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By Karl Fetters, John Chipman

The relationship between the composition of the slag and that of the underlying metal during the refining of a heat of liquid steel may best be studied in the light of the two broad physicochemical concepts of equilibrium and reaction rate. Actual steel-making processes, typified by basic open-hearth practice, involve such complexities of operating variables that it is impossible to distinguish with any degree of certainty between the general limiting conditions imposed by chemical equilibrium and the effects associated with rates of diffusion or of chemical reaction. Further advances in the physical chemistry of steelmaking will depend upon our ability to distinguish clearly between these two kinds of effects, and the experimental work that must be done falls naturally into two classifications. The first is the study of chemical equilibrium that cannot be carried out with assurance under operating conditions but must be done in the laboratory. The second is the -subject of rates of reaction and diffusion and the mechanism of the process as a whole, which can best be studied under operating conditions. The latter is not entirely independent of the former, since its interpretation often requires a knowledge of the equilibrium state. It is the purpose of this and of several papers that will follow to present the results of labora- tory investigations of equilibria involving liquid steel and slag. Open-hearth slag is a complex mixture containing at least eight major components and perhaps twice as many whose influence may be classified as probably minor. It is not surprising that progress toward a complete understanding of such a material at high temperatures has been slow. Attempts to apply the established principles of physical chemistry to the behavior of the individual components of this mixture have been beset by an almost complete lack of data on its chemical properties in the liquid state. This has necessitated the adoption of various methods of approximation based upon such assumptions as, for example, that for a given component the ratio of its mol fraction in the slag to that in the metal is a constant, or that the molecular composition of the liquid slag is the same as its crystalline constitution after solidification. From the thermo-dynamic viewpoint, such assumptions are merely useful dodges, which enable one to hazard a guess as to the magnitude of the more fundamental quantities, the chemical potentials and activities of the components of slag. The problem of determining the activity of each substance in an eight-component svstem seems too complex to be undertaken without the aid of generalizations derived from experimental data on similar systems containing a smaller number of components. Accordingly, it was planned in the present investigation to study the equilibrium of molten iron with the simplest

Jan 1, 1941

By Karl Fetters, John Chipman

The relationship between the composition of the slag and that of the underlying metal during the refining of a heat of liquid steel may best be studied in the light of the two broad physicochemical concepts of equilibrium and reaction rate. Actual steel-making processes, typified by basic open-hearth practice, involve such complexities of operating variables that it is impossible to distinguish with any degree of certainty between the general limiting conditions imposed by chemical equilibrium and the effects associated with rates of diffusion or of chemical reaction. Further advances in the physical chemistry of steelmaking will depend upon our ability to distinguish clearly between these two kinds of effects, and the experimental work that must be done falls naturally into two classifications. The first is the study of chemical equilibrium that cannot be carried out with assurance under operating conditions but must be done in the laboratory. The second is the -subject of rates of reaction and diffusion and the mechanism of the process as a whole, which can best be studied under operating conditions. The latter is not entirely independent of the former, since its interpretation often requires a knowledge of the equilibrium state. It is the purpose of this and of several papers that will follow to present the results of labora- tory investigations of equilibria involving liquid steel and slag. Open-hearth slag is a complex mixture containing at least eight major components and perhaps twice as many whose influence may be classified as probably minor. It is not surprising that progress toward a complete understanding of such a material at high temperatures has been slow. Attempts to apply the established principles of physical chemistry to the behavior of the individual components of this mixture have been beset by an almost complete lack of data on its chemical properties in the liquid state. This has necessitated the adoption of various methods of approximation based upon such assumptions as, for example, that for a given component the ratio of its mol fraction in the slag to that in the metal is a constant, or that the molecular composition of the liquid slag is the same as its crystalline constitution after solidification. From the thermo-dynamic viewpoint, such assumptions are merely useful dodges, which enable one to hazard a guess as to the magnitude of the more fundamental quantities, the chemical potentials and activities of the components of slag. The problem of determining the activity of each substance in an eight-component svstem seems too complex to be undertaken without the aid of generalizations derived from experimental data on similar systems containing a smaller number of components. Accordingly, it was planned in the present investigation to study the equilibrium of molten iron with the simplest

