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By F. A. Schaufelberger

METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on page 545. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.' The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited3 to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SO2,4 which may lead to contamination with sulfur, or C0,5 which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents,7 which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere.' It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution composition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farben10 claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic, antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373ºC), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred, probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

The negative charges on diaphragms of quartz, tungstic oxides, stannic acid, acid dyestuffs, soaps, and glass have for a number of years been explained on the basis of chemical equilibria-a hydrogen ion or light metal ion passes into solution leaving the solid complex ion negatively charged. While there are a number of observations which indicate a proportionality between the ( potential and the streaming potential it should be recognized that all the experimental evidence thus far presented shows that if hydrogen ion concentration is kept at a constant value, electrokinetic phenomena are influenced by salts. The multivalent ions exert the greatest effect on the reduction of osmotic flow. In the interpretation of all electrokinetic data the assumption is made that the potential of the solid remains constant. That this is not true is evidenced by the values of ( potential for quartz in contact with conductivity water as reported by the several investigators and by the authors of this paper.

Sep 1, 1956

By M. R. Todd, J. Szekely

THE mechanism of carbon oxidation in steelmaking processes has attracted considerable attention in recent years. The generally accepted model postulates that the reaction between carbon and oxygen occurs at the surface of CO bubbles that originate at the suitable nucleation points and subsequently rise through the metal bath.1-4 Although this model describes adequately the behavior of open-hearth type operations, it is not a satisfactory representation of carbon oxidation in oxygen steelmaking processes since it cannot account for either: i) the very high rate of oxidation per unit bath area,or ii) the commonly reported shapes of the curves showing the dependenie of the oxidation rate on the carbon concentration. The very high decarburization rates commonly encountered in oxygen steelmaking processes need no further elaboration; some typical plots of the rate of carbon removal against carbon concentration, taken from a publication by Li, Dukelow, and smith,' are reproduced in Fig. 1. It is seen from the curves that the decarburization tends to decrease from a peak or a plateau once the carbon concentration falls below a certain value; in the experiments reported, this critical value ranged from 1.2 to 0.2 wt pct C. The apparent dependence of the decarburization rate on the carbon concentration indicates that within this region phenomena associated with the transfer of car- bon must play an important if not predominant role. Since the concentration of oxygen in molten iron at steelmaking temperatures (removed from the immediate impact zone) is only about 0.1 wt pct,6 it is clear that simple simultaneous diffusion of carbon and oxygen to the surface of CO bubbles could not account for the rate of carbon transfer being the controlling step at carbon concentrations as high as 1.0 wt pct. The purpose of this communication is to present an alternative model which may explain at least qualitatively the apparent anomalies mentioned and may stimulate further experimental work. The Physical Model. It is suggested that the principal mechanism of decarburization is the reaction between CO bubbles and an emulsion consisting of molten iron and molten iron oxide particles in the vicinity of the "slag-metal interface9'.* This mech-

Jan 1, 1968

By M. van Swaay, C. E. Birchenall

A. S. lBrling (Johnson, Matthey & Co. Ltd., Laboratories)— Because of its initial emphasis upon the production of membranes by powder metallurgy and by normal casting and rolling techniques, this paper is of considerable interest to those concerned with the design and application of industrial diffusion units. As the subsequent performances of the three grades of palladium were not compared in detail, it can perhaps be concluded that specific permeabilities were very similar. A short table in which the absolute diffusion rates obtained by the Authors with their three grades of palladium were compared with those of other investigators18-25 would, however, have been of particular value in view of the very variable results obtained with this membrane material. The Authors state early in the paper that the permeability of the thoriated samples decreased in much the same way as that of the nonthoriated samples. Later, they emphasize that sintered palladium without thoria was very susceptible to poisoning and did not respond as well as the other materials to the decontamination treatment. These results, which suggest that sintered membranes are less effective than those produced by normal methods, have considerable industrial implications, and amplified experimental details would be very welcome. The results of the Authors differ in one important respect from those of other investigators. Thus, no "bleeding" was required to maintain a constant rate of diffusion, although Davis, Darling, and De Rosset found this to be necessary. Davisz3 found that "bleeding" was necessary even when the hydrogen had already been purified by diffusion through a palladium tube, and it would be of value to know the purity of the gas stream emerging from the purification train shown on Fig. 1 of the Authors' paper. The Authors show that diffusion rates varied according to the square root of the pressure difference providing that the palladium membrane was not contaminated in any way. This finding is in agreement with the results of those workers2,18,19,23,24 who diffused their hydrogen through the membrane into a partly or completely evacuated system.Those workers who did not find this square-root law dependence did not have a partial vacuum on the downstream-side of the membrane.'' The difference between the two experimental con- ditions appears to be significant, as the absolute diffusion rates per sq cm of diffusion area are lower when the square-root law dependence is not observed. While the effect could be attributable to poisoning of the membrane it is conceivable that a positive pressure on the downstream side of the membrane might influence the mechanism of diffusion. In view of the capricious behavior of palladium, factors of this type, which are likely to influence its industrial significance, should be carefully considered. M. van Swaay and C. E. Birchenall (authors' 9-eply) — Our Eq. 191 may be compared with several others for hydrogen diffusion in palladium: D = 5.95 x exp (-5770/1)' D = 3.55 x 10"3 exp (-5550/)' D = 4.3 x 10"3 exp (-5620/1')' Other values are given in the literature, but in many cases surface poisoning may have affected the results. No analysis was performed on the hydrogen gas stream after purification. It should be noted that the presence of liquid nitrogen traps near the heated membranes may have set up convection currents and provided the equivalent of "bleeding." The question of whether a partial vacuum existed on the downstream side of the membrane is not clear. Does it imply that there is something unique about the permeability measured near one atmosphere pressure? We do not believe that there is. When square root pressure dependence is not observed, diffusion rates are not measured. Is "absolute diffusion rate per sq. cm. of diffusion area" equivalent to permeability? The terminology is new to us. In any case we doubt very much that pressures of the order of several atmospheres can affect the mechanism of diffusion.

