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By A. E. J. Gallagher, W. D. Charles

The chapter is a review of published and unpublished data concerning energy usage and material wear in commercial crushing and grinding operations. Examples are given from practice and factors influencing power and wear are discussed.

Jan 1, 1982

By R. F. Burdyn

The inadequate use of centrifugation to economically recover solids from weighted drilling fluids reflects the need for better equipment and techniques for this putpose. Laboratory studies in the development of an improved separator are described in which an operating equation is derived and tested. Results show that the concentric cylinder geometry employed effectively separates bnrite from a suspension and that the operating equation provides a good approxinmtion for scale-up. INTRODUCTION Our current drilling technology frequently requires a high-density drilling fluid obtained by addition of barite. In the course of drilling, formation solids which are too fine to be removed either by screening or settling become suspended in the drilling fluid and gradually the volume of solids in the mud increases. The volume fraction of solids must be limited (if a satisfactory set of rheological parameters are to be maintained). A centrifugal separatorprovidesan economical way of accomplishing this. The barite recovery process can be considered as a separation of two solids. One, the light solids, composed of formation and added solids, has a specific gravity of 2.6 to 2.7; the other, barite, has a specific gravity of 4.2 to 4.3. This density difference, plus the fact that the average light-solids particle size is much smaller than the average barite particle size, permits separation by a centrifuge. In drilling fluids some of the coarse particles of the light-solids-range will settle faster than fine particles of the barite-particle range. As a result a complete separation of the two species is not possible. since the object of the process is not merely recovering the maximum amount of barite but includes as well removing the maximum amount of light solids, an optimum barite recovery efficiency exists. From a practical standpoint this optimum cannot be determined in the field for each drilling fluid system, and in practice the separation is less than optimum, with some sacrifice of barite. Drilling technology has included centrifugal separators for barite recovery for more than a decade. Results have been reported by a number of investigators indicating that the process is practical and economica1. l-4 The decision to use a centrifuge is based on economics in which direct cost savings and the indirect benefits in rig time derived from improvement of the drilling fluid are important factors. One would expect that centrifugal separation of barite from drilling fluids would significantly affect barite consumption; however, this is not the case. The Minerals Yearbook shows an annual domestic barite consumption in the drilling industry of nearly 1 million tons.5 By rough estimate there are perhaps 80 separators presently in field use. Assuming half of these in use at any one time, operating an average of four hours per day, at recovery rates averaging 3,000 Ib of barite per hour, total annual recovery is about 90,000 tons. This is less than 10 per cent of he total barite used. I conservatively estimate that barite consumption in drilling operations can be reduced by 30 per cent through greater utilization of centrifugal separators. To encourage more widespread acceptance of centrifugal separators in the drilling industry, improved equipment and techniques would be very desirable. The present paper, covering theory and results obtained from a laboratory model, is the first in a series on he development of an improved mud separator for field use. THE CONCENTRIC CYLINDER GEOMETRY AS A SEPARATING DEVICE Consider the geometry shown in Fig. 1, consisting of two concentric cylinders separated by an annular space. These are arranged so that the outer cylinder is fixed and the inner one can be rotated about its axis on shafts sealed against the ends of the outer cylinder. If the outer cylinder is fitted with openings at either end, the inner

Jan 1, 1966

By E. Gregory, C. G. Goetzel

The outstanding elevated temperature properties of materials made from sintered aluminum powder have been well established in recent years.1,2 and considerable investigation has been carried out on the structures which appear to be responsible for this type of strengthening.2,3 The maximum operating temperature of such materials is severely limited, however, by the low melting point of the aluminum matrix; and, therefore, considerable interest was aroused in methods of introducing the

Jan 1, 1959

By David B. Reger

New discoveries of gas in the southern counties featured the petroleum industry in West Virginia during 194;. Drilling for oil increased slightly over 1944 and a small increase of initial production resulted. Out of 28 wildcats drilled, there were 16 gas discoveries and 12 dry holes. No commercial oil was found in the 28 wells.