Jan 1, 1941

By S. Korman, S. B. Tuwiner

THE purpose of this study is to investigate the effect of agitation upon the flotation of chal-cocite. It is believed that the concentration of collector which is required to produce a water-repellent surface upon the mineral is determined among other things by the rate of collector diffusion through an impeding film of more or less stagnant fluid. Its thickness depends upon the intensity of agitation. In the first part of this study a method is developed for determining the thickness of the fluid film upon a polished surface of synthetic chalcocite. The film thickness is then determined as precisely as possible under three readily reproducible condi-tions of agitation intensity. These determinations serve as a quantitative evaluation of agitation. In Part 2 it is demonstrated that in solutions of lime at PH 10.5 and in the absence of air or dissolved oxygen the concentration of collector required to develop water-repellency upon the surface in any given time is a function of the fluid film thickness, and that after about 10 min the relation becomes linear. This points to the possibility that the collector ions may be involved in a diffusional process through the fluid film. In Part 3 it is shown that where air is present more collector is required to produce water-repellency than for the case in which air is excluded. Next, it is shown that for the latter case the most minute amount of sodium sulphide suffices to preclude development of water-repellency. Both oxygen and sulphide are in a sense, therefore, depres- sants for chalcocite in a lime solution at PH 10.5. When oxygen and sulphide are present simultaneously there is a region of minimum critical collector concentration for water-repellency which is very markedly lower than the concentration where oxygen alone or where sulphide alone is present. Moreover, this minimum appears to be identical with the collector concentration which is required where sulphide and oxygen are both excluded. This would appear to indicate that in certain ranges of concentration of oxygen and sulphide, each cancels the effect of the other. The range of concentration of solution for this effect in solutions saturated with oxygen is a function of the agitation intensity. Thus we are led to believe that a chemical reaction involving sulphide and oxygen occurs at the surface of the chalcocite. Part 4 of this study is a further development of this idea and some of its consequences from an electrochemical standpoint, while in Part 5 the disappearance of sulphide from pulps of several minerals is noted with an indication that both dissolved oxygen and the mineral are necessary, the reaction being catalytic or pseudocatalytic. Part 1. Determination of Fluid Film Thickness The Fluid Film Concept: The hindrance to the diffusion of collector to the surface of the chalcocite is a barrier of stagnant fluid in the vicinity of the surface. It is the same barrier that limits the rate of transfer of heat, the rate of solution of dissolving crystals, or any of the other rates pertaining to chemical engineering unit operations in which the film resistance to diffusion plays a principal role.' Fluid films are present upon the surface to an extent which varies with the geometry and intensity of agitation. They result from the fact that in the region within the fluid near a surface, motion is entirely parallel to it. From the standpoint of transfer to or away from the interface the effect is as though the fluid were stagnant. Outside of the film, movement of the fluid may be streamline or turbu-

Jan 1, 1951

By S. Korman, S. B. Tuwiner

THE purpose of this study is to investigate the effect of agitation upon the flotation of chal-cocite. It is believed that the concentration of collector which is required to produce a water-repellent surface upon the mineral is determined among other things by the rate of collector diffusion through an impeding film of more or less stagnant fluid. Its thickness depends upon the intensity of agitation. In the first part of this study a method is developed for determining the thickness of the fluid film upon a polished surface of synthetic chalcocite. The film thickness is then determined as precisely as possible under three readily reproducible condi-tions of agitation intensity. These determinations serve as a quantitative evaluation of agitation. In Part 2 it is demonstrated that in solutions of lime at PH 10.5 and in the absence of air or dissolved oxygen the concentration of collector required to develop water-repellency upon the surface in any given time is a function of the fluid film thickness, and that after about 10 min the relation becomes linear. This points to the possibility that the collector ions may be involved in a diffusional process through the fluid film. In Part 3 it is shown that where air is present more collector is required to produce water-repellency than for the case in which air is excluded. Next, it is shown that for the latter case the most minute amount of sodium sulphide suffices to preclude development of water-repellency. Both oxygen and sulphide are in a sense, therefore, depres- sants for chalcocite in a lime solution at PH 10.5. When oxygen and sulphide are present simultaneously there is a region of minimum critical collector concentration for water-repellency which is very markedly lower than the concentration where oxygen alone or where sulphide alone is present. Moreover, this minimum appears to be identical with the collector concentration which is required where sulphide and oxygen are both excluded. This would appear to indicate that in certain ranges of concentration of oxygen and sulphide, each cancels the effect of the other. The range of concentration of solution for this effect in solutions saturated with oxygen is a function of the agitation intensity. Thus we are led to believe that a chemical reaction involving sulphide and oxygen occurs at the surface of the chalcocite. Part 4 of this study is a further development of this idea and some of its consequences from an electrochemical standpoint, while in Part 5 the disappearance of sulphide from pulps of several minerals is noted with an indication that both dissolved oxygen and the mineral are necessary, the reaction being catalytic or pseudocatalytic. Part 1. Determination of Fluid Film Thickness The Fluid Film Concept: The hindrance to the diffusion of collector to the surface of the chalcocite is a barrier of stagnant fluid in the vicinity of the surface. It is the same barrier that limits the rate of transfer of heat, the rate of solution of dissolving crystals, or any of the other rates pertaining to chemical engineering unit operations in which the film resistance to diffusion plays a principal role.' Fluid films are present upon the surface to an extent which varies with the geometry and intensity of agitation. They result from the fact that in the region within the fluid near a surface, motion is entirely parallel to it. From the standpoint of transfer to or away from the interface the effect is as though the fluid were stagnant. Outside of the film, movement of the fluid may be streamline or turbu-

