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By R. A. Parra, Fuentes, C. Godoy, L. E. Arias, C. A. Toro, M. Marin, E. Balladares, V. Parra, G. Reyes, S. N. Torres, D. Sbarbaro

In this paper, we report on the detection of spectral molecular emission of iron oxide (FeO) and copper oxide (CuxO) emitted by reactions occurring in a laboratory scale flash smelting process of pyrite (FeS2) as well as copper concentrate. The novelty of the technique is that, the molecular spectral emission sensing is achieved by using a low spectral resolution and low sensitive radiometer, enhanced with signal processing and matrix factorization techniques. The method was validated using a highly sensitive spectrometer, with a high spectral resolution; achieving a similar FeO spectral pattern as the one obtained after signal processing techniques over low resolution spectral signals. INTRODUCTION Visible-near infrared (VIS-NIR) spectroscopy is an optical contactless sensing technique commonly used to capture information about the emitted, absorbed, transmitted or scattered radiation in a physical or chemical process, with the presence or absence of an excitation light source such as a laser or a broad spectral band source. These techniques coupled with signal processing and machine learning algorithms, sometimes referred as chemometrics (Pisapia et al., 2018), can be found in processes such as: pharmaceutical (Kandpal et al., 2016); food (Coelho et al., 2016); combustion (Ballester & García-Armingol, 2010); siderurgy (Strakowski et al., 2014) industry, among others. In the extractive copper industry there are several technological developments using optical sensing techniques aimed to retrieve information about copper ore and concentrate mineralogical composition such as X-Ray Fluorescence, Qemscan® (Quantitative Evaluation of Minerals by Scanning Electron Microscopy) and X Ray Diffraction (XRD) analysis, however, because of the manual procedures to analyze the samples with these laboratory instrumentation, only discrete information during a daily based operation can be retrieved, making impossible for the operators to take decisions over the involved processes in real time. The aim of our research work presented here is to contribute with sensing and data analysis procedures based on VIS-NIR spectroscopy for the flash smelting process characterization, particularly in this paper, with the detection of FeO and CuxO molecular emissions in a laboratory scale setup.

Jan 1, 2019

By Edgar C. Bain, William E. Griffiths

The results of an inquiry into the structural nature of some 70 iron alloys containing both nickel and chromium over a considerable range of concentration are briefly described in this paper. This study is a part of a comprehensive program of investigation into alloys involving chromium in progress at the Union Carbide and Carbon Research 1aboratories. All the compositions studied contained carbon in amount comparable to commercial alloys. The B Constituent In addition to locating the limits of composition for the three principal types of structure (polyhedral ferrite, martensite and austenite) and their combinations, certain other features of the system were observed. A hitherto undescribed brittle constituent (designated here as the "B constituent") was discovered. It is very hard, non-magnetic and forms in two modes from chrome-ferrite by recrystallization. It is the stable low-temperature condition for the equal-proportion chromium-iron materials containing less than 10 per cent. nickel. Although it partakes of the nature of an inter-metallic compound, yet it may exist over a considerable range of composition. It is non-existent above a temperalure zone, varying with composition, from 800° C. to 950° C., and heating above this critical temperature develops chrome ferrite persistent after average cooling rate; a few hours just below this temperature will develop the complicated brittle crystalline type. The B constituent, when found in the grain boundaries of alloys of lower chromium content, contributes a serious brittleness removable, however, by heating and cooling rapid enough to prevent its re-format'ion. By suitable means of precipitution, the hard B constituent can be made to strengthen the already stiff alloy matrix in the manner of submicro-scopic particles, as exemplified in duralumin or the Sykes iron-tungsten and iron-molybdenum alloys. A possible explanation is offered for the familiar brittleness developed in chrome iron at temperatures above about 475" C. and removable by

