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CONTENTS PAGE THOENEN, J. R.-Limestone Production as a Mining Problem. Discussed by Oliver Bowles, J. T. Singewald, S. R. Russell 1 GRIGGS, C. C.-Engineering in Limestone Production. Discussed by W. C. Phalen, John Rice, Samuel M. Shallcross, Oliver Bowles, Nathan C. Rockwood, George Milliron 2 WILDER, FRANK A.-Rotary Calciners for Gypsum. Discussed by L. K. Arm-strong 9 PORTER, JOHN J.-Manufacturing Problems of Cement Industry. Discussed by Samuel M. Shallcross 9 KIRKHAM, VIRGIL R. D.-Phosphate Deposits of Idaho and Their Relation to the World Supply. Discussed by F. A. Wilder, S. L. Willis, G. R. Mansfield, R. W. Stone, L. K. Armstrong 9 Limestone Production as a Mining Problem Discussion of the paper of J. R. THOENEN, presented at the New York Meeting, February, 1925, and issued, as Paper 1417-H, with MINING AND METALLURGY, February, 1925. OLIVER BOWLES, New Brunswick, N. J.-I am so thoroughly convinced of the growing importance of underground work in the production of limestone that I had the author make a detailed study of limestone mining for the Bureau of Mines and prepare a report on the principles of limestone mining. Many limestone operators, long accustomed to open¬pit work, are being forced to mining. About 6 months ago I thought there were twenty-five or thirty underground limestone operations in the United States but the author has been finding new ones until his list now runs nearer sixty. Some of these are very extensive; one at least has 4 ½ miles of underground workings. There is an ever-expanding field for the engineer in the operation of limestone mines and quarries. Some of the larger companies realize the need of skilled engineering advice, but many of the companies regard the engineer as an unnecessary expense. Although almost every metal mine, even those handling only a few hundred tons of ore per month, employs a mining engineer, many limestone operations ten times as large employ no mining engineers. Few mining engineers are at all familiar

Jan 6, 1925

IRON AND STEEL COMMITTEE ALBERT SAUVEUR, Chairman .A. A. STEVENSON, Vice-Chairman HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Cambridge, Mass. Guilliaem Aertsen, Robert W. Hunt, .-E: Gybbon Spilsbury, John Birkinbine, J. E. Johnson, Jr., J. S. Unger, William H. Blauvelt, William Kelly, Felix A. Vogel, Charles A. Buck, Charles Kirchhoff, Leonard Waldo, James Gayley, Richard Moldenke, William R. Walker, Henry D. Hibbard, Joseph W. Richards, William R. Webster, Henry M. Howe, C. F. W. Rys, Frederick W. Wood. Manuscripts of the following papers on iron and steel for the February -meeting have been received and accepted: Albert Sauveur, Notes on Heating and Cooling Curves of Professor Carpenter's Electrolytic Iron. H. M. Howe and A. G. Levy, Notes; on the Plastic Deformation of Steel during Overstrain.

Jan 2, 1914

By L. S. Castleman, R. K. Hotzler

We are currently studying the effects on recrys-tallization of impurities diffused into dispersion-hardened alloys. Our interest in this phenomenon was originally aroused by the observation that the recrystallization temperature range of tungsten "doped" with alumina and silica, or with thoria, is lowered drastically if nickel is plated onto the tungsten prior to heat treatment.' In this note, we report a similar effect that sulfur has on the recrystallization behavior of thoriated nickel. The experimental procedure for this exploratory phase of the investigation has consisted simply in heating commercially obtained stress-relieved samples of thoriated nickel for varying temperatures and times in sealed capsules containing air and small quantities of sulfur. The samples contain 2.4 vol pct thoria and initially less than 18 ppm S by weight; they are prepared either from 0.5-in.-ciiam rod stock or from 0.092-in. sheet and are in the "as-received" (stress-relieved) condition prior to exposure. In an atmosphere free of sulfur, such samples do not show evidence of recrystallization after being annealed for 1 hr at a temperature of 2500°F (1372C).2 The photomicrograph in Fig. 1 shows the microstructure of one of our samples annealed for 75 hr at 1000° C (1832°F) in a sulfur-free capsule. The grain structure is hardly evident (if at all) at 465 times magnification. In contrast, the photomicrograph of Fig. 2 shows the recrystallization that has taken place in a sample exposed to sulfur for 5 hr at 1000°C (1832°F). A nickel sulfide phase is visible at the grain boundaries of the light-appearing grains. We have also observed recrystallization to occur in a sample annealed at 600°C (1112°F) for 25 hr. This temperature is below the 637°C (1178°F) eutectic in the Ni-S system. In the latter case, no nickel sulfide phase is evident in the microstructure. Moreover, we have noticed the occur-

