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By G. W. King, A. Bogrow, L. F. Marek

The purpose of this paper is to present the data and some interpretation of the results of a laboratory study of the reduction of iron ore and the deposition of carbon from the reducing gas mixtures in such reductions. One major object of the study was to determine the effect of gas pressures on these chemical processes. Effort was made to approximate the conditions of temperature, gas composition, linear and mass gas velocities, pressure range, and extent of reduction prevailing in commercial blast furnaces. The results show that the reduction of Fe203 proceeds by two steps, largely consecutive under the conditions used herein: reduction of Fe203 to FeO, and reduction of FeO to Fe. Unless the gas has a CO!CO, ratio greater than 2.1 only the first step occurs under these conditions (850°C) but the following generalizations apply to either step or to the combination. The rate of reduction of relatively fine ore particles .at any time is proportional to the mass rate of supply of CO (provided some of it is thermodynamically available): the rate therefore is proportional to the linear velocity at constant pressure, or to the pressure at constant linear velocity. Thus, the rate of reduction may be increased without increase in linear velocity of the reducing gas by increasing the mass velocity of the gas and increasing the pressure correspondingly to avoid any increase in the linear velocity. The rate "constants"—i.e., the efficiency of conversion of the "available" CO supplied— is not actually constant but decreases as the reduction proceeds, and is a function only of the state of the ore; i.e., of the amount of reduction already accomplished and hence of the amount of CO passed. The particle size of ore used in nearly all the experiments was relatively small (8 to 14-mesh). The rate of reduction in run 16 with 3 to 8-mesh ore particles is within experimental error the same as with the finer ore. Although this would indicate an absence of effect due to particle size in this range of ore particles, it is desirable to have more data on other ore sizes and on ore of different densities before arriving at any generalizations on this point. Although it is possible to extend the analysis of these results to consideration of the more detailed kinetics and mechanism of iron oxide reduction, such extension is beyond the scope of the present paper. From the experiments on carbon deposition, it was evident that if carbon deposition is increased at all by the application of pressures up to 10 psi ga., such increase appears to be less than the experimental and analytical error. It appears safe to conclude that at top pressures on the order

Jan 1, 1948

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 L. F. Marek, G. W. King, A. Bogrow

The purpose of this paper is to present the data and some interpretation of the results of a laboratory study of the reduction of iron ore and the deposition of carbon from the reducing gas mixtures in such reductions. One major object of the study was to determine the effect of gas pressures on these chemical processes. Effort was made to approximate the conditions of temperature, gas composition, linear and mass gas velocities, pressure range, and extent of reduction prevailing in commercial blast furnaces. The results show that the reduction of Fe203 proceeds by two steps, largely consecutive under the conditions used herein: reduction of Fe203 to FeO, and reduction of FeO to Fe. Unless the gas has a CO!CO, ratio greater than 2.1 only the first step occurs under these conditions (850°C) but the following generalizations apply to either step or to the combination. The rate of reduction of relatively fine ore particles .at any time is proportional to the mass rate of supply of CO (provided some of it is thermodynamically available): the rate therefore is proportional to the linear velocity at constant pressure, or to the pressure at constant linear velocity. Thus, the rate of reduction may be increased without increase in linear velocity of the reducing gas by increasing the mass velocity of the gas and increasing the pressure correspondingly to avoid any increase in the linear velocity. The rate "constants"—i.e., the efficiency of conversion of the "available" CO supplied— is not actually constant but decreases as the reduction proceeds, and is a function only of the state of the ore; i.e., of the amount of reduction already accomplished and hence of the amount of CO passed. The particle size of ore used in nearly all the experiments was relatively small (8 to 14-mesh). The rate of reduction in run 16 with 3 to 8-mesh ore particles is within experimental error the same as with the finer ore. Although this would indicate an absence of effect due to particle size in this range of ore particles, it is desirable to have more data on other ore sizes and on ore of different densities before arriving at any generalizations on this point. Although it is possible to extend the analysis of these results to consideration of the more detailed kinetics and mechanism of iron oxide reduction, such extension is beyond the scope of the present paper. From the experiments on carbon deposition, it was evident that if carbon deposition is increased at all by the application of pressures up to 10 psi ga., such increase appears to be less than the experimental and analytical error. It appears safe to conclude that at top pressures on the order

