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By A. G. Guy

In a special type of electrodiffusion experiment the entire specimen is at constant temperature. The vacancies are then created at one end of the specimen and flow to the other end where they are destroyed. The energy required to operate the corresponding sources and sinks results in a super saturation of vacancies at one end of the specimen and an under -saturation at the other end. This gradient in vacancy concentration produces a chemical-diffusion flux, J(D), of vacancies in addition to the flux, J(E), caused by the electric current. Using the experimental data of Ch. Herzig,5 it is shown that a super saturation of 1 pct can cause J(D) to be about 25 pct of J(E), and thus account for the anomalous behavior of short specimens. THERE are advantages in a phenomenological treatment as contrasted to an atomistic one. For example, there are many reactions involving the element copper that are quantitatively and usefully understood from a phenomenological viewpoint, even though electron theory is not yet able to predict whether copper should be fcc or cph.' Similarly, the lack of a complete atomic theory of vacancies need not prevent the development of a treatment based on thermodynamics and chemical kinetics. In the following discussion, models will be used for the vacancies and for the mechanisms by which they move or are created or destroyed, but the phenomenological treatments are not dependent on the details of these models. The important product of a phenomenological analysis is an equation that describes the relation among the measurable quantities determining the behavior of the system. Based on such an equation, experiments can be performed to study these quantities in detail. Eventually atomic theory will supply an adequate theoretical base for the phenomena in question. A chemical species whose chemical potential was invariant during reactions in binary and ternary systems of varying composition would indeed be an anomaly. Yet this is the role that has frequently been assigned to the vacancies in pure metals, in dilute solutions, and even in ordinary alloys. The weight of available evidence supports the view that supersatu-rations of vacancies are on the order of 1 pct in usual diffusion processes.' Although it may seem strange that such a small deviation from equilibrium could significantly affect the thermodynamic properties of the vacancies, it is well known that the driving force for an ordinary chemical reaction is the departure of the components from their equilibrium state. Similarly, the reaction of vacancies that results in the formation of pores in various types of diffusion3 can reasonably be attributed to the supersaturation of vacancies. In the present paper, it will be shown that small degrees of supersaturation can significantly affect the kinetics of the diffusion process itself. ISOTHERMAL ELECTRODIFFUSION Two different experimental techniques are convenient for studying the behavior of vacancies in a pure metal in the presence of an electric field. Gilder and Lazarus4 studied self-electrodiffusion in a gold specimen in which only the central portion was at high temperatures. In this case the significant vacancy sources operate inside the specimen in the presence of a temperature gradient. In the laboratory of Th. Heumann a method has been devised for studying self-electrodiffusion at constant temperature.5 In principle, there is then no effect of thermodiffusion. It will now be shown why in this case the significant ATungsten disks \^^ ^^ ^Gold disks^^ ^^"T>.... "TTZA ? Up Iy'7 markers ///// ////// initial plane p I y/y/y of joining \I 7//// V7//A_________I_________V//// -I 0 +I Distance from center of specimen (a) -— Direction of flow of electrons —Direction of flw of vacancies %yy} Matano I z~irkendall /%W, vy/A inlerfacej "interface ///// -} HfiK- +/ 0 Distance from center of specimen (6) Fig. 1—-Schematic illustration of the essential features of isothermal self-electrodiffusion. (a) Initial condition of specimen. (b) Condition of specimen after electrodiffusion.

Jan 1, 1970

By J. W. Leomrd, B. A. Donahue

Results of research are presented examining the extent to which the analytical characteristics of the relatively distinct coal bands from a variety of coal seams can be related to each other. This paper dis-cusses an approach for developing a practical coal petrographic quality control program based on conventional analyses, most of which is part of the standard A.S.T.M. procedure. The work is a final follow-up to Part I of this series which was prepared by the authors as an approach to applying conventional coal petrography to single coal seams. Recent published work by the authors entitled Petrography for Coal Mining and Coal Prepration: Part I dealt with interrelating various chemical and physical properties of coal1 measured using conventional analyses made on distinct petrographic bands taken from single coal seams. Since most coal production facilities process coal from a single coal seam or from very closely related coal seams in the same area,2 emphasis on interrelating the properties within a single seam appeared appropriate. The distinct petrographic bands were analyzed on the assumption that such differentiated data would be more representative of a heterogeneous coal seam than the single analytical value commonly used to characterize each property of an entire seam.34 Effort was directed at demonstrating the extent to which the interrelated chemical and physical properties 5,6 could be developed into nomographs or petrographic standardization graphs. Thus, one analysis, determined on a series of petrographic fractions separated from a single sample, was used to estimate numerous other properties in each fraction by referring to the previously established petrographic standardization graphs. This conventional approach to coal petrography was undertaken as a suggested feasible means by which a few coal analyses could be employed to develope a more penetrating knowledge of the properties of coal from any given seam in order to monitor more extensively its performance at the point of utilization. Such procedures can support development of the type of in- formation commonly sought through automated testing and through the use of computers.7 The broad knowledge which can be developed through these procedures is intended for application in the generation of an analytical profile or broad characterization of coal. These estimates were not intended as replacements for individual coal analytical tests. In this expanded second part of the research program, distinct petrographic bands from nine coal seams in the Central Appalachian Region were physically and chemically analyzed to elucidate the extent to which this concept of conventional petrography could be broadened for application to numerous coal seams. In presenting this second phase of work, the relationships developed are presented individually and not in a connecting series of nomographs or petrographic standardization graphs as in the previous work, thus leaving open the combinations of possibilities to individual interpretation and application. MATERIAL AND EXPERIMENTAL WORK Nine coal seams, representing a wide range of rank, from the Central Appalachian coal fields were used in this study. The distinct petrographic bands from the Kittanning, Pond Creek, Jawbone, Tiller, Poca-hontas No. 3, No. 2 Gas, Eagle, Winifrede, and Pittsburgh coal seams were separated by carefully removing a portion of each band at the face of the seam. The following were determined: ash, sulfur, free swelling index, heating value, bulk specific gravity, volatile matter, Hardgrove Grindability Index, and Gieseler Plastometer measurements. Determinations, where procedures were available, were carried out using ASTM standard procedures.8 Bulk specific gravity was determined using a kerosene volume displacement procedure modified from a method applied by Headlee and McClelland of the West Virginia Geological survey,9 Those bands with a bulk specific gravity greater than 1.60, which is generally above the practical specific gravity cleaning range of bituminous coals, were excluded and no analyses were performed. Much of the initial organization of this second phase of work was developed through the extensive use of a computerized statistical monitoring program (see Ref. 4). However, in order to achieve the closest possible interpretation of results, the final organization of data proceeded mainly from exhaustive trial

