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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 R. H. Singleton

ThE purpose of this investigation was to determine the effect of cerium upon the nonmetallic inclusions found in cast and wrought steel containing various amounts of sulfur, oxygen, and nitrogen. Interest of the Physical Metallurgy Laboratory of the Watertown Arsenal Laboratories in this type of research was stimulated by the reports from industry that rare-earth metals imparted beneficial effects upon the mechanical properties of steel, but that the mechanism was not understood. Berry and Dorvel' found that misch metal improved the impact properties of aluminum-killed cast steels. They reported that the rare earths modified the intergranular-film type nonmetallic inclusion, present with aluminum as the sole deoxidant, to a randomly distributed globular type. Lilliequist and Mickelson2 observed the improvement of ductility and toughness of quenched and tempered cast steels through rare-earth additions. They also observed the change from angular to duplex inclusions when rare earths were present. They con-

Jan 1, 1960

By O. Cuscoleca

The Austrian plants at Donawitz and Linz were the first to blow steel with high purity oxygen. The paper shows how the process was developed and gives a survey of the results achieved to date. Compared with open hearth steel of equal quality, the obvious advantages of oxygen steel are the low investment and conversion costs. The nitrogen content of oxygen steel is not higher than that of good open hearth steel. Rimmed and killed steel products made by the oxygen process are superior to rimmed and killed steel products made by the best open hearth process. TWO new steel plants using the principle of making steel with high purity oxygen went into operation in Austria, one at Linz (Vereinigte oster-reichische Stahlwerke) in November 1952 and the other at Donawitz (dsterreichisch-Alpine Montan-gesellschaft) in May 1953. An estimated 330,000 metric tons were produced by the two plants in 1953, the first year of operation. In 1954 production by Austrian plants- using the high purity oxygen approach will be raised to 450,000 metric tons. This will be in addition to facilities in Huckingen (Man-nesmann A. G., Düsseldorf, Germany), those planned and under construction at Hamilton, Ontario, Canada (Dominion Foundries and Steel, Ltd.), and elsewhere. It is expected that by 1955 a total capacity of one million tons of high purity oxygen steel will be available. At the close of the last century, because of increasing availability of scrap, open hearth steel production forged ahead at an ever increasing pace. This caused world steel production to rise faster than pig iron production and finally to overtake it. In 1911 65 million tons of steel were produced against 64 million tons of pig iron. World steel production was 209 million tons in 1951, while pig iron output was only 147 million tons. The 1951 breakdown for steel shows 118 million tons made from pig iron, while the balance, 91 million tons or 44 pct of the total tonnage of steel produced, was made from scrap. This increase in crude steel production on a basis of high scrap consumption led to the world market scrap shortage and soaring scrap prices. In the United States and other nations, production of converter steel has fallen far behind that of open hearth steel. The surplus of processing scrap, un-absorbable by converting mills and thus a welcome source for open hearth and electric melting shops in the past, together with regular scrap purchases, no longer can meet requirements of both open hearth and electric steel production in Europe. In addition, recent modification of the basic bessemer process, blowing with oxygenated blast, substantially raised the scrap capacity of these plants. Any further expansion of world steel production will necessitate utilization of self-containing processes in regard to scrap because of the shortage.