Jan 1, 1948

By D. Turnbull, J. H. Hollomon

IN the most general sense, solidification refers to the formation of crystalline material from either a gas or a liquid. However, in this symposium, only the formation of crystals from liquids will be considered. Thus, in our present study the problem of solidification becomes that of determining the mechanism of the transition from a liquid to a crystalline solid, and our particular interest is in the transformation of metals from the liquid to the crystalline state. Metal liquids are seldom composed of only one kind of atom. Often solute atoms are added intentionally to make an alloy, or they may be present accidently because of incomplete purification. Furthermore, there may be small solid particles of various other crystals present in the liquid. Such small crystals may persist if their melting points are higher than any temperature to which the liquid is heated. Prior to solidification, the liquid metal usually is poured from one container to another. The second container, called the mold, usually is at a lower temperature than the container, or the crucible, in which the metal is liquified. The first solid that forms upon contact with the mold generally is of a different composition than the liquid, usually containing fewer foreign atoms or dissolved impurities. Heat is evolved upon solidification and is dissipated through the surroundings. Tree-like crystals, or dendrites, grow from the container walls and branch into the melt, enriching the remaining liquid in impurity atoms. In some alloys the remaining, relatively impure liquid continues to solidify until no liquid remains and the branches of the original crystal are cemented together. In other alloys, particles with a second type of crystal structure appear before solidification is complete. First the nature of the liquid and the solid states will be considered and then the mechanism of the initial formation of crystals from pure and alloy liquids. Later the problem of the growth of these crystals and the complexities of solidification in a mold, where the temperatures are not uniform and the composition of the melt changes continuously, will be discussed. LIQUID AND CRYSTALLINE STATES A liquid is an aggregate of atoms arranged with no apparent regularity (over distances of more than a few atom diameters). Nevertheless, any given atom generally has a definite number of nearest neighbors at definite distances, and thus order may be said to exist over a short range. In a crystal, on the other hand, a regular array of atoms continues for many hundreds or thousands of atom diameters, and a long-range order is apparent. Thus, a crystal having long-range order can be reproduced by linear translations for 10-5 cm or more of some fundamental unit possessing short-range order. A crude illustration of the difference between liquid and crystalline structures can be obtained by comparing the possible arrangements of oranges in a crate. If the oranges are simply dumped into the crate haphazardly until it is filled, the oranges will represent a static model of a liquid.

Jan 1, 1951

By C. R. Johnson, R. A. Greenkorn, L. K. Shallenbarger

This paper describes a study, based on core data, of the directional permeability of a sandstone reservoir. Directional air permeabilities are explained and correlated with lithology by the tensor theory of permeability, which is extended to the more general case of heterogeneous anisotzopic porous media. In this case, the permeability tensor is made up of two components: (I) anisotropy (variation around a point) which correlates with bedding, and (21 heterogeneity (variation from point-to-point) which correlates with grain size. INTRODUCTION Previous studies of directional permeabilityl.5-8 have concerned themselves only with anisotropy at a point, rather than with both point-to-point differences and local anisotropies. In this paper, we present the existing tensor theory of permeability for anisotropic porous media and then extend it to the more general case of heterogeneous anisotropic porous media. The laboratory measurements of directional permeability are explained in view of this extended theory and the data are discussed in terms of the lithologic factors that correlate with it. The results show what the heterogeneity and anisotropy of the reservoir element are, and that the directional permeability correlates with lithology. Data used in this paper are measurements of air permeability in eight directions, spaced at 45° intervals, on 142 2-in. vertical plugs from 30 cores. The core data are meaningful in terms of directional permeability because the cores were oriented to within 45O during drilling and coring.3 Although we initially thought that only 60 per cent of the core material was reliable, subsequent study showed that almost all of it was reliably oriented. After determining the air permeabilities, the data were reduced to three independent variables for each plug: the major and minor permeability axes, and the direction of the major axis. These were obtained by converting the permeability data to the reciprocal square root of permeability and fitting the transformed data with ellipses according to the tensor theory of permeability.8 The point-to-point areal variation of the minimum permeability axis is related to grain size. The direction of the permeability axes, where the major axis exceeds the minor axis by at least 5 per cent (measured variation is about 4 per cent), correlates with the bedding. The permeability tensor used in this study must be considered as the sum of a scalar and a tensor, with the scalar being the minor axis permeability as a function of position, and the tensor the directional effect, which is additive permeability over the minor axis. In this case, the point-to-point variation or heterogeneity (minor axis) is substantially larger than the variation at a point or anisotropy. It may be important that this separation of "directional permeabilities" be recognized when considering migration of fluids due to permeability variation. Local migration may be due to anisotropy and point-to-point migration may be due to heterogeneity, but the direction and magnitude of these may not be the same. Furthermore, in truly heterogeneous systems, one would expect that anisotropy would be the smaller of the two effects. THEORY TENSOR THEORY OF PERMEABILITY FOR ANISOTROPIC POROUS MEDIA8 Darcy's law for flow in porous media in its usual form is where qis the flow rate vector, k is the permeability, is the viscosity, is the vector differential operator, and P is the Pressure. Consider flow, q, through a unit area in the direction of the unit vector n from elementary flow tubes parallel