Jan 1, 1969

By W. W. Simpson, W. L. Staker, R. G. Sandberg

The Bureau of Mines investigated selective extraction of Au and Ag from a low-grade Au ore containing Hg. Gold and silver were extracted from the ore in cyanide slurries, and Hg extraction was suppressed with sodium or calcium sulfide. Maximum Au extraction and minimum Hg extraction were obtained using solutions containing 17 kg NaCN/t of solution (0.34 lb NaCN/st). Increasing the cyanide concentration increased Hg extraction without increasing Au extraction. Mercury extraction from the ore was suppressed with 0.5-2.9 kg CaS/kg Hg (0.5-2.9 lb/lb) in the ore. Gold-to-mercury ratios of 100:1 to 400:1 were obtained in the leach solution, and on the activated carbon in a CIP circuit.

Jan 1, 1985

Boundary and general corrosio~z rates for higkpurity alutninum were ~rzeasured irz 16 pct HC1 at sJmllow penetrations (< 25 p). The rates for several high-angle random tilt boundaries, several [001] synzmetrical tilt boundaries, a 54-deg [010] twist, and a 15-deg randorn tw~st boundary were one-fourth to one-third higher than that of the (001) surface used as reference. Boundary attack was slower for 23 and 37-deg [001] tilt boundaries and a 16-deg [010] twist boundary. The corrosion rate for a (111) surface was roughly om-third higher than for (001) and was thus about as high as the corrosion rate of the fastest boundaries. The boundary attack did ?lot appear to parallel the variatiorz of boundavy energy. The signvicance of the anisotropy of corrosion was discussed.

Jan 1, 1966

By E. H. Mohr

At the McGill concentrator of the Nevada Consolidated Copper Co., all flotation operations have been carried out in Forrester cells since November, 1926. In respect to cost of operation, the new cell has proved to be superior to the Callow, which it supplanted, and its incorporation in the flow sheet has resulted in a marked improvement in the metallurgy. Before citing the advantages of the new machine over the old, it should be explained that the Forrester has not only replaced the Callow, but it has made possible the elimination of a number of tables as well. When Callow cells were in use, table concentration preceded flotation. The ball mill pulp was elevated, by means of air lifts, to roughing Wilfley tables situated two floors directly above the flotation floor. On an intermediate floor were additional tables which cleaned the concentrate from those above. The finished table concentrate constituted approximately 60 per cent. of the total mill production, and contained about 40 per cent, of the recovered copper. The table tailings were returned to the classifiers, the overflow from which went to the flotation cells and the oversize to the ball mills. As soon as the Forrester cells were installed, this tabling operation was discontinued. The ball mill pulp now discharges into the classifiers direct, without the intermediate tabling. It was impracticable to ernploy the present flow sheet when Callow cells were in use, for the reason that unless the great,er part of the heavy mineral was first removed, it accumulated on the mats and adversely affected the flotation operation. By tabling ahead of flotation, it was practicable to maintain the concentrator at 10 to 20 per cent. greater capacity (depending up on the pyrite contnt of the ore) than was possible by flotation alone. This was due to the necessity for finer grinding in the latter case. Even though the table conecntrates contained only 6 to 8 per cent&apos;. copper content, the low smelting costs made it advantageous to operate at high mill capacity, at the cost of low grade of product. Standard Section equipment With the old flow sheet, a standard section consisted of four ball mills and classifiers, one air. lift, 20 roughing tables, 10 cleaner tables, 12 primary