Jan 1, 1927

By Francis F. Lucas

A microscope objective of given numerical aperture, when used with light of given wave length, has some fixed limit of resolution. This may be expressed as potential resolving ability—the ability to resolve is inherent in the lens but whether this limit is achieved in practice is quite another matter. Nearly 50 years ago Abbe evolved theoretical considerations which indicated that the ability of a lens to resolve detail is directly proportional to twice the numerical aperture of the objective and inversely proportional to the wave length of the light used. It is true, unquestionably, that as the numerical aperture of the objective is increased the potential resolving ability of the lens is increased and likewise when the wave length of the light used is decreased, the degree of resolution is increased. Whether Abbe's formula expresses the exact relationship is not a matter of great concern. It suffices to know that to improve resolution, other things being equal, two avenues of approach are available. Either the numerical aperture of the objective may be increased or the wave length of the light decreased. With the apochromatic system it is possible to employ successfully wave lengths from 400 to 500 uu and still secure reasonably short exposures. The present limit for numerical aperture is 1.40 N. A. although objectives of 1.60 N. A. are now an experimental possibility for metallurgical work. Thus certain well defined limits are set for those who work within the range of the visible spectrum. In order to take advantage of the increase in resolving power which accompanies a decrease in the wave length of light employed, Dr. A. Kohler and Dr. M. Von Rohr of the Zeiss Scientific Staff developed the "monochromats." These are quartz objectives corrected for the single wave length 275 uu which lies in the ultra-violet region of the spectrum. They also developed a series of quartz oculars and a complete photo-micrographic equipment with which to use the quartz optics. Quartz must be used for the optical parts because glass absorbs ultra-violet light almost completely. Thus there was made available about 20 years

Jan 1, 1926

By K. Huessener

In presenting the following data on combustion in the open hearth furnace and the advisability of automatic combusion control, the author finds himself much more severely handicapped by the lack of reliable test results than he had anticipated when he first undertook to write this paper. In order thoroughly to investigate how the results of an open-hearth furnace are influenced by combustion, one would have to draw up a large number of heat-balance sheets, as Kinney and McDermottl have given for one heat in their extremely able paper on "Open Hearth Efficiency,' presented before the American Iron and Steel Institute on October 27th,1 1922. Instead of covering only one heat, however, such heat-balance sheets would have to embrace a large number of heats, and not only for one kind of fuel, but for all the various fuels in customary use. Use of Radiation-protected Pyrometer Such tests necessitate extremely careful temperature readings, and here the first serious difficulty presents itself. Nearly all the temperature readings so far published have been taken with thermocouples for the lower ranges and with optical or radiation pyrometers for the higher ranges. This method of measuring reveals the temperature of the surrounding walls, or in the case of optical or radiation measurements, the temperature of that part of the opposing walls which has been focused by the instrument. The error in ascertaining the temperature of the gases entering or the waste gases leaving the checker chambers is probably not very large, as the flowing gases impart their temperature to the walls of the flues. On the other hand, the uptakes, where the preheat temperature of gas and air are usually measured, are under the influence of radiated heat from the port ends, and correct temperature readings can here be taken only by using a radiation-protected pyrometer of the aspirating type.

Jan 1, 1926

By Sir Albert E. Kitson

The manganese ore deposits of the Gold Coast, British West Africa, occur in very ancient rocks, of both sedimentary and metamorphic types. In certain respects they have a strong resemblance to those of India and Brazil, as contrasted with those of Tertiary age in Georgia, but in this paper no careful comparison with them can be made. Viewed from the present condition of the manganiferous rocks, the oldest deposits are in the sediments. Later than these are the progressively metamorphosed representatives of these sediments. Youngest are the products of decay and degradation with the concentration of manganese oxide in the rocks of both groups. The oldest occurrences are in argillaceous and siliceous phyllites and slates, which show only a moderate degree of metamorphism. They belong to a series which also includes mudstones, sandstones, grits, conglomerates and subordinate limestones, with tuffs and lava-flows, largely of basic types. This has been named the Birrim System. Its age is unknown, for no definite fossils have been discovered in it. Since these non-fossiliferous strata at many plaees are of a character which in many parts of the world are suitable for the preservation of fossils, and which contain them, it is assumed that the Gold Coast deposits are pre-Cambrian. These rocks of the Birrim System have normally a northeast-southwest strike, and are folded, but not to any very great degree except in certain belts. From the Eastern Province of the Gold Coast they may be traversed diagonally across their strike for upwards of 600 miles, to the extreme northwestern corner of the Northern Territories. Thence they probably extend much farther into French territory.