Jan 1, 1962

By Terkel Rosenqvist

THE desulphurization of molten iron and steel is a very complicated process. One way to arrive at a better understanding of this process is to break it down into several simpler chemical processes that can be studied individually in the laboratory. For a study of the different factors that influence the equilibrium distribution of sulphur between liquid metals and slags, several simpler equilibria may be investigated. One very important subject is the determination of the escaping tendency of sulphur in the liquid metal and its dependency on temperature and composition of the melt. Several papers in this field have recently been published.', ' Another subject is the study of the sulphur capacity of the slag. A molten slag is indeed complex, and even if sulphur distribution data for a large variety of molten slags may give empirical data about their desulphurizing power, the importance of the individual components is still not quite clear. It is accepted generally that lime is the most important desulphurizing component in the slag. The present investigation has as its purpose to study the desulphurizing power of lime in its standard state, and to provide a basis for thermodynamic calculations of the desulphurizing power of various lime-containing slags. The standard state of lime at steelmaking temperatures is solid calcium oxide, CaO. It can react with sulphur to form solid calcium sulphide, CaS. The relative stability of calcium oxide and calcium sulphide is expressed by the free energy of the reaction: 2Ca0 (s) + S1 (g) = 2CaS (s) + O2 (g) The existing free energy data for this reaction, listed by Kelley5 nd Osborn,' are uncertain to about 10 kcal and are of limited value for a calculation of equilibrium constants. Under the conditions prevailing in a melting furnace, the sulphur pressure may be expressed conveniently by the ratio H,S/H2 and the oxygen pressure by the ratio H,O/H, (or CO,/CO). The desulphurizing power of calcium oxide may, therefore, be studied by the reaction CaO + HIS = CaS + H2O. A study of this reaction may be complicated by certain side reactions: Water vapor and hydrogen sulphide may react. to form sulphur dioxide, and calcium sulphide may be oxidized to calcium sulphate. A thermodynamic calculation shows that these side reactions will be suppressed to insignificance if the equilibrium is studied in the presence of an excess of hydrogen. The apparatus used is shown in Fig. 1. About 10 g calcium oxide and 20 g calcium sulphide (laboratory qualities) were intimately mixed, and some water was added to make a thick paste. The paste was put into a thimble of zirconium silicate, which was placed within the constant temperature zone of a furnace, and capillary refractory tubes were attached in both ends. After the mixture had been heated in dry hydrogen at 1000°C for several hours all Ca(OH), and CaCO, had decomposed and CaSO, was reduced, so only CaO and CaS remained in the thimble forming a porous plug. The mixture was examined by X-ray diffraction after the initial reduction in dry hydrogen as well as after the subsequent experimental runs up to 1425 °C. It was shown that crystalline calcium oxide and calcium sulphide were always present together in about equal amounts. The unit cell edges were found to be 4.80A for CaO and 5.68A for CaS in good agreement with existing literature values." This shows that the mutual solid solubility is very small, and that the compounds are present in their standard states. Purified hydrogen was passed through water sat-urators kept at constant temperature in a thermostat bath. The amount of water vapor saturation was checked by means of a dew point method, not shown on Fig. 1. The gas mixture was passed through the capillary inlet into the furnace, where it was sifted through the porous plug of calcium oxide and calcium sulphide. The hydrogen sulphide present in the outgoing gas was absorbed in a zinc acetate solution and the hydrogen was collected over water. When one liter of hydrogen had been collected, the amount of hydrogen sulphide was determined by iodometric titration. As one molecule of H,O is used for the formation of each molecule of H,S, the equilibrium ratio H,S/H,O would be , where (H,O) is the molar concentration in the ingoing gas, and (H,S) the molar concentration in the outgoing gas. In the present work (H,S) was always very small compared to (H20). In order for the observed H,S/H20 ratio to represent the true equilibrium ratio the gas flow has to be: 1—Sufficiently slow to give a complete establishment of equilibrium, and 2—sufficiently fast to counteract thermal diffusion. Incomplete reaction would give a value decreasing with increasing flow rate, and thermal diffusion would give a value increasing with decreasing flow rate. When inlet and outlet tubes of about 2 sq mm cross-section were used, the observed gas ratio was independent of the flow rate between 15 and 125 cc per min, Fig. 2. In this range, therefore, the observed gas ratio represents true equilibrium.* For the rest of the in-