Jan 1, 1946

Jan 1, 1952

By D. S. G. Hanson

The Flin Flon Mine has been in production for over fifty years, and current mining is dependent on pillar and remnant recovery. One of the last major blocks of ore, and an important economic entity to the Mine, is the North Main Shaft Pillar. A rock mechanics program was initiated through under' ground instrumentation and other subsequent analyses, to establish the degree of instability as min¬ing progressed. Several studies have been and will be undertaken to evaluate the general stability, and possibly improve the chances of stability during pillar recovery. The North Main Shaft Pillar is immediately bounded by cemented cut and fill supporting rib stopes which inturn are bounded by slag and waste filled stopes. The min¬ing method involves a modified longhole open stoping and slag fil¬ling sequence for each mining block in a general mining upwards scheme.

Jan 1, 1983

By Dorsey Lyon

INTRODUCTION THE electric furnace has always been found to be especially adapted to melting, refining, and finishing processes throughout its gradual acceptance by metallurgists, as a practical apparatus for conducting metallurgical operations. In the steel industry, the electric furnace is firmly established in the manufacture of steel of the highest grade, equal to crucible steel. For the production of the cheaper grades of steel in large tonnage, the electric furnace gives a higher-grade product than the open-hearth or converter, but due to the high cost of power prevailing in steel centers, considered from the electric furnace standpoint, it is not economical to produce tonnage steel in the electric furnace. As a refining and finishing agent for open-hearth or Bessemer steel, the electric furnace has had some degree of success in the production of tonnage steel. After a study of the use of the electric furnace in the steel industry, it appears that there may be a possibility of its use to advantage for the melting of cathode copper. In the case of copper the problem is not one of actual refining, because the copper if refined properly y the electrolytic method needs no further refining; it needs simply to be cast into a marketable shape. The name" refining". is applied to the present finishing process, because in the operation oxygen and other impurities are removed, which the electrolytic copper absorbs in being melted in the reverberatory furnace. Considering that processes may be positive, negative, and neutral; the electrolytic method would be positive; reverberatory melting of cathode copper, negative; and electric furnace melting, neutral. The electrolytic method produces about as pure a copper as is possible, if operated properly and the anodes are not too impure. The final reverberatory melting of this cathode copper lowers the grade of the final product, due to the absorption of gases and impurities.