Jan 1, 1927

By Chas. Y. Clayton, Francis B. Foley, W. E. Remmers

DuRing the summer of 1919, the late Dr. Henry M. Howe, then Chairman of the Division of Engineering of the National Research Council, organized a committee to obtain a better insight into the behavior of carbon steels under the influence of various treatments by a proper control of the time and temperature factors. During part of 1919 and 1920, work in connection with this investigation was carried on at Dr. Howe's laboratory at Bedford Hills, N. Y. During 1921 there was an enforced hiatus in the work, occasioned by the illness which resulted in Dr. Howe's death in 1922. At that time one of the present authors compiled the results of the work which had been done and this was published in 1923.' Following the publication of this work, it seemed desirable to carry on in the same manner an investigation of steel of C 0.75 per cent., which steel had not been as fully treated as had the other steels of C 0.34 and 0.52 per cent., used in the published work. Furthermore, certain unusual results have been obtained in the treatment of C 0.52 per cent. steel by quenching and drawing, and repetition of this part of the work seemed advisable. This has been done during the past year at the School of Mines and Metallurgy of the University of Missouri at Rolla, Mo., by a cooperative undertaking of the School and the Bureau of Mines, working in conjunction with the Committee on Heat Treatment of Carbon Steels of the National Research Council. The present paper is a report of the results obtained in this work.

Jan 1, 1926

By C. E. Wood, E. P. Barrett, T. L. Joseph

The invention of the Bessemer converter process in 1856 added great impetus to the manufacture of steel and is one of the outstanding contributions to process metallurgy. Although the process of refining pig iron by passing air through the molten metal bears the name of Henry Bessemer, it should be mentioned in passing that William Kelley of Eddysville, Ky., worked on the process as early as 1847. Kelley was granted a patent on the process in 1857, inasmuch as he was able to prove priority in discovery.' After considerable litigation in 1865 the respective interests of Kelley and Bessemer were combined. On Sept. 10, 1856, Robert Mushet of England obtained his first patent on the application of manganese to cast steel. Mushet anticipated trouble in purifying iron by passing currents of air through it: His patent specified that steel made in this way often contained flaws and was red short or cold short. Mushet understood the refining of pig iron into steel well enough to realize the difficulties likely to be cncountered from oxidation of the iron. Mushet was not only an inventor; he was also an investigator. He understood the principle of selective oxidation which takes place in the converter process, and he realized therefore that the remedy for over-oxidation was attainable if a suitable metal could be found at a reasonable cost and in sufficient quantities. His first experiments were made in small crucibles holding a few ounces of metal. Later his work was conducted on a larger scale and with complete success. Manganese had been used in making steel a quarter of a century before the converter

Jan 1, 1927

By Marcus A. Grossmann

This paper offers for consideration certain somewhat radical modifications in the iron-carbon diagram, these modifications being the result of the presence of notable amounts of alloying elements. When only small amounts of alloys are present, the standard iron-carbon diagram (Fig. 1) can be used with but insignificant changes; when larger amounts of alloys are present, however, it assumes a distinctly altered appearance. No comment is offered for the present except to call attention to the delta area, A4BM, which represents a region of mixtures of austenite and delta iron, just as area A3SP represents mixtures of austenite and alpha iron. Absence of Carbon We may turn at once to the effect of the presence of alloys. It has been found that in the complete absence of carbon, the gamma change will sometimes disappear entirely when sufficient alloying element is