Jan 1, 1952

By T. J. Whalen, S. M. Kaufman

Surface-tension measurements for liquid Fe-C-Co and Fe-C-Ni alloys were performed by the sesszle-drop technique at 1350o and 1425°C. Cobalt was shown to he more effective than nickel in lowering the surface tension of Fe-C alloys A minimum value for surface tension of 1640 dynes per cm was found in the Fe-C-Co system at a concentration of 1.5 pet C and 12pet Co. Analysis of these measurements in terms of adsorption and desorption behavior indicated that cobalt and nickel lower surface tension in Fe-C alloys by replacing carbon at the liquid-vapor interface. Comparison of results to date for Fe-C liquid alloys has shown that most substitutional-type elements having about the same atomic diameter as iron also have relatively the same influence on surface tension when present in dilute amounts. It has been shown previously that surface-adsorption behavior in liquid Fe-C ternary alloys is related to the manner in which the ternary addition affects the activity of carbon in the bulk solution.' Certain ternary additions, such as chromium, tending to decrease carbon activity cause adsorption of carbon and chromium to the liquid-vapor interface. Additions, such as silicon, increase the carbon activity, resulting in a desorption of carbon and an adsorption of silicon. Both cases were shown to cause a decrease in surface tension due to adsorption. It is the object of this paper, as part of the writers' continuing interest in the effect of alloying additions on the surface tension of Fe-C alloys, to present and discuss surface-tension data on solutions in the ternary systems Fe-C-Co and Fe-C-Ni. Available activity measurements for these systems in the solid state indicate a strong increase in carbon activity when either nickel or cobalt is added to Fe-C alloys.2, 3 EXPERIMENTAL PROCEDURE The alloy compositions used are shown in Table I. These alloys were prepared by vacuum melting in stabilized zirconia crucibles and then vacuum casting into cold-steel molds. The nominal analyses for the alloys used in this investigation are given in Table I. Surface tensions and densities were measured by the sessile-drop method4,5 in conjunction with the tables of Bashforth and bdams.' Specimens were prepared by slicing 1/4-in. cubes from the center of the vacuum-cast ingots and grinding the edges of these cubes until their shapes approximated spheres with flat bottoms. Proper handling techniques, including an acetone rinse immediately before use, assured minimum contamination from sources extraneous to the actual melting. For each experimental run a sample was placed on a BeO plaque and positioned and leveled inside a vacuum induction heating apparatus. The sample and plaque arrangement sat inside a molybdenum tube which acted as the susceptor. Diagrams of this apparatus may be found in the literature.= After heating to temperatures just above the liquidus at pressures of the order of 10-4 to 10- 5 mm Hg, photographs of the drop profile were made using its natural thermal radiation as a light source. Some measurements were made with partial pressures (-1 cm Hg) of a mixture of H2 and He gases. The H2-He atmospheres proved to be necessary at higher nickel contents to retard excessive vaporization losses. Chemical analysis for carbon and the ternary addition was performed for each alloy sample after completion of the experimental run.

Jan 1, 1964

By J. P. Timmons, J. H. Moran, G. K. Miller, M. A. Coufleau

A prototype equipment has been designed and built for the digital recording of well logs on magnetic tape at the same time that the regular film recording is made. The format of the digital tape produced is such that it can be used directly at the input of the ZBM 704, 7090 or other models of ZBM computers which accept digital magnetic tape. This apparatus has been used for the experimental field recording of dipmeter tape logs which were subsequently computed by means of an ZBM 704 or 7090. In this paper the equipment and the digital tape are described briefly, and their application to the computer-interpretation of dipmeter data is discussed. A principal element in the interpretation of the dipmeter log is the correlation of the three microresirtivity dipmeter curves to determine the depth displacements between them. Several correlation methods for computer use are considered, with particular attention to their sensitivity to error and their consumption of computer time. The tape data were used to compute information content of the dipmeter microresistivity curves in terms of their frequency spectra. The results show that the sampling rate used in recording the digital information is quite adequate and illustrate a use of the digital tape in evaluating the characteristics of new tools. Some examples of field results are shown. It can be foreseen that, when digital tape recording becomes available for general field use, a whole new realm of possibilities will be opened up for the processing of other well logs through computations, which hitherto were not feasible because they were too laborious and time-con.sunzing. INTRODUCTION The last few years have seen a revolution in the design and production of data-processing equipment. Stored-pro-gram digital computers have progressed from a research curiosity to the basis of a major industry. There are now hundreds of such machines in daily use in the United States. With the acceptance of a technique that was, in fact, already clearly described by John von Neumann in 1945, the last decade has seen great strides in the development'of components, reliability, programming systems and, most spectacularly, in the sheer number of machines built and in use. In 1957 there were enough digital computers available to the oil industry to justify the suggestion that it would be worthwhile to investigate the possibility of using these machines in processing well log data.' The first result of this investigation was the appearance of what may be referred to as the input-output bottleneck. Well logs are customarily recorded on film. To get these data into a machine required then (and still does): a time-consuming semi-automatic reading of the film; conversion of the log data to digital form; and recording these digital data in some medium acceptable for computer input, such as cards, magnetic tape, or punched paper tape. However, the recording, reading, and re-recording could only result in deterioration of the data. Therefore, it was concluded that the fist step should be the development of a new, more direct recording technique supplemental to the film recording, which would provide easy access to the digital computer. There are many solutions to the problem of recording log data in an easily recoverable form. After careful consideration it was decided to adopt the boldest solution which, it was felt, was also the most elegant. It was decided to record well logs directly, in the field, on magnetic tape in such a way that this tape could be used without further modification as an input to the IBM 704 or 7090 computer. To realize practical field recording of magnetic tape logs, it became necessary to develop in a rather small package, an analog-to-digital converter, a tape recorder, and the necessary multiplexing and control circuits to allow the simultaneous recording of a multiplicity of logging signals. The magnetic tape recording was to be made simultaneously with the conventional logging operation in such a way as not to interfere with it. Along with the development of hardware, it was necessary to begin development of interpretation techniques and machine programs that would exploit the power of the digital computer. Here, again, there is a long list of possible applications. After much consideration it was decided to concentrate on the interpretation of the dipmeter log as a first application. It is the object of this paper to describe in some detail the developments sketched in the last three paragraphs.

