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By R. Venugopal, T. C. Rao, M. Vanangamudi

Introduction The kinetic approach, to understand a process in detail, has been extensively used in the unit operations of many engineering systems. In green pelletization, the kinetic studies have been mainly oriented towards quantifying the growth mechanism (Kapur and Fuerstenau, 1964; Sastry and Fuerstenau, 1977; Capes and Danckwerts, 1965; Kapur and Fuerstenau, 1966; Kapur, 1972) and in a few cases, relating the rate of growth with added liquid content (Kapur and Fuerstenau, 1964; Newitt and Conway-Jones, 1958). Studies on the kinetics of green pelletization, in terms of the order of the kinetics are virtually non-existent. Sastry and Fuerstenau (1970) classified the agglomeration process into "free in-space" (dilute particle system) and "restricted-in¬space" (highly dispersed particle system) and noted that the former is a second-order process while the latter corresponds to a pseudo first-order rate process. The present paper attempts to describe the kinetics of green pelletization, in terms of order of the kinetics, using pyritiferrous shale as the material system. Experimental Pelletization experiments were carried out using -100 mesh pyritiferrous shale, in a laboratory disc pelletizer, at four intervals of pelletization time (15, 20, 25 and 30 min). The green pellets obtained were size analyzed. The size distribution of pellets has generally been represented by a single parameter such as the mean granule diameter, ratio of maximum and minimum pellet diameter, etc. In the present study, the d50 (50% passing size) of pellets has been considered to represent the size distribution of pellet. Kinetic equations The process of size enlargement is considered analogous to chemical reaction and a general kinetic equation of nth order for growth of pellets is given as

Jan 1, 1990

By J. R. CAIN

SAMUEL L. HOYT, ? Nela Park, Cleveland, Ohio (written discussion?). The work that Dr. Cain is doing on gases in steel should have a highly important bearing on investigational work in connection with steel-making practice. We found, for example, in our work in connection with the use of manganese in open-hearth practice that we needed expressions for the manganese efficiency and the "condition" of the steel. To get these figures we assumed that we would need to know the amount of FeO at different stages of the heat and the amounts of the gases present. This required simultaneous analyses of our samples for FeO and the gases and Dr. Cain seems to be the only investigator who has considered the analytical work from this point of view. That he has done so is very encouraging and it is to be hoped that his work will solve the mys-teries now surrounding this neglected phase of steel metallurgy. Those interested in the Ledebur method for use in connection with the efficiency of manganese as a "deoxidizing " agent will he disappointed to learn that more recent work at the Bureau indicates that Ledebur determinations are not reliable. The principal source of error seems to be due to the partial reduction of the ferrous oxide by the carbon present in the steel. However, it seems like an unnecessary criticism of the Ledebur method to state (p. 1319) that it proved of little value because it showed little differences in oxygen for a series of steels treated with ,various reagents and showing variations in physical properties and free-

Jan 12, 1919

By W. J. Vlasblom, A. M. Talmon, A. J. Nobel

In initial laboratory tests with a travelling submerged jet on artificially prepared clay it was found that the cavity depth is dependent on the stagnation pressure of the jet and the undrained shear strength of the clay. In addition, it has been observed that the increase in cavity depth with jet pressure is stronger at higher jet pressures. It is assumed that this can be explained by cavitation of the jet at higher jet pressures. At cavitation a cone of bubbles is formed around the jet, which reduces the exchange of momentum between the jet and the surrounding water. This results in a higher jet velocity and a higher stagnation pressure at a specified distance from the nozzle exit. In literature, no relation between the jet pressure of a free submerged cavitating jet and stagnation pressures was found. Additional tests were carried out to determine this relationship. Because practical dredging occurs at relatively large water depths, these tests were performed in a pressure vessel at different pressure levels. It is concluded that the efficiency of a jet (defined as the stagnation pressure at a certain distance divided by the jet pressure), for stand-off-distances smaller than 45 times the nozzle diameter, increases significantly by cavitation in comparison to the non-cavitating situation. However, the jet pressure required for a fully developed cavitation cone increases strongly with water depth. At dredging depths of 20 m and more, the necessary jet pressures are higher than normally applied in dredging practice. Thus in spite of the importance of cavitation in laboratory tests at atmospheric pressure, in normal dredging practice cavitation is of less importance.