Jan 1, 1927

By B. M. Larsen, J. W. Campbell

Several articles have recently been published discussing the conditions necessary for accurate measurements of temperatures in the open-hearth steel furnace. In the course of a study of refractories service conditions in steel furnaces, the present writers have taken temperatures in several open-hearth shops in the Pittsburgh district. The conclusions, as to conditions necessary for accurate measurements of temperature, are somewhat at variance with those of other investigators. The subject is closely connected both with the close control of steel-making and the prevention of overheating of the silica refractories used in roofs and walls. It is becoming more and more important to obtain furnace temperatures of fairly definitely known accuracy. At present, the most useful instrument for such measurements is the disappearing-filament type of optical pyrometer. This method of measurement has formed the basis of most other discussions on the subject and was also used by the writers. Previous Investigations In 1916, Burgess' made perhaps the first systematic series of measurements in steel furnaces. The emissivity figures of 0.40 for liquid steel and of 0.53 to 0.65 for liquid slags had been determined by the Bureau of Standards and were used by Burgess in this work. These correction factors are still being used and are regarded as fairly accurate, so that the tapping and teeming temperatures on metal streams given by Burgess should be very nearly correct. Most of his temperatures of furnace roofs and slag surfaces were taken while flames were present in the furnaces and include a few roof temperatures above 1700' C. (3100' F.).

Jan 1, 1927

By V. N. Krivobor

The study and use of low-carbon manganese steels have been curiously neglected in the general history of developments in alloy steels. Hadfield1 made an extensive study of manganese-iron-carbon alloys about 1886, which culminated in the wide application and use of Hadfield austenitic manganese steel. His alloys were nearly all high in carbon, as compared with the steels discussed in this paper, and he found a marked tendency toward brittleness in the alloys of medium and low manganese content, that is, below 7 per cent. manganese. As a result, there has been a widespread prejudice against the use of manganese steels containing between 1.0 to 3.5 per cent. manganese with comparatively low carbon. Steels of this composition have never been studied adequately in comparison with other alloy steels, and have had litttle use in practice. In a very recent paper by Sir Robert Hadfield2 the following statement appears: 6L... manganese-iron alloys with little or no carbon do not seem to offer any practical employment; they only become valuable in the presence of quite high percentages of carbon, 0.90 to 1.50 percent." The results of the present investigation are so contrary to the findings of Hadfield that the writers feel fully justified in presenting the preliminary report incorporated in this paper. Previous Investigations As early as 1886 the Terre Noire CO.3 in France produced alloys containing up to 2.5 per cent. of manganese, using ordinary low-grade

Jan 1, 1927

By W. P. Sykes

In connection with a study of tungsten steels, Honda and Murakamil reported an investigation of the system iron-tungsten. This report included a tentative equilibrium diagram, photomicrographs of various alloys in the series, and qualitative measurements of hardness and magnetic properties. The present investigation originally had as its object the study of the hardness and tensile properties of a series of carbon-free iron-tungsten alloys. But, as the work progressed it became evident that the system possessed other features of interest, so the scope of the investigation was enlarged. Materials The iron powder used in preparing the alloys was obtained as follows : Iron oxalate was precipitated from a ferrous-sulfate solution by the addition of a solution of oxalic acid. This oxalate, after thorough washing, was ignited to iron oxide, which after reduction in hydrogen at about 1000" C. yielded iron powder containing but about 0.2 per cent. iron oxide and about 0.005 per cent. carbon. Tungsten metal in the form of powder, such as is used in the manufacture of filaments for incandescent lamps, was the other constituent. This material analyzed 99.8 per cent. tungsten and contained no carbon. The metal powders, in the desired proportions, were mixed by tumbling and formed, under pressure of 20 tons per sq. in., into rods 3/8 by 3/8 by 10 in. To form the alloys without contamination, sections of the pressed rods were placed on alundum slabs and heated in an alundum tube wound with a tungsten resistor and packed in heat-insulating material. While the resistor was heated, a stream of hydrogen was continually passed through both the tube and the case containing it. The tungsten winding on the tube, as well as the material heated within the tube, was thus protected from oxidation. Such a furnace will operate constantly for several days at temperatures up to 1500' C. and for shorter periods

Jan 1, 1926

By Robert S. Williams

NO new ferrous alloys have been produced in the last five or six years that are as outstanding contributions to civilization as were the high-speed steels of the early part of the century or the stainless steels announced at the close of the World War. There have been, however, many developments of major importance having to do either with modifications of existing alloys or with new methods of treatment of older iron or steel alloys. Only a limited number of these new developments can be discussed and their selection does not necessarily imply that these are the most important but merely that they are of general interest rather than perhaps of greater importance in highly specialized fields.