Jan 1, 1928

By R. A. Garling

INTRODUCTION Since the infancy of in situ uranium mining, a growing number of hydrometallurgical processes have been incorporated into pilot and commercial scale flowsheets. Although initial design efforts were geared toward maximizing uranium recovery and minimizing plant and wellfield flow circuit maintenance, recent emphasis has shifted to improved means of water conservation and aquifer restoration. As mining units approached depletion, evaporation ponds reached minimum freeboard, and state and federal agencies demanded proof of groundwater restoration, processes including mixed bed and conventional ion exchange, reverse osmosis and electrodialysis were adopted by the industry. These units served the additional function of reducing process bleed flows during mining in states where the deep disposal well permitting ice remains unbroken. This report concerns the use of electrodialysis as an alternative to the more conventional processes used in in situ mining. In addition to a brief history and description of the process, a comparison to reverse osmosis and operational data derived from testing an Ionics, Inc. 1.31 x 10-3 m /s (30,000 gallon/day) unit at the Teton-Nedco Leuenberger Research and Development pilot will be presented. HISTORY Commercially practicable electrodialysis was contingent upon the development of synthetic ion exchange membranes in 1940&apos;s. In 1952, Ionics Inc. demonstrated that the process was amenable to the treatment of salt and brackish water and, in 1954, made their first commercial sale. The following decade saw several major electrodialysis unit sales which were generally targeted for use on private or municipal potable water treatment. Major increases in membrane desalting unit capacities, facilitated by technological advances in the reserve osmosis industry, were noted during the 1970&apos;s. The development of polarity reversing electrodialysis equipment which reduced feed pretreatment requirements, increased water recovery rates, and simplified unit operation, kept Ionics Inc. competetive in the water treatment industry. Engineering advances which incorporated automated equipment, non-corrosive construction materials, and improved ion exchange membranes allowed the electrodialysis process to compete in industrial waste treatment among other commercial markets. PROCESS AND APPARATUS DESCRIPTION The electrodialysis process utilizes direct electrical current passed across a stack of alternating cation and anion selective membranes in order to achieve an electrochemical separation of ionized materials in an aqueous solution. The membrane stack has the appearance of a plate and frame filter press and auxilliary equipment includes solution pumps, electrically actuated valves, filters, piping and a direct current power source. The ion separation membranes are thin sheets of synthetic cation or anion selective resins. Attaching sulfonate or quaternary ammonium groups to the cross linked copolymer structure determines the ion selectivity of the membrane. The membranes are separated from each other in the stack by non-conductive spacers that house flow channels which route the flow tortuously and parallel to the membranes. Direct electrical current passing perpendicularly to the membranes and solution passages attracts cations toward the cathode and anions toward the anode (Figure 1). As the ions from the feed stream pass through the ion selective membranes, they become concentrated in the adjacent brine channel and are retained there by the combined attractive force of the electrode and the repelling force of the next membrane toward the electrode. Limiting factors on the degree of demineralization possible include chemical solubilities in the brine flow and the current density that will produce an unacceptable degree of polarization (Figure 1). Feed or brine solution treatment with complexing agents or acids has been successfully applied to prevent membrane scaling. Polarization can occur when sufficient current density is applied to dissociate water in the ion depleted region of the diluting compartments near the membrane surfaces. Significant polarization is evidenced by large electrical resistances across cell pairs and notable pH differences between diluting and concentrating streams. Limiting current densities have been increased in U.S. manufactured equipment by utilizing tortuous flow paths of relatively high linear velocities thereby promoting continous solution mixing. Energy consumption is due to separating electrolytes and solutions, oxidation and reduction reactions occurring in electrode compartments, overcoming electrical resistance, conversion from AC to DC power, solution pumping and auxiliary equipment actuation. A major improvement to the basic electrodialysis process was applied in 1970 which resulted in frequent, automatic cleaning and descaling of membrane surfaces. The process, polarity reversal, incorporates alternating the cathode and anode on a periodic basis while exchanging product and brine flow channels via electrically actuated values. The reversal reduces the potential of stack plugging with CaCO3 (calcite), CaSO4 (gypsum), and colloidal materials and, in most waters, eliminates feed pre-treatment requirements. For approximately two minutes during and following the reversal, off spec. water is flushed to waste or reintroduced to the feed supply. The usual feed treatment on polarity reversing electro-