By S. B. Patterson, A.R. Amos

Log washers have been used for many years in the washing of clay iron ores, phosphate rock and manganese ores, but not until the past 15 years have they been employed to any extent in the preparation of aggregate materials and fluxing stone. For a machine of such importance where tenacious clay or soft rock must be eliminated, there are few data generally available. The purpose of this paper is to set forth the results obtained from several operations, together with a few suggestions for planning a specific installation. Where the material to be washed out consists of loose surface soil, silt, or small amounts of quickly soluble clay, there is little competition with other forms of washers, because greater power and maintenance are required for the operation of log washers, but where the foreign matter is a stiff clay, such as occurs with high-calcium limestones and in marginal gravel deposits, the ability of other kinds of washers to eliminate completely the hard clay balls is at least uncertain. Then the log washer comes into its own field, for with the breaking and churning action of the logs it will clean out the toughest clay. Even with material from the hydraulic dredge, if it contains tough clay, the log washer is desirable unless the gravel is subjected to a costly soaking and rehandling process. Recently there has been a considerable development in other types of machines to accomplish these results but it is not within the scope of this paper to make comparisons between competitive types, but to present the best obtainable data on log washers only. From the primitive design that gave it its name, a long log hewn from a tree, with paddles forged to shape from strap iron and attached by lag screws, the log washer has gradually been developed to the present all-steel type. As now manufactured, the log washer consists essentially of two built-up logs on which are mounted a series of paddles, carried by shafts fitted at the ends of the logs on bearings fastened outside the enclosing steel box, or trough, which is set at an angle of about 5" to 10" and into which the material is fed. Stuffing boxes at the places where the shafts pass through the box at the lower end are equipped with water-

Jan 1, 1938

By A. R. Amos, S. B. Patterson

Log washers have been used for many years in the washing of clay iron ores, phosphate rock and manganese ores, but not until the past 15 years have they been employed to any extent in the preparation of aggregate materials and fluxing stone. For a machine of such importance where tenacious clay or soft rock must be eliminated, there are few data generally available. The purpose of this paper is to set forth the results obtained from several operations, together with a few suggestions for planning a specific installation. Where the material to be washed out consists of loose surface soil, silt, or small amounts of quickly soluble clay, there is little competition with other forms of washers, because greater power and maintenance are required for the operation of log washers, but where the foreign matter is a stiff clay, such as occurs with high-calcium limestones and in marginal gravel deposits, the ability of other kinds of washers to eliminate completely the hard clay balls is at least uncertain. Then the log washer comes into its own field, for with the breaking and churning action of the logs it will clean out the toughest clay. Even with material from the hydraulic dredge, if it contains tough clay, the log washer is desirable unless the gravel is subjected to a costly soaking and rehandling process. Recently there has been a considerable development in other types of machines to accomplish these results but it is not within the scope of this paper to make comparisons between competitive types, but to present the best obtainable data on log washers only. From the primitive design that gave it its name, a long log hewn from a tree, with paddles forged to shape from strap iron and attached by lag screws, the log washer has gradually been developed to the present all-steel type. As now manufactured, the log washer consists essentially of two built-up logs on which are mounted a series of paddles, carried by shafts fitted at the ends of the logs on bearings fastened outside the enclosing steel box, or trough, which is set at an angle of about 5" to 10" and into which the material is fed. Stuffing boxes at the places where the shafts pass through the box at the lower end are equipped with water-