Jan 8, 1914

By K. Sallmann

Spurred by a variety of factors, coal flotation is making headway among the preparation plants of West Germany. The author gives some statistics on German coal flotation plants and information on the properties of the feed and quality of the derived products. Types of machines and reagents used, dewatering practices, tailings disposal, and thickening operations are covered. There is special emphasis on the many-sided problems that confront German coal preparation engineers. The coal mining industry of West Germany is concentrated in three coalfields: the first on the Ruhr and the Rhein rivers, the second on the Saar river, and the third near the frontier between Germany and the Netherlands, around the towns of Aachen and Erkelenz. The total run-of-mine production of these three coalfields amounts to 736,000 tpd which come from 145 collieries. There are 121 washeries, 43 of them with a flotation plant. The total throughput of these 43 washeries is 280,000 tpd, out of which 26,000 tons (9.3 pet of the washery feed coal) are cleaned by flotation. The capacity of the individual flotation plants varies within relatively wide limits, the average being 40 tph and the capacity of the largest flotation plant being 120 tph. During the last few years, the number and size of flotation plants have been steadily increasing, although flotation must be looked upon as an expensive and rather complex cleaning process. The considerations which have led to the widespread application of flotation may be summarized as follows: 1) In making coking coal, it is seldom possible to add uncleaned fines to the coke oven charge, as their ash content is too high. If, however, the ash content of the fines is reduced to a maximum of 7 or 8 pet, they can be admixed to the washed and crushed small sizes without difficulty. This means, naturally that revenue is increased since the price of coking fines is always higher than the price for dust or uncleaned wet fines. 2) To prevent silicosis and pneumoconiosis, water infusion and spraying of the coal are practiced much more today than ever before. As a result, moisture content of run-of-mine coal has markedly increased and the washery feed coal contains more and more slurry instead of dry dust. The price of slurry, how- ever, is very low, and in many cases it is impossible to sell filtered raw slurry with a moisture content of 20 to 25 pct and, at the same time, 20 to 25 pct of ash. Reduction of the ash content of these slurries improves the possibility of dewatering them and, in this way, also enhances the marketability of this product. 3) The new severe laws and regulations against pollution of air and rivers make it necessary to de-dust coal better than in the past and to reduce the quantity of the waste water from coal preparation plants and their solids content to a minimum. 4) Even if there were no compulsory reasons to clean the fines, flotation will often lead to an increase in the overall yield. Although not the only application, it appears that the treatment of coking fines is the primary field for the flotation process in coal preparation. It must not be overlooked, however, that a series of arguments may be advanced against flotation: 1) Flotation is an expensive process because, in addition to the cleaning operation itself, the dewatering of the froth and the disposal of the tailings is very costly. 2) Operation of a flotation plant requires well trained personnel. 3) Filtered froth has about a 20 pct moisture content and, therefore, if mixed with the cleaned small coal it causes an undesirable increase in water content of the coke oven charge. For this reason it is necessary to take additional measures for dewatering washed small coal and this, of course, entails additional expense. 4) Disposal of flotation tailings involves very difficult problems, particularly in the highly industrialized regions. An investigation covering 32 flotation plants of Western Germany shows the following composition and properties of their feed:

Jan 1, 1961

By David R. Mitchell

Many of the difficult operating problems of the preparation of coal for market, of sampling coal shipments and in the utilization of coal are caused by segregation in the coal mass. Segregation may be of two kinds: i.e., "size segregation," in which particles of the same size in a mass of coal containing a range of sizes collect together and "density segregation," in which particles of the same density or specific gravity in a mass of particles of varying density gather together. Mechanics of Segregation Size segregation cannot take place with closely sized coal. As the size range increases, the tendency for size segregation increases. Similarly, cleaned coal with particles of approximately the same specific gravity have very little tendency for density segregation. The wider the density range of particles and the more particles of different density, the greater the chances are for density segregation. The following discussion deals primarily with coal of a wide size range as screenings and of wide density differences as uncleaned or run-of-mine screenings. If a mass of coal containing particles of a wide size range is subject to the stream action of a moving current of water, the small particles are transported farther than the coarser. Particles of different density in a stream of moving water are subject to the laws of classification, the heavier settling out first. The familiar sluice box of the gold miner and the action of rivers and other streams in classifying material according to

Jan 1, 1938

By David R. Mitchell

Many of the difficult operating problems of the preparation of coal for market, of sampling coal shipments and in the utilization of coal are caused by segregation in the coal mass. Segregation may be of two kinds: i.e., "size segregation," in which particles of the same size in a mass of coal containing a range of sizes collect together and "density segregation," in which particles of the same density or specific gravity in a mass of particles of varying density gather together. Mechanics of Segregation Size segregation cannot take place with closely sized coal. As the size range increases, the tendency for size segregation increases. Similarly, cleaned coal with particles of approximately the same specific gravity have very little tendency for density segregation. The wider the density range of particles and the more particles of different density, the greater the chances are for density segregation. The following discussion deals primarily with coal of a wide size range as screenings and of wide density differences as uncleaned or run-of-mine screenings. If a mass of coal containing particles of a wide size range is subject to the stream action of a moving current of water, the small particles are transported farther than the coarser. Particles of different density in a stream of moving water are subject to the laws of classification, the heavier settling out first. The familiar sluice box of the gold miner and the action of rivers and other streams in classifying material according to

