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By M. D. Vilarinho, W. Xuan, F. Vasconcelos Guimarães

"This article summarises the efforts to reduce the energy consumption in grinding in a magnetite ore beneficiation plant. ArcelorMittal Kryvyi Rih ore beneficiation plant produces magnetite concentrate at 65% Fe and 8% SiO2, of which the D80 is approximately 44µm after three stages of grinding with ball mills and magnetic separation. Characterisation and laboratory scale bench tests performed on samples from the beneficiation plant indicate that the industrial flowsheet could be simplified. After the first stage of grinding and magnetic separation, a significant size fraction of the intermediate concentrate is already well liberated. Therefore, it can be directly concentrated in a second stage magnetic separation without further grinding. If a screen of 150µm size can be implemented after the first stage of grinding-magnetic separation, only the oversize of screening, representing 35% of the material, requires secondary and tertiary grinding and magnetic separation. The combined concentrate from the two fractions already meets the industrial specifications. This new route can provide the same final product, with fewer mills; it saves around 30% in energy consumption only in the grinding step without changing the main structures of the processing plant.INTRODUCTION Comminution, including crushing and grinding, is responsible for at least 40% of total energy usage in mining and mineral processing. This paper shows an example to reduce grinding cost, by changing the flow sheet design strategy in ArcelorMittal Kryvyi Rih (AMKR).AMKR is one of the most important mining and steel complexes in Krivoy Rog basin in Ukraine, which has been studied over 100 years because of mining of iron ores. The iron ores are associated to Banded Iron Formation of the Saksagan suite, with an average iron grade of around 36 percent Fe. The total thickness of the Krivoy Rog Supergroup reaches 5-6 km, whereas that of the iron-ore Saksagan Group comprises up to 1400 m. High-grade iron ore extends to more than 2,000 m below present surface"

Jan 1, 2018

By S. Moodley

In the chloride process for TiO2 pigment production, various titania feedstocks (i.e. rutile, synthetic rutile, slag, and upgraded titania slag (UGS)) are chlorinated in a fluidized bed reactor with petroleum coke at temperatures between 1000°C and 1100ºC to yield gaseous metal chlorides. Although feedstock preference is largely based on TiO2 content, feedstock physical properties (i.e. density, sphericity, size distribution, and porosity) differ; these differences will affect fluidization behaviour and can inadvertently affect conversion efficiency. For example, a high carryover from the reactor reduces particle residence time and decreases conversion rates. Owing to dwindling rutile reserves in the world, most chloride producers are forced to feed blends of feedstocks to their chlorinators; and so it becomes important to understand whether blends have an effect on the hydrodynamic properties of the bed. This paper describes the physical characterization of different feeds and the determination of the elutriation constants for slag, rutile, synthetic rutile, and a blend (i.e. 50 wt% rutile, 50 wt% slag).A common feature of the tests was that particles finer than 75 µm tended more than any other size to be elutriated. The tested rutile, classified as a Geldart Group B material, had the lowest carryover, whereas the slags had the highest. Interestingly, the elutriation constant ([ki]) of the blend is lower than those of either of its individual components.

Jan 1, 2012

By Zamel G. I, Zenari L. P

Technological developments in modem Tunnel Boring Machines (TBMs) and associated back-up equipment are offering significant alternatives for mining operators to consider, in the selection of equipment for coal mine development drifts, roadways, longwall gate roads as well as metalliferous mining declines and development drives.Greater flexibility in handling variable ground conditions, muck disposal and radius of turn as well as advance rates, are just some of the areas where modem TBMs can accomplish the flexibility that mine operators require to achieve cost-effective developments.Compact TBMs are achieving this acceptance because of the fundamental design of a shielded machine containing electrics and hydraulics within the forward shell, ability to achieve tight radius of curvature and grades, and ability to provide highly flexible support systems to meet all possible ground conditions.However, a single TBM design will not suit all mine developments, as each development method - while having common goals with all mine developments - will also require certain unique criteria to be fulfilled.