Jan 1, 1951

By C. F. Allen, G. B. Walker

The sink-float methods designated by heavy-media separation processes were pioneered by C. Erb Weunsch for the treatment of base metal ores as an improvement over jigs. The work of Weunsch was further developed by Victor Rakowsky and The American Zinc, Lead and Smelting Co. Early in the development of the processes, the inherent unsuitability of galena as the solid constituent of the medium was recognized and ferrous media amenable to magnetic recovery and control were developed. The high efficiency and low cost of magnetic recovery and cleaning of ferrous media regardless of particle size, slime contamination, or surfacial oxidation had led to the adoption of ferrous media by all of the sink-float plants operating under the heavy-media separation processes patents controlled by American Zinc, Lead and Smelting Co. Approximately 2,000,000 tons of base metal and nonmetallic minerals are treated each month by these methods. Heavy-media separation processes are a modern practical and economical adaptation of the well-known laboratory procedure for separating a mixture of two solids by immersing the mixture in a liquid having a specific gravity intermediate the specific gravities of two solids. The lighter solid floats while the heavier sinks. This method of separation has been attempted on a commercial scale, but the high loss and high cost of the organic liquids halted the development of the process. Many attempts have been made to simulate a heavy liquid by using a suspension of a finely divided solid in water. If the solid phase of the suspension is ground fine enough, the suspension can be made stable or so slow settling that a substantially uniform specific gravity can be maintained from top to bottom of the bath. However, any material separated by such methods will inevitably be contaminated by some slime which will eventually accumulate in the bath and cause a viscous medium at the expense of separating efficiency. Therefore, it is necessary to provide means for continually cleaning a portion of the medium to eliminate slime at the same rate at which it is introduced to the medium. The problem of efficiently cleaning the medium limits the minimum grain size of the solid of the suspension in the case of the Chance sand process for cleaning coal, because de-cantation is the only cleaning method available. If the sand is too fine, it will be lost along with the slime. Therefore, coarse sand must be used, and to maintain a semblance of a uniform suspension, it is necessary to use strong rising water currents. The combination results in a separation based more on hindered settling classification than on sink-float principles. As previously mentioned, galena was used as the solid constituent of the medium during the early stages of the development work. The high specific gravity of galena made it suitable for the preparation of medium for high specific gravity separations. Galena can be cleaned by either decantation or by froth flotation. As with sand, de-cantation limits the minimum particle size of the media that can be cleaned without excessive loss. Froth flotation for cleaning galena medium has been used, but the problem of floating fine galena that has been exposed to extensive oxidation is well known to be a most difficult one. Last year the largest heavy-media plant m the world, and the second plant to be installed, converted from galena medium to ferrous medium despite the fact that the ore contains galena which can be used as medium. The change to ferrous medium has been beneficial in many ways. Today all the heavy-media plants have been converted from galena to ferrous media. Unquestionably, ferrous media have the widest application of any media developed, for the following reasons: 1. Ease of recovery and cleaning by magnetic means. Particle size or surface condition not a factor. 2. Low consumption per ton of ore treated. 3. Resistance to abrasion. 4. Widest range of media densities, including higher workable densities (1.25 to 3.4) than have been found possible with nonferrous media. 5. Space required for recovery and cleaning of ferrous media is considerably less than that for nonferrous media. 6. Ferrous media require lower capital investment and operating costs for media recovery and cleaning. Advantages of Heavy-media Separation Processes Heavy-media separation processes offer the following positive advantages, amply demonstrated on a wide variety

Jan 1, 1950

By Orson Cutler, Shepard

THE OBJECT of this paper is twofold: (1) To analyze the forces that cause air bubbles to spread on mineral surfaces in the flotation process; and (2) To develop a rational expression that will serve as a criterion of the floatability of minerals, to the end that the efficiencies of various flotation reagents can be accurately compared. Heretofore, the subject of the spreading of air bubbles has been dismissed with the statement that the surfaces of minerals on which bubbles spread are water-repellent. Imperfect understanding of the forces involved has led to the use, hitherto, of various erroneous formulas for the calculation of the comparative effectiveness of flotation reagents.