Jan 1, 1938

By David B. Rushmore

Torches were used by the early Romans for mine-lighting, and these were followed by open lamps or earthen jars filled with tallow or oil, and later by candles. In early coal-mining, explosive gases seldom occurred, and, if they were encountered, the danger of explosion was materially diminished by the absence of any ventilating-system and the consequent insufficient circulation of air to form with the methane an explosive mixture. As the art advanced, the danger of fire-damp became more apparent, and methods for testing the air were resorted to as early as in the fifteenth century. The method of testing consisted in lowering a dog in a basket down the shaft. As soon as he encountered fire-damp he would commence to howl, after which he was withdrawn, and a leafy bush was fastened to the end of the rope and run rapidly up and down the shaft. This so disturbed the accumulation of gas as to cause it to rise out of the shaft. Later this odd method of testing was improved upon through the discovery that a light inserted in a body of fire-damp Gould produce a blue flame. Candles were used for this purpose, and, when fire-damp was thus discovered, brushing or some other primitive method of fanning was resorted to for driving out the gas. In some instances the gas was burned away, regardless of the danger thereby incurred. A man, wearing a well-moistened coat and a mask with glass spectacles, descended in the mine a few hours before each shift. With a long stick, to which was fastened a burning torch or candle, he would crawl on the floor with the stick so raised that the light would sweep the roof and ignite the gas which it encountered. In this position the flame of the explosion would pass over him, after which he would retreat from the gases resulting from the combustion. The occurrence of serious accidents resulted in

Jan 1, 1913

By Paul F. Kerr

Uranium mineralization occurs in the footwall of the Sunshine vein from the 2900 to the 3700 level. Veinlets of uraninite associated with pyrite and jasper have been so extensively divided and recemented that units more than a few feet in length are seldom observed. The wall rock is St. Regis quartzite of the Belt series. The age of the uraninite, on the basis of isotopic analyses, is 750 t- 50, which agrees with geological data suggesting that phases of the Sunshine mineralization are pre-Cambrian.

Jan 5, 1953

PORPHYRY mining in the Bisbee district in Arizona did not begin until 1923, though Bisbee had been the scene of profitable copper-mining operations since 1880, and during the interval had contributed roughly 2,000,000,000 lb. of copper to the world's supply. At that time it ranked third among the copper districts of the United States, first place for total production going to Butte, Montana, and second to the district centering around Calumet, Michigan. Bisbee's production had come from the so-called "limestone" mines operated principally by the Phelps Dodge Corporation and the Calumet & Arizona Mining Co. Each of these companies had a large smelting plant at Douglas, 25 miles southeast of Bisbee on the Mexican border. The town of Douglas owed its existence primarily to the copper mines of Bisbee, the particular location having been determined, first, by the fact that water in adequate supply could be obtained by sinking wells; and, second, by its position about equally distant from Bisbee and the mines in Sonora, Mexico, of the Moctezuma Copper Co., a Phelps Dodge subsidiary. Three partners, Martin, Reilly, and Ballard, conducted the first operations of consequence at Bisbee about 1880; and in 1881 a smelting plant consisting of two 36 in. water-jacketed blast furnaces was erected near by. The ore came from open-cut workings on the later-to-be-famous Queen orebody. The furnace charge is said to have averaged 23 per cent copper-twice as rich as the concentrates from the mills and four times as rich as the smelting ore shipped from Bisbee in recent years. As early as 1881, disputes arose among owners of various claims, and groups of claims, over the ownership of orebodies under the law of apex and extra-lateral rights. This law gives a miner the right to follow his vein downward on its dip, even