Jan 1, 1982

By Donald Barton

THE theory of gravitation is based on Newton&apos;s law that any two bodies exert a mutual attraction which is proportional to the product of their masses and inversely proportional to the square of the distance between them; i. e. A= K MM/R2 (1) where K is a constant, M and m are the respective masses of the two bodies, and R the distance between them. In the earth&apos;s gravitational system, the earth is one of the bodies; the other may be any body within or without the earth. In theoretical discussions and calculations in regard to gravity, that other body usually is taken as a unit of mass: in the C. G. S. system, a body of one gram in mass.

Jan 1, 1928

By R. H. Wightman, C. D. Chandler, P. B. Nalle

SURFACE quarrying at the Crestmore Div. of Riverside Cement Co. in California was started in 1909. In the early 1920&apos;s it was considered that these deposits were nearly exhausted for the equipment available at that time, and in 1927 the company began a block caving system. This mine continued operating until February 1954. In 1941 trucks and crawler-mounted shovels had reached a stage of development that permitted reopening the quarries in conjunction with the underground mine. In 1948 surface reserves and the well developed limestone of the caving system neared depletion. To go deeper with the caving system was unattractive because of the economics, changes in physical structure of the rock at depth, and the perched water table

Jan 4, 1957

By John P. Weir

Coal&apos;s participation in the domestic energy market depends to a very large extent upon the cost of coal delivered to consumers. Today the principal use of coal in the U.S. is in steam-electric generating stations. Generally, it is the delivered cost per million Btu&apos;s that is given the greatest weight in choosing either oil, natural gas or coal as the fuel used in these power plants. There are three major cost components of generating electric energy in steam-electric plants. These expenses expressed in terms of "dollars per kilowatt year" are: (1) operation and maintenance of necessary facilities, (2) fixed charges of necessary capital investment, and (3) fuel. For a modern large plant, the first two items would be approximately as follows:

Jan 9, 1962

By John A. Bonucci

AMAX Base Metals R&D, Inc. has developed technology for extracting and recovering platinum and palladium from spent automobile exhaust emission control catalyst. Our most promising route is a chloride-based hydrometallurgical flowsheet in which catalyst pellets or crushed monoliths are leached in HC1 with an oxidant at 95°C without agitation. Alumina co-dissolution can be limited by thermal pre-treatment of the catalyst. The leach solutions are treated by one of several precious metals recovery techniques to produce a high grade PGM concentrate. For the new generation of three-way catalytic converters which contain rhodium, an H2S04 preleach could selectively extract much of the rhodium while leaving the platinum and palladium behind. Capital and operating costs will be discussed.

Jan 1, 1984

By AIME AIME

THOUGH Frank Wardlaw was born in the East- at Schroon Lake, N. Y., on July 14, 1887-and was educated in New York City-Columbia, E.M., 1916 he has spent his entire professional life in the West, and is still there, as assistant general manager of the Inspiration Consolidated Copper Co., in Arizona. His first jobs were as miner and surveyor for the Utah Consolidated Mining Co., at Bingham, where he worked under A. S. Winther, now general manager of Inspiration&apos;s adjoining big neighbor, the Miami Copper Co. After rising to the position of chief engineer and geologist, Mr. Ward- law left Utah Consolidated to go to Chile for two years with the Braden Copper Co. Then he returned to his

Jan 1, 1940

By AIME AIME

JOHN ROY THOENEN, supervising engineer of the non-metal mining section of the U. S. Bureau of Mines, was one of the founding fathers of the Industrial Minerals Division. For the first three years of its existence, through 1937, he was its Secretary-Treasurer, and during 1938 serves as its Chairman. Jack was born in Ithaca, Mich., No\,. 8, 1886, attended high school at the Soo, and then spent a year and a half at Michigan State. Apparently this was when the mining bug bit him, for he set out for the Michigan College of Mines. After leaving Houghton in 1907 he tried the motion? picture business for a year and had he stuck to it might have been living in a Hollywood palace by now.