Jan 1, 1965

By Arthur W. Gray

The thermal analysis of a metal or an alloy is ordinarily made with the aid of heating and cooling curves in which transitions are indicated by the rapid changes in curvature that accompany changes in the rate of heat absorption or evolution. Analysis by the method that depends on the change in thermal expansivity is not customary, partly, at least, because of the difficulties involved in making the necessary measurements. However, under certain circumstances, the dilatometric method of analysis may possess advantages over the thermometric method that will justify the additional trouble required. The addition of 1 per cent. of zinc to an alloy has been found to produce upon the volume changes that take place during transition effects that suggest the possibility of using the dilatometric method of thermal analysis as a rather sensitive means of obtaining chemical information. Although the illustrations presented in this paper are drawn from data obtained during an investigation of dental amalgams, similar phenomena can doubtless be observed with other alloys. Some of the results found during an investigation made in 1917l have been confirmed by data on the thermal expansivity of amalgams published by Souder and Peters of the Bureau of Standards in reporting tests of dental materials.2 Although the Bureau of Standards made experiments for the purpose of discovering effects of including zinc as one of the constituents of a dental alloy—a matter much discussed in dental literature but without the presentation of reliable experimental evidencae to support the views of either side—the reports of the tests made by the Bureau give the impression that certain striking phenomena associated with the presence of zinc were not noticed. Among such phenomena arc those connceted with the conditions that determine whether or riot a specimen of amalgam becomes covered with droplets from which crystals develop.

Jan 1, 1921

By Gealy W. Wallwork

INTRODUCTION The administrative processes of coal mines are becoming increasingly complex. As society evolves into a more complicated structure with greater emphasis on individuality, government regulations reach deeply into every activity in an effort to force individuals into a standardized mold. These contradictory pressures add an extra burden to the administration of a mining operation. Recent years have brought a substantial change in the skills needed by mine supervisors and managers. As a result, a better understanding of the administrative functions is necessary. The mine superintendent has the overall responsibility for the mine; for effective operation he must be sufficiently knowledgeable to oversee all the complex functions that make up the mine. This chapter does not cover all the administrative requirements because of the variation in mine operation and in company policies and organizational structure. It does attempt to identify the administrative functions that would be required at a large mine with a preparation plant. It is assumed that the mine operation is decentralized with very little duplication of functions at the organizational levels above the mine. Thus each function is assumed to be relatively complete at the mine and under the general supervision of the mine superintendent. EMPLOYMENT PROCEDURES Throughout the mining industry, in deep or surface mining, in union or nonunion companies, the success or failure of an organization is directly related to the caliber of employees who make up the organization. A company is nothing more than a group of people working together with

Jan 1, 1981

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By E. D. Gardner, E. M. Sipprelle