Jan 1, 1968

By E. Miller, N. Chou, K. Komarek

The solid solubilities of the compounds PbS, PbSe, and PbTe have been determined by equilibrating single crystals with two phase alloys. The solubilities were determined by measuring the Hall coefficient of the equilibrated samples. The observed maximum deviations from stoichiometry on the lead rich and the chalcogen-rich side of the phase fields were: at. pct excess Pb at pct excess S at 850°C; PbSe--4 x 10'" at. pct excess Pb at at. pct excess at 800°C; and PbTe-2.8 x 10 4 at. pct excess Pb at 780°C, 10"1 at. pct excess Te at 720°C. The previously developed theory of retrograde solubility has been expanded to include intrinsic disorder in the compounds, and the experimental results are in agreement with the theory. THE solid solubility limits of intermetallic semiconducting compounds are of considerable interest, since many of these compounds have potential use as thermoelements in thermoelectric devices, as infrared detectors, or in semiconductor devices. The solidus curves of a significant number of these compounds have been reported to be retrograde with the maximum solid solubility occurring between the eu-tectic and the maximum melting temperatures. In a previous paper,' equations were derived which permit calculation of the maximum solid solubility of an AB compound exhibiting retrograde solubility. Derivation of these equations was based on the assumption that the compound is a nondegenerate semiconductor at the temperature under consideration, that the defects were unassociated, and that the vibrational contribution to the entropy of the compound could be evaluated by the Einstein approximation. It was shown that at the temperature of the maximum solid solubility The entropy term ASS is composed of the entropy of formation of the solid stoichiometric compound (AS$)*, and the entropy due to deviations from stoichiometric composition which is the sum of a con-figurational term (aS*), a vibrational term (AS,), and an electronic term (AS,). In the previous paper the positional entropy was evaluated considering the con- N. CHOU, Member AIME, formerly Graduate Student, New York University, N. Y., is with IBM, Yorktown Heights, N. Y. K. L. KOMAREK, Member AIME, formerly with New York University, is Professor, Department of Inorganic Chemistry, University of Vienna, Vienna, Austria. E. MI LLER, Member AIME, formerly with New York University, is Associate Professor of Mechanical Engineering, California State College at Long Beach, Calif. The paper is based on a thesis submitted by N. CHOU to the Graduate Division, School of Engineering and Science, New York University, in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Materials Science. tributions from defects arising from deviations from stoichiometric composition. The derivation is generalized in the appendix to include intrinsic disorder. The electronic entropy term is also recalculated in the appendix. Of the various semiconducting compounds, the solidus curves of Pbs,' and ~b~e,~ have been most extensively studied. The solidus of PbSe has also been determined, but the temperature of maximum solubility has not been accurately established.5129 The present investigation was undertaken to compare the experimental solid solubility data for these systems with the values predicted theoretically. Since the temperature and composition of the maximum solubility of PbSe has not been accurately determined, experimental emphasis was placed on determining the solidus curves for PbSe in the region of maximum solubility, although experiments were also performed on PbS and PbTe at several temperatures. X-ray diffraction studies were also made on carefully prepared powder samples of PbSe to determine the variation of lattice parameter with composition. EXPERIMENTAL PROCEDURE The procedure of Brebrick and Allgaier was employed for determining the solidus data. Monocrystal-

Jan 1, 1970

By Frederick L. Knouse

The south border of Espirito Santo begins about 400 km. north of Rio de Janeiro and extends along the Atlantic Coast northward some 325 km. and inland 100 to 150 km. The area under consideration, where quartz crystal of strategic grades has been mined, extends from 19º to 21º and 30º south latitude; and from 40º to 41º and 30º west longitude. This includes the central part of Espirito santo, chiefly south of the Rio Doce from the Atlantic ocean, and west across the border into Minas Gerais near the town of Aimores, in the municipalities of Aimores, Minas Gerais; Baixo Guandu, Santa Teresa, Santa Leopoldina, Colatina, Joao Neiva, Fundao and Domingo Mar-tines, Espirito Santo (Fig. I). During 1943 and the first half of 1944, this region accounted for approximately 3 to 5 per cent of the quartz crystal produced in Brazil. Shipments of crystal have been made chiefly by rail to Rio de Janeiro. This region is serviced by the E. F. Minas-Vitoria and E. F. Leopoldina to Rio de Janeiro through vitoria; and by the E. F. Minas-Vitoria and E. F. Centra] do Brasil through Bello Horizonte, Minas Gerais to Rio de Janeiro. The major deposits are accessible from the railheads by dirt roads, some being 5 to 30 km. off the road, reached by trail. In 1943 and the first half of 1944, the bulk of the production was from inter- mountain marshes and adjoining hillside alluvial placer deposits in the zone surrounding the town of Santa Teresa. Most of these deposits were formed from the erosion of pegmatite~, quartz veins and pockets in the gneiss, with minor quantities produced from miarolitic cavity fillings in the granitic rock. Early Operations Mining of quartz crystal in this region began in 1928 and has been stimulated by the market demand for military uses. Before 1936 little attention was given to it, either in Espirito Santo or eastern Minas Gerais. From 1936 to 1941 the Japanese sent agents to various points of production or potential production to acquire quartz through purchase. They bought crysta1 as small as 10 grams. Since '94' only the United States and Great Britain have received quartz from Brazil. The United States purchases crystals of 100 grams and larger for strategic purposes. The first known discoveries were made either in the municipalities of Aimores, Minas Gerais, or in Baixo Guandu, 01 Domingos Martines, Espirito Santo. Marketable quartz crysta1 was first found either in the massive quartz replacement veins of the Victor Hugo mine in the municipality of Domingo Martines, or in the large 'ores of quartz in the pegmatites near Baixo Guandu, extending into Minas Gerais. Production The production of quartz in Espirito Santo from 1936 through 1941 as recorded