Jan 1, 1955

By J. Chipman, H. Towers, M. Paris

A simple radioactive tracer technique is used to measure the diffusion coefficient of calcium ion in molten slags. In a slag of 40 pct Ca0-40 pct Si0,-20 pct Al203, Dc " at 1450°C is 1.3x10-6 cm' sec-'. THE application of the principles of thermodynamics to steel and iron making problems has proved so fruitful that the kinetic approach has tended to be neglected. It seems probable that in some reactions the rate-determining step is the dif-fusivity of the reactants or of the products. But knowledge of the diffusion coefficients of the constituents of liquid slag and metal is singularly lacking. The present work was undertaken as a first step toward supplying such data for slags. Furthermore, any additional information on the physical properties of liquid slags might be expected to help in elucidating their structure. It is essentially a preliminary investigation, the course of which was determined more by the necessity of establishing a method than by the immediate intrinsic interest of the results. For example, the selection of calcium ion to be studied was dictated by the suitability of the isotope Ca45 in that it is a simple emitter with a long half-life. Of the other ions commonly encountered in slags, the isotopes of iron and manganese have relatively complex radiations as well as the normal disadvantage of requiring control of the oxygen potential of the atmosphere; Mg27 and Al29 have half-lives measured only in minutes; Si3' has a simple decay process but its half-life of 2.8 hr is too short for preliminary studies; the only useful oxygen isotope is the stable O18; and there remain only sulphur and phosphorus both of which have suitable isotopes but were rejected as being of less fundamental interest than calcium. Similarly a lime-alumina- silica slag was used in preference to calcium silicate primarily because of its low melting point and its capacity to form a glass on fairly rapid cooling. Literature Review Very few studies of diffusion in liquid silicate systems have been reported. In order to determine the origin of diopside inclusions in felspathic rocks, Bowen1 investigated the diffusion between diopside and various mixtures of albite and anorthite. Platinum crucibles were used with diopside, the heavier of the two liquids, forming the lower half of the cell and diffusion taking place against gravity. Change in concentration along the diffusion path was found by measuring the refractive index of the quenched glass. Nearly thirty years later McCallum and Barrett2 used essentially the same method to determine the diffusion coefficient of lime in lime-alumina-silica slags. In this case the interest was to find the rate-determining step in the process of slag attack on refractory materials. In an investigation of the kinetics of the sulphur reaction, Derge, Philbrook, and Goldman8 determined the diffusion coefficient of sulphur in a typical blast furnace slag by the simple procedure of melting a slag containing 2 pct S over an identical slag sulphur-free. They make no claim to a high degree of accuracy but suggest that D, is of the order of 10-6 cm2 sec-l. Other high temperature liquid diffusion studies have been concerned with metals. Holbrook, Furnas, and Joseph4 determined the diffusion coefficients of silicon, phosphorus, sulphur, manganese, and carbon in liquid iron by immersing a small carbon crucible containing pure iron-carbon alloy in a large vessel containing iron with a high concentration of the particular element. Their results were confirmed by Paschke and Hauttmann5 using a similar method. Diffusion coefficients in silicates in the glassy state have been studied by Johnson, Bristow, and Blau6 Both Na24 and Ca45 were used as tracers but only the

Jan 1, 1954

By K. L. Komarek

Based on theoretical and experimental evidence a discussion follows of the behavior of phosphorus -bearing iron ores in the R-N Direct Reduction Process and suggestions are made of methods of reducing the amount of phosphorus in the metallic end product. In ferrous metallurgy a direct reduction process is one in which iron ores are reduced to metallic iron with gaseous or solid reductants without the appearance of a liquid phase. A number of attractive features have induced several companies and government agencies to invest in the development of direct reduction processes. A summary of all direct reduction processes up to 1954 has been given by Barrett,' and Wiberg,2 and Willems3 have reviewed the most recent developments in this rapidly expanding field. Many difficulties have been encountered in direct reduction processes and the nature of these difficulties has varied from process to process. One problem common to almost all of them is the removal of phosphorus which is one of the reasons for the rather pessimistic outlook given by some government publications4'5 to direct reduction processes. In this paper an attempt is made to give a theoretical explanation of the variations in phosphorus removal observed in the R-NY Direct Reduction Process. However, many conclusions are general enough to be applicable to other processes. Most iron ores treated by the R-N process yield products lower in phosphorus than the original ore. A qualitative account of the factors has been given by Stewart, Reed, and Herasymenkoe but the erratic removal of phosphorus from some ores and the general importance of this problem make a more careful analysis of the theoretical aspects desirable. In the R-N process mixed ore or balled fines, ex-