Jan 1, 1932

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The mechanical properties of Ti-C and Ti-C-0 alloys can be altered by heat treatments to dissolve or reject carbon from solid solutions. The maximum strength is obtained by annealing just below the peritectoid temperature. Quenching from the ß-carbide field results in softening. Impact behavior is influenced by the extent of solution of interstitials CARBON is not as important in titanium alloys as it was in earlier years when graphite induction melting was more prevalent. With induction melting, carbon pickup is about 0.5 to 0.8 pct. Cold-mold arc melting with graphite electrodes, which is among the more current methods, results in carbon pickup of 0.1 to 0.2 pct. The titanium-sponge melting stock itself contains about 0.02 to 0.07 pct C, picked up from the magnesium used in the reduction process. Thus, carbon is still one of the more important contaminants in titanium and needs careful study and evaluation in order to understand titanium and titanium alloys. Moreover, it is equally proper to consider carbon as an alloying addition because, in controlled amounts in titanium alloys, it may serve a most useful function. This is particularly the case where the ultimate in toughness is not required. The addition of carbon to titanium results in a peritectoid-type system as illustrated in Fig. 1. The solubility of carbon is seen to be higher in the a phase than in the ß phase in the temperature range of interest. Below the peritectoid temperature, the solubility of carbon in a titanium decreases with decreasing temperature. This type of system permits many microstructural and heat-treatment variations which may influence the properties of the alloys. The study of how the microstructure variations affect mechanical properties is described in this paper. Experimental Procedures The experimental techniques and testing methods used in this work were the same as those described in detail in a previous paper.' No further descriptions will be given except where changes have been made. High purity iodide titanium, produced by the New Jersey Zinc Co., was used in all of the alloys. Carbon additions were made using high purity spectro-graphic carbon electrodes in order to obtain the highest purity carbon available. The alloys were prepared by double arc melting to reduce the possibility of segregation. The alloys were forged at 875°C to ¾ in. round, descaled, vacuum annealed for 5 hr at 900°C to remove the residual hydrogen, and swaged to ¼ in. round at 750°C. All heat treatments were made on material in this initial condition. Two of the early Ti-C ingots were found to have been contaminated in melting. Vacuum-fusion analyses showed that the two contaminated alloys had picked up oxygen, so the test results on these two alloys permitted an evaluation of ternary Ti-C-0 alloys. A list of the alloys and their compositions are given in Table I. Properties of Ti-C Alloys In a peritectoid-type system, such as the Ti-C system, the chief microstructural variable which influences the properties is solid-solution strengthening. For a given composition, it is possible to control the disposition of carbon, either in solid solution or as the compound Tic, by suitable heat treatments. When in solid solution, the carbon present in the alloy makes a definite contribution to the strength of the alloy. However, when present as Tic, it has very little effect on the strength. Other microstructural variables considered in this investigation were transformation structures and grain size. As discussed in subsequent sections, these variables have only a minor effect on properties as compared to the solid-solution effect. Solid-Solution Strengthening: The principal strengthening mechanism for Ti-C alloys has been found to be solid-solution strengthening. Carbon in interstitial solid solution strengthens titanium, but has very little strengthening effect if present as the compound. Since carbon has a higher solubility in

Jan 1, 1956

By Kenneth K. Humphreys, F. R. Zachar, A. G. Gilbert

INTRODUCTION by F. R. ZACHAR and A. G. GILBERT Coal producers are not only faced with the problems of mining coal, but must also decide to what extent they can invest capital and what operating and maintenance expense they can afford, after mining, to market their product in sufficient volume and at a reasonable profit. Regardless of whether the operator is contemplating a new operation or merely considering expanding present facilities, market requirements, ability to make a product meeting requirements, probable costs and possible future changes in raw coal or finished product must be considered. In addition, such items as flow sheet, structural designs, storage facilities, etc, must be examined individually and collectively. In estimating preparation costs to meet predetermined market specifications, the operator must calculate the economics of present preparation practices to anticipate the increase to total production which results when the quality of the finished product is increased. The consumers of coal are continually seeking to obtain the best and most adaptable product for their money. Regardless of whether coal is used for coking, industrial requirements, electric power generation, domestic fuel or for other purposes, it will be scrutinized from such standpoints as delivered cost, suitability for utilization in certain equipment, ease of ash disposal, adaptability to material handling system plans and its potential for generating dust problems. Utilities, due to large capacity volume requirements, are generally in a position to select coal that will result in the lowest over-all cost per million Btu. Freight costs, paid by the utility, are important and are given utmost consideration when a coal is under consideration. Steel companies, whether producing or purchasing coking coal, are continually seeking coal that will result in lowering the cost of pig iron production. Since it is usually necessary to clean to lower specific gravities, say 1.40, to turn out a product meeting metallurgical requirements, it follows that a high ash "middling" product is created. These low quality middlings do not command a good price. Therefore, unless the metallurgical coal can command sufficient realization to carry or subsidize the middlings, the operator may be ahead economically to prepare steam coal at a higher specific gravity. While the "unit-train" rate reductions have been helpful to the economy of the coal industry, the establishment of these rates has made mandatory the installation of storage and rapid car loading facilities at mines and plants shipping utility coal (see Chapter 15). A study of the economics