The Synthetic Liquid Fuels Act (58 Stat., 190; 30 U.S.C. Sup., Secs. 321-325) was approved by Congress April 5, 1944; it directed the Bureau of Mines to build demonstration plants to produce synthetic liquid fuels from coal, oil shale, and agricultural products. The most important oil-shale deposits in the United States are in the Green River formation of Colorado, Utah, and Wyoming. The oil shale of western Colorado generally is more amenable to exploitation, more persistent, and apparently richer than elsewhere in the Rocky Mountain Region. It occurs at the top of a high plateau surrounded by bold, nearly vertical escarpments 500 to 600 ft in height. The top 400 to 500 ft of these escarpments comprises an oil-shale measure that averages 15 gal of shale oil per ton; the bottom 70 90 100 ft of the measure, called the Mahogany Ledge, averages over 30 gal per ton. The full measure in a 1000-square-mile area is estimated to contain 300 billion barrels of shale oil;' the Mahogany Ledge is estimated to contain 100 billion barrels of oil. These estimates are based on numerous surfac,e samples and on core-drill holes drilled by the Government and by private enterprise. The oil-shale beds are undisturbed and lie nearly horizontal. The name "oil shale" is unfortunate, as the rock is a tough, strong marlstone. Organic matter named "kerogen" is a constituent of the rock. The oil-shale demonstration mine is on Naval Oil-Shale Reserve No. 1; it is about 5 1/2miles by mountain road from the plant site, which, in turn, is 2 miles from U.S. Highway 6 and 10 miles west from Rifle, Colo. The highway parallels the Colorado River, the Denver and Rio Grande Western Railroad, and a 66,000-volt public-utility power line. Early in the program it was realized that an oil-shale enterprise would have to be on a large scale to be commercial, and that unusually low mining costs would be necessary. The physical characteristics of the Mahogany Ledge and an overlying roof stone are unusually favorable both for large-scale operation and low mining costs. Quarry practices largely will be followed underground to mine the Mahogany Ledge. The aim has been toward complete mechanization of all mining operations. A mining unit would comprise a square mile containing 100,000,000 tons of oil shale with allowance for mining losses. An investment of $1,000,000 would be $0.01 a ton; such an expenditure, therefore, could be made to save, say, $0.015 per ton daily operating cost. A goal of a mining cost of $0.50 per ton was set up in 1945. Open-cut mining costs then were about $0.25 per ton of material handled; it was hoped that a cost double this amount could be obtained in mining the Mahogany Ledge. Costs of labor and supplies have increased since 1945 and so has the selling price of petroleum products. To those unacquainted with the character of the Green River deposits, the name "shale" suggested high mining costs. Others assumed that coalmining costs of $2 to $5 per ton would apply. To many, the expected mining costs appeared the principal handicap to the establishment of an oil-shale industry. The purpose of the Bureau of Mines is to demonstrate methods and to establish costs for mining the oil shale on a large scale. It is hoped this work will lead to the establishment of a large-scale, commercial oil-shale enterprise.

Jan 1, 1950

By J. M. Schopt

COAL petrology is the study of the lithologic composition and texture of coal and includes megascopic as well as microscopic differentiation. Coal petrography is a quantitative study, principally (but not exclusively) microscopical in nature. The distinction between coal petrologic and coal petro-graphic studies usually is not important, but it is important to recognize that these studies differ materially from other types of petrology that deal primarily with minerals. The petrologic entities* of coal are less clearly distinguished than most minerals and the basis of distinction is not always clearly expressed. The relation of coal petrology to geologic, mining, and technologic problems is most evident when results of coal petrologic studies can be stated quantitatively. The chemical and physical composition of coal and the determination of its quality and properties are continuing problems. The source of these problems lies in the heterogeneity of coal and in its almost complete insolubility in ordinary solvents at normal temperatures. The empirical and comparative character of standard chemical coal analytic values is one of the consequences resulting from heterogeneity and insolubility of coal. Nevertheless, these coal analytic methods are highly technical and diversified. Coal petrol.ogy employs a group of similar analytical methods which provide information about coal that the other methods cannot supply. The heterogeneity of coal is most clearly demonstrated by means of petrologic studies. The properties utilized in coal petrologic studies are related to texture (size, form, and association), hardness, light reflectance, and light absorption and transmission (color). Size relations are most evident but are commonly overlooked. Coal is classed chemically as a mixture, and chemical analyses thus show the composition of the sample as a whole. Geologically coal is an organic clastic deposit, derived from diverse plant fragments and particles having a size range comparable to that of a conglomerate or breccia. The mixture of different materials that compose coal, large and small, can be realized only by microscopic study. This is because the fundamental cellular units of plants, from which coal is formed, are microscopic in size. The kinds of altered plant particles and fragments in coal have specific differences in hardness, reflectance, and color that signify differences in composition. These differences must be taken into account in evaluating the aggregate properties of coal. Terminology and Texture Full discussion of terms applied by various petro-logists in analysis of coal is beyond the scope of this article. For convenience the simpler types of petrologic entities that are defined without reference to lithologic occurrence or texture will be called coal components. Fig. 1 lists reactive and relatively inert