Jan 1, 1938

By G. Nabi, W-K. Lu

Cylindrical specimens of natural dense hematite were reduced to magnetite at atmospheric pressure in H2-H2O mixtures of known composition over the temperature range 1084° to 1284°K. The rate of reduction was measured by the rate of movement of the interface between hematite and magnetite. The diffusion of gases through the gaseous boundary layer, the magnetite layer, and the interfacial chemical reaction were all considered in the interpretation of experimental data. The mass transfer coefficient through the boundary layer was calculated using accepted correlations. Values of the chemical reaction rate constant and the diffusivity of hydrogen in the magnetite phase were determined. THE present investigation is concerned with the reduction kinetics of natural hematite to magnetite by H2-H2O mixtures in the temperature range 1084" to 1284°K at atmospheric pressure. This reaction is the first step in the series of topochemical reactions in the process of reducing hematite to iron. Kinetic information of the simple steps such as hematite-magnetite transformation is necessary in order to have a better understanding of the complex processes of hematite reduction in iron-making. It also has direct industrial significance because magnetic roasting is one of the most important methods in benefication of lean ore.&apos; Although many technical papers have been published on the process of magnetic roasting and iron oxide reduction, very little information is available in the literature concerning the fundamental nature of hematite reduction to magnetite by reducing gases. Hansen et al.2 reduced the dense synthetic pellets of high-purity oxide in CO-CO2 mixtures and determined the reaction rate by weight-loss method. They were able to interpret most of their results by applying the interfacial area control theory developed by Mckewan.3 In contrast, Wilhelm and St. Pierre,4 who studied reduction of hematite to magnetite in H2-H2O mixtures by weight-loss method, stressed that the resistance of the porous magnetite layer to the diffusion of gases cannot be neglected in consideration of the overall reaction rate. In the present study the contributions of interfacial chemical reaction, diffusion of gases through the magnetite phase, and the gaseous boundary layer to the overall reaction rate will be considered. APPARATUS AND PROCEDURE Hematite Specimens Preparation. Natural hematite ore from Vermillon range of Northern Minnesota was selected for the present investigation because of its high purity and thermal stability. Chemical analysis of five samples gave the following average values: 67.52 pct total iron (96.62 pct Fe2O3, 0.28 pct FeO, 0.03 pct metallic iron), 2.53 pct SiO2, <0.07 pct MgO, 0.03 pct CaO, 0.05 pct combined mixture, 0.07 pct loss on ignition, and 0.34 pct other. Cylindrical specimens of 0.93 cm in diam and 2.7 cm in length were drilled from slabs of ore with a water-cooled diamond core drill. These specimens were heated to 1000°C and furnace-cooled. Specimens with silica pockets developed large cracks. The uncracked specimens were heated a second time, and their surfaces were carefully examined with a microscope. Those with hairline cracks or surface inhomoaenitv-- were rejected. Preparation of H2-H2O Mixtures. H2-H2O mixtures were prepared by the combustion of H2-O2, mixtures in a pyrex glass chamber in the presence of a catalyst. Alumina pellets coated with palladium, supplied by Englehard Industries, were used as the catalyst. Purified grades of hydrogen and oxygen were used which were repurified by usual techniques. Hydrogen before entering the combustion chamber was passed through an activated alumina H2O absorption bulb, with copper turning at the top. The cover of this bulb was not made pressure-tight so that any pressure development in the hydrogen line would cause the cover to blow off and also the copper turnings would act as a flame arrester in the case of a flashback from the combustion flame. Oxygen flow rates were measured with a bubble flow meter after purification with 1 pct accuracy. Hydrogen flow rates were measured by "precision wet test meter" and the amount of unburnt hydrogen was accurately measured by a bubble flow meter, after condensing water vapor in the gaseous stream. The Pyrex glass bulb contained concentric Vycor glass tubes as shown in Fig. 1. Oxygen was prevented from diffusing into the hydrogen line by threading platinum wire through pores at the combustion end of gas inlet tube. The glass bulb was heated with a Kanthal heating wire pasted in asbestos paper. The surface temperature of the bulb was measured with a thermocouple and adjusted to remain at approximately 350°C. The gaseous reaction chamber also served as a preheater for gases to avoid thermal segregation. The following sequence of operation was adopted. 1) Nitrogen was passed through the outer concentric tube to purge the catalyst bulb of oxygen. 2) Hydrogen was introduced through the inner tube until a steady flow was obtained. 3) Oxygen was then introduced into the nitrogen stream passing through the outer tube. 4) When combustion had commenced and a flame was visible over the platinum wire, the N2 was turned off.

Jan 1, 1969

By M. H. Childs, K. E. Merklin

Blast furnace feed specifications are being revolutionized because of the large increase in iron pellet production from low-grade ores of the Lake Superior region. Recent laboratory findings aimed at a better understanding of factors influencing the physical quality of pellets produced from taconite concentrates are reviewed. Tests for determining better product quality, the effects of additives, and production factors are discussed. The current revolution in specifications for blast furnace feed is typified to a great extent by the recent tremendous growth in iron ore pellet production from low grade ores of the Lake Superior region. Indeed, pellets are responsible, at least in part, for many of the stringent new requirements that are being placed on the suppliers of furnace raw materials. As the tonnage of pellets going to the steel mills increases, more and more attention is being turned to the detailed characteristics that make this product an ideal blast furnace feed. Control of quality in pellets is similar to that of any other product. A basic understanding of the factors that are encountered in their production, from the crude ore through to the finished product, is required, along with careful process supervision and frequent quality checks. Normally, chemical grade is not a problem. This usually can be controlled within the desired specifications by minor operating variations in the con- centrator. While future changes in requirements may result in the need for self-fluxing pellets1 or other chemical changes, today&apos;s quality demands center primarily around the physical characteristics of the pellets. It is in this area that many of the recent laboratory studies have proven helpful to the operating plants. A better understanding of the physical factors involved in pelletizing has provided the basis for a continuing program of quality improvement. Tigerschiold and Ilmoni2 and Cooke with various associates are responsible for the development of much of the basic understanding of the pelletiz-ing process. These earlier findings have served as a most useful background for this work. LABORATORY PROCEDURES Magnetite concentrates produced from eastern Mesabi Range magnetic taconites were used for all of the work reported herein. The sizing and chemical analysis of a random sample are shown in Table t Additives usually are mixed with the concentrates in taconite plants before pelletizing to improve the strength characteristics of the unfired balls. Ben-tonite, soda ash, and coal are in common use. The bentonite used in these studies was of the Wyoming sodium type; the soda ash was a standard commercia1 brand. Anthrafines were used where coal was called for. The procedure for making batches of balls at the Hibbing Laboratory is as follows: In an especially designed mulling equipment 2800 g of dry ore are mixed for 10 min with the desired additives. Water is added and mixing continued for 1 1/2 min. The charge is removed from the muller and put through a mechanical shredder to break down any lumps that may have formed. sixty previously formed seed balls are placed in the balling drum, which is in fact a 6 x 16-in. diam airplane tire turning at 53 Wm. Two thousand grams of the shredded concentrate and additive mix are fed by hand into the tire at a con-