Jan 1, 1968

By Floyd C. Kelley

The literature of the last decade is rich with information relating to the cause and means of control of grain growth in pure metals, but is deficient concerning the role diffusion plays in grain growth, although during this period many new products that depend on diffusion for their properties and success have been developed. Among these are cementation products, produced by calorizing, chromizing, and carbonizing, or by mixing, pressing, and sintering powdered metals such as Syke's iron-molybdenum die material, Genelite, and Elcon Metal (copper, tungsten) etc. This is a fertile field for new developments, but before it can be utilized to the fullest extent there must be a thorough invest,igation of the processes by which diffusion and grain growth take place. Grain growth plays no small part in the process and certainly the physical properties of these products depend largely on the grain size and state of equilibtiuni produced. The field of investigation does not end here, but may be extended to the effect of diffusion on impurities, segregations and dendrites in the broad field of ferrous and non-ferrous metallurgy. A number of years ago the author investigated several of these cases and noted, with striking regularity, the pronounced effect of diffusion in promoting recrystallization and grain growth. An example of this phenomenon is given in his paper on chromizingl which contained photomicrographs of large radial or columnar crystals produced by diffusion of chromium in the solid state. Another manifestation of this effect was discussed by Austen,2 who showed the part hydrogen plays in the decarburization of steel and the effect of diffusion upon the grain structure. Diffusion of Metals in Iron It seems to be a general law, whenever two metals are brought into intimate contact at a temperature at which diffusion takes place, that a comparatively rapid, or abnormal, grain growth results. The grains

By R. W. Moore, A. B. Kinzel

Although the iron-carbon diagram has undergone many changes in the last 20 years, the region below the eutectoid line and up to approximately 1.7 per cent carbon has been little affected. This region is generally considered to consist of cenlentite and ferrite. Graphite has been noted occasionally in the hypereutectoid steel region, and the ready formation of graphite nodules in malleable cast iron is a phenomenon difficult to interpret in the light of cementite, supposedly stable at sub-eutectoid temperatures. In this case the graphite formation has been partly explained by the presence of silicon, and many have believed that silicon acts to change the stable state rather than to accelerate reactions so as to arrive at the stable state in a briefer period of time. Consideration of this phenomenon indicates that cementite is not the stable phase in the temperature composition zone referred to. In the course of examining a low-carbon steel tube taken from a petroleum cracking still, which had been in service for approximately three years at temperatures somewhat below the eutectoid temperature, observations were made that shed light on this entire subject. The tube in question analyzed:' C, 0.15 per cent; Mn, 0.49; Si, 0.02; S, 0.023; P, 0.015. The microstructure of the tube after service is shown In Figs. 1 and 2. From these it is evident that cementite as such is absent, and that in its place nodular graphite has been formed. In order to check this observation further, samples taken from the tube were heated at 850" C. for varying periods of time. The small samples were put into a large hot furnace, and the total time is recorded. The structure of the sample after 5 min. at 850" C. is shown in Figs. 3 and 4, and the nest of pearlite surrounding the graphite nodules is most satisfactory evidence of the character of the nodules. As the length of time of heating at this temperature increases, the pearlitic zone increases, with final restoration

Jan 1, 1935

By R. W. Moore, A. B. Kinzel

Although the iron-carbon diagram has undergone many changes in the last 20 years, the region below the eutectoid line and up to approximately 1.7 per cent carbon has been little affected. This region is generally considered to consist of cenlentite and ferrite. Graphite has been noted occasionally in the hypereutectoid steel region, and the ready formation of graphite nodules in malleable cast iron is a phenomenon difficult to interpret in the light of cementite, supposedly stable at sub-eutectoid temperatures. In this case the graphite formation has been partly explained by the presence of silicon, and many have believed that silicon acts to change the stable state rather than to accelerate reactions so as to arrive at the stable state in a briefer period of time. Consideration of this phenomenon indicates that cementite is not the stable phase in the temperature composition zone referred to. In the course of examining a low-carbon steel tube taken from a petroleum cracking still, which had been in service for approximately three years at temperatures somewhat below the eutectoid temperature, observations were made that shed light on this entire subject. The tube in question analyzed:' C, 0.15 per cent; Mn, 0.49; Si, 0.02; S, 0.023; P, 0.015. The microstructure of the tube after service is shown In Figs. 1 and 2. From these it is evident that cementite as such is absent, and that in its place nodular graphite has been formed. In order to check this observation further, samples taken from the tube were heated at 850" C. for varying periods of time. The small samples were put into a large hot furnace, and the total time is recorded. The structure of the sample after 5 min. at 850" C. is shown in Figs. 3 and 4, and the nest of pearlite surrounding the graphite nodules is most satisfactory evidence of the character of the nodules. As the length of time of heating at this temperature increases, the pearlitic zone increases, with final restoration