Jan 1, 1957

By G. Purcell, S. C. Sun

The objective of the present study was to detennine the role played by double bonds in the flotation of a very pure mineral using 18-carbon unsaturated fatty acids as collectors. Streaming potential measurements were made on a plug of pure synthetic rutile in solutions of inorganic electrolytes and unsaturated 18-carbon fatty acid soaps. Experimental results from these tests are detailed in the paper. The collector effectiveness of oleic acid with one double bond, linoleic acid with two double bonds, and linolenic acid with three double bonds has been a matter of speculation for many years, and conflic- ting experimental evidence1-8 has not clarified the issue. The overall objective of the present study was to determine the role played by double bonds in the flotation of a very pure mineral using 18-carbon un-saturated fatty acids as collectors. Since zeta potential is dependent on adsorption and orientation of ions at the solid-liquid interface, its variation under different conditions of pH and collector concentration should throw some light on the behavior of unsatu-rated fatty acids in flotation pulps. Titanium dioxide, in the form of rutile, was chosen for the investigation because it is now available in a very pure, synthetic, crystalline state, and despite the fact that it is one of the most important synthetic inorganic chemicals in commercial use, its electro-kinetic properties have not been closely studied. Electrokinetic properties of rutile in various aqueous solutions are discussed in this paper. Adsorption information gained from the streaming potential measurements enabled the flotation resultsg to be explained in a qualitative way, thus providing a clearer

Jan 1, 1963

By L. W. Eastwood

The structure of eutectics has been studied by a number of investigators, and the complexity of the structural relationship of the components has been agreed upon, especially that of the "eutectic colony," type III of Portevin's1 classification. This paper does not attempt to alter the present classifications of eutectics; rather, it discusses the relationship between the macrostructure and the microstructure of the copper-cuprous oxide eutectic, and describes in detail the mechanism of the formation and the structure of the eutectic. Further, throughout the entire discussion it attempts to point out certain misconceptions in regard to the interpretation of the observed structure of the copper-cuprous oxide eutectic, one of the so-called "eutectic colony" types, and to correlate as much as possible the work done by the writer with that done by other investigators. Of the three types of eutectics listed by Portevin,2 the eutectic colony type has presented the greatest difficulty in interpretation. Although the copper-cuprous oxide eutectic is typical of the eutectic colony type in appearance, it may not be truly representative because the copper forms about 96 per cent of the eutectic and the cuprous oxide about 4 per cent. The interpretation of the origin and structure of the "eutectic colony" given here is strictly limited, therefore, to the copper-cuprous oxide eutectic. Macrostructure Fig. 1 shows the macrostructure of the eutectic at 3 diameters, the melt having been chill-cast into an iron mold, the resulting specimen sawed into two parts and the section polished and etched with the usual mixture of hydrogen peroxide and ammonium hydroxide. This specimen contains 0.48 per cent oxygen and is only slightly hypereutectic. If such a melt is allowed to cool slowly, large macrograins will form without the columnar structure of Fig. 1 and the well-known phenomenon of liquation will occur, forming copper oxide dendrites at the top and copper

Jan 1, 1934

By Edwards Wichers

The purpose of this paper is to set forth the matters of principal interest in connection with work done in the past few years on the purification of the metals of the platinum group, including the study and modification of methods already in the literature and the development of new procedures. For the most part, the results will be given in summary form, reserving the publication of detailed data and directions for a forthcorning paper to be issued by the Bureau of Standards. In recent years increasing interest has been shown in the preparation of the pure platinum metals, both by those concerned with the manufacture of the metals and their alloys for scientific and industrial purposes and those who are engaged in the study of the chemical or physical properties of the elements. The purification of the metals usually has been regarded as a matter so involved and difficult as to require the attention of specialists. It is hoped that this paper will show that any of the metals can be prepared in any desired degree of purity by relatively simple straightforward chemical methods. For the most part, it is thought that the methods given are suitable for small-scale refineries as well as for the laboratory; also, that they will bring the time required for the purification of any of the metals within reasonable limits. The new procedure suggested for purifying platinum should prove to be much shorter than any methods described in the literature. Treatment of Platinum Ore As is well known, the principal source of the platinum metals is a mixture of several native alloys of the metals, found chiefly in naturally concentrated deposits in stream beds or alluvial material. Without attempting to enumerate all of the minerals present, it may be said that the concentrated ore from such sources contains all of the six platinum