Jan 1, 2007

By Walter S. Weeks

THE process of cooling air by allowing it to expand and do work in an engine is well known, but the theory of obtaining cold air by free expansion without the aid of an engine operating with cutoff has been little discussed. Case 1 If compressed air is allowed to expand to the atmospheric pressure through an orifice in an sir line that is supplied by a running compressor, no cooling results except the negligible one due to the Joule-Thompson effect, which will not be considered in this discussion. The effect of moisture will also be neglected. Symbols P1 Absolute pressure in pipe line, lb. per sq. ft. P3 Atmospheric pressure, lb. per sq. ft. V1 Volume occupied by 1 lb. air in pipe. V3 Volume occupied by 1 lb. air at P3. Cv Specific heat of air at constant volume, B.t.u. per lb. per deg. F. Cp Specific heat at constant pressure, B.t.u. per lb. per deg. F. T1 Absolute temperature of air in pipe, deg. F. T3 Absolute temperature of air outside after expansion and mixing and coming to rest. J Mechanical equivalent of heat (778 ft. lb.) R Gas constant for air, ft-lb. per deg. F. = 53.3. Formulas Consider 1 lb. of air moving out of a pipe. The air behind it does work on it to the extent of P1V1 ft-lb. This work is really done by the thrust of the piston of the compressor and does not come from any energy that exists in the air in the pipe. The pound of air contains

Jan 1, 1937

By James Boyd

REACTIVE metals are not only those sufficiently radioactive to be used as fuels, such as uranium and thorium, but all metals that will find application in power reactors. It is required of such metals that they be relatively inert or chemically unreactive, dimensionally stable at high temperatures and pressures, and either very absorbent of radioactivity or transparent to it. To gain the right perspective concerning these metals it is necessary at this point to explode some erroneous concepts propounded so often they have become accepted as fact. The first of these is that the great industrial nations, especially the U. S., have reached their pre-eminent position chiefly because they possess abundant mineral resources. Some U. S. mineral economists, echoed by the politicians, have taken this position so often that many of their theories and policies are based on the presence of developed mineral resources as a sine qua non to the country's greatness. Actually the reverse is true- under a social and political system granting free rein to the initiative and creativeness of its people, many hidden mineral resources that otherwise would have lain fallow have been developed into productive enterprises to the benefit of the national industrial economy. Again, once the proper incentive was furnished, other countries have also been able to establish valuable mineral enterprises in recent years; resources long dormant for lack of a proper economic environment suddenly have become valuable and productive. It is possible to name immediately several nations where such domestic economic developments have had favorable repercussions within the last decade. The absence of productive mines in any country is no indication that workable deposits do not exist within its territory.

Jan 11, 1957

A process was developed based on the thermal hydrolysis and precipitation of iron from solutions resulting from the leaching of zinc plant residue. A study was made of the hydrolysis of iron, at temperatures in the range 140-220°C, in both pure solutions of ferrie sulphate and in leach solutions derived from plant spent electrolyte.At 200°C hydrolysis of pure ferric sulphate solutions results in the precipitation of ferric oxide, Fe2O3, at low acid. concentrations, and a basic salt, Fe2O3.2S03.H20, at hIgher acid concentrations. At 180°C ferric oxide is precipitated at low acid concentrations, but at higher acidities. carphosiderite, 3Fe203.4SO.3.9H20, is the stable phase. Frequently a mIxture of ferric oxide and carphosldente IS produced at 180°C, the ratio of phases being dependent on the non-equilibrium experimental conditions.With solutions derived from plant spent electrolyte hydrolysIS at elevated temperatures results in the precipitation of jarosite compounds of the type NaFe3(S04)2(OH)6 The precipitation of natrojarosite jarosite, and ammonio-jarosite was studied in detail. Temperature, free acidity, and the concentration of sodium potassium, and ammonium ions are critical factors which affect the extent of precipitation.A process based on ammonio-jarosite precipitation was tested in a pilot plant.An alternative method of iron removal based on the addition of zinc oxide calcine, to neutralize excess acidity, and the precipitation of ferric oxide was also tested in the pilot plant. Both processes appear economically favourable...