Jan 1, 1963

By G. W. Healy

G. W. Healy (union Carbide Metals 0.)-The author'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's recently published one1 on the CaO-FeO-Fe2O3 system will be most helpful to others learning to apply Schuhmann'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. F. Hosford

W. F. Hosford, (Massachusetts Institute of Technology) —evelopment of methods for predicting the plastic anisotropy of textured metals is an important step toward the improvement of properties by texture control. The engineering value of the present analysis is indicated by the good agreement between prediction and experimental findings. The purpose of this discussion, however, is to point out the weakness of the assumptions on which the analysis is based. The authors state that "the relative width and thickness strains are believed to depend only on the slip direction" and accordingly they disregard the orientation of the active slip plane. where E,, cW, and et are the tensile, width, and thickness strains, A,, A,, and At are the angles between the tensile axis x, the width direction w, and the thickness direction t, respectively; and G,, GW, and 4 are the angles between the slip-plane normal and x, w, and t, respectively. Therefore, the ratio of width to thickness strains resulting from slip on a single system would be These relations hold regardless of whether the slip plane is a crystallographic plane of the {110}, (1121, or (123) type or whether noncrystallographic slip occurs. If noncrystallographic slip occurs, it might be reasonable to assume that the effective slip plane is the most highly stressed plane containing the slip direction. In this case the slip direction, S.D., the slip plane normal, S.P.N., and the tensile axis, x, are coplanar (Fig. 19) and the angles are related by following expressions: where 9 is the angle between t and the projection of the slip direction in the w-t plane (igs. 1 and 2). The normal strains, Eq. [9], become

Jan 1, 1963

G. McMEANS*—This paper is a very good demonstration of the use of a new tool for the solution of industrial problems of a physical nature. To have solved this problem without the use of radioactive tracers would have required a far greater amount of investigation and work. The authors have described their work in such detail and in such a manner as to suggest the possibilities of the use of such tracer studies in the solution of many perplexing problems of industry. R. E. BREWER †—The authors are to be congratulated on this very excellent paper, which describes the results obtained by utilizing radioactive tracers in investigating the complicated reactions in the coking process. The paper has especial merit because the study was made under typical operating conditions in a commercial coke oven. Considering all the difficulties involved, the results obtained are excellent. My brief comments will relate primarily to the method used for determining the sulphur in the gas and to the value of the data obtained in stimulating further research. In discussing their results, the authors state (p. 17) that "Of the total sulphur charged to the oven in the coal 95 pct was accounted for in the coke and gas. Most of the sulphur unaccounted for is believed to have been lost in the gas, since the gas sampling system removed all the H2S but probably only part of the organic sulphur compounds present in the gas. Although sulphur in the acid-insoluble tar residue in the gas scrubbing bottles was determined and added to the total sulphur determination of each sample, it is doubtful whether an aliquot portion of tar for each sample was obtained." The reviewer believes that the authors might have obtained a better sulphur balance had they used an improved procedure for determining sulphur in the gas. The absorption train should have included a trap to remove the tar and am-moniacal liquor and a wash bottle containing 5 pct sulphuric acid to remove ammonia in the coke-oven gas before it entered the gas scrubbing bottles containing the ammoniacal cadmium chloride solution. Sulphur in the tar and

Jan 1, 1950

By H. Margolin, E. Ence

A. J. Goldak and J. Gordon Parr University of Alberta) —Margolin and Ence's paper reached us only a few days after we had submitted a paper on the structure of Ti2Cu to the AIME. Here, however, we only wish to point out an error in the paper (page 321): "Karlsson has reported the crystal structure of the first intermediate phase occurring in the Ti-rich portion of the Ti-Cu system to be face-centered tetragonal." Karlsson actually reported the structure of Ti3Cu (i.e., "the first intermediate phase") to be primitive tetragonal with four atoms per lattice point: Cu at 0, 0, 0; and Ti at 1/2, 1/2, 0; 0, 1/2, 1/2; and 1/2, 0, 1/2. Thus, Karlsson suggests a primitive lattice with an ordered arrangement of atoms located at corners and face-centers: Ence and Margolin suggest a random body-centered tetragonal structure—-with which our results agree. E. Ence and H. Margolin (azlt1zo.l-s' reply)— We do not agree that Karlsson has not reported the structure of Ti3Cu as face-centered tetragonal. The fact that Cu atoms are located at the corners and titanium at the face-centers does not indicate that the lattice is not face-centered. We are pleased that the discussers' results agree with our own.