Jan 1, 1928

THE composition and quality of finished steel depend upon selection and proportioning of the raw materials of the charge as well as upon control of furnace practice. This chapter deals only with the raw materials of the basic open-hearth process that are important in determining the composition of the steel or slay. They are the metallic charge, oxygen-bearing materials, fluxes, alloying and deoxidizing additions, and certain refractory materials used for maintenance of bottoms. Other refractories, which may affect the slag composition, are discussed in Chapter 3. Wide variations are possible in the type and composition of charged materials but certain limiting relations among the elements of the charge must be observed. Since the process consists essentially of refining by the oxidation of undesired elements, a balance must be established between the sources of oxygen and the elements in the charge that are subject to oxidation (see Chapters 2 and 7). For example, if it is desired to use a high ratio of blast-furnace hot metal to scrap, it is necessary to add an oxygen-bearing material such as ore or mill scale to eliminate the excess carbon and silicon that are present in the hot metal. An example of the opposite extreme is the use of a metallic charge composed entirely of steel scrap. With this type of charge, it is common practice to substitute burnt lime for limestone as a flux and to charge some carbonaceous material such as coke to avoid an excess of oxygen in relation to the elements of the charge that are subject to oxidation. Elements such as copper and nickel, which are not oxidized or eliminated by any other reaction, may be introduced into the charge only to the extent to which they are permissible in the finished steel. An example of adjustment of the charge for elements of this type is found in the use of steel scrap high in copper. In this case, metallic components of the charge other than the scrap should be low in copper, or a sufficiently high ratio, of pig iron to scrap should be charged to dilute the copper from the

Jan 1, 1964

IN the preceding chapter on thermochemistry and the reactions in and between metal and slag phases and in the following chapter on fuel combustion the main emphasis is placed on the equilibrium or "static" conditions. This equilibrium viewpoint is not concerned with the rate of change in the process or with the mechanisms or paths followed between initial and final states. The questions of just "how it works" and "how fast" belong to the kinetic aspect of any process; their answers are helpful in speeding up or slowing down and thus controlling its operation, and also in understanding its limitations. Any treatment of kinetic factors in the open hearth such as is attempted here and in Chapter 22 must at present be largely qualitative and incomplete. We are only beginning to get quantitative data on rates of reaction and diffusion at high temperatures, as indicated in Chapter 15. Empirical data in the literature on furnace operating rates do not help much to illuminate the details of gas-flow patterns and the complexities of heat flow in the many parts of the furnace system. This chapter is intended to give the reader an introduction to the problems of the flow of gases through the furnace system and the flow of heat in this system. An adequate discussion would require several times the space available here; it is possible here only to outline a few fundamentals and to indicate some of the conditions of heat and gas flow peculiar to the open hearth. Several good general treatments of these subjects may be found in the literature (see references at the end of the chapter). For the designer of open-hearth furnaces, the principles of gas flow are of paramount importance. They are also important to the operation of the process, at least to the extent of a general qualitative picture of the movement of gases in the system. MOTION OF GASES IN FURNACE DUCTS Fluid flow in general can vary between the extremes of laminar or streamline flow with a minimum energy loss, to irregular

Jan 1, 1951

By R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-C and Fe-Ni solid-solution alloys has been investigated at 25°C. It is found that the rate of solid-solution strengthening is dependent upon the strain at which the yield stress is measured, the macroyield stress being much more concentration-dependent than the microyield stress. In fact the addition of nickel does not lead to any increase in the microyield stress of iron. The primary effect of increasing the carbon or nickel content is to increase the slope of the stress-strain curve in the microyield region; this effect has been correlated, by means of transmission electron microscopy, with a decreased ability of the dislocations to cross-slip. It is concluded that the Mott-Nabarro theory is a good description of true solid-solution hardening in these and other iron-base alloys. A.LL theories of the solid-solution strengthening1-4 indicate that the flow stress of an alloy increases both with solute concentration and "misfit" between the solvent and solute atoms. The functional relationship between strength, solute concentration, C, and misfit depends upon the particular theory. Mott and Nabarro1,2 and Schoeck and Seeger3 both predict a linear increase in strength with concentration, while Fleischer4 indicates that the strength should be proportional to C1/2; there are in the literature experimental observations to support both these compositional dependencies.1'8 The experimental evidence used to support the theories is the change in macroscopic yield stress (strain, e, = 10-3) with composition. However, recent investigations have revealed that solid-solution strengthening in a Cu-Al single crystals7 and in Fe-V polycrystal-line" alloys depends upon the strain at which the flow stress is measured; a flow stress in the microplastic range (e = 10-6 to 10-5) is much less concentration-dependent than the macroyield stress. Since the theories of solid-solution strengthening are concerned in particular with the stress to move a dislocation in a dislocation-free matrix, they should only be compared with microyield-stress data; it will be shown that in a material deforming homogeneously the microyield stress (e = 10-6) is approximately the stress to move through the matrix those dislocations which have been nucleated by stress concentrations such as particles or grain boundary ledges.9-11 In contrast, the macro-yield stress is more complex in that it is affected by several phenomena: dislocation multiplication, dislocation interactions, and the ease of propagating slip across grain boundaries. For example, it is experimentally observed that when long-range order12'13 or solute effects10 restrict cross alip the grain boundary