Jan 1, 1938

* A demonstration pipeline for transporting coal will be constructed by Pittsburgh Consolidation Coal Co, at the Georgetown strip-mining operation near Cadiz, Ohio, The 12-in., 17,000-ft line, special crushing and preparation equipment, and pumps especially designed for the operation will cost about $550,000. A slurry of fine coal and water will be fed into the line and moved through it under pressure. * Sulphur resources in the U.S. are being rapidly exhausted with no new major deposits being found, This common mineral may become one of the most strategic items during the next five years. Recovery of sulphur from pyrites is being considered in case of an emergency. Already the British have adopted stringent measures to conserve sulphur supplies.

Jan 3, 1951

THOSE MARKED THUS * ARE MEMBERS, MARKED THUS t ARE ASSOCIATES THESE SIGNS DOUBLED INDICATE LIFE MEMBERS AND ASSOCIATES RESPECTIVELY THE FIGURES AT THE END OF THE ADDRESS INDICATE THE YEAR OF ELECTION HEAVY FACED TYPE SIGNIFIES HONORARY MEMBERSHIP ` *AARONS, JULIAN B , Mine Supt, The Boulder Deep Levels, Ltd , Boulder, Western Australia, &apos;05 *ABADIE, EMILE R, Cons and Min Engr, 1004 James Flood Bldg, San Francisco, Cal &apos;76 *ABBE, CLEVELAND, JR, GeOl Aid, U S Geological Survey, Washington, D C &apos;00 *ABBOTT, AI ARTHUR, Cerro de Pasco Mining CO , Cerro de Pasco, Peru, So America &apos;95 *ABBOTT, ARTHUR V , Electrical Engr , Westinghouse, Church, Kerr & CO , 8 Bridge St, New York, N Y &apos;82 *ABBOTT, CLARENCE E, Chief Min Engr, Care Fayal Mine, Eveleth, Minn &apos;04

Jan 1, 1910

By William S. Springer

A NEW preparation plant has been put in operation to treat coal from the recently opened Concord mine, located about 15 miles west of Birmingham, Ala., by the Tennessee Coal, Iron & Railroad Co., a U. S. Steel subsidiary. The mine produces metallurgical grade coking coal from the American seam for use as coke in the company&apos;s blast furnaces at the Fairfield and Enseley works. The capacity of the operation is 1000 tons of run-of-mine per hr, approximately half of which is delivered to the by-product coke plant at Fairfield after beneficiation to metallurgical grade. The remaining portion of the mine run is rock and refuse removed during preparation. No boiler coal or other fuels are produced by this mine.

Jan 12, 1950

By M. H. Caron

D. C. Ralston—The fact that none of the organizations that have worked on these ammoniacal leaching processes have contributed discussion of Mr. Caron&apos;s papers today is a matter of some disappointment. Adaptations, modifications and improvements have been made by several organizations or individuals and to complete the record I want to document a number of them. The Nicaro Nickel Co. operated a Government owned plant at Nicaro, Oriente, Cuba, during the past war. A report on the project was written for Reconstruction Finance Corp. and is in the document file collected by the Office of Technical Services, Commerce Department and filed with the Library of Congress, where it can be consulted or bibliofilm or photostat copies obtained by asking for copies of PB 97271. Nicaro Nickel Co. has obtained a series of U.S. Patents, my list (probably incomplete) of which bears the following numbers: 2,400,098; 2,400,114; 2,400,115; 2,400,461; 2,400,612; 2,458,902 and 2,473,795. International Nickel Co. has also studied the problem and U.S. Patent 2,478,942 shows that some of the complications involving occasional low extractions have been unraveled. Forward, Samis, and Kudryk, of the University of British Columbia, have also published a study of copper-nickel sulphide concentrate.&apos; Others are interested and it is evident that this type of hydrometallurgy is likely to find a happy application in the not-too-far distant future. Caron&apos;s two papers practically amount to a summation of his life&apos;s work on the important subject of nickeliferous iron ores and the American Institute of Mining and Metallurgical Engineers is fortunate to have been chosen the medium of publication. M. Rey—The ammonia leaching process has been the subject of certain studies in New Caledonia, but at the present time, the conditions are not very favorable to its adoption. The process is a combination of a thermal and a hydrometallurgical process. As a result, the first costs and the operative costs are rather high. To counteract this unfavorable situation, it would be necessary to make a very high extraction. But unfortunately, the process is delicate and in spite of all of Caron&apos;s valuable work, there are still many unknown factors. It is difficult to obtain regularly a high extraction, exceeding 75 to 80 pct. It would be interesting to have the opinion of Inter-national Nickel on the process and to know what the Dutch are doing in Celebes. M. H. Caron (author&apos;s reply)—I am quite familiar with the different types of nickel and cobalt ores as found on New Caledonia, and it may be pointed out that the Celebes ores are quite the same in their properties. Their behavior when treating the ores by the ammonia-leaching process is also alike and in my opinion, there is no reason why a high extraction of the New Caledonian ores could not be obtained if the process is properly applied. For the sake of completeness I may add that one of my patents has not been discussed in the papers. This patent deals particularly with the treatment of serpentine nickel ores. (Netherlands No. 62693 40a, French No. 965.786 April 21. 1948. and Cuban No. 13.625 Jan. 1950.) O F. A. Forward, C. S. Samis, and V. Kudryk: Trans. Canadian Institute of Mining and Metallurgy. (1948) 151 (Bull. 434) 350-355.