Jan 1, 1993

By M Rayner, C Tsouris, A Komelkov

X-ray fluorescence (XRF) is a widely accepted technique for the elemental analysis of iron ores and their concentrates. Wavelength-dispersive, or WDXRF, and energy-dispersive, or EDXRF, spectrometers offer distinct advantages for particular applications, elements and concentration ranges and are, therefore, more complimentary than people might realise. A key example is the ability of EDXRF to identify, and often quantify, unexpected elements in production samples that would typically be missed by routine WDXRF. In this paper we discuss recent technological advances in XRF and present a novel application example that demonstrates the additional technical and practical benefits of using both EDXRF and WDXRF to characterise iron ores and concentrates.CITATION:Tsouris, C, Komelkov, A and Rayner, M, 2015. A novel approach to the characterisation of iron ores and concentrates using recent advancements in wavelength- and energy-dispersive x-ray fluorescence spectrometers, in Proceedings Iron Ore 2015, pp 591–594 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Jul 13, 2015

By J. H. Bassarear

Conventional crushing and grinding circuits are compared to semiautogenous circuits. Recent installations of each circuit are reviewed and seven methods of using autogenous or semi- autogenous techniques are described. Steel and power consmption data are reported and benefits of a dedicated digital computer are discussed.

Jan 1, 1981

By M Chen, Q D. Gao, Y G. Hu, P Yan, W B. Lu

The safety and stability of construction structures are often affected by blast-induced waves. Investigating the generation mechanism of shear wave (S-wave) during blasting is important, because it has a strong effect in blasting damage. In this paper the generation mechanism and verification of S-wave was studied analytically and numerically. Under the finite velocity of detonation (VOD) of cylindrical charge or the compression wave (P-wave) communicating with the interface of different media during the propagation, the generation mechanism of S-wave was analysed. Propagation of blasting wave in cylindrical charge was simulated with the elastic model, and the generation of S-wave induced by finite VOD was proved. To compare with different numerical methods in simulating the generation of S-wave, the blasting process of instantaneous detonation was simulated by using the elastic model, elastic-plastic model and smoothed particle hydrodynamics and finite element method (SPH-FEM) coupled model. Results demonstrate that the S-wave could not be found in middle section of the charge if the elastic model is employed. But when using elastic-plastic model and SPH-FEM coupled model, the generation of S-wave could be verified. Under the SPH-FEM condition, the amplitude of S-wave is larger and the arrival time difference between P-wave and S-wave is closer to theoretical results.CITATION:Gao, Q D, Lu, W B, Hu, Y G, Chen, M and Yan, P, 2015. Comparison of the generation of shear wave with different simulation approaches, in Proceedings 11th International Symposium on Rock Fragmentation by Blasting, pp 79–88 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Aug 24, 2015

By R. D. MacDonald

The papers presented in this chapter cover a wide range of hydrometallurgical topics and might be considered to be unrelated to each other. All of the authors, however, utilized the basic methods of process mineralogy to characterize the reactants in their experiments and the products produced. The wide range of research topics which can be pursued successfully by the use of the methods of process mineralogy is a matter of interest in itself. One might speculate that the methods could be even more widely applied if only their utility were better recognized. These methods for characterizing reactants and products include principally x-ray diffraction, optical micros-copy, wet chemical analyses, instrumental chemical analyses, high intensity magnetic separation, micro-scale gravity separation, differential thermal analysis, micro-hardness testing, and judicious use of the sledgehammer and cold chisel. It is perhaps not by coincidence that most of the papers in this chapter were prepared not by mineralogists, but by hydrometallurgists, who are recognizing the importance of thinking in terms of mineral phases, and not just assays! It appears that the gap between process mineralogy and the mineral industry is closing, and that future AIME sessions promise to become established forums where mutual discussion of such topics as metallurgical "troubleshooting" and process design may become commonplace between plant engineer and process mineralogist.

