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By P. Schutte

It is evident from most admired companies, globally, that they drive key priorities such as teamwork, customer focus, fair treatment of employees, initiative and innovation into their organisations. It is clearly proofed in all the research that the role of the human factor, and therefore human behaviour, is pivotal to companies striving to accomplish goals such as competitiveness, customer delight, high quality, growing productivity as well as a safety-committed work force. The challenge of leadership is to change the worker’s poor perception of safety to an excited, empowered, valued employee who is continuously committed to the achievement of high levels of health, safety and conformance – the challenge therefore is to transform from within. Any work force needs a set of behavioural rules which work for it – including safety rules and critical safety behaviours, which are accepted through involvement leadership, encouragement and support.

Jan 1, 2003

By Jom Kresta

Fundamental changes in the Bitumen Production process at Syncrude have led to the integration of Mining and Extraction operations. Successful operation of the integrated process requires the coordinated effort of several business units. Hence, decision-making has become increasingly more complex and better tools are required. IO2 is a collaborative effort to develop a proof-of-concept prototype of a distributed decision-support system for integrated short-term production and maintenance planning with fleet allocation and dispatching. The prototype includes three main modules (planning, dispatch, and maintenance), a shared database, and a simulation module. At this stage, this prototype is used to plan and operate a simulated mining operation. It is used to demonstrate the viability of the chosen systems architecture and algorithms, as well as the information flows and interactions necessary for improving the overall performance of the integrated operation. While the problem is demonstrated using Syncrude?s site, the methodology is applicable to most integrated resource allocation problems.

May 1, 2002

Ion exchange (IX) has been in use for a long time, references to IX are made in The Bible, Exodus Chapter 15 vs. 22-25 ?and the waters were made sweet?.1, 2 Aristotle noted a reduction in the salt content of water when passed through certain types of sand, a phenomena probably associated with ion exchange characteristics of zeolites. Some major milestones in IX development include; ? ~ 1400 BC Moses ? ~ 330 BC Aristotle ? 1850 the discovery of the IX process3 ? 1909 Gans proposed zeolites for gold recovery ? 1935 sulfonated coals used for water softening ? 1939 copper recovery from Rayon Production ? 1940 The Rare Earth Project at Ames ? 1952 first South African U IX mine at West Rand (first SX of U using amines 1957) ? 1954 first U IX in USA at Shiprock Mine N.M. USA. ? Late 1950?s U IX over 50 fixed bed systems installed in North America ? 1950?s-1960?s FSU introduce U IX both fixed bed and RIP ? 1968 Gold IX (RIP) Muruntau Uzbekistan (CIL wasn?t commercialized until 1973) ? Mid 1970?s FSU & USA independently develop ISL combined with IX for U recovery ? 1978 Chinese Tungsten IX commercial Plant ? 1984 Uranium extraction from seawater ? 2004 Recovery of Gallium using hydroxyamic acid ligands ? Current ? Commercialization of IX for recovery of gold thiosulfate. Ion exchangers can be naturally occurring or synthetic; the majority of ion exchange materials in use today are synthetic resins based upon organic polymers such as polystyrene or methacrylate. Into more modern times the use of ion exchange for metal recovery was first proposed for the recovery of gold using zeolites in 1909.4 In 1939 copper was being recovered from the manufacturing of Rayon using ion exchange5 a development that continued applicability through to current times in the production/recovery of copper and nickel in ammoniacal leach processes. In early 1949 researchers at the Rohm & Haas Company discovered that hexavalent uranium existed as an ionic complex in sulfuric acid leach liquors, and that quaternary ammonium anion exchange resins exhibited a high selectivity for this ionic species6 The first commercial application of this technology went on-stream in October 1952 at the West Rand Consolidated Mines, Ltd operation in South Africa. 7 Ion Exchange has been applied for the recovery and purification of a range of metals;8 ? Uranium, Thorium and transuranic elements ? Rare Earths ? Gold, Silver and platinum group metals (PGM?s) ? Chromium, Copper, Zinc, Nickel, Cobalt ? Refractory Metals; Molybdate, Vanadate, Tungstate, Rhenium Mercury.

Feb 27, 2013

In general, the metallurgical industry has so far been slower than the chemical industry to adopt ion exchange materials for industrial processes. The atomic energy industry presents a marked exception to this general situation, and the literature shows a rapidly increasing use of ion exchange techniques for the recovery of atomic energy metals on scales ranging from the ultra micro up to that of the largest mining operations. In many cases, the processes used would be equally applicable to more common metals and it is hoped that this review will be of interest to metallurgists outside the specialised atomic energy field. The review is intended to describe developments of ion exchange processes made during the last three years. Earlier studies have been summarised by Kunin and Preuss (1956) and Roland (1957). In order to restrict the number of references discussed, purely analytical procedures have been omitted and only those processes which have been conducted on a reasonably large scale or which, from their nature, areclearly capable of being upscaled, have been considered. The paper is divided into five main sections concerning respectively:Water treatment and effluent disposal.Metal recovery and purification.New ion exchange materials.New ion exchange equipment.Membrane cells.WATER TREATMENT AND EFFLUENT DISPOSALA high proportion of atomic reactors, and particularly those of American design, are cooled by water which is...

Jan 1, 1961

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