Jan 1, 1933

By W. A. Tiller, W. C. Johnston

A high-temperature electromagnetic stirrer is described in which heating and stirring are accomplished by independently controlled power sources. The appavatus is suitable lor use at temperatures up to 1700°C in a variety of ambient atmospheres. Some typical examples of the homogenizatimz capabilities of the system are given. THERE are few processes in solidification that are not markedly affected by motion in the melt during freezing. In many instances, the mechanisms are diffusion-controlled, and the transport in the melt may be greatly accelerated by deliberately stirring the melt. In zone-refining, stirring1 assists the removal of rejected impurities from the interface, so the process proceeds at a faster rate. The transition from a planar to a cellular interface is caused by constitutional undercooling in the melt ahead of the interface: and stirring delays its onset. Stirring is valuable for homogenization of melts: and chemical reaction with sluggish kinetics may be accelerated. Finally, it has been observed that grain refinement is related to motion in the melt. Fine grain castings are usually produced by the addition of catalysts to the -melt,' catalysts which are thought to act simply as hetereogeneous nucleation centers. Even here motion is important. Richards and Rostoker 5 applied ultrasonic vibration to a solidifying A1-Cu alloy which had been innoculated with a catalyst and found that the grain diameter fell linearly with the amplitude, the peak acceleration and the power input to the melt from the transducer. Finally, mechanical and electrical stirring alone have been used to generate a fine-grained structure.6,7 Johnston ef a1.' have carried out a series of systematic investigations of grain refinement by electromagnetic stirring in a number of low melting point alloys. They found, for example, that the number of grains per unit volume in Pb-Sn alloys could be increased several orders of magnitude by stirring an undercooled melt at the moment of recalescence. In general, a relation AT .H = constant prevailed for a given grain size, where AT was the undercooling of the melt and H the field strength. In more recent work, deliberate homogeneous nucleation of slightly undercooled melts established that the mechanism of refinement must be one involving crystal fragmentation and subsequent multiplication, rather than a "shower" of nuclei effect.9 It is the purpose of this note to describe a stirring device suitable for use up to 1700°C. At low temperatures mechanical stirring and direct-current methods are feasible, but at high temperatures the problem of a protective atmosphere and of electrode corrosion rules out such procedures. The most convenient method for high temperatures is to use externally generated ac fields for both stirring and heating. With rf induction heating alone, considerable stirring and agitation can be achieved, but in general the penetration of field into the melt is small, and the stirring cannot be controlled independently of the heating. In the present experiments, separate power sources of different frequencies for heating and for stirring were used. A susceptor design was chosen so that the 450 kc rf heating field was completely absorbed in the susceptor. The stirring frequency, 400 cps, hereafter called the af field, was chosen so that a high penetration of the melt proper was achieved. EXPERIMENTAL APPARATUS The apparatus, Fig. 1, consists of a quartz tube and end plates, surrounded by an rf induction coil and six equally spaced af stirring coils, four of which are shown in full and a fifth in section. Each af stirring coil is a transformer of which the secondary is a single-turn water-cooled copper loop and the primary is composed of two 10 amp-117 v Variac cores as shown. These cores are cooled by forced air, as each of the six pairs will carry maximum currents of 15 amp for short periods. Each set of Variac windings are connected in series, but opposite sets are connected in parallel with a three-phase 400 cps 400-v source. By properly phasing the coils in this way, a rotating field is produced. Capacitors C1, C2, and C3 in Fig. 2 are used to match this inductive load to the generator. Fig. 3 shows a cutaway view of the quartz tube. The sample (1 in. diam by 1 in. high) is placed in a tapered alumina crucible. An axial W-26 pct Re thermocouple, enclosed by a protection tube, is provided. The cruci-

Jan 1, 1968

The Garfield plant of the American Smelting & Refining Company is situated about seventeen miles west of Salt Lake City, on the Los Angeles & Salt Lake Railroad, and has freight service by the Denver & Rio Grande Western. Western Pacific and Bingham & Garfield Railways. The site lies between the picturesque Great Salt Lake, with its mountain islands and the northern point of the Oquirrh Range, which forms the western boundary of the Salt Lake Valley.