Jan 1, 1948

By A. G. Roach

This paper deals with a plant built under joint agreement between the Canadian and United States Governments to supply the strategic mineral, corundum, at a time when African production was dwindling and war demands still increasing. The operation began in September 1944, retreating the tailings from a former mill by gravity methods, and is still in production (Sept. 1946). In 1942, when it became apparent that South African production would be insufficient to meet mounting wartime requirements of corundum, a survey was made of Canadian sources of the mineral, at the request of the Foreign Economic Administration of the U. S. Government. The investigation' indicated that the quickest and cheapest supply would be obtained by reworking the tailings deposit at Craig-mont, Ontario. Sampling of the dump by Canadian Government engineers revealed that 125,000 tons of tailings, averaging 2.96 pct corundum, was available for retreat-ment. Ore-dressing tests on representative samples of the deposit were conducted by the writer in the laboratories of the Industrial Minerals Section of the Department of Mines and Resources at Ottawa; and gravity concentration on tables was indicated as the most suitable method of treatment. Decision to proceed with the project was deferred until May 9, construction was begun on May 18, and tune-up operation of the plant begun on Sept. IS, 1944. Corundum—Its Properties and Uses Corundum is an oxide of aluminum having the formula Al2O3. Its outstanding characteristic is its great hardness; 9 in the Mohs scale. In this respect it is second only to the diamond. It usually occurs in barrel-shaped crystals in nepheline syenites and other feldspathic rocks deficient in silica. It has a specific gravity of 3.95 to 4.1 and is insoluble and infusible. In color it ranges from white, through red and green, to black. Ruby and sapphire are gem varieties of corundum. Corundum is supplied to industry as closely graded grain.= The coarser roducts (10 to 24-mesh) are used largely for snagging wheels in the steel-castings industry, while the finer grades (from 70-mesh down to flours) find a wide application in the polishing of lenses and for other uses in the optical trade. All sizes of corundum grain are in close competition with synthetic abrasives such as carborundum and alundum. In some fields of application the artificial product is superior to the natural grain but not in' all. The shape of the particle and its behavior under conditions of actual use determine its sphere of employment. The United States is the largest 'Onsumer of corundum, annual consumption in peacetime approaching 3000 tons; during the war this figure was roughly doubled. During the years 1902 to 1913, the bulk

Jan 1, 1948

By L. L. Newman

As soon as the Congress recognized the alarming rate at which our domestic oil resources were being depleted during the war, it took action to step up the rate of research and development which the Bureau of Mines had been conducting for several years on the production of synthetic liquid fuels from coals. Under Public Law 290, approved April 5, 1944, funds were authorized for the Bureau to proceed with research, development, design and construction of demonstration plants for the hydrogenation of coal, the synthesis of oil from carbon monoxide and hydrogen, and the distillation of oil from shale. During the latter part of 1944, when it became evident that the collapse of Germany was near, a Technical Oil Mission was organized to study the German techniques of synthetic oil production. Since the cost of hydrogen or synthesis gas is one of the major factors of expense in the operation of hydrogenation or synthesis gas processes, the Bureau of Mines considered it of prime importance to include on the mission gas engineers whose instructions were to examine closely the methods employed by the Germans in solving the problem of providing low-cost hydrogen or synthesis gas for their very extensive operations on synthetic liquid fuels. The Solid Fuels Mission and the Utilities Mission, as well as the Army and Navy Missions, also included teams for the study of German gas production. Although their objectives naturally differed from those of the Technical Oil Mission and from each other, it was recognized that there was considerable overlapping of their fields of investigation. Duplication of effort, however, was largely avoided through the close cooperation between the group leaders of these missions. For example, although I went to Europe as a member of the Technical Oil Mission, my first Gcrman assignment was actually made by Dr. Harry F. Yancey, leader of the Solid Fuels Mission— to investigate the brown-coal gasification methods in central Germany. The art of gasification in the United States and England, and to a large extent in the proximity of the coking-coal regions of Germany and the rest of continental Europe, depends essentially on two stages of operation; namely, carbonization and intermittent water-gas generation. As far as the United States is concerned, complete gasification in a single stage of operation is rarely practiced, except in gas-producer operations where the product is a relatively lean gas consumed close to the point of manufacture, and for water-gas production with anthracite as a generator fuel. Complete gasification of bituminous coal has been the subject of numerous investigations. Many relatively simple modifications of the water-gas generator have been tried to permit the direct gasification of low-cost bituminous coal instead of high-cost coke and anthracite for the production of water gas. Although varying degrees of Success have been achieved and the water gas produced generally has been higher in

Jan 1, 1947

By Nicholas J. Grant, John Chipman

A full understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization;the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag—i.e., equilibrium conditions—and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck:20 V radio = % CaO/%SiO, Körber and Oelsen's _ % CaO'. 100/% CaO + % SiO2 where (%CaO') = % CaO- 1.18% P2O5. Herty's B ratio = % CaO - (0.93 . % SO2) - (1.18% P205) Among others there appear the following: 20 References are at the end of the paper.