Jan 1, 1981

By Howard N. Evanenson

WASTE of coal, or perhaps more properly the percentage of its recovery in mining, has keenly interested me during an experience of over a half century in coal mining. In the early part of that time and until a few years after World War I the use of better mining plans and supervision resulted in an increased recovery. Since then, and particularly since controlled prices have been effective and mechanized mining has been extensively practiced, the tendency has all been toward lesser recovery in mining. The purpose of this paper is not to criticize the methods being used, which after all are the result of economic forces, nor to point to any particular mining method or to any locality where the best recovery is obtained, but to call attention to the tremendous waste of our national coal resources that is constantly continuing. A possible method of reducing this loss will be suggested, but without any illusions that it will be followed or that such attention will be paid to it. AVERAGE RECOVERY The actual average percentage of recovery of coal in the ground is not known. Many papers giving figures of recovery have been published but no definite base of measurement has been agreed upon by those presenting the data. As an example, the Pittsburgh bed can be considered-it has produced a greater output than any other and has been sold or leased at higher prices in place than any other coal bed. Over a large part of its area where high prices have prevailed it has been customary for many years to draw pillars. In these mines it has been usually assumed that the average recovery was higher than in other beds and percentages of recovery of 85 to 95 per cent are usually said to be realized. In all of these mines, however, it has been customary to leave from 4 to 8 in. in the bottom, and 10 to 16 in. in the roof; thus from 14 to 24 in. of coal has been left in the mines out of a total seam thickness of about 96 in., or 15 to 25 per cent of the total coal. No attempt is made to mine this coal for metallurgical purposes, owing to its impurities, although this unmined coal is of excellent quality and better than much of the coal used for steam purposes. If we add to this discard the coal usually lost in mining and those parts of the bed that must be left because of bad seam conditions, barrier pillars, reservations for buildings, gas and oil wells, one can easily see that the actual recovery from this bed cannot be more than 65 to 75 per cent. In addition, the rooster or rider or wild coal over the mining bed often 3 to 4 ft. of coal, high in ash and sulphur but still good steam coal-is hardly ever mined, nor is any attempt made to mine it. It is safe to say that from a broad economic viewpoint not more than 50 to 60 per cent of the fuel value of this great seam is actually being recovered.

Jan 1, 1946

By John F. Blandy

THE map on Plate I illustrates a part of the works of the Red Bank Mining Company, on the Upper Freeport seam of coal, in Armstrong County, Pennsylvania. The contour lines give a careful representation of the conformation of the surface, showing also the line of outcrop of the seam, and the gangways of the mines are shown by the black lines. Upon assuming charge of the works in January last, I found that the first and greatest difficulty lay in the great uncertainty of the

Jan 1, 1876

This paper is intended partly as a summary of the conclusions that have been arrived at by various authorities on this matter, and also with a view to initiate some discussion on the subject, especially as most of the quartz gold mines in Victoria are operated without having any proper assay plans or any idea of the real values other than those given by the mining managers, who, from experience in the particular cases, are supposed to be able to arrive at a correct idea of the true values of- the ore, and, in many cases, oppose any other methods than their own, holding the view that no sampling is equal in correctness to the bulk sample of the battery. The necessity of properly sampling and estimating the ore in a mine in every case, perhaps hardly needs to be urged on the members of the Institute, but is not, apparently, so obvious to others.It is proposed to confine this paper to the sampling of ore reserves in a mine, and the various points which have to be taken into consideration in arriving at values, from the assayer's point of view, leaving the methods of sampling metallurgical products out of consideration for the present. "It is advisable to define" ore reserves" as ore exposed on three sides at least, and accessible to the sampler on all three. "Prospective ore" would include all ore not so fully exposed; but which may, from the nature of the case, and the geological conditions prevailing, be reasonably supposed to exist.