Jan 1, 1961

By E. Hoek

INTRODUCTION Rock slope stability research has been in progress for the past four years at the Royal School of Mines in London under the sponsorship of a consortium of 23 companies* with interests in open pit mining. This paper reviews the principal aims and achievements of this research project. In order to assist the reader in following these details, the basic philosophy underlying the formulation and direction of this research project is discussed. DISTRIBUTION OF RESPONSIBILITY In open pit mining, the economic necessity of keeping waste rock removal to a minimum generally means that the mine slopes have to be excavated to the steepest possible slope angle. On the other hand, excessive steepening of these slopes can induce failures, which may negate the economic benefits that have been aimed at and which may also result in loss of life and damage to equipment. Consequently, where slope failures are likely to prove to be a problem, an evaluation of the stability of the slopes to be created should be included as part of the overall pit design. How is the stability of a rock slope evaluated? When this question was examined, during discussions on the research policy to be followed at the Royal School of Mines, it was clear that relatively few satisfactory techniques were available in a form that would be comprehensible and therefore useful to the practical mining engineer. It was recognised that the research project must be directed towards two distinct aims: a) The evaluation of existing techniques for rock slope stability analysis and the provision of new techniques where these existing methods were found to be inadequate and b) The presentation of the results of this evaluation and research in a form that would be useful to engineers without specialist training in rock mechanics. It was soon realized that a university based research team, however large and efficient, could not achieve these aims without the co-operation and assistance of mining engineers,

Jan 1, 1972

By W. J. Uren, Charles R. Kuzell

The industries engaged in winning minerals from the earth, because of their widespread dissemination, are faced with perhaps as wide a variety of labor-management problems as may be found in any other broad sphere of productive activity. Those problems are continually increasing in volume and complexity, and management has become aware of their growing importance. For the past quarter century at least, labor-management problems have largely been union-management problems. During this period tremendous assistance has been given labor unions through legislation and administrative and political action. In the United States, legislation favorable to unions has come about in the form of the now defunct National Industrial Recovery Act; the Wagner Act, most of which has been carried forward in the Taft-Hartley Act; the Norris-La Guardia Act; the Wage and Hour Law; the Walsh-Healey Act; and others. The result has been to transfer from the hands of management to those who direct the affairs of the unions a large share of control over the industry and to hamper in many ways the remaining control left to management. In the United States there are many examples of the power of unions to injure whole industries seriously with- out regard to the interests of management, the employes, or the public. This chapter deals with the various phases of labor-management relations as they affect the principal segments of the mineral industry in North America. To the greatest extent possible available data is presented pertaining to the unions involved, their relative strengths, labor law, compensation and fringe benefits of employes, working conditions, and related matters. As background, the historical development of union-management relations in the respective segments is included where possible. The section dealing with the United States has been divided into separate

Jan 1, 1959

By P. W. Gilles, B. D. Pollock

THE pioneering work of Steinitz1 and Steinitz, Binder, and Moskowitz2 has shown conclusively the existence at high temperature of two additional phases in the molybdenum-boron system and thus brings to a total of six the number of structures appearing in this system. To the structures Mo2B, MOB, and Mo2B5 they have added MO3B2, a new -MOB form, and have shown that MOB,, which has the same range of composition as Mo2B5, is only a high temperature structure of the latter. This solid solution, interestingly enough, includes neither of the compositions corresponding to the stoichiomet-ric compounds, MOB, or Mo2B5, but rather at all temperatures has intermediate values of composition. These workers have also, in the course of their work, measured melting points, transition temperatures, eutectic and peritectic points in the system and have shown that Mo3B2, because of its dispro-portionation at low temperature to Mo2B and MOB, is stable only in a limited high temperature range. During the course of the present work on the vaporization properties of the molybdenum-boron compounds, a few transition temperatures were observed. When the report of the other workers appeared, it was decided to repeat, in part, their study of the system. As a result, considerable evidence has been obtained that substantiates the specific kinds of melting processes they report as well as the general features of their diagram. However, a marked difference was found between the temperatures they report and the ones observed in this study, with the latter being higher. The purposes of this paper are to present the evidence obtained in this laboratory that verifies their diagram of the system, to give some important temperatures in the system, to compare them with those previously published, and to seek an explanation of the difference. Samples The metal starting material was 400 mesh molybdenum powder with a purity stated by the manufacturer to be 99.9 pct. The initial treatment, designed to remove volatile contamination, consisted of heating in a vacuum for 10 min to a temperature of from 800" to 1000°C during which a loss of 0.3 to 0.4 pct occurred. An assay following this treatment showed it to be 99.4 pct pure, with the principal impurity probably being oxygen. The boron starting material was obtained from the Cooper Metallurgical Laboratories and the Fair-mount Chemical Co. as 325 mesh powder with manufacturers&apos; analyses of 99 pct or better. Initial treatment consisted of heating in molybdenum in a vacuum at about 1700°C for 10 min. During this time a loss of 3.5 pct occurred. An assay following this treatment showed the different samples to have purities ranging from 95.5 to 99.0 pct with iron and carbon as the principal impurities. Following the initial treatment, the elements were combined to form stocks of Mo2B and MOB by heating pressed mixtures in a vacuum to 1100" to 1200°C to accomplish reaction and to 1500" to 1900°C for a few minutes to evaporate the more volatile impurities. Analysis of the two compounds for boron by a modification of the method of Blumenthal3 and for molybdenum by the lead-molybdate method indicated them to have purities greater than 99 pct. The individual samples to be studied had compositions in the Mo2B-MOB range and consisted of mixtures of the stock compounds. Procedure As is usually the case in high temperature work the selection of containers for the samples posed some problems. For vapor pressure studies tantalum crucibles, allowing little contact with the pressed samples, were used and some of the observations made during these experiments are pertinent to the study of the phase diagram. Most of the experiments, however, were performed in graphite containers, as were those of the previous authors. Two kinds of spectroscopic grade graphite crucibles were used. One was a % in. cylinder, 3/4 in. high, containing seven 3/16 in. holes drilled 1/2 in. deep into which were packed samples of the different mixtures weighing 250 to 500 milligrams. The other, consisting of separate crucibles, was prepared by drilling 3/16 in. holes, 1/2 in. deep into 1/4 in. graphite rods % in. long. The 7/8 in. cylinder was heated directly by induction while the small crucibles were packed in a tantalum heating element for induction heating. All heating was done in a high vacuum system in which the pressure was generally less than 1x10-5mm and never rose above 2x10-5mm when the samples were hot. The general pattern of the heating in graphite was to heat rapidly to a temperature somewhat below the desired one, then to raise the temperature slowly. The samples were held for 2 to 5 min at the maximum temperature, which in all cases was far higher than that needed to produce reaction. The short time was employed to reduce possible contamination by the crucible material and to reduce composition changes that would occur because of vaporization. After examination following the heating, the samples were reheated to a higher temperature. Temperatures were measured with a Leeds and Northrup disappearing filament optical pyrometer, certified by the National Bureau of Standards, by sighting through a window at the top of the vacuum

