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By M. Mikhaylenko

The most common methods of processing of uranium ores is sulfuric or carbonate leaching with conversion of hexavalent uranium to uranyl carbonate or sulfate anionic complexes followed by sorption of the later by strong base anion (SBA) exchange resins. It is known that chloride anion has high affinity for SBA resins so that it depresses sorption of anionic complexes of uranyl. Application of the SBA resins becomes impractical for recovery of uranium when chloride concentration in pregnant leach solution exceeds 3-5 g/l [1-3].

Jan 1, 2012

By M. Mikhaylenko

Rhenium, molybdenum and tungsten are the elements demanded by high-end technologies. These metals are found in process solutions in forms of their oxyanions: ReO4-, MoO42- and WO42-. The later two can exist in forms of iso- and/or heteropolyanions. Basically all three metals demonstrate very similar chemical behavior in aqueous solutions. Unfortunately, in their mineral sources these elements commonly accompany each other, like pairs of rhenium-molybdenum or molybdenum-tungsten. Their economical separation is a challenging task.

Jan 1, 2012

By A. Deepatana

Bioleaching of nickel laterite ores is based on the use of heterotrophic fungi organisms and their metabolites (organic acids) to dissolve nickel and cobalt from oxide minerals to form metal-organic complexes. Metal recovery from this process using an aminophosphonic acid based chelating resin (Purolite S950) was investigated as a function of metal concentrations, complexing agent including citric, dL-malic and lactic acids. Batch adsorptions were conducted using synthetic leachate solutions of nickel and cobalt with concentrations from 15 to 2000 mg/L prepared in 0.01 and 0.1 M organic acids. Adsorption equilibrium data were interpreted using the Langmuir, Freundlich and Dubinin-Kagner-Radushkevich (DKR) models. The results showed that equilibrium adsorption data for nickel-organic complexes followed the Freundlich model and those for cobalt agreed with the Langmuir model. It was observed that the maximum adsorption capacities of nickel and cobalt were 3.26 and 10.48 mg/g resins respectively. These were achieved in metal complexes prepared from 0.01 M lactic acid. Metal elution was conducted using 2 M nitric acid. High metal recoveries were achieved from low metal concentrations but were found to decrease with increasing metal concentration. The results suggest that effective recovery of nickel and cobalt from low concentration of metals, such as those generated from bioleaching operations, can be achieved suitably using chelating resins.

Jan 1, 2006

By A. P. Paiva

The solvent extraction properties exhibited by some /V,N'-tetrasubstituted malonamides to efficiently and selectively recover iron(III) from concentrated chloride leaching solutions can be found in the recent literature. The iron(III) extractive chemistry exhibited by some of these derivatives is revisited, in order to compare their chemistry with that shown by a few of the new malonamide compounds. The generally good extraction efficiency towards Fe(III), from >4 M hydrochloric acid solutions, and the relative ease of Fe(III) stripping by distilled water are remarkable findings that are confirmed for the malonamide derivatives described in this work. Furthermore, additional data regarding their selectivity towards Fe(III) extraction over several base metal ions and their behavior when subjected to successive Fe(III) extraction-stripping tests are also presented and discussed.

Jan 1, 2006

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 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 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 G. W. Healy, W. D. Forgeng, N. R. Griffing

The liquidus surface of the C-Cr-Fe system to 1900°C has been mapped from carbon solubility and freezing point measurements, metallographic observations, and published data. In the graphite field, the surface drops precipitously to meet a slope descending from the Cr3C2-C join through the mixed carbide fields to a meandering eutectic valley; this flows from the Cr-C to the Fe-C edge. On the low-cavbon side of the valley, the surface rises to the chromium corner. 1 HE purpose of this inquiry was to gain a more complete knowledge of the C-Cr-Fe liquidus surface. This required an extensive study of carbon and chromium-rich alloys which, in the past, have received the least attention. Sanbongi el al.1 measured the solubility of carbon in liquid alloys containing up to 25 wt pct Cr at temperatures of 1460" and 1545°C and found that it increased with chromium content and temperature. Lucas and wentrup2 also made solubility experiments in graphite crucibles, but at higher chromium contents in the range of 38 to 80 pct and at temperatures of 1550" to 1700°C; however, their experiments were relatively few, and the effect of temperature was not consistent. The present investigation included compsitions ranging from 0 to 94 pct Cr and 1.4 to 11.7 pct C at temperatures up to 1800°C. Saturation experiments in graphite crucibles, thermal analyses during freezing, and metallographic and X-ray diffraction studies were employed to obtain desired information which, together with published data from other investigations about the binary edges and the ternary system at lower carbon levels, made possible the construction of a comprehensive C-Cr-Fe liquidus surface. C-CR-FE LIQUIDUS SURFACE The derived ternary liquidus surface is shown in Fig. 1 where the solid curves are liquidus isotherms. The dashed curves and the binary edges are the liquidus field boundaries of the primary crystals, the arrows along these boundaries indicating their direction with decreasing temperature. Each intersection of three internal boundaries is the composition of liquid involved in four-phase isothermal equilibrium with the three primary crystals whose liquidus fields touch there. It may be observed that a total of six four-phase equilibria occur at melt temperatures. The general topography of the liquidus surface consists of a eutectic valley sloping down from the Cr-C edge at 3.2 pct C to the Fe-C edge at 4.25 pct C. The liquidus surface rises in two directions from the valley, one hillside terminating at the Cr-Fe edge while the opposing hillside rises toward the carbon corner out beyond the top edge of Fig. 1. Both hillsides are interrupted by intersections of surfaces or joints representing the liquid colmpositions of various three-phase equilibria. Seven primary crystals occur, namely a(bcc), ?(fcc), graphite, (Fe, Cr)3C capable of dissolving as much as 15 pct Cr, and three different chromium carbides in which iron is partially soluble by substitution for chromium. The composition ranges of the primary l~hases at melt temperatures are shown

Jan 1, 1962

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