Jan 1, 1904

By Yuexin Han, Wenbo Li, Yan Shan, Yanjun Li, Shumin Zhang

"With the accelerating pace of resource extraction, the quality of resources is decreasing, and the old tailing dams which have served for several decades have become the focus of attention. The secondary recovery of valuable metals in the tailings is an important aspect of the comprehensive utilization of tailings. The average iron content of iron tailing is 8%-12% in China. The research aimed at exploring the low-cost and efficient technical route to recycle eastern tailings of Anshan iron mining area. The purpose of the research is to scientifically find the rational conditions of magnetizing roasting and to provide an increase in recovery and quality of concentrates. The eastern tailings of Anshan mining area belong to high silicon bearing iron tailings, iron mainly exists in form of hematite-limonite with an iron grade of 10.60%, the main component of gangue is SiO2 with a grade of 76.22%. In order to reduce the influence of the tailings on the environment, fluidized magnetizing roasting and low intensity magnetic separation for the eastern tailings of Anshan mining area were carried out to improve the utilization of the tailings. The results indicated that an iron concentrate with an iron grade of 65.30% and a recovery of 85.85% could be obtained under the conditions of gas flow rate 8 m3/h, H2 concentration 50%, fluidized magnetizing roasting temperature at 600? for 20s. Phase analysis, magnetism analysis and XRD analysis on roasted materials indicated that hematite-limonite could be transformed to magnetite during the fluidized roasting, then the effective separation of iron and gangues could be made easily by the weak magnetic separation. INTRODUCTION It is universally acknowledged that the grade of iron ore in China is low, the output rate of iron ore tailings is high, usually more than 60%. At present, the comprehensive utilization rate of iron ore tailings is low in China. Generally, the iron ore tailings are stockpiled in the tailings dam. The tailing dams not only occupy a lot of land, but also takes a lot of money to construct and maintain. In addition, the noxious substances in the tailings, such as residual flotation agents and heavy metals, have a severe impact on the ecological environment. There is little doubt that tailing dams have a visual impact on the environment due to their regular geometric shape. Iron tailings can be treated as compound mineral, which is an important component of comprehensive utilization of mineral resources, and is an has been widely concerned. Lots of scholars have done a large amount of research work on a large number of iron ore tailings. Since the iron mineral crystal grain size is fine and the iron grade is low, the iron tailings have failed to achieve good selection criteria."

Jan 1, 2018

By R. Salter, C. K. Chase

Although Asarco's Silver Bell Unit, 40 miles west of Tucson, Ariz., is known primarily for copper production, molybdenite is also produced as a byproduct in the 8000 tpd flotation mill. The Silver Bell ore comes from two pits approximately two miles apart. Copper mineralization is essentially chalcocite resulting from two to three-fold secondary enrichment in a highly altered zone. A typical porphyry copper deposit, Silver Bell ore is of medium hardness. The ore consists of about one part molybdenum to 65 parts of copper. In the copper concentrate which is the starting point for separate molybdenum recovery, the ratio is also one part molybdenum to 65 of copper. Molybdenum mineralization is primary. Enrichment is not evident but it is notable that the molybdenite is more common in the more siliceous, harder rocks. The actual molybdenite occurs as diversely oriented flakes of fairly constant grain size, mostly in fractures associated with quartz veins. Most of the mineral appears unoxidized; secondary coatings on the molybdenite flakes are fortunately rare. In May 1962 a modified, improved version of the molybdenite circuit was put into operation.

Jan 7, 1964

By Chas. F. Jackson

This circular is an abstract of a manuscript-completed in August 1932, which cannot be published in its entirety due to lack of printing funds. It was originally planned to publish the manuscript as one of a series of bulletins dealing with the mining and milling of ores of the principal metals. Because of the common association of lead and zinc minerals in many ore deposits, and because a considerable proportion of the zinc produced in this country is obtained as a by-product of lead mining or vice versa, it seemed necessary to treat the mining and milling of lead and zinc ores in the same volume.