Jan 1, 1954

By A. D. Hodges

The great mining region of Peru is a mountainous belt of country, running nearly the whole length of the republic, and comprising the two grand ranges of the Andes with the elevated table-lands between them. On the east of this belt are the extensive plains and fertile valleys of the Amazon and its tributaries. On the west is a narrow strip of coast 20 to 50 miles wide, for the most part a sandy desert, but producing abundant crops where irrigated ; and here are found petroleum (Department of Piura), salt (at Huacho and elsewhere), nitrate of soda in enormous amounts at the south, silver in a few localities (Province of Tarapaca), copper and other mineral products. The Western Cordillera, running nearly parallel with the shoreline, rises like a wall on the eastern side of the coast-belt, with passes from 15,000 to 18,000 feet high and peaks attaining 18,000 to 20,000 feet. Further east, at a varying distance, is the Eastern Cordillera, composed of broken mountain ranges which, considered as one group, have a general parallelism with the western chain, but individually vary greatly in direction, sometimes running nearly east and west, in places projecting out into the Amazonian lands, or here and there curving around to unite with the western ridge, and with this enclosing immense inter-alpine plains. These general features are indicated in Fig. 1. The surface of these plains is uneven and traversed by lower ranges of hills which surround large lakes, or rolling pampas, or fertile valleys; and through many of these last run rivers of considerable size. The whole country has a high altitude (averaging up to 15,000 or 16,000 feet), and slopes gradually north and east towards the Amazon, into which drain all its waters. Its bounding mountain chains are scored on all sides by narrow, picturesque and pre-

Jan 1, 1888

In a straight caving system, the ore is first undercut and then broken down by its own weight or .by the weight of the overlying rock, or by a combination of both. Operations that involve the caving of the material overlying an orebody as an essential part of the work are also classed as caving, though practically all the ore is broken by drilling and blasting. Actually there are two distinct methods—sublevel caving and block caving, and modifications thereof. The mines described are Miami and Alaska Juneau.

Jan 1, 1925

By J. C. Yannopoulos, N. J. Themelis

Ah electronic thermogravirnetric balance was used to measure the veductioiz rule o single cirpric oxide particles suspended in a stream of hydrogen. Very jzne thermocouples embedded in lie center and at the surface of the sphere recorded the variation of terw perature during reduction. In contrast to iron oxide reduction, where in most instances the rate of interface reactiokl is controlling, the heat- and mass-transfer phenotnena play a predolrinant role in the reduction of cupric oxide. The correlation of experitnental data or tnass lransfev lhrough the boundary layer at Reynolds nunlber 0-4 50 was as jollocs: ThE reduction of cupric oxide by hydrogen is represented by the equation: It is a highly exothermic reaction and the amount of heat released varies only slightly with temperature (-21,430 cal per g-mole at 400°C). Most of the published studies on this system have been conducted at temperatures in the range of 34 to 280c.l-&apos; The concensus of opinion has been that at temperatures below 200°C the reaction is preceded by an induction period during which there is very little or no reduction. The length of this period diminishes as the temperature of the reaction is increased1l5 and aseawa found that at 280°C reduction starts practically immediately when the oxide is exposed to hydrogen gas. The existence of an induction, or incubation, period has led experimenters to believe that the reduction of CuO by hydrogen is catalyzed by metallic copper.&apos; Boldurev and rmolaev found that mechanical additions of powdered copper to oxide did not affect its reduction, although metallic copper produced during the reduction seemed to have a catalytic effect. At least three other authors2&apos;5&apos;7 have reported that addition of copper had no effect on the rate of reduction. Pease and alor&apos; observed that water vapor had a strong inhibiting effect on the reduction at 1503C, but its effect was greatly diminished at 200 C. Pavlychenko and Rubinchik5 studied this reaction at 159 to 235 C and found that, once the reaction had been initiated, there was no inhibiting effect due to the introduction of water in the hydrogen stream; at temperatures above 183°C there was no inhibiting effect due to water vapor, either before or during reaction. The same authors noted that the rate of reduction was independent of pressure in the range of 200 to 700 mm Hg. aseawa investigated the kinetics of the CuO-Hz system at 160 to 280°C and estimated the apparent activation energy at 14,000 cal per g-mole. A similar value (13,500 1200 cal per g-mole) was reported by ond&apos; in the temperature range 148 to 216°C. Bond also reported that there was no incubation period and that water vapor had no inhibiting effect on reduction at temperatures above 190 C. The above studies have been conducted at temperatures below 280°C and the physical configuration of the system under investigation has not been defined adequately. However, it is well-known that the mechanism of gas-solid reactions depends on a number of in series physical and chemical rate prcesses.&apos;&apos; It is, therefore, essential to include among the experimental factors the geometry of the solid system and the mass-transport characteristics of the reducing gas. Scott studied the reduction of packed beds of cupric oxide cylinders by Hz-He streams of very low hydrogen concentrations at temperatures 400 to 600 C, pressure of 10 to 30 atm, and gas velocity from 0.18 to 5.8 ft per sec (3 < Rep < 30). The reduction rate was found to be mainly controlled by diffusion through the boundary layer and through the pores of the reduced copper phase. The following correlation was proposed: Scott in an earlier work studied the reduction of fixed beds of cupric oxide wire and found that the rate of flow of the gas stream through the bed had a controlling effect on the rate of reduction. The same mass-transfer phenomenon was observed by Bond and clark13 on a similar reduction system. The analogy between mass and heat transfer through the boundary layer which exists between a solid surface and the bulk stream stems from the similarity of the differential equations representing these phenomena