Jan 1, 1967

By E. C. Rien

When the electrical system for a surface or open pit mine is designed, four major considerations should be satisfied in the following order: safety, reliability, flexibility, and cost. Careful planning initially will make expansion for future growth economical as well as possible without extended shutdown of operations. Electrical requirements in surface and open pit mining can be divided into three categories: main substation, plant power, and pit distribution. These systems are integral to each other, but will be dealt with separately here. 11.2-1. Main Substation. A main substation for a mining operation may vary from a 500 kva transformer supplying 480-v power to motor-driven pumps and conveyors, to a 50,000 kva substation serving a large beneficiation plant or a large strip mining operation. Regardless of size, it should be designed with the realization that a failure of the main substation will totally shut down the operation (Fig. 11.2-1.). Location of a main substation usually is a compromise between expense of running the incoming high-voltage transmission lines and the voltage drop of long secondary runs. Based on a geological survey for immediate and future areas of excavation, the main substation should be located as near to the center of load as possible. The site should be out of the blasting area, readily accessible to authorized personnel, and situated where prevailing winds will keep it free from dust or snow. DISCONNECTS AND OVERLOAD PROTECTION. The main substation should have a primary disconnecting device-either a pole top gang-operated switch and fuses of adequate interrupting capacity or, preferably, an oil circuit breaker with properly coordinated relay protection.

Jan 1, 1968

By L. McFarlane, D. Rollwagen

"Madawaska Mines produces a uranium precipitate (83-85% u3o8) using a magnesium oxide slurry to precipitate the uranium from solution. The solution, at approximately 9""0 g/l u3o8 is neutralized to a pH of 7.0. At the Eldorado Nuclear Refinery in Port Hope, the precipitate is not acceptable as a single feed to the refinery process. It was discovered that a 2% silica impurity caused emulsion problems in the solvent extraction column.After extensive studies of possible solutions, such as two-stage precipitation and solvent extraction, an acceptable solution was found. The selective precipitation of uranium at a pH of 3.5-4.0 using Hydrogen Peroxide produces an almost silica free product of higher purity (90-93% u3o8) to that of straight magnesium oxide precipitation. Introduction Madawaska Mines Limited is located four miles southwest of Bancroft, Ontario. The annual production of u3o8 is approximately 610,000 pounds. To produce the final product or yellowcake, nine separate steps are required. These are (1) grinding, (2) dewatering, (3) leaching, (4) acid filtration, (5) clarification, (6) ion exchange, (7) precipitation, (8) washing, and (9) drying and packaging. To illustrate these steps, a complete flowsheet of the mill is displayed on page three.The yellowcake is sent to Eldorado Nuclear Limited in Port Hope, Ontario for further concentrating and refining. As part of their routine specification check, a test called the amenability test is performed. This test indicates how a particular dissolved yellowcake product reacts to solvent extraction. The Madawaska yellowcake did not pass the test."

Jan 1, 1982

By J. H. Bowden

The shaft-plant here described was put in operation in September, 1895, and the No. 6 slope-motor was started in May, 1896. The plant comprises : One Norwalk three-stage compressor l21/2, 91/2 and 5 in. diameters of air- and 20 in. diameter of steam-cylinder, all 24 in. stroke; capacity at 100 revolutions, 296 cu. ft. of free air per minute, compressed to 600 Ibs. per sq. in. A main pipe, 5 in. diameter, 4380 ft. long, with five charging-stations in No. 6 Shaft, and a branch of 3 in. pipe, 3100 ft. long, with three charging stations, in No. 6 Slope. These pipes on each line charge a Porter compressed-air motor, with 7 by 14 in. cylinders, and four 24 in. drivers, weighing about eight tons, with a tank-capacity of 130 cu. ft. of air at 550 lbs. pressure in the main tank, reduced to 160 lbs. in the 8-in. auxiliary tank of 4.2 cu. ft. capacity, supplying the cylinders. The No. 6 shaft run averages 4000 ft. each way on grades of $ to 23/4 per cent., and averaging close to one per cent. in favor of the loaded cars. The No. 6 slope run averages 2100 ft. with nearly the same grades. The mine-cars weigh 2800 Ibs. empty, and about 9800 lbs. loaded, and are hauled in trips of 12 to 20, averaging about 15 cars. The shaft-motor now hauls about 355, and the slope-motor 320 cars per day of 10 hours, replacing in the shaft 17 mules, and