Jan 1, 1939

CHARLES KIRCHHOFF, Chairman. ALBERT SAUVEUR, Vice-Chairman. A. A. STEVENSON, Vice- Chairman. HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Cambridge, Mass. John Birkinbine, J. Esrey Johnson, Jr., Felix A: Vogel, William H. Blauvelt, William Kelly, Leonard Waldo, James Gayley, Richard Moldenke, William R. Walker, Henry D. Hibbard, Joseph W. Richards, William R. Webster. Henry M. Howe, E. Gybbon Spilsbury, Frederick W. Wood. Robert W. Hunt, A. A. Stevenson is appointed an additional Vice-Chairman of the Committee. He will serve as Acting Chairman during the absence abroad of Professor Sauveur. For the meeting of the Institute which is to be held in New York City, Oct. 16 and 17, 1913, the following papers are now assured

Jan 7, 1913

Correlation between Metallography and Mechanical Testing By H F MOORE (Henry Marion Howe Memorial Lecture Trans, vol 120 11,000 words ) The lack of effective correlation between metallography and mechanical testing from the days of Reaumur to the present is noted, and two general problems of such cor¬relation are stated (1) the correlation of qualitative test results with quantitative, and (2) the correlation of average results with maximum or minimum results Some correlation has been achieved, notably in the field of heat-treatment and in the study of elastic strength of metals Correlation is in the process of being developed in several other fields, including the quantitative study of the effect of grain size of metal on mechanical properties, of grain size and type of crystalline structure on the sensitivity of metals to weakening at holes, notches and other "stress raisers," and in the study of the starting phases of spreading, "fatigue" cracks Correlation of mechanical test results and metallographic study is needed in the study of such problems as the various theories of failure of metals, the meaning of and tests for service ductility of metals, and the relative damaging effect of defects inherent in metals, such as minute cracks and segregation, as compared with the damaging effect of "imposed" stress raisers, such as screw threads, sharp shoulders, etc The neces¬sity for more correlation of metallography and mechanical testing during student days is emphasized, and also the need of a better understanding on the part of engi¬neers of the significance and limitations of metallographic apparatus and results and of X-ray diffraction This should be matched by a better understanding on the part of metallurgists of the significance and limitations of mechanical tests of metals, of testing machines and strain-measuring apparatus