Jan 1, 1934

By Evgueni Jak

Pyrometallurgy is an important sector of modern industrial society actively participating in solving current environmental, economic, materials scarcity and other challenges. Recent advances in analytical methods, experimental techniques, thermodynamic, phase equilibria and process modelling tools provide new opportunities to increase the productivity of pyrometallurgical reactors, the treatment of complex feeds and metal recoveries. Fundamental theoretical models can now be used to make a significant next step towards the development and implementation of computerised models describing real industrial processes—Virtual Reactors, and computer-aided smart-decision-making systems that may be called Pyro-GPS by analogy to GPS; these developments can facilitate knowledge-based improvement and optimisation strategies. The implementation of these improvements require ongoing collaboration between researchers, industry and government.

By E. A. Steigerwald

E. A. Steigerwald (Thompson Ramo Wooldridge, Inc.1— he authors' results clearly indicate that cracking can be produced by the hydrogen pressure developed during a charging operation. This type of cracking or blistering has also been observed in polycrystalline materials24"28 when the charging conditions are sufficiently severe and is often referred to as irreversible embrittlement since it cannot be removed by a baking treatment. There are additional data, however, which must be considered before a pressure theory can be generally employed to account for all failures which occur as a result of hydrogen. In many cases, hydrogen embrittlement in a tensile test or in delayed failures under static loads is a reversible phenomena which cannot be simply explained on the basis of preexisting cracks generated by the charging operation. It is this aspect of the problem which has prompted many investigators to seek mechanisms other than hydrogen pressure to explain their results.24'n728 Fig. 15 indicates an example where, under specific experimental circumstances, hydrogen embrittlement can occur at liquid nitrogen temperatures. In this case, which has been previously decribed,'' specimens were charged with varying quantities of hydrogen, immediately quenched, and tested in liquid nitrogen (-320°F). A companion set of identical specimens were charged, aged at 300°F to remove the hydrogen, and also tested at -320°F. When the current density was greater than lo-' amp per sq in., embrittlekent occurred in both sets of specimens, indicating that cracking had occurred during charging and the embrittlement, as in the case of Fe-Si single crystals, was irreversible. At current densities between approximately 103 and lo-' amp per sq in, the embrittlement was present only for those specimens which contained hydrogen during the testing sequence. The embrittlement was therefore reversible with respect to the aging and charging operations. Since extensive hydrogen movement would not be expected at -320°F, it is difficult to reconcile these data with a mechanism which requires pressure and pressure dependent growth of preexisting cracks. There are other features of hydrogen embrittlement such as the reversibility of the incubation time for delayed failure with respect to applied stressg0 and the influence of prestraining31 which are also difficult to explain using a pressure model. Any general mechanism of hydrogen embrittlement will have to consider the reversible aspects of the embrittlement data as well as the irreversible portion which has been clearly presented for the Fe-Si crystals and which is consistent with a pressure model. A. S. Tetelman and W. D. Robertson (authors' reply)—he authors agree with Dr. Steigerwald that a general mechanism of hydrogen embrittlement must be applicable in all cases where embrittlement occurs. Dr. Steigerwald's experiments were performed on an iron alloy which has an extremely complex microstructure, and therefore does not lend itself to the direct and detailed observations that can be made in Fe-Si. The change in the characteristics of cracks as a consequence of annealing at 300°F is not really known in detail but it is probable that stress-relaxation (blunting) occurs, dislocations produced near the crack tips will be pinned by carbon atoms, and hydrogen will be lost to the atmosphere. Any, or all of these effects of annealing will alter the ease with which a crack subsequently propagates under applied stress. A quantitative treatment of the problem must take these effects into account. Since diffusional processes are presumably eliminated at -320°F, the general mechanism proposed by Dr. Steigerwald's colleagues cannot be operative at this temperature. A detailed discussion of the general' inapplicability of this mechanism has been presented elsewhere. However, the data presented by Dr. Steigerwald in his discussion can be explained in terms of a pressure model. Crack propagation under internal pressure P and applied stress occurs when where is the total energy expended in creating new surface area and by plastic work at the crack tip. The total crack length increases with increasing current density, since we have shown that it systematically increases with hydrogen concentration and Dr. Steigerwald has shown that hydrogen concentration increases with current density. For large L (high current density) Eq. [I] can be satisfied even if P = 0 and the embrittlement process does not require the presence of hydrogen. Specimens charged at a lower current density will con-