Jan 1, 1901

By W. L. Austin

The only essential difference among the three methods of collecting the precious metals from their low-grade ores by fusion is comprised in the nature of the vehicle in which those metals are concentrated. If lead- or coppper-ores are used, the processes are respectively lead- or copper-smelting; but when the sulphide of iron forms the matrix in which the gold and silver are collected, the process is known as pyritic smelting. The latter method presents rarely any advantages when lead- or copper-ores are available at rates which permit profitable treatment. Pyritic silver-smelting, defined by Percy as " the smelting of silver-ores, which are either free from lead or do not contain it in sufficient quantity to collect the silver, in conjunction with pyrites, in order to produce a regulus in which the silver may be concentrated," is not, as the name would imply, confined to ores of this metal alone, but embraces auriferous silver-ores, or even gold-ores simple. This method of collecting the precious metals from lowgrade dry ores, employed at Freiberg by Barthel Kohler in 1585, does not appear, up to the present, to have been introduced into this country on a working scale. And yet the possibility of getting rid in a single operation of all the earthy or siliceous gangue of a lowgrade ore and concentrating the precious metals in a matte without loss of lead (which includes gold and silver) by slagging, or volatilization, at the same time producing a highly siliceous slag, very nearly if not quite as clean as is usual in lead-smelting, certainly commends itself. In some parts of the country, owing to the com-

Jan 1, 1888

By Charles W. Goodale

The attention of the Institute has been called by Prof. John A. Church* and Mr. W. Lawrence Austin? to the free-milling ores of the Tombstone mines and their treatment, but the silver-bearing man ganese ores of the district have received only a passing notice. As these ores show some interesting peculiarities, and have yielded not less than 750,000 ounces of silver, they are worthy of some study. The Knoxville, Lucky Cuss, Luck Sure, and Wedge mines (named in the order of their importance) are situated along the northern border of the district. They have been the leading producers of this manganese ore, and possess the same general characteristics. Special attention will be given to the Knoxville, as it has been the one most extensively developed. The limestone belt, in which the Knoxville ore bodies occur, has an easterly and westerly trend, is about 1680 feet wide, and rests on granite on the north, the plane of contact being nearly vertical. It is overlain by quartzite, the contact-plane having a dip of 82°. Some mining has been done along these contacts, and a considerable amount of pay ore has been extracted, but development has been very superficial. The ore found along these contact planes contains very little manganese, and differs entirely from the ore in the lime stones. No attempt will he made to assign this limestone country-rock to a particular geological horizon, as no fossils have been found in it. Prof. Blake, in a paper on "The Geology and Veins of Tombstone, Arizona" (Trans., x., 334), speaks of the middle and upper strati-