Jan 1, 1951

By D. R. Irving

Prior to this time, ample supplies of high grade mineral fillers, such as clay, have been available close to consuming centers. Now depletion of these accessible deposits, coupled with other factors such as increasing demand due to population expansion and standard of living rise, has made development of upgrading techniques attractive to producers. Various investigations being carried out by the U.S. Bureau of Mines are described. Factors making the development of improved methods for upgrading clays attractive to producers include: depletion of accessible deposits of high-grade clays, rising transportation and labor costs, more exacting specifications, and increased demand resulting from an expanding population and a constantly rising standard of living. Industry recognizes the need for upgrading presently unusable materials and has cooperated with the U.S. Bureau of Mines by providing samples from submarginal deposits and by evaluating the products that USBM upgrades. Following are some examples of recent clay beneficiation work by the Bureau. FIRE CLAY BENEFICIATION At the Rolla Metallurgical Center, Rolla, Mo., the Bureau is conducting research to develop technically and economically feasible mineral-dressing methods to remove quartz, pyrite, and other impurities from submarginal fire clays. The research has been spurred by the growing shortage of high-grade bur-ley, flint, and plastic clays in the Missouri fire-clay district resulting from increased consumption and the low rate of discovery of new deposits of adequate quality. There apparently is ample tonnage of submarginal flint and plastic clays to maintain the industry for many years if such material can be upgraded to commercial quality. Samples have been submitted to USBM by several major producers of refractories, including A. P. Green Fire Brick Co.; Harbison-Walker Refractories Co.; Mexico Refractories Div., Kaiser Aluminum and Chemical Corp.; and Wellsville Fire Brick Co. Research on some samples has been completed and still is in progress on others. The Bureau has found that specimens containing quartz or pyrite in grains coarser than the accompanying clay generally can be upgraded either with a gravity table or hydraulic cyclone. The improvement in quality is notable not only in chemical analysis but in an increase in pyrometric cone equivalent (PCE) of one or more cones. As an example, consider the results attained on a sandy flint—a fine-grained mixture of kaolin and halloysite with quartz and minor quantities of iron and manganese oxides. Chemical analysis was: 35.4 pct alumina (A12O3) and 47.8 pct silica (SiO2). The sample contained 9.2 pct free silica as quartz. The PCE was 33. The sample was crushed to -10-mesh, blunged with water, and then stage-ground to -48-mesh. The ground sample was tabled to yield a clay fraction containing 37.6 pct A12O3, and 45.3 pct SiO2 of which 2.4 pct was free silica. The PCE was 34. Recovery of alumina by this process was 73.6 pct. Concentration of the same clay in the hydraulic cyclone was even more effective in respect to quartz removal. The clay fraction analyzed 38.6 pct A12O3, 45.0 pct SiO2 of which 0.5 pct was free silica as quartz, and had a PCE of 34. Recovery of alumina was 71.9 pct. The hydraulic cyclone was also effective in reducing the pyrite content of a plastic clay which likewise was a mixture of kaolin and halloysite, plus some pyrite, quartz, and carbonaceous material. It analyzed 30.6 pct Al2O3, 52.3 pct SiO2, 2.3 pct Fe2O3, and 0.76 pct S. The sample was blunged and screened through 10-mesh to remove some coarse pyrite, then ground to -65-mesh and cycloned to remove most of the remainder. The final product recovered 81.8 pct of the alumina at a grade of 32.3 pct A12O3, 50.9 pct SiO2, 1.4 pct Fe2O3, and 0.1 pct S. The PCE was 32-1/2, compared with a PCE of 31-1/2 for the crude clay. The fine beneficiated clays, of course, must be pelletized and dried or fired to meet commercial acceptance. This operation has already been solved by industry. Little progress has been made on two remaining problems. One is that of fine-grained impurities, not separable by table or cyclone. Flotation is being investigated to solve this. Although fine pyrite is readily rejected, a satisfactory quartz-clay separation has not been attained. The second problem, a stubborn one, is that of alkali. Samples containing as much as 5 pct potas-