Jan 1, 1963

By August Wendel

It is a well-known fact to all Bessemer steel manufacturers using a blooming mill, that ingots show large cracks in the first few passes of the rolls, which, in the following ones, do not always roll up satisfactorily. This deficiency in the quality of the product is generally called "red-shortness," though, in the writer's opinion, mostly unjustly so. Different explanations for the said peculiarity are given by the leading authorities, each works selecting one element as a special scapegoat for the inferior quality of the ingot. The sulphur is generally first charged as being the principal cause of all mischief in this direction ; then, after ascertaining that sulphur is not higher than the average, and sometimes lower in the very worst heats, silicon has to bear its share of abuse. How and why silicon should affect the working qualities of the metal, the writer could never precisely learn, but is convinced that the doctrine of its pernicious influence is an established one with many. In cases where silicon failed to explain everything, resort was taken to calcium, aluminum, and some other known or unknown elements, without settling the difficulty; and lastly, when the skill of the chemist became exhausted, " practical men " came to the same conclusion, which many leading blast-furnace managers had arrived

By M. M. Fan

In Florida?s phosphate industrial practice, the most favorable upper size limit of froth flotation is 1.18 mm which corresponds to particle weight of about 2.8 mg. Conventional froth flotation is not efficient in upgrading coarse particles (+0.425-1.18 mm). A limited number of studies have been devoted to understanding and improving coarse particle flotation. We have shown that the coarse particle flotation performance can be significantly improved by the presence of picobubbles generated by hydrodynamic cavitation. In this study, the size of picobubbles produced under certain hydrodynamic conditions was measured by a laser particle size analyzer. A size-by-size flotation performance analysis of coarse phosphate froth flotation in the presence of picobubbles is conducted in terms of flotation kinetics, selectivity and recovery. It was found that picobubbles doubled the flota-tion rate, increased the P2O5 recovery more significantly for +0.85-1.18 mm particles than +0.425- 0.6 mm and +0.60-0.85 mm particles. At a given acid insolubles (A.I.) rejection, the presence of picobubbles increased the P2O5 recovery by up to about 25%.

Jan 1, 2014

By S. K. Dutta

Enormous amount of iron ore fines is generated, due to partly soft and friable nature, during mining. Coal fines are also produced during their processing. These fines cannot be used directly in ironmaking reactors. Utilization of these fines for extracting metal is of vital concern for resource conservation and pollution control, and therefore, a novel concept of agglomeration by cold-bonding is developed. Composite briquettes/pellets of iron ore fines with coal fines were prepared in the laboratory by cold-bonding technique. Various binders such as lime, Ca(OH)2, slaked lime, dextrin, molasses, fly ash etc were employed either alone or in combination in different proportions for making composite briquettes/pellets. It was possible to obtain dry strength of composite briquettes more than 300 N/briquette in some cases and more than 200 N/briquette in many trials. The combination of fly ash with slaked lime and molasses produced the highest strength, more than 400 N/briquette. Drop strength and shatter index values of composite briquettes/pellets were also measured. In briquettes, best compressive strength (978 N/briquette) is observed by using polyvinyl alcohol (PVA) binder. In pellet, best compressive strength (362 N/pellet) is achieved by PVA; shatter index (0.1%) and dry drop strength (158 numbers) are also good. Compressive strength above 200 N/pellet is obtained by fly ash, slaked lime and molasses combination.