Jan 1, 1937

By B. M. Larsen, T. E. Brower

A perspective is presented of the steel plant sulphur distribution and elimination problem from coal to liquid steel ready for teeming, giving distributions of sulphur over a range of coke sulphur content, and some methods of sulphur control, in the blast furnace, external desulphuriza-tion between blast furnace and open hearth, distribution between fuel, slag, and metal, and methods and limitations of control of sulphur in the open hearth furnace. AS a part of the 1951 AIME symposium on sulphur in steelmaking, it was thought that a discussion of the distribution of sulphur throughout the whole series of operations, from coal and ore to finished steel ingots, might have some value in giving a perspective on the whole problem. The following discussion is an attempt to present such an overall picture. The order is that of the actual plant operations, beginning with a very brief consideration of the coking process. Sulphur in Coal and Coke Since by far the largest source of sulphur entering the steelmaking cycle is in the coal used to make coke for the blast furnace, it would seem reasonable to eliminate some of it, either from the coal, or the coke, or during the coking process. This has appeared impracticable up to the present, at least, for two main reasons: the low activity of the organic sulphur in either coal or coke, and because of price limitations involved in treating a low cost material such as coke. A variable portion, usually M or less, of the sulphur is present in coal in the form of pyrites or similar compounds, and a large part of this sulphur may be removed in the coal washery. Most of the sulphur, however, is normally present as "organic" sulphur, intimately associated with the coal structure. Its distribution prevents any separation by mechanical means. Its low activity makes improbable ' any rapid chemical removal, although hydrogen will remove sulphur from both coal and coke. Thus, prolonged recirculation of coke oven gas in the coking process would tend to leave a smaller percentage of the total sulphur in the coke residue. Table I shows a typical distribution of sulphur from coal into products in the coking process. As the sulphur in the coal increases, the sulphur in the coke tends to increase in about the same proportion. Sulphur in the Blast Furnace The best picture of the situation in the blast furnace is provided by a sulphur balance of raw materials entering, and of products leaving, the furnace. The difficulties in accurate weighing and sampling of the variable solid materials entering this process, and the number of hours required for the raw materials to descend through the furnace under variable operating conditions, make it difficult to obtain an accurate balance. However, balances made over periods of weeks or months tend to average out some of these uncertainties. Table I1 presents three typical sulphur balances similar to a number that the writers have calculated. In most of these the slag volume calculated from the sulphur balance is, in some instances more, and in other instances less, than the value corresponding to the best input and output balances of the other slag constituents (lime, silica, alumina, etc.). Probably the greatest source of error in these calculations is the sulphur content of the slag. Despite some possible inaccuracies the balances of Table II show rather definitely the following points: 1—That 87 to 95 pct of the total sulphur input is in the coke and 95 to 97 pct of the total sulphur output is in the slag. Also, that if any sulphur leaves the furnace with the gas it is relatively small, amounting to a possible 1 pct or less. 2—At the lower sulphur coke level of 0.86 pct the total amount of sulphur charged is 15 Ib of sulphur per ton iron increasing to 26 lb per ton at the higher sulphur, intimately associated with the coal struc-rare burdens containing sulphur-rich ores will the total sulphur burden fail to be nearly proportional to the content in the coke used. 3—The 7 to 9 pct of the total sulphur input from the limestone of furnaces B and C is due to the relatively high sulphur content of the stone, 0.226 and 0.265 pct, respectively. In the case of furnace A, the sulphur content of the limestone was only 0.06 pct which resulted in only 3 pct of the total sulphur input coming from this source. It is rather interesting to compare the sulphur balances of a typical ferromanganese furnace with

Jan 1, 1952

By T. C. M. Pillay, John Chipman

The Si-0 equilibrium in liquid iron was investigated in some detail by Gokcen and Chipman1 who reported equilibrium constants of the following reactions: In each case the thermodynamic equilibrium constant K was obtained by extrapolating K' to infinite dilution. Their results on reaction [I] were consistent with those of earlier observers, and there seems to be little doubt as to the approximate validity of the equilibrium product determined. On the other hand, the results on reactions [2] and [3] indicated unusual curvilinear relationships between the activity coefficients of silicon and of oxygen and the silicon concentration. Since a linear relation is observed in all other similar instances, it was concluded that some source of error had affected the gas-metal equilibrium relationships. Recently the authors undertook a restudy of these equilibria with the view especially to establishing the equilibrium constant of reaction [2]. Their experiments, however, were discontinued before a tbroughly satisfactory answer had been obtained and consequently have remained unpublished until the present time. Quite recently Matoba, Gunji, and Kuwana2 published the results of a very thorough study of these equilibria. It is the purpose of the present note to Compare these three sets of experimental data, a comparison which leads to Confirmation of the results of Matoba and coworkers. The experimental arrangements described by Dutilloy and Chipman were employed. A controlled mixture of Hz, H,0, and argon was led into the induction furnace over the surface of the Fe-Si melt contained in a silica crucible. On account of the slow approach to equilibrium, runs were continued for at least 8 hr and, in some cases, as much as 12 hr. Samples were taken by means of silica tubes at the start and during the final 4-hr period of each run. Out of twelve runs only seven appeared to have approached equilibrium with sufficient certainty to be reported here. The results of these experiments, all at 1600°c, are shown by the triangles in Fig. 1. Equilibrium was approached from both oxidizing and reducing conditions and the direction of approach is indicated by the shape of the triangle. Attempts to extend the study to higher silicon concentrations were unsuccessful on account of the transfer of silica from the metal bath to the upper portions of the crucible by means of a silicon-monoxide mechanism. Matoba, Gunji, and Kuwana used similar methods and approached equilibrium from both sides. Their results at three temperatures are shown by the solid lines of Fig. 1. A line corresponding to 1600 deg is interpolated from their equations and is shown by the dotted line. The results of Gokcen and Chipman at 1600 deg in the range 0.02 to 2.0 pct Si are also shown. At concentrations up to about 0.6 pct Si, these investigators approached equilibrium from both directions, and their results in this range appear to be trustworthy. Above 1 pct Si, however, all of their experiments involved oxidation only, as shown by a decrease in the silicon content of the bath. It now seems certain that they failed to reach equilibrium at these higher silicon concentrations and that the curvilinear relation shown by their results is incorrect. It is evident that their results in the lower silicon range are in good agreement with those of Matoba and coworkers. In fact, a straight line drawn through their results would parallel the dotted line and would differ from it by only 0.05 in log K. The new data also lie close to that line. It may thus be concluded that the three sets of data are in good agreement and that the equations proposed by Matoba and coworkers for reaction [2] are satisfactory . They take the limiting value of log K', at 0 pct Si as log K ,. The slope of each line gives the value