Jan 1, 1967

By Karl L. Fetters

In the process of making steel in the open-hearth furnace the refining of the metal during the working period of the heat is largely accomplished through the agency of the slag. From the birth of the process until the present day steelmakers have recognized the importance of the slag in determining the composition of the metal and the quality of the product. The general relationships between slag composition and metal analysis have long been known, at least in a qualitative or approximate fashion. For examples, the iron oxide content of the slag is higher on lower carbon heats; the more basic slags are higher in iron oxide for a given carbon content; certain amounts of iron oxide and lime arc required for phosphorus removal and a high lime-silica ratio is needed if the sulphur content of the metal is to be diminished. In recent years a number of quantitative relationships involving these and other variables have been developed through plant and laboratory studies by numerous investigators in this country and abroad. The direct comparison of laboratory and open-hearth data involves the question of the degree to which each approaches the conditions of chemical equilibrium, a question which, from the open-hearth standpoint, we are scarcely yet in position to answer. And, although a considerable body of dependable equilibrium data has been obtained in the laboratory, this work has not yet been extended to cover the ranges of slag composition encountered in basic open-hearth practice. In the present study we shall not attempt to draw comparisons between data from the two sources; nor do we attempt to draw conclusions as to the approach to chemical equilibrium in the open-hearth furnace. Many of the operating variables that are likely to be erratic or unrecorded during the earlier stages of the heat become more consistent and arc more readily subject to observation and control during later stages. For example, undigested lime or ore gradually goes into solution, the rate of carbon drop levels off, and the temperature of the metal is brought under control. For these and other reasons a greater degree of self-consistency is likely to be found among data obtained during the

Jan 1, 1940

By G. K. Williams

The continuous process of lead refining as at present operated at the Port Piric plant of The Broken Hill Associated Smelters Proprietary Ltd. was a development from investigations conducted in connection with the ordinary Parkes desilverizing process. It is not proposed here to discuss the theoretical considerations involved in continuous desilverizing because this aspect has already been dealt with in previous publications.1 Continuous Softening Process For economical desilverization of lead bullion, the bullion must first be subjected to refining processes for the removal of such impurities as copper, sulphur, arsenic, antimony and tin. This refining is effected by first drossing to remove copper and sulphur and then preferentially oxidizing the arsenic, antimony and tin from the bullion in the softening process. The theoretical basis of the continuous softening process is illustrated by the portion of the Pb-Sb-O ternary equilibrium diagram shown in Fig. 1. Under conditions of complete liquefaction, metal of the composition of softened bullion is in equilibrium with an oxide slag containing about 9 per cent antimony. In practice, of course, arsenic also is always present, and while the 0Pb-Sb-As-O quaternary system has not been worked out in detail, it has been found that in softening drossed smelter bullion of the composition produced at Port Pirie, arsenic is always reduced to 0.001 per cent or less when the antimony in the bullion is reduced to a satisfactory figure. In the operation of the continuous softening process, a two-phase system of a bullion low in arsenic and antimony and an oxide slag relatively high in those components exists in equilibrium. To this system is added continuously a bullion containing 0.2 per cent As and 0.8 per