Jan 1, 1935

By S. B. Twiss, P. R. Basford

The relationship between areas of iron powders, briquettes, and sintered compacts and tensile strength has been determined. It has been found necessary to distinguish between two types of areas which exist in such powders—a macroscopic area due to the shape and size of particles and a microscopic area due to pores and cracks in the surface. Only the macroscopic area, specifically the area due to particle irregularity, contributes to tensile strength; the microscopic area cannot be forced into contact with adjacent particles ond does not participate in bond formation. Of the two methods of area measurement employed in this study—permeability to liquids and gas-phase adsorption—only the former is useful for determining the roughness factor. A measure of this roughness, (area measured by permeability to liquid) -f- (orea of powder with the same size distribution, but made up of spherical particles), is shown to be uniquely related to tensile strength at constant density. The other important factors in determining the strength of sintered-metal compacts are the density and presence or absence of surface oxide. THE manufacture of metal parts by the process of powder metallurgy is an important and rapidly growing industry. Progress has been rapid and continuous, largely because of the excellent research in the field. Nevertheless, the process remains inherently complex and empirical. Several investigators have shown that the properties of the final compact must depend on many variables; namely, shape,' size distribution,"-" nd compositiona of the original particles, the pressure necessary to compress to the desired density, the density of the compact, the time and temperature of sintering, and so on. Through the application of some new techniques to the study of powders and compacts, and the correlation of a number of observations of known variables, the present paper attempts to clarify and simplify the underlying theory of the powder-metallurgy process. Any theory must start with the obvious fact that the strength of a compact, its most useful property, is due to the formation of welded areas between adjacent particles, and attempt to deduce what effect other variables will have on (a) the area and (b) the intrinsic strength of these welds. Such welded areas can be demonstrated by electron micrographs, as in Fig. 1. It was believed that (a) could be most directly studied by means of surface-area measurements on the original powders and on the compacts made from them; the area decrease should be related closely to the welded area. A representative group of eleven iron powders from commercial sources, and made by a variety of processes, was chosen for this study. In addition to the surface-area measurements, correlations were established between the tensile strength and all the known variables which might possibly affect it. The results are quite unexpected. They indicate that the situation is much simpler than the authors had anticipated. The strength of the sintered compact is determined, indeed, by no more than three variables; viz., the irregularity of the original particles, the density of the compact and, in exceptional cases, the amount of surface oxide. All three had been recognized previously as having some effect on the tensile strength, but in the absence of the special techniques and interpretations to be developed here, there could be no suspicion that they were the only relevant variables. Materials and Methods Material—All the iron powders were commercial products obtained from the Amplex Division of Chrysler Corporation. Powders A, B, C, and J were very pure electrolytic iron. Powder D was made from oxidized scrap reduced by heating with an excess of cast iron. Powder E was a high-grade iron ore reduced by hydrogen. Powder I was prepared by atomizing molten cast iron in an air blast, quenching the droplets in cold water, and crushing the coarse powder. Mill scale (oxide) is added and the mixture heated to reduce the high carbon content. The other powders were all prepared by reduction of iron oxides, such as mill scale. They

Jan 1, 1959

By AIME

Cores must be cut in half to secure workable samples for saturation, porosity, and permeability tests. They come from the field labeled as to the type of core, well, and depth from which they came.

Jan 1, 1948

By Y. Okahara, I. Iwasaki

Chlorination behaviors of pure iron and manganese oxides were investigated by combining a thermogravimetric analysis (TGA) technique with batch-boat roasting followed by leaching. Ferrous and manganous oxides could be chlorinated readily, but, in the absence of a reductant, the higher oxides of both iron and manganese were dificult to chlorinate. Thermogravimetric analysis curves were drawn to illustrate the complexities of the reactions, and the possible mechanisms were discussed. Then three manganif-erous materials from the Cuyuna Range of Minnesota were treated by a process involving the selective chlorination of manganese followed by leaching. The results were interpreted in the light of the chlorination mechanisms observed on the pure iron and manganese oxides. One of the unsolved problems challenging Minnesota's mining industry is the development of an economic process to utilize the manganiferous iron ores of the Cuyuna Range. Although these ores constitute one of the major domestic reserves of manganese (estimated at 432 million tons'), their grade is too low for them to be mined solely for manganese. The nearly exclusive dependence of the U.S. steelmaking industry on foreign manganese ores has stimulated research over the years in treating the low-grade Cuyuna ores. As a result, a number of processes have been proposed.'-' Among these processes is chlorination. Chlorination is the high-temperature conversion of metallic oxides to chlorides by either chlorine or hydrogen chloride gas, or by solid chlorides of sodium, calcium, or magnesium. The metallic chlorides are then recovered by either vaporization or leaching. Although chlorination is an old art, it has become popular in recent years for the recovery of such new metals as titanium, zirconium, and niobium; for the removal of impurities like copper, lead, and zinc from pyrite cinder for ironmaking raw materials;' and for the segregation roasting of coppera and nickel' ores. The chlorination processes proposed for manganifer-ous iron ores have been relatively few (hydrogen chloride chloridization-leaching, hydrogen chloride and calcium chloride chloridization-volatilization,' and chlo-rination-selective condensation6), due presumably to the economics and to the corrosion problems involved. However, the successful application of chlorination processes to other ores will undoubtedly contribute to technological advancements in the chlorination of man-