Jan 1, 1962

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'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'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'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'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 M. G. Benz, J. F. Elliott

A. J. Goldak and J. Gordon Parr (U)iuersity of Alberta) —Margolin and Ence's paper reached us only a few days after we had submitted a paper on the structure of Ti2Cu to the AIME. Here, however, we only wish to point out an error in the paper (page 321): "Karlsson has reported the crystal structure of the first intermediate phase occurring in the Ti-rich portion of the Ti-Cu system to be face-centered tetragonal." Karlsson actually reported the structure of Ti3Cu (i.e., "the first intermediate phase") to be primitive tetragonal with four atoms per lattice point: Cu at 0, 0, 0; and Ti at 1/2, 1/2, 0; 0, 1/2, 1/2; and 1/2, 0, 1/2. Thus, Karlsson suggests a primitive lattice with an ordered arrangement of atoms located at corners and face-centers: Ence and Margolin suggest a random body-centered tetragonal structure—-with which our results agree. E. Ence and H. Margolin (authors' reply)— We do not agree that Karlsson has not reported the structure of Ti3Cu as face-centered tetragonal. The fact that Cu atoms are located at the corners and titanium at the face-centers does not indicate that the lattice is not face-centered. We are pleased that the discussers' results agree with our own.

Jan 1, 1962

By P. T. Carter, A. B. Murad, H. B. Bell

The distribution of manganese and oxygen between molten iron and FeO-MnO-SiO2 slags not saturated with SiO2 has been determined and used to calculate activities of MnO and SiO2 in MnO-SiO2 slags. These were found to be intermediate between the corresponding activities in FeO-SiO2 and CaO-SiO2 slags. THE equilibrium constant for the reaction between molten iron containing manganese and slags containing FeO and MnO, namely: FeO(slag) + Mn = MnO (slag) + Fe(1iquid) is most conveniently represented by: (MnO) Kmn== (FeOHMn] [Fe] is omitted, since for dilute solutions of manganese in iron, afe is approximately constant. When activities are used for (MnO), (FeO) and [Mn], Kmn is a true equilibrium constant and will apply to all types of slags, but when weight percentages are used, the values obtained for Kmn for different slags vary considerably. The equilibrium between iron containing manganese and relatively pure FeO-MnO slags has been investigated by several workers;1-4 the most recent investigation reported is that of Chipman, Gero, and Winkler.4 Their results, corresponding to slags containing up to 4 pct SiO2, were represented by the equation: 6440 log KMn = +2.95 In this case both slag and metal may be assumed to be ideal solutions, therefore the values of Kmn so derived represent the true constant for the manganese reaction. As the molecular weights of MnO and FeO are almost equal, weight concentration of these oxides may also be used in the above expression. Acidic oxides such as SiO2 and P2O5 affect the activities of FeO and MnO differently, so that when total concentrations by weight of FeO and MnO are used in the above expression for Kmn the values obtained are no longer constant. These will be denoted by K'mn. Körber and Oelsen5 investigated the manganese reaction using silica-saturated iron-manganese-silicate slags and found: 7940 logK'mn =3.172 This corresponds to Kmn values much higher than those obtained for pure oxide slags. The results of Körber and Oelsen, and Chipman, Gero, and Winkler are summarized in Table I. In the present investigation it was decided to study the manganese reaction using iron-manganese-silicate slags not saturated with silica, and which fell mainly between the orthosilicate join 2FeO . SiO2 - 2MnO.SiO2 and the FeO-MnO side of the ternary system FeO-MnO-SiO2. It has been shown" that the phases present in solidified slags of this part of the diagram are (FeO, MnO) and (2Fe0.Si02, 2Mn0-SiO,) solid solutions. Such an investigation would be of interest in deoxidation and also gives information on activities in liquid slags. This equilibrium has not as yet been investigated successfully. Hilty and Crafts7 attempted to examine this reaction in a rotating crucible furnace, but were unable to obtain suitable slag samples. In the present investigation one series of experiments was carried out in a rotating crucible furnace, because the success of Taylor and Chipman8 with such a furnace in their study of oxygen distribution between molten iron and (CaO, MgO) — FeO-Si0, slags suggested that it would minimize contamination of the slag by the crucible material. A second series was carried out using a wire-wound resistance furnace. Rotating Crucible Furnace Experiments In all cases the metallic charge consisted of 800 to 1000 g Armco iron containing 0.02 pct C, 0.03 pct Mn, and traces of Si. Manganese and silicon additions consisted of electrolytic manganese (99.9 pct)