Jan 1, 1937

By Walter Knox, J. D. Doherty

IN 1939, at the request of The Koppers Coal Co., the Koppers Company Research Department established a Stoker Coal Research Laboratory for the purpose of investigating the performance characteristics of stoker coals in typical domestic stoker installations. Fig. I is a photograph of part of the laboratory. The material in this paper deals with the performance of one coal in a single installation. Presented are details of this installation, mechanical characteristics of the stoker, and the results of a series of burning tests in which adjustments were systematically varied. SUMMARY OF RESULTS Mechanical Features I. A large percentage of the total power consumed by a domestic stoker is used to operate the gear case and motor (Fig. 3). 2. The power consumption per ton goes down with an increase in rate of coal feed (Fig. 4). 3. The automatic air control in this stoker showed advantages over manual control (Fig. 5). 4. The air velocities through the retort tuyeres were uniform around the retort, but varied between the rows of tuyere rings (Fig. 6). 5. The crushing of coal with this stoker increased the minus 1/8-in. from 1 1.6 per cent to 19.2 per cent. There was a noticeable segregation of coal as it came from the retort and distribution was not uniform (Fig. 7). 6. Measurement of air entering over the fire showed that with some not uncommon adjustments this air may he a high percentage of the total air supply (Fig. 8 and Table I). Operating Performance I. The removal of clinker was shown to give a period of poor performance characterized by a high fuel-bed resistance and a high percentage of carbon monoxide in the flue gases (Fig. 10). 2. The fuel-bed resistance was found to decrease as the fuel bed built up in a normal response to heat demand after a prolonged hold-fire (Fig. II). 3. With intermittent operation the burning rate was almost always less than the feeding rate. The wide variations were found to be greatly dependent upon the length of the On period and the length of the intervals between On periods (Fig. 12). 4. The maintenance of a low furnace draft led to less fly ash, better clinker formation, and higher efficiencies (Fig. I3). 5. The maintenance of a minimum of excess air also resulted in less fly ash, better clinker formation, and higher efficiencies (Fig. 14). GUIDING PRINCIPLES In planning the investigations, the following principles were adopted: Selection of Healing Equipment.-Use only standard models of stokers and furnaces representative of those widely used.

Jan 1, 1942

By R. T. Hukki

THE accepted basis of comparisons between mills of different diameter is the percentage critical speed. If n = actual mill speed, rpm, nc = calculated critical speed, rpm, np = calculated percentage critical speed, and D == inside diameter of the mill in feet, then n, In the following analysis capacity, T, is expressed in short tons per hour, tph, and power consumption, P, in kilowatts, kw. Accordingly power consumption per unit of capacity, P will be expressed in kilowatt hours per short ton, or kw-hr per ton. In all equations D refers to the inside diameter of the mill in feet and v to the peripheral speed of the mill in feet per minute inside the liners. ' Comparison between separate mills must be based on equivalent grinding conditions, i.e., same feed, same size distribution of feed, same size distribution of product, and same percentage of solids. In addition, comparisons between separate rod mills must be based on the same rods, same type of liners, and same percentage rod load. Comparisons between separate ball mills presuppose the same balls, similar liners, and same relative ball load. The practical np-range through which the equations apply varies, being narrower for fine grinding in ball mills and wider for coarse crushing in rod mills. The Relationship between Capacity and Speed It is the general belief that the capacity, T, of a tumbling mill is directly proportional to the speed of the mill, other things remaining constant.' Mathematically this is represented by the equation T - c¹ n tph [4] where c, is a factor related with the grinding characteristics of the ore, method of reduction, and the units chosen. It is proposed here that the general equation relating mill capacity and speed should be of the form T = c¹ nm tph [5] In other words, the capacity should be proportional to the mill speed raised to power m, the numerical value of the exponent being 1 5 m 5 1.5, depending on the circumstances. Eq. 5 can also be written in the following forms: T = c, (np)m tph, and [6] T=Ca vm tph, [71 where v = peripheral speed of the mill in feet per minute. If the observed capacity of a mill at speed n¹ is = T¹ tph, the capacity T² of the same mill at speed n² should be T² = T¹ (n²/n¹)tph [8] The Relationship between Power Consumption, Mill Diameter, and Speed The only well known theoretical deduction relating power consumption, P, and mill diameter appears to be the formula of duPont introduced by Gow, Guggenheim, Campbell, and Coghill.' According to duPont, the power required to operate a mill is a function of the mass of the balls, of the lever arm of the ball mass, and of the speed of the mill. The ball mass per unit of mill length is proportional to the square of the diameter, the lever arm is directly proportional to the diameter, and the critical mill speed or any percentage thereof is inversely proportional to the square root of the mill diameter. Following this reasoning, the original duPont formula is of the form P = c4D² c D • c6D-0.5 = c7D2.5 [9] If the mill speed in the above equation is expressed in terms of Eq. 3, the duPont formula may be written as follows: P=f1(D2) f2(D) f³(—np) or [10] vD P = c np D2.5 kw [11] Eq. 11 may also be derived from the mechanical principle of force, which is equal to mass x acceleration. Power necessary to operate a mill may be considered to be an homogeneous linear function of the force developed. Ball or rod mass per unit of mill length is a function of D2. The acceleration factor of the ball or rod mass is a function of the peripheral speed of the mill. Thus P = f4(F) = /x(D2) f5(v) Indicating that v = nDn, and n = c9 np /vD, the above equation becomes P = f2 (D2) -fa (D ca np/vD

Jan 1, 1955