments on these stainless steels are not consistent, and sometimes even contradictory. Since no mechanism has been presented which satisfactorily accounts for the claimed improvements, the effects of rare earths are a qualitative matter. The work described in this paper was initiated to expand the knowledge of the effects of rare-earth additions on melting variables such as ingot structure, chemical analysis, and nonmetallic inclusions. REVIEW OF LITERATURE Ingot Structure—Rare-earth additions to stainless steels have been reported to cause a change in primary ingot structure in that there are fewer coarse columnar grains. However, the results are inconsistent. While one investigation1 has shown a large reduction in coarse columnar crystals, another2 has been unable to observe this effect, particularly when small ingots were poured. Post and coworkers3 observed ingot structures for a number of years and found that the columnar type of structure is not definitely a cause of any particular trouble in rolling or hammering, provided the alloy is ductile. Knapp and Bolkcom4 found rare-earth additions to be quite effective in preventing grain coarsening in Type 310 stainless steel. Chemical Analysis—Many effects of rare-earth treatment on chemical analysis have been claimed in the literature. Russell5 observed that some sulfur is removed by rare-earth metals, and that a high initial sulfur content improved the efficiency of sulfur removal. Lillieqvist and Mickelson6 report that rare-earth treatment causes sulfur removal in basic open-hearth furnaces, but not in basic lined induction furnaces. Knapp and Bolkcom found no sulfur removal in acid open-hearth and acid electric furnaces, probably because the acid slag can not retain sul-fides. snellmann7 showed that sulfur could be lowered apprecfably with rare-earth additions; however, a sulfur reversion occurred with time. Langenberg and chipman8 studied the reaction CeS(s) = Ce(in Fe) + S(in Fe), and found the solubilit product [%Ce] [%S] equal to (1.5 + 0.5) X 10-3&apos;at 1600°C. Results in 17 Cr-9 Ni stainless were about the same as those in iron. Beaver2 treated chromium-nickel steels with 0.3 pct misch metal and observed some reduction in the oxygen content. He also noted an inconsistent but beneficial effect of rare earths when tramp elements were present in amounts sufficient to cause difficulty in hot working. It is not known whether rare earths reduce the content of the tramp elements or change the form in which these elements appear in the final structure. No quantitative data are available concerning a possible effect of rare-earth treatment on hydrogen and nitrogen contents. However, Schwartzbart and sheehan9 stated that additions of rare earths had no effect on impact properties when the nitrogen content was low (0.006 pct), but served to counteract the adverse effects of high nitrogen content (0.030 pct) on these properties. Knapp and Bolkcom4 analyzed open-hearth heats in the treated and untreated conditions and found the nitrogen content (0.006 pct) to be unaffected. These two results lead to the speculation that rare-earth additions can reduce the nitrogen content to a certain level. Decker and coworkers10 have observed that small amounts of boron or zirconium, picked up from magnesia or zirconia crucibles, increased high-tem-

Jan 1, 1961

By W. O. Philbrook, K. M. Goldman, G. Derge

THIS is the third in a series of papers from the Metals Research Laboratory dealing with the transfer of sulphur across the iron-slag interface in a carbon-saturated system. The first paper&apos; showed that the transfer obeyed first-order kinetics. The second&apos; presented detailed evidence in support of the three-stage mechanism: FeS(Fe) FeS(slag) FeS(slag) + CaO(sing) ? CaS(slag) + FeO(slag) FeO(slag) + C ? Fe + CO. This emphasized the role of an iron-sulphur complex as the transfer agent across the interface and as an essential intermediate in the overall process. The present paper shows the influence on the process of the individual elements, carbon, silicon, manganese, and phosphorus, the alloying elements normally present and of interest in commercial blast furnace operations, aluminum, which has a pronounced accelerating influence, and nickel and copper, which are common minor impurities in the raw materials. The experimental methods and procedures for interpretation of data are the same as described earlier.1,2 Induction heated, graphite crucibles were used, and sulphur-free slag was added to the molten iron containing sulphur and the selected alloy. Slag samples were taken at regular time intervals and analyzed for sulphur and other components of interest. The authors wish to state specifically that these experiments were not intended to simulate industrial blast furnace operations. However, they do represent a study of the kinetics and mechanism of sulphur transfer at the slag-metal interface under specified laboratory control of the major variables in the system. It is believed that the results can be usefully applied to the blast furnace if consideration is given to the differences which are known to exist between the two conditions. A rigorous evaluation of the accuracy of rate studies is difficult. Recognized sources of error include sampling and analysis of both slag and metal, temperature measurement and control, selection of zero time, composition of the gaseous atmosphere over the reaction system, and extraneous sources of sulphur from the graphite crucible and reagent materials. In this study carefully standardized procedures were followed consistently in order to minimize the errors. It is believed that the reproducibil-ity of duplicate runs indicates that errors have been rendered negligible relative to the observed effects from intentional variables. For example, original experimental points for duplicate runs are shown in Figs. 1, 2, 7, etc. In most cases in this paper the drawn curves represent an average of at least two heats. The spread in sulphur values at a given time ranges from 0.02 to 0.08 pct, which is a small frac-tioi of the total values ranging up to 2 pct S in slag. In the systematic study of the influence of alloy additions, each element was added over a range of concentrations. The two slags used in this study were designated as "acid" or 1530 and "basic" or 1545. They had the nominal compositions given in Table I. Rates were measured in the temperature range 1500" to 1650°C. Data will now be presented to illustrate the various features of the study. Silicon The first alloying element examined was silicon, because its presence is unavoidable in any silicate slag system through the reaction y/2SiO2(slag) + xM?y/2Si(liq.Fe) + MxOy where M is any reducing agent such as iron or carbon. It is known that the attainment of equilibrium by this reaction is extremely slow and probably not reached in the blast furnace." The influence of silicon on the final stages of the sulphur reaction has also been studied.&apos; It has been shown5 hat silicon increases the activity of sulphur in iron. For such reasons silicon may also be expected to influence the kinetics of the reaction. The observed effects will now be described. The general procedure was to melt 530 grams of ingot iron in a graphite crucible, 3 in. OD, 2 1/4 in.

Jan 1, 1955