Jan 1, 1947

By Charles T. Holland

Miners have observed for many years that as pillars are removed in mining operations the pillar adjacent to those mined out frequently shows evidence of being compressed. Although this has been known for a long time, little or no information is available concerning how far from the mining area the pillars are affected in this manner, or how great is the magnitude of the compression, or concerning the manner or characteristic way in which the compression acts, as the mined-out area approaches the pillar under consideration. The writer made a study of pillar action in the Mona mine of the Arkwright Coal Co., partly to get some quantitative data on the deformation of coal-mine pillars. The study was not completed but it seems best to present the information that was obtained. Method of Measurement Fig. 1 shows the details of the apparatus used for measuring the deformation. This is permanently attached to the pillar. Fig. 2 shows the details of the gauge that records the deformation. This gauge is removable and was used to measure the deformation at all the stations. The recording dial is graduated in thousandths of an inch and records measurements up to one inch. Fig. 3 shows how the removable gauge is placed in the instrument. When installing the instrument in the side of the pillar, all loose coal near by was removed and a trench 4 to 6 in. deep, and approximately 1 ft. wide, was dug in the pillar. In this trench near the top and the floor, the holes holding the instrument were bored. These holes were then partly filled with thin cement and the rods were inserted. The remaining space in the holes was tamped full of cement. At this time, by carefully manipulating the permanent rods and clamps and adjustable pin, it was possible to adjust the instrument so that the removable gauge would stand true and measure any vertical deformation between the top and bottom rods. Fig. 4 is a photograph of one of the instruments installed, showing the removable gauge in place.

Jan 1, 1938

By John L. Lamont, Walter Crafts

STUDIES of the effect of composition of steel on hardenability by Grossmann,1 and as-quenched hardness by Field2 and by the authors,3 have made it possible to predict the results of quenching when the composition and cooling rate are known. In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tempered properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq. in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as- quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content- Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after lie heat-treatment, differ considerably in tensile strength. PROCEDURE In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08-to 0.65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc. The accuracy of the method was finally checked on a variety of carbon, low-alloy and high- alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from ¼ to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability specimens quenched from a normal temperature for austenitization were used to obtain a range of as-quenched Rockwell C

Jan 1, 1946

By G. A. Croes, N. Schwarz

The dimensionless groups, to which the variables that govern the displacement of oil from reservoirs by liquids can be combined, are derived. Three types of displacement are considered, viz. cold-water drive, hot-water drive and solvent injection. The derivation of the dimerzsionless groups is carried out by means of the relevant basic equations (in-spectional analysis). The resulting sets of groups are afterwards completed by means of dimensional analysis. The form of the groups is given in such a way that they can be adapted to suit the various boundary conditions that are encountered in practice. The physical meaning of the groups is discussed. They have all been brought together on a chart, from which their mutual relation and their corresporzdence to related dimensionless groups in common use in other engineering sciences can be read off. The limitations of dimensionally scaled model experiments as a useful tool for studying liquid flow in porous media, as occurring in oil reservoirs, are discussed. The use of models to study fluid mechanics has an appeal for everyone endowed with natural curiosity. What active boy has not played with ship and airplane models, or crude models of dam and drainage systems Even in the most advanced technical engineering, such models play a fundamental and indispensable role. "And yet in few departments of the physical sciences is there a wider gap between theory and practice, between scientific knowledge and the state of art, than in the use of models to study hydrodynamic phenomena." Garrett Birkhoff1 INTRODUCTION Laboratory displacement experiments are extensively used to investigate, directly or indirectly, the production behavior of petroleum reservoirs. Such experiments are representative of the reservoirs as a whole, if they are carried out with models that are "properly scaled." The performance of oil reservoirs is governed by the values of a number of variables, which can be combined to dimensionless groups. Two general methods are available for the derivation of these groups. In the first of these, dimensional analysis, combination of the variables is done essentially by trial and error. Its only premise is knowledge of the complete set of relevant variables. In the second method, inspectional analysis, the dimensional homogeneity of the equations describing the behavior of the system to be studied is used. The resulting dimensionless groups can be divided into: (a) independent (variable) groups, such as dimensionless length, time, etc.; (b) dependent groups, giving the dimensionless form of the variables, such as recovery and pressure, that can, at least in principle, be measured during an experiment; (c) similarity groups, which are independent constant groups, such as ratio of length to height of the reservoir and ratio of

Jan 1, 1957

By W. O. Philbrook, K. Natesan

A mathematical model was derived for the temperature change in a particle undergoing heterogeneous chemical reaction and heal exchange with a stream of fluid. The model has been applied specifically to the exothermic oxidation of spherical particles of zinc sulfide. Very good agreement was obtained between the theoretical prediclion and experimental observation. It was found that at no stage of the reaction was the particle subjected to a state of thermal instability. In studies of gas-solid reactions, it is generally assumed that the gaseous and the solid phases are at the same temperature throughout the reaction period. This is not strictly true since most of the reactions are either exothermic or endothermic in nature. This paper deals only with heterogeneous gas-solid reactions of noncatalytic type. In the case of exothermic reactions (e.g., roasting of sulfides), there may result an increase in temperature of the particle due to the release of the heat of reaction, and this increase in temperature may enhance the reaction rate and thus cause further release of heat. Such a "spiralling" effect may lead to a thermally unstable situation within the particle. On the other hand, in the case of endothermic reactions (e.g., calcination of limestone), there may occur a decrease in temperature of the particle as the reaction proceeds, leading to a virtual "quenching" of the reaction front. A general discussion of autothermic processes with emphasis on properties and reactor design is given by Van Heerden. 1 Levesque and cubicciotti 2 observed self heating of the sample in the oxidation of thorium. Anous et al. 3 observed self cooling of the sample in their dehydration studies on chrome alum. Cannon and Denbigh, 4 and Ong et al.5 reported self heating of the sample in their studies of the kinetics of oxidation of zinc sulfide. A typical plot of heat generation and heat loss rates with reaction temperature is shown in Fig. 1.'14 The Sigmoid curve represents the heat generation rate while the straight lines represent the heat loss rate. The main objectives of this analysis are to estimate the temperature increase of a single particle undergoing an exothermic reaction and to study the possibility of a thermally unstable situation within the particle. Also, a study of the dependence of the tempera- ture increase on different process variables has been attempted. A "she ll-by-shell" method has been proposed to analyze the problem. The shells may be made as small as necessary, and equations may be set up for heat transfer by various mechanisms. Such equations will have to be solved for each shell, with the boundary conditions for ith shell being obtained from the (i - 1)th shell, using a high speed digital computer. The oxidation of spherical particles of zinc sulfide is considered for this analysis, but the treatment is general enough to be applicable to other reactions and particle shapes. The oxidation reaction can be written as AH =« -115 kcal/mole ZnS [1] Such a reaction has been found to proceed in a topo-chemical manner; i.e., as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,4-6 that the particle retains its original dimensions. Therefore, at any given time, the particle may be