Sep 1, 2012

By A. C. Smith

Although it is only utilized in a few U.S. longwall mines, a bleederless ventilation system can be an effective spontaneous combustion control method in mines with a demonstrated history of spontaneous combustion. In order to provide insights for the optimization of bleederless ventilation systems for U. S. underground coal mines, a computational fluid dynamics (CFD) study was conducted to model the spontaneous heating in longwall gob areas with a bleederless ventilation system. A single longwall panel with a bleederless ventilation system was simulated, and typical ventilation data for a longwall mine was used in the simulations. The permeability and porosity profiles for the longwall gob were estimated using a geotechnical model and were used as inputs for the CFD modeling. The effects of gob permeability and resistance of the collapsed entries on the spontaneous heating were studied. The effectiveness of nitrogen injection to prevent spontaneous heating in the gob was also examined. Disclaimer: The findings and conclusions in this report are those of the authors and do not necessarily represent the views of the National Institute for Occupational Safety and Health.

Jan 1, 2008

By R. E. Carter, C. Wagner, F. D. Richardson

By means of inert markers of radio-platinum, it has been shown that cobalt metal oxidizes by out-ward diffusion of cobalt atoms through the oxide. Oxidation rates have been measured at various temperatures and oxygen pressures and have been found to agree with the rates calculated from the Wagner equation and the authors' values for the diffusion coefficient of cobalt in the oxide. The distribution of radio-cobalt in growing oxide loyers has been accurately measured and found to be different from that predicted from the Wagner oxidation theory. Attempts have been made to measure the change of lattice parameter of the oxide with composition. SEVERAL investigators have shown that cobalt metal oxidizes according to the parabolic law,1-3 but no detailed study has been made of the oxidation mechanism. Cobaltous oxide has a metal-deficient lattice, but the defect concentration which is dependent on the oxygen pressure is only approximately known.' From the similarities in the structures of "CoO" and "FeO" and the rate laws governing the oxidation of cobalt and iron, Gulbransen- as suggested that cobalt, like iron," oxidizes by diffusion of cobaltous ions through the oxide layer. To substantiate this hypothesis, he has attempted to measure the oxidation rate of cobalt as a function of the oxygen pressure but has been able to report only that the rate depends on a "small" power of the pressure. On the other hand, Preece," Valensi,' and Arkharov' all have suggested from indirect evidence that oxygen diffuses through the COO to the metal-oxide interface. The present authors, in a previous paper,' have shown that the rate of diffusion of cobalt in cobaltous oxide is dependent on the oxygen pressure. In that investigation, they also found that cobaltous oxide disks made by complete oxidation of cobalt metal were porous at their centers (Fig. 5L, ref. 4). Both these facts strongly suggest that oxidation of the metal proceeds via outward diffusion of cations. In order to establish the mechanism unequivocally, oxidation experiments were made with inert radioactive platinum markers, and the dependence of oxidation rate on oxygen pressure was measured. In addition, an attempt was made to determine the form of the cation vacancy gradient, which the marker experiment showed must exist across a growing oxide layer. This was done by depositing radioactive Co on the surface of a cobalt disk and then measuring the tracer distribution across the oxide layer produced by partial oxidation of the metal. Finally, an X-ray examination was made in an attempt to find the expected change of lattice parameter of COO with oxygen pressure. Experimental The apparatus and materials used were substantially the same as those previously described by the authors.4 Marker Studies: The use of inert markers to follow oxidation reactions was first attempted by Pfeil" in 1929, and radioactive markers have recently been used by Davies et al.' In the investigation reported here, the markers were applied as an (NH4)2PtCI6 slurry in several thin streaks across both faces of four disks of cobalt metal 1 mm thick and 14 mm in diameter. The disks were then oxidized almost to completion at 1200°C in pure oxygen. After oxidation, they were mounted and sectioned and auto-radiographs were taken to locate the markers. Oxidation Rate: The oxidation rate of cobalt was measured at 1148°C at oxygen pressures ranging from 0.0055 to 1.0 atm and at 1000°, 1148", and 1350°C under 1 atm of oxygen. The rate was deter-

Jan 1, 1956