Jan 1, 1971

By E. H. Bunce, E. C. Handwerk

The inherent difficulties of zinc smelting arise from the fact that metallic zinc is volatilized at the reducing temperature of zinc oxide and thus is liberated in the form of a vapor. This vapor must be subsequently condensed to obtain metallic zinc, first in molten and eventually in solid form. Zinc vapor is sensitive to oxidation not only by air but by combustion gases containing carbon dioxide. It is, therefore, necessary to carry out both the reduction and the condensation operations in a closed system consisting of an externally heated muffle with attached condenser from which extcrnal oxidizing agencies are excluded. However, the reoxidation of zinc vapor cannot be entirely prevented by excluding external sources of oxidation. Internal sources of oxidation are necessarily present when oxidic zinc ores are reduced by a carbonaceous reducing agent. The reduction reactions themselves involve, first, the production of carbon monoxide in an amount at least equal in volume to the zinc vapor produced in the reaction, and, second, the formation of carbon dioxide. Not all of the carbon dioxide is reduced again to carbon monoxide by the excess carbon in the time available, and the slightly oxidizing condition, which results, seriously affects the efficiency of the condensation of the zinc vapor to the metallic state. In the past the difficulties arising from these causes have limited practical zinc smelting on an industrial scale to the use of small retorts equipped with small condensers. The retorts had to be small, because a closed refractory container capable of excluding oxidizing gases from the heating chamber surrounding the retort could not be built in large dimensions. The size was also limited because ordinary refractories when thin enough to conduct heat readily are not capable of sustaining a heavy load of charge at high temperature. Moreover, a loose charge of zinc ore and carbonaceous reducing material such as fine anthracite coal or coke breeze is a poor conductor of heat, thus limiting the cross section of the retort. The operation of these small retorts requires arduous

Jan 1, 1937

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem' has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.' show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967

By E. C. Tveter, R. B. Tippin

The separation of minerals by heavy liquids is a standard laboratory technique which goes back at least 50 years, but commercially economic application of this principal to ore concenfration has been prevented by problems of liquid recovery. Recent investigations which demonstrate the different types of liquid-solid systems on various ores using the two major heavy liquids - methylene bromide and tetra-bromoelhane — are discussed in this article. As a result of these studies, over-all liquid recovery, and especially desorption of heavy liquid from the mineral surface, was improved by the use of surfactants as well as both thermal and mechanical energy. The examples given in the article indicate that heavy liquids which should find major commercial use in ore concentration are now available. The sink-float process using a heavy liquid medium has long been recognized as a nearly perfect method of mineral separation based on the differences in density of the minerals. The use of heavy liquid separation (HLS) offers the potential of an ore dressing method that provides the maximum possible natural concentrate grade and high recovery. In addi- tion the process requires no water, causes no waste disposal problems, and is extremely simple — the crushed ore is merely introduced into a liquid whose density is between that of the minerals to be separated. The minerals lighter than the liquid float while those heavier than the liquid sink. As such, HLS has become a standard laboratory tool but major commercial application has been prevented by the requirement for complete recovery of the heavy liquid, imposed by economics and materials handling hazards. Investigations, both in the United States and abroad, have shown that improved liquid stability as well as improved chemical engineering techniques brighten the future for HLS in ore dressing. The available commercial heavy liquids suitable for mineral separation cost from $2.00 to $20.00 per gallon1 and on this basis alone their complete recovery is economically desirable. Possibly of even greater importance is the fact that any residual heavy liquid remaining on the products could create a serious toxicity hazard. Consequently, to make the process commercially attractive requires (1) essentially complete removal of the liquid from the ore products and (2) optimum recovery of the liquid for reuse. Until recently these two stipulations have remained as obstacles but laboratory and pilot plant research now in progress suggests that these may soon be overcome. Various heavy liquid recovery systems have been proposed to meet these requirements and might be classified into one or more of the following three general classes: Solvent Wash (Fig. 1): The dissolution of the heavy liquid from the ore with a less expensive solvent,

Jan 1, 1969

By Joseph Domenico

AMONG others, one of the most important duties of the accounting department is to disclose to the management the cost of production accurately and as quickly as possible after the ore has been produced and treated. A report is issued daily showing man shifts and the cost of labor, supplies, power, and miscellaneous charges to each department of the operation: mining, crushing, milling, packing and loading, and general expense. Mining costs are broken down into stoping, handling, development, exploration, and miscellaneous, and each of these subdepartmental costs are further broken down into the branches making up the subdepartment. Costs of crushing, milling, packing and loading, and general expense are detailed in the same manner. With such a detailed daily report as this, the management is able to keep in close touch with the efficiency of the entire operation. Because no expense items are deferred or spread over a period, and so that the report does not lose its comparative valve, appearances of unusual charges are explained.