Jan 1, 1953

By P. T. Carter, A. B. Murad, H. B. Bell

N. A. Gokcen (Michigan College of Mining and Technology, Houghton, Mich.)—The activities of silica, represented in Fig. 5 for the systems MnO-SiO2 and CaO-SiO2, are in disagreement with the established binary phase diagrams. At Ns102 = 0.50 in MnO-SiO2, and at Ns102, = 0.65 in CaO-SiO2, each binary system is saturated with respect to silica at 1550°C, and therefore as102, is unity in each case. The curves for as102 (FeO-SiO2) and as102, (MnO-SiO,) should nearly co-

Jan 1, 1953

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'/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 J. Chipman, N. J. Grant, R. Rocca

D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—With reference to eqs 7 and 8, at what temperature do they apply John Chipman (authors&apos; reply)—That was 1600°C. Dr. Babcock—You have l x 10-4 as the component for the lime and 1 or 4x10-. Now, is it by dividing one into the other you get the 400? That is assuming equivalent activity on the part of oxygen, sulphur, and magnesia. Dr. Chipman—Yes, they are calculated for 1600. Now, the first one for CaO was calculated before we had a glimpse of Dr. Rosenqvist&apos;s paper." If you take his calculation you get 14,000 cal which is very good agreement, but our calculation would be superseded by Dr. Rosenqvist&apos;s new data. Dr. Babcock—The state you assume those to be in is the liquid state, as near as you can measure? Dr. Chipman—Naturally it is based on the solid CaS, but if you add the effect of fusion on both sides it just about balances out, so the ratio would be about the same. B. M. Larsen (U. S. Steel Co., Kearny, N. J.)—If we knew the activity of sulphur in the slag instead of merely the percentage, we might be able to find some conflicting factors that balance one another out, and find that the FeO or oxygen pressure effect is really present over the whole range. Dr. Chipman—I am fairly sure we would. The activity of sulphur in the slag and the activity of CaO in the slag, if we just knew those quantities, would enable us to save a lot of this computation and assumption and all the approximations we are doing now. Mr. Larsen—Two other points perhaps should be included: 1—an independent effect of manganese in helping the desulphurization; and 2—the number of mols of constituents or number of mols of ions or whatever there is in the slag could vary with these compositions in such a way that you get dilution effects. Dr. Chipman—You can figure all that in if you want to and it might improve the degree of approximation a little bit. Maybe enough to justify the labor of calculation, inaybe not, but we did not do it. L. S. Darken (U. S. Steel Co., Kearny, N. J.)—The authors have tackled a very complicated problem in trying to tie together in one picture the desulphurizing problem over the wide range of basicity and oxidation level from that of the open hearth to that of the blast furnace. At the present state of our knowledge of slags such an ambitious undertaking necessarily involves the adoption of numerous hypotheses. Their formulation (eq 11) for the higher FeO range

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