Jan 1, 1961

By J. Philibert, A. G. Guy

Diffusion in the presence of deformation was studied by the method of vacuum dezincification of copper-rich and silver-rich solid solutions containing 7 to 30 pct Zn. The specimens were designed to permit the study of diffusion in separate portions of a given specimen characterized by strain rates ranging from essentially zero to approximately 10 sec-. No effect of deformation on diffusion was observed. BEGINNING with the work of Buffington and Cohen: interest in the question of the effect of stress or strain on diffusion has largely been concentrated on the enhancement of diffusion in specimens subjected to Continuous plastic deformation. The present research is a contribution to this limited area. However, as a preliminary to focusing attention on this special topic, it will be desirable to make a broad survey of the larger question, especially since there has been considerable foreign work in areas outside those of current interest in the United States. Since most of the topics referred to in the following section are both complex and imperfectly understood at present, it has been expedient in most instances to offer only a guide to the general nature of the work rather than a critical evaluation. PREVIOUS WORK The effect of elastic stress on diffusion has received considerable attention, especially with regard to the thermodynamic driving force for diffusion. The thermodynamic treatments have been based on the work of Gibb, Voigt, Planck, and Leontovich.&apos; Konobeevskii and Selisski6 made a first attempt at treating the problem in 1933, and Gorskii7 a few years later gave a solution applicable to single crystals as well as to polycrystalline specimens. In 1943 Konobeevski8 published treatments that have been the basis of much Russian work up to the present. For example, Aleksandrov and Lyubov used his work in explaining the velocity of lateral growth of pearlite. Early work in the United States was that of Mooradian and Norton, which showed that lattice distortion tends to be relieved before it can significantly affect the diffusion process. Druyvesteyn and Berghoutl1 observed a slight effect of elastic strain on self-diffusion in copper, while de Kazinczy12 found that both elastic and plastic deformation increased the rate of diffusion of hydrogen in steel. On the other hand, Grimes58 observed no effect of either elastic or plastic straining on the diffusion of hydrogen in nickel. High-frequency alternating stresses have been reported by various investigator s13-l5 to increase the rate of diffusion. A special form of elastic stressing is the imposition of hydrostatic pressure, a condition that is amenable to Conventional thermodvnamic analysis. Most of the experimental results in this area are consistent in showing a slight decrease in diffusion rates at high pressures.16-l8 Although Geguzinl reported a pronounced effect of relatively small pressures, Barnes and Mazey20 failed to Corroborate this finding, while Guy and Spinelli21 advanced an explanation of the phenomenon observed by Geguzin. It has been recognized that the thermodynamic treatment of diffusion phenomena in an arbitrarily stressed body is complicated by the fact that the desired state of quasi-equilibrium of the shear stresses cannot be maintained during a general diffusion process. However, attempts have been made by Meix-ner22-24 and Fasto to treat certain restricted cases, such as relaxation. FastovZ7 has also incorporated the general stress tensor into the thermodynamics of irreversible processes. The lattice strain that accompanies the formation of a solid solution has been the subject of much study,28-s0 and indirectly it has entered into many recent theories of diffusion. However, some Russian investigators31&apos;32 have taken other views of this matter and have predicted large effects on diffusion rates because of concentration stresses.o In completing this brief resume of previous work involving elastic strains and before proceeding to a consideration of the effect of continuous plastic deformation, it should be pointed out that deformation of various additional types may also influence diffusion. The effect of cold-working on subsequent diffusion has been studied directly by AndreevaS and by Schumann and Erdmann-Jesnitzer, while indirect evidence has been obtained by Miller and Guarnieri and by Vitman.38 Thermal stresses may also influence diffusion, contributions to this subject having been made by Fastovs7 and by Aleksandrov and Lyubv. The work of Johnson and Martin,o Dienes and Damask,3Band DamaskS considered the question of radiation-enhanced diffusion. In considering previous work on the subject of plastic deformation and diffusion, attention will be directed to those studies concerned primarily with diffusion rather than with its relation to Creep, e.g., the work of Dorn, or to the acceleration of diffusion -controlled reactions. Observations of the effect of