Jan 1, 1970

By John G. Hall

The pumping operations at the Chief mine have been unique in the respect that for many years the entire flow of water into the mine has been disposed of by pumping into natural underground "caverns" or "sinks." Volumes up to 4000 gpm have been pumped into these caverns with no apparent tendency for the caverns to fill with water, and it has never been proven that any of the water returns to the mine workings. Major pumping operations have been carried on during two periods, the first from 1918 to 1927, and the second from 1942 to the present time. Early Pumping Operations CHIEF MINE The Chief Consolidated Mining Co. was organized in 1909, and for the following nine years ore was developed and mined from the 600 level down to the 1800 level, all above the permanent water table, the 1820 level. The ore occurs as extremely-irregular pipes of replacement ore in limestone, and to date a total of approximately 2 1/2 million tons of ore has been produced. The ore was highly oxidized down to the permanent water level, and some highly-oxidized ore runs occur beneath the permanent water table. In 1916, with extensive mining being done on the 1800 level, 20 ft above the water table, there were indications that a zone of secondary enrichment might exist below the water, and in order to follow the ore runs to greater depth, it was realized that arrangements would have to be Made to pump water to the surface. The original pumping installation was designed to pump 350 gpm in five stages against a 1900-ft head to the surface. By January 1919, the water had been lowered to the 1900 level and an excellent grade of silver-lead ore was being produced from the zone of secondary enrichment. At this point. the flow of water equalled the capacity of the pumps, and pumps of an additional 1000 gpln were installed to supplement the original system. By January 1920, the water had been lowered approximately 100 ft, and the total flow of water was 1000 gpm. The water was being pumped from many different places in the mine where ore was being followed downward, with 27 different pumps operating below the 1800 level, mainly Cameron air-driven sinker pumps. These first sinking pumps were cumbersome and inefficient, and each of the larger pumps weighed approximately three tons and required tremeridous volumes of compressed air. During this period, an exploration drift being extended north and west from the Chief shaft on the 1600 level encountered a large natural cavern some 2000 ft from the shaft. This cavern in places measured 60 ft in diameter. Sometime later the disposing of water into this cavern was suggested, and as an experiment to determine the results of such an operation, an attempt was Made to fill the cavern by pumping in a small volume of water, but the water disappeared as fast as it was discharged into the cavern. It was decided then to try the cavern as a drainage outlet for the entire volume of water being pumped to the surface, and the water apparently did not return to the mine workings. Subsequently water up to 3000 gpm was pumped into this cavern. An attempt was made to determine whether any water was being returned from the cavern to the lower workings, and 100 lb of sodium fluorescein salt was added to the water discharged into the cavern, but no trace of it was found in the drainage water in the mine. Results of another such test will be described later.

Jan 1, 1950

By F. F. Poland

The purpose of this paper is to describe the recent applications and improvements made in the process and equipment for the recovery of metallic zinc from secondary metals by means of high temperature electric resistor furnace distillation. The process and high temperature furnace, as developed by Revere Copper and Brass Incorporated, Research and Development Department, was described in a previous paper. † Since the publication of that paper the process and equipment have been licensed to others. Consequently its field of application has been expanded, particularly for the treatment of scrap brass, galvanizers dross and scrap zinc. Other applications are being considered, particularly the melting of metallic titanium and special alloys requiring a controlled atmosphere. Consideration is also being given to modification in design that would allow the melting of copper cathodes for the production of oxygen-free and electrolytic tough pitch copper shapes without the necessity of blowing and poling. In the design of a furnace for melting copper cathodes it is intended that the fundamental principle of charging the solid material into a large pool of molten metal through a double door charging vestibule as shown in Fig 3 of the previous paper, † would be adhered to and, in addition, either dehydrated and desulphurized producer gas or commercial nitrogen, that is, approximately 96 pct nitrogen, 2 pct hydrogen 2 pct CO, also dehydrated, would be used to provide a protective atmosphere for the resistors and to flush out more soluble gases from the molten copper. The operation of a small unit producing approximately 1000 lb of copper per hr has shown that the commercial nitrogen will allow the production of tough pitch electrolytic copper when the metal is transferred from the meltdown unit contemplated to a special type induction unit where the oxygen absorption and temperature can be controlled. Standard practice in treating low grade scrap brass has been to oxidize the zinc by blowing air through the molten metal. This operation results in the recovery of approximately two-thirds or less of the zinc content of the brass in the form of an impure zinc oxide having only a fraction of the value of the zinc in metallic form. The balance of the zinc is lost to slag, fume and drosses. Fig 1 shows the revised flow sheet of the process for the treatment of scrap brass. For this application and as shown on the flow sheet a low frequency induction furnace has been substituted for the Wilkins-Poland type as a melting unit. This type of furnace has been found the most suitable for the purpose as will be shown by the following discussion. Serap Brass The melting of refinery scrap brass preparatory to distillation presents a melting problem quite different from the usual melting of brass mill scrap for recasting because refinery scrap is a heterogeneous mixture of alloys each having different melting and boiling points, and coated with a variety of corrosion products and foreign materials. In addition, brass and copper plated pieces of sheet iron, stainless steel, ceramic materials, and others are present that do not melt except at temperatures above the boiling point of the liquid bath. In the previous paper it is noted that difficulty was encountered in the melting of refinery grade scrap brass without excessive loss of zinc by volatilization and that 5 to 10 pct razorite flux was used to alleviate this condition. While this flux was successful in preventing the excessive loss of zinc by volatilization it interposed a low heat conductivity layer between the source of heat and liquid charge and resulted in lowering the melting rate of the furnace. This same problem presents itself in all types of furnaces in which the metal is heated by radiation and conduction from above the charge. It has been found in melting this type material that the melting rate per hour or per square foot of hearth area