Jan 1, 1889

By Arthur S. Coffinberry, Ralph Hultgren

WE have studied the gold-aluminum system by X-ray diffraction and by the microscope over the entire range of composition for temperatures between 300° and 500° C. Results obtained are shown in Fig. 1, combined with the work of Heycock and Neville1 at higher temperatures. The diagram differs in important details from that given by Hansen2 in his critical compilation of the literature of binary alloy systems. This work was undertaken both because of the intrinsic value of a knowledge of the phase diagram of this system and because of the need of theoretical metallurgy for precise and accurate data, particularly X-ray diffraction data. Systematic studies of equilibrium diagrams, particularly by Hume-Rothery,3 have shown regularities that yield a certain insight into the nature of alloying forces. It has been shown, for example, that solid solubility depends on the concentration of free electrons in the alloy, on the relative radii of solvent and solute atoms, on the forces of attraction between atoms, and on the relative stability of intermediate phases. The well-known Hume-Rothery rule states that the crystal structures and compositions of many intermediate phases depend on the electronto-atom ratio. This has been confirmed and extended by wave mechanical calculations.4 A knowledge of the forces between atoms in alloys, even an imperfectly developed empirical one, should be a valuable guide in the preparation of technological alloys of desirable properties. Furthermore, such information is basic in such problems as rate of diffusion, age-hardening, phase transformations, and others. The most valuable data for this purpose are furnished by X-ray diffraction studies. Unfortunately, work has been

Jan 1, 1938

By Walter S. Weeks

The process of cooling air by allowing it to expand and do work in an engine is well known, but the theory of obtaining cold air by free expansion without the aid of an engine operating with cutoff has been little discussed. Case I If compressed air is allowed to expand to the atmospheric pressure through an orifice in an air line that is supplied by a running compressor, no cooling results except the negligible one due to the JouleThompson effect, which will not be considered in this discussion. The effect of moisture will also be neglected. Symbols P1 Absolute pressure in pipe line, lb. per sq. ft. P3 Atmospheric pressure, lb. per sq. ft. V1 Volume occupied by 1 lb. air in pipe. V3 Volume occupied by 1 lb. air at P3. C, Specific heat of air at constant volume, B.t.u. per lb. per deg. F. C, Specific heat at constant pressure, B.t.u. per lb, per deg. F. T1 Absolute temperature of air in pipe, deg. F. T8 Absolute temperature of air outside after expansion and mixing and coming to rest. j Mechanical equivalent of heat (778 ft. lb.) R Gas constant for air, ft-lb. per deg. F. = 53.3. Formulas Consider 1 lb. of air moving out of a pipe. The air behind it does work on it to the extent of P1V1 ft-lb. This work is really done by the thrust of the piston of the compressor and does not come from any energy that exists in the air in the pipe. The pound of air contains

Jan 1, 1937

By G. R. Speich

RECENT studies by Smith and Olney,1,2 Olney,3 Greifer and Salli,4 Rys etal., and Olney and smith 6 have established that graphite is the first decomposition product to format the surface of hypereutectoid plain-carbon steels when they are austenitized in a vacuum or inert atmosphere and slowly cooled. This graphite evidently forms directly from the austenite and only at the surface of the specimen. The interior of the specimen is found to be free of graphite. The graphite layer can almost completely cover the specimen surface and the rate of its formation is markedly sensitive to the orientation of the austenite. The present work was undertaken to study this phenomenon further, especially with regard to the effect of temperature and austenite orientation. The material studied in this work was a high-purity iron-carbon alloy containing 0.88 pct C, 0.005 pct Mn, 0.016 pct Si, 0.005 pct S, and 0.002 pct P. Specimens were heat-treated in a commercial hot stage modified for rapid quenching.7 This permitted direct observation of the formation of the surface graphite. A vacuum of 10"" to 10-5 mm of Hg prevented oxidation or decarburization of the specimens. Specimens were austenitized for 30 min at 1100°C and quenched to a series of lower temperatures where they were isothermally transformed. Surface graphite was observed to form at 700°, 750°, and 780°C but not at 825°, 900° or 1000°C. Since the maximum solubility of austenite for graphite is 0.88 pct C at 800°C,8 surface graphite only forms at tem-