Jan 1, 1962

By Arnulf Muan, Egil Aukrust

Activities of COO in the three solid solution series COO-MgO, COO-MnO, and COO-"FeO" have been determined at 1200°C by equilibrating oxide samples with a metal phase (cobalt or a Co-Fe alloy) in atmospheres of known oxygen activities. The systems COO-MgO and COO-MnO are ideal, within limits of experimental error, whereas the system COO-"FeO" shows a slight positive deviation from ideality at the temperature of this investigation. KNOWLEDGE of activities of oxide components in solid solutions is necessary for the calculation of the cation distribution among coexisting oxide phases in many important metallurgical, ceramic, and geochemical systems. Very few activity-composition curves are available for such systems at the present time. A start on the prodigious job of obtaining such data has been made by studies of solid solutions with simple sodium chloride type structure containing NiO or "FeO" as a component.1-3 The present paper describes similar studies for solid solutions with sodium chloride type structure containing COO as a component. For the systems COO-MgO and COO-MnO, the activity solid solution is determined by the equation Here po and are the oxygen activities of the gas phase in equilibrium with the phase assemblages metallic cobalt plus oxide solid solution, and metallic cobalt plus pure COO, respectively. In the system CoO-"Fe07', the metal phase is a Co-Fe alloy rather than pure cobalt. In this case the activity of COO in the oxide solid solution is calculated from the equation where a& is the activity of cobalt in the metal phase. Because the system Co-Fe is close to ideal4 and the metal phase appearing in the present work contains less iron than cobalt even at the lowest COO concentrations of the oxide phases used may be set equal to N . Hence, Eq. [2] becomes The value of Nc, can be estimated from the relative stabilities of the oxides COO (see below) and I) EXPERIMENTAL METHOD Two different but closely related procedures were used in the present investigation to determine the activity-composition curves. In one method, the oxide solid solutions were equilibrated against