Jan 1, 1946

By E. Kendall Cork

The traditional financial objective for a single mine company has been to operate as frugally as possible and to pay out most of the earnings as dividends. If the business is cyclical (as it is for most metals) the dividends might fluctuate quite widely. When the mine is exhausted the company disappears. This is still quite a viable strategy for a single mine company. It is not however a viable strategy for the world as a whole. The mining industry is built by mine development companies who can mobilize the people and capital to bring new mines into production. Their skills must include marketing, engineering, finance and other politics. It is very rare for a property to be brought in without the support of a major company that can provide all these services. The exceptions will usually have some other form of big brother support, for example the U.S. government uranium contracts at guaranteed generous prices. The mine development company will seek as a minimum to perpetuate itself by developing new mines in order to replace those which are running out. The more common and more ambitious objective is to grow -- that is to add to its ore reserves and current production by developing more new mines. The financial objectives for that company are very different. Obviously if all the earnings were paid out in dividends there would be nothing left to work with. The first financial policy then is to spend an appropriate amount on exploration for new properties. The next is to retain enough of the earnings to provide the capital for new projects at least sufficient for the equity. There is no magic formula as to what proportion of earnings should properly be distributed as dividends by a growth-oriented mine development company. As a rough rule of thumb distributing half or more will probably leave too little to work on and 30% or so is probably a good balance. However the circumstances differ widely from company to company. It may be useful to set an objective for the rate of growth of a company's earnings. Some have picked rates such as 15% per annum compounded. Others have set a target in real terms which might appear as 10 or 11% plus inflation. Obviously the arithmetic of compound interest is very attractive; however in practice there is much variation. Indeed current returns from existing operations swing widely with the business cycle and there is no assurance that economic new properties will be found according to someone's arbitrary time schedule. For example, Western Mining Corporation Limited in Australia explored for 30 years with little to show for it, but then found the great Australian nickel deposits and more recently the huge Roxby Downs copper. That long dry spell could not have fitted anyone's arbitrary calendar of growth and yet they would not have found such orebodies without that long period of effort. Should they have abandoned the search? Once a new property has been found or acquired there has to be a threshold rate of return on the new capital to be invested against which to evaluate the property's economics. Conventionally this seems to be 15% after tax, a number common in other heavy industries as well. In some cases it is expressed as a lower number plus allowance for inflation. Discounted cash flow analysis is a very useful tool but it does not make the decision. In the end a "go" decision depends on judgment of many factors some of which are numbers used in the DCF calculation whose credibility must be examined. It is curious how frequently investment proposals come in with the rates of return very close to 15%. The project advocates know that a number much less than 15% will not fly and that a number much more is not necessary. With much higher nominal and real interest rates of recent years, even though before tax, logic suggests that the hurdle rate should also rise. The power of compound interest is so great that 20% is very hard to achieve in any cash flow projection but 18% may be a sensible yard - stick. Once again it is remarkable how many project proposals come in with an 18% return. On the record the mining industry as a whole has not been overly restrictive in choosing its hurdle rates of return. This is shown by the abundance of metals in recent years and the failure of metal prices to keep up with inflation. All of the foregoing is standard text book stuff.

Jan 1, 1985

By John K. Berry

The handling and disposal of mine water is a much larger problem than is apparent at first glance. Many more tons of water are removed from underground coal mines in the United States each year than tons of coal. In the old anthracite region of Pennsylvania the average was around 36 tons of water for each ton of coal produced, while bituminous mines average about 5 or 6 tons. Water encountered in the mines may come from several different sources. In mines with light cover and without a firm solid roof, rain may seep directly into the workings. This is also true of deeper mines where pillar falls have broken the roof to the surface. The top under creek beds is generally faulty and broken and water comes through the roof at this point. Deeper mines are frequently overlain by water-bearing strata and pillar breaks and faulty top can admit water, while places running to the dip often accumulate water which comes up through the bottom. In all cases, except where passing under a year-round stream, the amount of water made is usually pretty closely connected with the weather-more water during the rainy season, less in the dry, although the deeper a mine is, the longer it is before changes in rainfall are felt. Another source of water, not connected with seasonal changes, is old water, accumulated over a period of time in abandoned workings of the mine, or from flooded adjacent mines. Here the water filters through the coal, the parting, or comes up through cracks in the bottom. Similarly, core holes, drilled to prospect the property, can be a source of unexpected water and modern safety requirements for dust-allaying water at the working faces can turn a pleasant working area into a soggy mess over the weekend if the system is not properly maintained and operated. Why water must be disposed is obvious. If allowed to accumulate, sooner or later the mine will fill up, or at least it will become "roofed" in low places, blocking ventilation and traffic. But it must also be controlled long before it reaches this stage. Water standing in the working faces is unpleasant for the men who have to work there and also cuts down on the amount of work they can do, as they must watch where they step all the time. It is especially unpleasant in low coal.

Jan 1, 1973