Jan 1, 1925

The Institute is custodian of funds for support of numerous gold medals and prizes and has representatives on boards awarding still others. Details regarding the Institute Awards are given below. The Institute is represented on the boards of the John Fritz Medal, the Hoover Medal and the Washington Award, in connection with the three national societies of Civil, Mechanical and Electrical engineering; and, also, in the case of the Washington Award, with the Western Society of Engineers. The Institute is represented with these four societies on the committee in charge of the Alfred Noble Prize.

Jan 1, 1939

By H. Hansen, A. U. Seybolt, P. Yurcisin, B. W. Roberts

The Bi-Mn phase diagram in the region near BiMn was investigated, using principally thermal analysis and changes in magnetization with temperature. Of chief interest are the findings related to the magnetic transformation in Bi-Mn. THE Bi-Mn system is of both theoretical and practical interest because of the occurrence of the compound BiMn which exhibits unusual ferromagnetic properties. Because the Bi-Mn phase diagram reviewed by Hansen' (see Fig. 1) in 1936 is based on work done by BekierY in 1914 and by Siebe" in 1919, which left considerable doubt about the nature of the diagram. it appeared desirable as an aid in understanding the alloying characteristics and magnetic behavior to examine the pertinent regions of the phase diagram. The most interesting reaction is the peritectic at 445°C which forms BiMn by the reaction: Liquid + Mn(sulfield) ? BiMn(sol field) There is also a eutectic at 262° C between pure bismuth and BiMn. Hansen draws in BiMn dotted, since in 1936 evidence for its existence was uncertain. Experimental Materials—Preparation of Alloys Electrolytic manganese of about 99.97 pet purity and bismuth of 99.99 + pet purity were used as starting materials.

Jan 1, 1957

By Richard Miller

WORK was undertaken two years ago at the Hammond Laboratory for the purpose of determining the magnitude of the elastic range in single crystals of pure metals by means of creep tests, the assumption being made that if a true elastic range exists, the elastic limit represents the maximum stress for no creep. A sensitive extensometer was constructed, and creep tests were made on zinc single crystals at a variety of loads and temperatures1. It was soon discovered that there is tip measurable elastic limit in ductile zinc single crystals at, or above, room temperature. The inference that pure metallic single crystals may not possess a definite elastic range was not justified, however, since zinc had been tested in creep only above its recrystallization temperature, and several investiga-tors2,3,4 had already shown that above the recrystallization temperature polycrystalline metals will flow under very small stresses, while below that temperature stresses of a much larger magnitude are required. For that reason, it was decided to extend the study of the elastic limit to other metals having a higher recrystallization temperature than zinc. Aluminum and silver were selected, because of the ease of obtaining pure materials and of preparing large single crystals, and because the crystallo-graphic glide system of these metals is well known. Owing to the limited time available, the elastic range was investigated by slow tensile tests rather than by creep tests.

Jan 1, 1937

As already said Pattin's map and the later one of Evans' showed coal in several places in Ohio as early as 1750, and possibly 1748; the reference on the latter map was' to an exposure near Bolivar, in Tuscarawas County, as well as along the Hocking River. So far. as now known, it 'was not mined in either place until 1810. George Croghan, in descending the Ohio with his party in 1765, mentions an "Alum Hill" which they saw near the present site of Pomeroy, probably an exposure of saline deposits, but does not mention coal. As settlement north of the Ohio River was prohibited until 1787, no coal was mined until long after that date. In 1785 a survey of seven ranges in the Ohio country was made, the line running west from a point on the north bank of 'the Ohio River, due north of the western termination of the southern boundary of Pennsylvania. The surveyors noted, "from hence to Stoney Brook between two very steep and high Ridges; it is eight yards wide, its bottom is of Slate and Sand Stone, and in many parts of it are large pieces of excellent Coal washed by, the Rains from the Neighboring Hills."' This was the present Yellow Creek, and the coal was from some of the lower measures. The Scioto Company published a pamphlet in French in 1787, to promote the sale of their lands and emigration to them, in which was said,

Jan 1, 1942

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970