Jan 1, 1967

By C. F. Park

Hog Mountain is in the north central part of Tallapoosa County, Alabama, about 13 miles northeast from Alexander City. The Hog Mountain Mining and Milling Co. controls 1658 acres of land and is the only company operating in the district. The principal mine workings are in sections 10 and 15, T.24N., R.22E. The region has been visited by geologists many times, has been briefly described in several papers,&apos; and mentioned in many others. No detailed map of the mine or vicinity has been published. The field work for this report was started in March, 1934, as part of the Public Works reemployment program. About a month and a half was spent mapping both the surface and underground geology. The mine owners and operators have cooperated in every way possible to facilitate the work. N. 0. Johnson, the mine engineer, E. W. Ellsworth, J. E. McCoy and J. G. Englebert have acted as assistants for part of the work. The University of Alabama and the State Geologist&apos;s office have aided materially by permitting free use of their libraries and laboratory equipment. Geography Hog Mountain forms a conspicuous ridge that rises to a height of a little more than 1000 ft. above sea level, and about 400 to 500 ft. above the adjacent country. The ridge is composed of granitoid intrusive rock and silicified schist that are more resistant to erosion than the surrounding softer schist. The topography of the area around the ridge is gently rolling and is typical of the subdued forms of the deeply eroded Southern

Jan 1, 1935

By C. F. Park

Hog Mountain is in the north central part of Tallapoosa County, Alabama, about 13 miles northeast from Alexander City. The Hog Mountain Mining and Milling Co. controls 1658 acres of land and is the only company operating in the district. The principal mine workings are in sections 10 and 15, T.24N., R.22E. The region has been visited by geologists many times, has been briefly described in several papers,&apos; and mentioned in many others. No detailed map of the mine or vicinity has been published. The field work for this report was started in March, 1934, as part of the Public Works reemployment program. About a month and a half was spent mapping both the surface and underground geology. The mine owners and operators have cooperated in every way possible to facilitate the work. N. 0. Johnson, the mine engineer, E. W. Ellsworth, J. E. McCoy and J. G. Englebert have acted as assistants for part of the work. The University of Alabama and the State Geologist&apos;s office have aided materially by permitting free use of their libraries and laboratory equipment. Geography Hog Mountain forms a conspicuous ridge that rises to a height of a little more than 1000 ft. above sea level, and about 400 to 500 ft. above the adjacent country. The ridge is composed of granitoid intrusive rock and silicified schist that are more resistant to erosion than the surrounding softer schist. The topography of the area around the ridge is gently rolling and is typical of the subdued forms of the deeply eroded Southern

Jan 1, 1935

Hog Mountain is in the north central part of Tallapoosa County, Alabama, about 13 miles northeast from Alexander City. The Hog Mountain Mining and Milling Co. controls 1658 acres of land and is the only company operating in the district. The principal mine workings are in sections 10 and 15, T.24N., R.22E. The region has been visited by geologists many times, has been briefly described in several papers,&apos; and mentioned in many others. No detailed map of the mine or vicinity has been published. The field work for this report was started in March, 1934, as part of the Public Works reemployment program. About a month and a half was spent mapping both the surface and underground geology. The mine owners and operators have cooperated in every way possible to facilitate the work. N. 0. Johnson, the mine engineer, E. W. Ellsworth, J. E. McCoy and J. G. Englebert have acted as assistants for part of the work. The University of Alabama and the State Geologist&apos;s office have aided materially by permitting free use of their libraries and laboratory equipment. Geography Hog Mountain forms a conspicuous ridge that rises to a height of a little more than 1000 ft. above sea level, and about 400 to 500 ft. above the adjacent country. The ridge is composed of granitoid intrusive rock and silicified schist that are more resistant to erosion than the surrounding softer schist. The topography of the area around the ridge is gently rolling and is typical of the subdued forms of the deeply eroded Southern

Jan 1, 1935