Jan 1, 1962

By G. Falalakis

The Perama Hill gold project is an environmentally friendly project designed with the principle of zero discharge to the environment. The main issues of the proposed mine that are addressed in this paper are the water management, the dam and tailings management facility parameters as well as the mine closure plan, which demonstrate the sustainable design of the project. The water plant circuit will operate using 87% of recycled water and rainfalls, while the pumped aquifer is completely unsuitable for any other use. The proposed water management plan is based on different meteorological conditions for every month and optimizes the external water needs. The tailings pond area that is sited on intensely argilized rocks, will be composite-lined resulting in a permeability value of less than 10-10 m/s, and will exceed the safety parameters for maximum earthquake intensity, flood conditions and seepage. Tailings will contain less than 1 ppm cyanides (almost potable water ranges) and will be free of heavy metals (oxide ore material). The proposed rehabilitation plan comprises of decommissioning and demolition of the plant and auxiliary facilities, open pit partial back-filling and recontouring, appropriate capping of the tailings impoundment, revegetation, maintenance of area drainage system and monitoring for 5 years after rehabilitation. The plan is fullycosted, will be prepaid and through the agreed final land uses with the local community and the proposed actions of the corporate responsibility will attribute to the sustainable development of the area. The design of the Perama Hill project according to new EU and UN legislation and practices ensures that it will be the best example of gold mining operations in Greece.

Jan 1, 2008

By Kohra A, Shoji S

The amount of copper production by flash smelting process occupies about 17% (equivalent to 1.4 million t/year) of total free world production. In Japan, 650,000 tons of copper is produced annually by flash smelting. This is 65% of the gross copper production of Japan. To reinforce pollution control, promote energy saving, and enhance production efficiency by increasing the size of furnaces, conventional blast furnaces and reverberatory furnaces are being replaced with the flash smelters worldwide. The Ashio Smelter started copper production in 1884 and developed in association with the Ashio mine. In those days, the Ashio smelter produced copper by using the blast furnace process designed for the high-grade ore from the copper mine. At that time, this process was specialized in Japan. In 1956, for the first time in Japan, the Ashio Smelter introduced the flash smelting process developed by Outokumpu Oy of Finland (it is suitable for treating the copper concentrate, producing sulfuric acid and improving production efficiency). The flash furnace in Ashio, the first ever in Japan, had a capacity of 230 t/day for copper concentrate and was operated up to 1962. During this period, various operational troubles were solved, and further improvements were made; and, in 1962, a Furukawa-type flash smelting furnace was completed in Ashio. This improved version of a flash furnace had a capacity of 450 t/day. There was one flash furnace and one waste heat boiler, which were arranged in a unique pattern for that time. This furnace may be said to be the prototype of the present flash smelting process in the world.

Jan 1, 1987

By Arthur Coffinberry

EVE have studied the gold-aluminum system by X-ray diffraction and by the microscope over the entire range of composition for temperatures between 300° and 500° C. Results obtained are shown in Fig. 1, com-bined with the work of Heycock and Neville1 at higher temperatures. The diagram differs in important details from that given by Hansen2 in his critical compilation of the literature of binary alloy systems. This work was, undertaken both because of the intrinsic value of a knowledge of the phase diagram of this system and because of the need of theoretical metallurgy for precise and accurate data, particularly X-ray diffraction data. Systematic studies of equilibrium diagrams, particularly by Hume-Rothery,3 have shown regularities that yield a certain insight into the nature of alloying forces. It has been shown, for example, that solid solubility depends on the concentration of free electrons in the alloy, on the relative radii of solvent and solute atones, on the forces of attraction between atoms, and on the relative stability of intermediate phases. The well-known Hume-Rothery rule states that the crystal structures and compositions of many intermediate phases depend on the electron-to-atom ratio. This has been confirmed and extended by wave mechanical calculations.4 A knowledge of the forces between atoms in alloys, even an imperfectly developed empirical one, should be a valuable guide in the preparation of technological alloys of desirable properties. Furthermore, such informa-tion is basic in such problems as rate of diffusion, age-hardening, phase transformations, and others. The most valuable data for this purpose are furnished by X-ray diffraction studies. Unfortunately, work has been