Jan 1, 1963

By E. T. Turkdogan

Jan 1, 1962

By John Chipman, Peter J. Koros

The distribution of copper between liquid silver and liquid iron, Fe-C, and Fe-C-Si alloys was studied at 1600°C. From the data and the activity of copper in silver obtained from the phase diagrams, the activity coefficients of copper in iron up to 3 atomic pct are log y, = 0.90 — 2.4 N, and y": = 8.0. The effect of carbon up to saturation is expressed as log y = 1.8 Ni. The effect of silicon up to 11 atomic pct is insignificant. SLOWLY rising copper content of steel being produced is focusing attention on the lack of information on the behavior of copper in liquid steel. Chou' measured the activity coefficient of copper in liquid iron through its distribution between liquid silver and iron. He obtained a value of 9.12 at infinite dilution. Chipman' calculated the activity coefficient of copper in liquid iron at 1600°C from the phase diagram and obtained a value of 12. Ameiln and Pfeiffer- investigated the possibility of removing copper from liquid steel through the use of lead, silver, and bismuth as solvents. They also calculated that the activity coefficient of copper in liquid iron would be increased five or sixfold by addition of 4 pct C. Langenberg and Lindsay' are investigating the effectiveness of lead and sodium sulfide in removing copper from liquid iron. The experimental method was similar to that used by Chou' and Chipman and Floridis." Silver, copper, and iron were melted together, the copper distributing itself between the two layers so that at equilibrium a,.,, (in Ag) - a,.,, (inFe) and N,.,, (in Ag) yc,, (inFe) (in Ag). [21 N,.,, (inFe) Thus, from the concentration of copper in each layer and the activity coefficient of copper in liquid silver, the activity coefficient of copper in liquid iron can be calculated. The effect of an alloying element such as carbon on the activity coefficient of copper can also be determined from its effect on the distribution, provided the new element is essentially insoluble in silver. The one serious limitation of this method is the increasing mutual solubility of silver and iron in the presence of a third component. The mutual solubilities of pure iron and silver are negligible, but increase with increasing copper concentration beyond the range investigated. Ag-Cu System—The activity coefficient of copper in silver at 1600°C had to be estimated, since direct experimental data are not available. Kawakami" measured the heat of mixing of Ag-Cu alloys at 1200°C by a calorimetric technique. Scheil' calculated the heat of mixing in this system by use of the phase diagram, assuming that the solution is random and that the heat of mixing is independent of temperature. The terminal solid solution may be assumed to obey Raoult's law within the requirements

Jan 1, 1957

By C. E. Lesher

Two processes for agglomerating fine sized ores with low temperature coke are described. One process (Orcarb) agglomerates ores with limited amounts of carbon; the other (ore-carbon pellets) pelletizes fine sized ores, using low temperature cokes as the binder. Data are presented on the products obtained when taconite, magnetite, and hematite concentrates and several titanium oxide ores were used. REDUCTION of finely divided oxide ores has long been a major metallurgical problem. Various methods of agglomerating, notably briquetting, sintering, nodulizing, and pelletizing, have been developed and are in industrial use. Carbon is the usual reducing agent for oxide ores and attempts have been made to agglomerate fine ores with coking coal in order to get the metallurgical advantages of intimate contact and increased particle sizes suitable for subsequent smelting or reduction.1-3 For the past three years, research has been in progress on two processes for combining fine sized ores with reactive carbon in the form of low temperature coke. By one process, designated Orcarb, the ore is coated with coke carbon in amounts limited to that required for reduction and the result is an appreciable but limited increase in product particle size over that of the original ore. The second process, called ore-carbon pellets, produces pellets of fine ore bound by low temperature coke. The first objective was to develop a process for combining an oxide ore with only enough carbon for its reduction, the amount being that derived from the simple reduction equations. The carbon (that amount theoretically required for the reduction of the oxides in an agglomerate with ore), calculated to CO, ranges from 10 pct for zinc calcines Or phosphate Ores to 21 pct for rutile and 26 pct for silica. The carbon required for reducing iron oxides falls between the extremes—10 and 26 pet' When the carbon in the agglomerate is low temperature coke, reduction by hydrogen may be expected to take place, thus modifying the calculated carbon require- ment. On the other hand, in practice, an excess of reducing agent over that required in theory is normally used. Screen sizes of three iron ores on which the greater part of the experimental work was performed are given in Table I. Most of the testing was done with Freeport (Renton Mine) coal, but Pittsburgh and Elkhorn bed coals were also used. The first objective was to agglomerate the ore with sufficient low temperature coke to provide carbon for reduction, i.e., in the range from 10 to 25 pct. This was accomplished by preheating the ore, mixing with pulverized coking coal, and completing the coal carbonization in a plain steel rotating retort. The pilot retort, as it is now constituted, is shown by diagram in Fig. 1 and photograph, Fig. 2. Ore is fed into the upper kiln by a screw; it is heated to 900° to 1100°F by direct flame and it is then discharged into an insulating hopper from which it goes

Jan 1, 1956