Jan 1, 1962

By T. R. Ingraham

The thermal decomposition of cupric sulfate and of cupric oxysulfate has been examined by deter-mining the equilibrium gas pressure generated over each pure compound. The equilibrium data have been used to calculate the thermodynamic properties of both compounds, and the results have been combined with previously published data to establish a predominance-volume diagram for the Cu-S-O system over the normal range of roasting temperature and gas composition used in the treatment of copper minerals. Copper oxysulfate recrystal-lizes at 1100°K with an apparently irreversible en-dothermic heat requirement of 2.9 * 0.3 kcal per mole. WHEN mixed sulfide minerals containing copper are roasted, either of two procedures may be followed, depending on the nature of the other metals. In the first procedure, the roasting is controlled to produce a maximum amount of water-soluble copper sulfate which may be removed selectively from the water-insoluble compounds of the other metals. In the second, control is directed toward the production of water-soluble sulfates of the other metals and an insoluble salt of copper. Effective control of either of these processes would be enhanced by knowledge of the thermal stability of cupric sulfate and of cupric oxysulfate. In this paper, established data for the thermal stability of cuprous and cupric sulfide and of cuprous and cupric oxide will be combined with new data for the therma1 stability of cupric sulfate and cupric oxysulfate, to designate the volumes of stability of the significant compounds in the Cu-S-O system in the temperature range 750° to 950°K. EXPERIMENTAL Materials, Apparatus, and Procedure. The copper source material used in all experiments was Fisher Certified Reagent Grade "anhydrous" cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared from the normal sulfate by two procedures. In the first, equimolar quantities of cupric oxide (prepared by decomposition of the sulfate) and cupric sulfate were ground together and heated under vacuum in a sealed silica vessel at 800°C. This procedure was subject to failure because of explosion of the silica vessels due to the pressure of the final traces of water released from the sulfate on the initiation of its decomposition. The second procedure involved roasting the cupric sulfate, with frequent rabbling, in a muffle furnace at 725°C for a period of 48 hr. This produced an excellent product, which was confirmed as copper oxysulfate by X-ray and chemical analyses. The experimental technique used was that of measuring the total pressure exerted by the sulfur trioxide, sulfur dioxide, and oxygen produced by the following reactions: 2 CuS04 = cuo • CuSO4 + SO3 [1] cuo . CuSO4 = 2 cuo + SO3 [2] SO3= SO2 + 1/2 O2 [3] The apparatus used in the experiments has been described previously.1-3 Its main feature of a U-tube mercury manometer in which the mercury is protected from corrosion by enclosure in a flexible Pyrex bellows. Before beginning a run, the interior of the apparatus, including the bellows-manometer and all connecting tubing, was thoroughly washed with hydrochloric acid and distilled water to remove any

Jan 1, 1965