Jan 1, 1950

By W. L. Phillips

Single crystals of aluminum, brass, and copper oriented for (100) and (110) slip were extended at 25°, 400°, and 600°C in simple shear. Aluminum specimens oriented for nonoctahedral slip began to shear at a higher critical resolved shear stress than specimens oriented for octahedral slip. Parabolic stress-strain curves were obtained from zero strain. The initial rate of parabolic hardening was lower for specimens sheared on the (100) plane in a close-packed direction <110>, than for specimens sheared in a nonclose-packed direction <100>. metallographic evidence, however, showed that all slip traces could be explained in terms of (111) <100> slip. All attempts to cause nonoctahedral slip in copper and 70-30 a-brass single crystals were unsuccessful. Instead of shearing, the crystals bent, allowing {111} type planes to come into action. NONOCTAHEDRAL slip in aluminum has been reported under three different conditions: first, as the main mode of slip in tension experiments at elevated temperatures;&apos;-&apos; second, as the main mode of slip in direct shear experiments at room temperat~re; and third, as a minor mode of deformation, i.e., as cross-slip, in tension, shear, and bicrystal experiments at room and elevated temperatures."-l2 However, as far as the author knows, nonoctahedral slip has not been reported in either copper or 70-30 a-brass. The present study was undertaken to determine whether nonoctahedral slip could be obtained in aluminum, brass, or copper at room or elevated temperatures when the shear stress was approximately constant over the cross-section, a maximum at the center, or a maximum at the surface. EXPERIMENTAL PROCEDURE A detailed description of the crystal preparation and shearing apparatus has been given previo~sly. Cylindrical crystals 1/2 in. in diam and 8 in. long were grown from the melt in a temperature-gradient furnace. The aluminum contained 0.001 pct Zn, 0.001 pct S, and 0.001 pct Fe; the 70-30 brass contained 0.015 pct Pb, 0.001 pct Fe, 0.01 pct Ni, 0.02 pct Sn, and 0.005 pct Se; the copper was certified OFHC of 99.98 pct purity. All samples were electropolished prior to testing. The shear apparatus was a modified Bausch type. The strain sensitivity was 4 x lob4 Load was applied by clamping the rods attached to the shear plates in an Instron tensile machine. The rate of loading was 0.02 in. per min. In all cases a 1/8-in. gage length was used. For the tests performed at 400° and 600°C the shear plates, collars, and rods were made of stainless steel. These elevated-temperature tests were performed in an argon atmosphere. A) Aluminum at Room Temperature. Values of a and ß for the various slip planes and slip directions investigated are shown in Table I where a is the complement of the angle between the specimen axis and the slip direction, and ß is the angle between the specimen axis and the normal to the shear plane. The shear stress is a function of a (assuming ß - 0);10 when a is less than 27 deg, the shear stress on the slip plane for which the specimen is oriented has a maximum at the center of the crystal; at a = 27 deg the shear stress is constant across the slip plane; for a greater than 27 deg the shear stress is a minimum at the center. Fig. 1 shows the stress-strain curves for specimens cut from crystals 1, 2, and 5, which were sheared on the (010) plane in the [loll direction at room temperature. These three crystals have shear-stress distributions corresponding to the three dif-

Jan 1, 1962

By definition the word "grout" means a thin mortar, or a kind of plaster or cement, and "grouting" means to fill up or finish with grout. The words "cement," "plaster" and "mortar" mean a substance that is used in a soft state which subsequently hardens. Thus, grouting is the filling of void space with a substance that hardens. Construction cements are the most common substances used, either by themselves or in mixtures, but the term grouting is applied quite correctly when other substances such as plastics and certain chemicals are used. Also, the use of the term grouting to cover the filling of voids with materials that do not actually become hard, such as the flotation tailings used in grouting in the southeast Missouri lead district, should be considered correct, as some stiffening does take place and, anyway, it is a better descriptive term than any substitute. Engineers are interested in grouting because some of the materials with which they must work contain voids, and certain conditions can be improved if these voids can be filled with something solid and permanent. Grouting is done to accomplish several purposes: I. To stop the passage of fluids and gases, 2. To cement materials together to make them stronger, and 3. To prevent consolidation of materials by filling void space with something solid as a replacement for the air and water that could be forced out under load. The construction industry uses grouting extensively for all three purposes. Grouting is used to stop water percolation under and around dams. It is used to control water flow in tunnel driving and in shaft sinking. It is used to improve foundation conditions under civil engineering structures by permanently filling void space and thereby reducing settlement, or by cementing broken rock together and increasing its supporting strength. The oil and gas industry does a lot of grouting, primarily to stop the passage of gases and fluids. The search for oil at increasingly greater depths has meant greater investment per well, and the oil industry has spent large sums on development of improved drilling methods. This