Jan 1, 1938

By D. Lee Petersen, Charles R. Nelson, Marvin Marshak

INTRODUCTION Construction is underway on a laboratory cavern 713 m below surface at the Soudan Mine, Tower-Soudan State Park, in northeastern Minnesota. The 13.9 in wide by 11.6 m high by 71.8 in long cavern will provide a laboratory space for basic research in physics, in which experiments can be conducted with greatly reduced interference from cosmic radiation. A first generation experiment, called the Soudan 1 detector, is currently operating in a converted drift 591 in below surface at the mine. The initial phase of the Soudan 2 detector will be an 1100-metric ton unit, which will occupy approximately a 19 m length of the cavern. Control and monitoring equipment will be in a prefabricated shop office enclosure erected in the cavern. The location and planned usage for the laboratory cavern present special excavation, lining, and outfitting requirements. Temperature and humidity control, a relatively clean dust-free environment, and a long service life are required. Low cost and risk to the owner were basic requirements due to the nature of the funding. The most common type of site selected to meet these two constraints is either an operational mine or a civil works facility such as a road tunnel. There are often serious problems for such laboratories because of ongoing operations such as blasting, hauling, etc. Most of these problems do not exist for the Soudan 2 laboratory because the mine is used as a historical site with regular tours only in the summer season. The laboratory owner, the University of Minnesota, and the park owner, Minnesota Department of Natural Resources, are both public agencies of the

Jan 1, 1985

By Koichi Kashida, Mayumi Someno, Kazuhiro Goto

The present work has two objectives: first to develop an experimental method which would give some new information on the micromechanism of the reduction of oxides by gases at elevated temperature; second to clari,fy the intermediate phases of the W-0 system, formed during the reduction. A Galvanic cell with the solid electrolyte , ZrO2 . CaO, was imbedded in powders of W03, CuO, or Fe20s with two measuring electvodes and with a reference electrode. The change of the intraparticle gas composition was measured at An oxygen concentration cell consists of two electrodes separated by an electrolyte through which the transference of electrical charge is accomplished predominantly by the migration of oxygen ions. Many works have been reported on the oxygen con- 600" to loo@ C during the reduction by the gas mixture of hydrogen and argon. The intraparticle gas composition changes stepwise with time. The electromotive force of such temporary interruption corresponds to the equilibrium electromotive force of two solid phases formed during the reduction. The intermediate phases of W-0 system, which are formed in a large quantity during the reduction by hydrogen, are W0 2 W02.72 and WOz. The micromechanism of the reduction of oxides by gases is discussed. centration cells with the solid electrolyte of solid solution of zirconia and lime, since Kuikkola and wagnerl demonstrated the possibility of determination of standard free energy of formation of oxides by an electromotive-force method with the Galvanic cell. One of the present authors (K.G.) and his coworkers have applied the cells with the solid electrolyte of zirconia and lime to the following measurements:

Jan 1, 1969

By Arthur S. Coffinberry, Ralph Hultgren

We have studied the gold-aluminum system by X-ray diffraction and by the microscope over the entire range of composition for temperatures between 300° and 500° C. Results obtained are shown in Fig. 1, combined with the work of Heycock and Neville1 at higher temperatures. The diagram differs in important details from that given by Hansen2 in his critical compilation of the literature of binary alloy systems. This work was undertaken both because of the intrinsic value of a knowledge of the phase diagram of this system and because of the need of theoretical metallurgy for precise and accurate data, particularly X-ray diffraction data. Systematic studies of equilibrium diagrams, particularly by Hume-Rothery,3 have shown regularities that yield a certain insight into the nature of alloying forces. It has been shown, for example, that solid solubility depends on the concentration of free electrons in the alloy, on the relative radii of solvent and solute atoms, on the forces of attraction between atoms, and on the relative stability of intermediate phases. The well-known Hume-Rothery rule states that the crystal structures and compositions of many intermediate phases depend on the electron-to-atom ratio. This has been confirmed and extended by wave mechanical calculations.4 A knowledge of the forces between atoms in alloys, even an imperfectly developed empirical one, should be a valuable guide in the preparation of technological alloys of desirable properties. Furthermore, such information is basic in such problems as rate of diffusion, age-hardening, phase transformations, and others. The most valuable data for this purpose are furnished by X-ray diffraction studies. Unfortunately, work has been

Jan 1, 1938