Jan 1, 1949

By Carl H. Samans, Charles R. Austin

In an earlier serics of studies on 18-8 stainless steel at 600º, 700º, and 800ºC.l one pretreatment was used throughout; viz., 15 min. in hydrogen at 950°C., followed by an air quench. Several manufacturers of this alloy since have expressed doubt as to the suitability of the temperature employed, recommending instead the more customary Strauss treatment as promising superior results. In this subsequent investigation on the effects of the temperature of pretreatment several interesting points have arisen, which are described in this paper. Previous work on our equipment had shown a marked difference between alloys of "similar chemical composition" that had been manufactured by different companies. Accordingly, one mill-bar length was selected from which to prepare all specimens. It could then be assumed that any marked differences in creep characteristics would be due to effects resulting from variations in the pretreatment of the alloy. The material was furnished by the Allegheny-Ludlum Steel Co. in the form of 5/16-in. dia. rod, finished by air cooling from a mill anneal at 1950°F. (1066°C.). It was analyzed only for the elements shown: carbon, 0.07 per cent; chromium, 18.73; nickel, 9.46; manganese, 0.40. Three pretreating temperatures were chosen, the specimens being held for 15 min. in hydrogen at either: (1) 1150°C., to conform to the recommended Strauss treatment; (2) 950°C., to compare with the results of previous tests; or (3) 75Q°C., to initiate precipitation of carbides in the material before testing. As the test cross sections were only 1/8-in. dia., air cooling followed the annealing treatment. These treatments permitted two direct comparisons: (1) between the 1150" and 950°C. treatments to indicate the effect of grain size when all carbides were probably in solution at the start of the test; and (2) between the 950" and 750°C. treatments to indicate the effect of carbide "nucleation" for similar grain sizes.

Jan 1, 1940

By T. L. Joseph

Blast furnaces are most efficient thermally when the CO2 in the top gas is highest. Oxygen introduced in the air blast is converted to CO in the combustion zones. The extent to which CO, generated in front of the tuyeres, is converted later to CO2 depends upon the ratio of ore to coke in the charge and the degree to which CO2, formed by reduction of iron oxides with CO, reverts to CO by the secondary reaction C + CO2 = 2CO. About 300 to 400 lb. of carbon&apos; per ton of pig iron is normally involved in the solution-loss reaction or direct reduction of FeO with carbon, which produces the same over-all results; that is, lower CO2 in the top gas. Rich2 has recently reported a reduction in fuel consumption at slower rates of blowing on two furnaces in spite of higher heat losses per ton of iron. Lower fuel consumption at slow operating rates was due to more complete reduction of the ore that resulted in higher CO2 in the top gas and consequently more efficient use of carbon. Kinney3 has reported substantial savings in fuel as a result of crushing and sizing the ore charge. Improvements in practice brought about by sintering magnetite concentrates, flue dust and fine ores have been due to the establishment of conditions favoring more complete reduction of the ore in the upper part of the furnace. The extent to which oxides and fluctuations in composition in pig iron affect the quality of steel and finished product needs further study. There is evidence that more thorough preheating and reduction of the ore in the upper part of the furnace tend to give a better quality of iron. Bogatzkii4 found from laboratory work that the amount of oxygen entering electrolytic iron, melted under various slags, was directly proportional to the concentration of free FeO in the slag and inversely proportional to the basicity of the slag. Herty and Gaines5 concluded that the silicate content of open-hearth steel before deoxidation is related to the concentration of silica in the pig-iron charge, indicating that most of the persistent inclusions are silica from the iron. They also found that

Jan 1, 1936

By Edwin F. Brush, John Chipman

Published data on the activity of carbon in binary and ternary austenite at 1000°C are reviewed. The composition variables are . The coefficient, Vj, has the value for substitutional elements but may be assigned a ualue -1 for silicon to effect a simplification on the mathematical treatment. The activity coefficient PC = is obtained from gas equilibrium data. For the ternary systems studied the Henrian activity coefficient is given by the expression: The principle advantage in cornparison with the analogous expression in terms of atom fractions is found in the fact that for most systems the final term and in many the last two terms are zero. Values of the interaction parameters are tabulated and the graphical comparison of the equation with experirt~ental data is sho,wn in several figures. The thermodynamic properties of the solid solution, austenite, are of considerable importance in the heat-treatment of alloy steels and in other aspects of ferrous metallurgy. Early studies embodied in the Fe-C diagram have been extended to include other binary and some ternary diagrams. Our best hope of obtaining a useful thermodynamic treatment of reactions in complex alloy steels will not be found in quaternary and quinternary phase diagrams but in determinations of activities and interaction relations among the several solute elements. The foundation for such a development was laid by smith&apos; in his early studies of the activity of carbon in Fe-C alloys and his subsequent work on Fe-C-Si, Fe-C-Mn, Fe-C-Ni, and Fe-C-Co solid solutions.2"4 Other observers have also made noteworthy contributions and these will be discussed and correlated here in the light of a somewhat simplified mathematical treatment of solute interactions. Fe-C AT 1000°C In a recent review of the thermodynamic properties of binary Fe-C austenite it was shown that the simple mathematical treatment employed by smith&apos; was capable of describing all the published results on this solution. The treatment utilizes the atom ratio, yc = nC/nF,, rather than the atom fraction. The activity of carbon is proportional to the equilibrium gas ratio, either measured on a scalk in which the activity of graphite is taken as unity or, alternatively, aC may be set equal to yc at infinite dilution. In either case the ratio aC/y = (PC, the activity coefficient. It was found that the experimental data of smith1 and those of Diin-wald and wagner; Bungardt, Preisendanz, and Lehn-ert,&apos; and Scheil, Schmidt, and Wiinnings at temperatures of 800" to 1200° C as well as reliable data on the solubilities of graphite and cementite could be represented by the equation for which graphite is the standard state: The data on alloyed austenite have been obtained at 1000°C. For this temperature, the "Henrian" activity coefficient (which is unity at infinite dilution) is: FOr an interstitial solute such as carbon in austenite it has been shown by statistical mechanicsg that the activity in the infinitely dilute solution is proportional to the ratio of the number of lattice sites occupied by carbon to the number of yet unfilled lattice sites. A variable zz proportional to this ratio serves as a useful measure of concentration:" in which b is the number of lattice sites provided by each atom of solvent; in austenite b = 1. The Henrian activity approaches zz at infinite dilution and the ratio a is the activity coefficient. The effect of a change in concentration is then given by: It has been shown further that in some systems the derivative in Eq. [4] remains constant over a wide range of concentrations. In such a case second-order terms become negligible and the Henrian activity coefficients is:

Jan 1, 1969

By G. R. Fitterer

Trends in slag composition in acid open hearth practice, particularly the variation in iron and manganese oxides during refining, are reviewed. A procedure which is currently being used to control the refining reactions is described and partially explained through slag phase diagram considerations. In addition, the ionic nature of these slags is considered and it is proposed that silica combines with the oxide ion and forms a series of complex silicate ions. The effect of basic oxides such as FeO, MnO, and CaO is apparently additive in furnishing the oxide ion for this purpose. IT is now possible to control192 the refining of steel in an acid open hearth furnace to a surprising degree. This control has been brought about through the knowledge and use of several facts and tests. These are: 1—A planned charge analysis based on a knowledge of the type of fuel, the bath depth, etc. 2—Knowledge and control of rate of fuel input as well as its method of atomization, if any. 3—Determination of the slag fluidity. 4—Bath temperatures (use of the Pt-Pt-Rh thermocouple). 5—Periodic determination of carbon content (use of the Carb-analyzer or Carbometer). Through the use of these control methods, a heat may be made to "melt-in" with or without residual manganese and silicon. The rate of refining or carbon elimination may be controlled accurately, and the desired tapping (or "go-ahead") carbon may be approached at a rapid or slow rate according to preference and type of steel being made. Thus operating time may be predetermined and greatly reduced. Further, all of the refining can be done without any ore or other oxidizing additions, and the heat may be brought to the desired tapping temperature simultaneously with the attainment of the desired carbon analysis. This control procedure is being used in most acid plants in the United States today and has been de- scribed.&apos;, &apos; Although the slag metal relations are sufficiently well known to control the heat as stated, yet it is possible to account for only about two-thirds&apos; of the 0, which must have been used for the elimination of the carbon and other metalloids. Phase diagram studies&apos; of the slags, slag weights, the metal particle theory,&apos; ore additions, limestone additions, etc., may all be taken into consideration; yet, the mechanism of oxidation and source of all the oxygen remain to be explained. This paper reviews some of the principles upon which the control methods were based and proposes other possibilities regarding the unexplained phenomena. Old and New Acid Open Hearth Practice Some of the recent statements in the literature regarding acid open hearth operation are based on old heat data which are not typical of modern American practice. These old heat logs have been responsible for many misconceptions regarding the acid hearth practice and represent heats which do not coincide with modern methods. In recent years, American practice has been altered materially and these changes will be briefly described. Modern American Practice: A typical log of a modern American acid open hearth heat&apos; is shown in Fig. 1 which indicates that the refining time was only two hours, during which the carbon was eliminated rapidly and the bath temperature increased at a fast rate. The manganese and silicon contents of the metal were essentially eliminated and their oxides had become constituent parts of the slag at the "melt-down" period. During the course of the heat, the MnO content of the slag remained practi-

Jan 1, 1954

By William J. Potter, Roger N. Pyle

Introduction The primary ingredient for survival of mining companies during a recessionary period is to be innovative and resourceful in the structuring and financing of operations. Over the past decade, many mining companies have had to retrench and restructure their operations and to redeploy their assets just to survive. During the same period, traditional sources of financing for mining companies -- commercial banks, subsidized export credit loans and long term straight debt financing in the public markets -- became less available and more expensive. Meanwhile, new markets and new financing instruments provided new alternatives for mining companies. Those companies which exploited these alternatives greatly enhanced their capacity for survival and even for profitability. This article considers the strategies adopted by some companies to adapt to changes in this recessionary environment; the inadequacy of traditional sources of financing; certain of the new financing instruments, structures and markets which have become available; and how several mining companies have utilized these new instruments, structures and financial markets to improve their competitive positions. THE IMPACT OF RECESSION ON MINING COMPANIES AND TRADITIONAL FINANCING SOURCES In its 1983 year-end article "The New Economic Order" Mining Journal characterized many of the large private sector mining companies with operations in the industrialized countries as being "gripped between the jaws of high working costs and stagnating metal commodity prices." The article went on to characterize the Canadian mining industry in particular as being "in the difficult position of having to seek to sell the bulk of its output in a world market characterized by over-capacity, where production costs were determined by internal political and economic factors while prices were set by external competitive forces of supply and demand." Miners of a wide range of commodities in the industrialized countries have come to realize that their domestic mineral resources are in many cases no longer competitive with global sources of supply. To compete and survive they would have to rely on their technical and financial expertise in mineral exploration and development and in mining and processing. Strategies For Survival Global competition has compelled management in the extractive industries to improve their worldwide cost position. This is the only means whereby a mining company can differentiate its product and attain a substantial competitive advantage. During the past decade, for example, ASARCO Inc. and Inco Ltd. chopped their payrolls, postponed expansion plans and otherwise retrenched. ASARCO reduced its capital expenditures and cash requirements for operations in 1984 to a level almost equal to its internally generated cash. The company&apos;s finances were also strengthened by increasing total lines of credit from outside sources, by selling common stock, and by reducing annual pension funding through a change in actuarial assumptions. Other companies returned to their traditional organizational structure where they had a demonstrated competitive strength. Consolidated Gold Fields, for instance, resumed its operation as a mining finance house. Its capital investment programs are now devoted solely to resource development. In mid-1984, at a time of firming zinc prices, Union Miniere S.A. used the opportunity to integrate its smelting capacity and to direct investment to certain subsidiaries at the expense of less viable operations. Smaller corporations realized that it was not enough just to be the low-cost producer. For example, Drummond Coal Company in Alabama, which dominates its regional market due to its low-costs, has also developed a world-wide trading capability and has placed incremental tonnage from its own mines as well as brokered coal produced by others, thereby minimizing capital risk. In Canada, Campbell Resources has exploited difficult times by acquiring assets cheaply. In the process it improved its capacity to withstand cyclical economic swings by diversifying from solely a copper and gold producer to a company based upon asbestos, coal, copper, gold and natural gas.

Jan 1, 1985