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By L. Burris, C. H. Stockman, I. G. Dillion

Zone melting is a purification process in which separation of impurities is effected by slowly moving a narrow melted zone through a bar of solid material. Equations are presented which 1—predict the concentration profiles after successive passes of the zone and 2—give the limiting distribution of solute along the bar after an infinite number of passes of the molten zone. These equations take into account the effect of normal freezing in the last zone length. These equations were solved numerically using an electronic computer, and the concentration profiles are presented as a function of the solute distribution coefficient and the ratio of molten zone to total bar length. ZONE MELTING is a purification process in which separation of impurities is effected by slowly moving a narrow melted zone through a bar of solid material. Separation occurs if the solid freezing from a solution at any moment has a composition different from that of the liquid from which it is freezing. Solutes which lower the freezing point will tend to remain in solution and will be moved in the direction of zone travel. Solutes which raise the freezing point will preferentially freeze out, and they will be moved in a direction opposite to that of zone travel. After repeated unidirectional passage of a molten zone through a bar of material, impurities will be concentrated in the ends of the bar. A limiting concentration gradient will be reached in the bar after a large number of passes of the molten zone. Both the magnitude of this limiting concentration gradient and the rate of movement of solute in any pass depend on the zone length and on the equilibrium concentrations of solute in the liquid and solid phases. The basic theory of zone melting was thoroughly covered by Pfann.1 The purpose of this paper is to extend the theory of zone melting by presenting 1—equations which relate the concentration profiles in successive passes of the zone and 2—equations which give the limiting distribution of solute along the bar after an infinite number of passes of the molten zone. These equations take into account the effect of normal freezing* in the last zone length concentration of a given solute in the solid to the concentration of the same solute in the liquid. Analytical methods for determining the concentration profiles after any pass have been developed by Lord2 and Reiss. The method developed by Lord does not take into account normal freezing in the last zone and also becomes very complicated when the number of passes becomes large. The method developed by Reiss enables the direct calculation of the complete concentration profiles (including that in the last zone) after any pass for values of k close to unity (0.9 < k < 1.1). Both methods are useful and provide valuable insight into the zone melting process. The equations given in this article are based on the same assumptions used by Pfann. These are: 1—uniform composition in the liquid, 2—negligible diffusion in the solid, 3—constant distribution coefficient, 4—constant length of the liquid zone (except at the ends), and 5—solubility of the solute in the melt is not exceeded at any point. Equations for Concentrations in Successive Passes For a melted zone of length 1 at the left-hand end of a bar of uniform unit cross-section, the amount of solute in the liquid is J0Cn-1(x) dx [1] where the subscript is the number of the pass. Cn-1(x) represents the concentration (expressed as weight per unit volume) obtained in the previous

Jan 1, 1956

By D. A. Norrgran, J. A. Marin

Introduction The recent development of rare earth permanent magnets has revolutionized the field of magnetic separation. The advent of rare earth permanent magnets in the 1980s provided a magnetic product that was an order of magnitude stronger than that conventional ferrite magnets. This allowed for the design of high-intensity magnetic circuits that operated energy free and that surpassed electromagnets in the strength and effectiveness. New applications and design concepts that focused on the mineral and metal processing industries have evolved. This technology led to the development of various magnetic separators specifically designed for mineral processing applications. Applications that were not previously considered are now being used in primary mineral upgrading, recycling and secondary recovery. Historical perspective Lodestone was the first naturally occurring permanent magnetic material known. Lodstone was most likely used to upgrade iron ore by early civilizations. By the 1600s, the early magnet technology had advanced to quench-hardened iron-carbon alloys. The practical significance of magnetic separation was formally recognized in 1792 when an English patent was issued for separating iron ore by magnetic attraction. By today&apos;s standards, carbon steel is a very poor magnet material. It is easily demagnetized and has a very low energy product of much less than I MGOe (Million-Gauss-Oerstads). This was state-of-the-art technology for almost 300 years until chromium was added to magnet feedstock, which resulted in a three-fold increase in the energy product. The well documented addition of cobalt to permanent magnets in 1917 initiated the 30-year era of "Alnico" magnets that at the time provided a superior magnetic energy product. Since then, the science of magnetism has advanced rapidly and is now considered a highly developed branch of physics and material science. Permanent magnets have had an extremely long history. Figure 1 presents a chronology of permanent magnets that illustrates the increase in energy product. Amazing developments in material science have taken place in the last two decades. The gradual advancement of permanent magnet technology was shattered in 1967 with the initial development of samarium-cobalt (rare earth) magnets. Since that time, the advent of neodymium-boron-iron magnets provided such an increase in energy product that new design concepts were considered. New avenues of study were introduced by the complexities in the material science and physics involved in describing these new permanent magnets. Furthermore, applications for permanent magnets that were previously not considered were now viable. Rare earth elements Rare earth elements have claimed the attention of scientists for the past century. These elements were originally termed "rare" because they were thought to be quite scarce. Since then, however, geological studies have shown them to be relatively abundant. The discovery and identification of rare earth elements is complicated by the inherent difficulties in separating them from each other. The rare earth elements comprise the fifteen transition elements of Group IIIB, Period 6, of the periodic table. These elements extend from lanthanum to lutetium and are commonly called the lanthanide series. Samarium and neodymium are the two most common elements used in the commercial manufacture of rare earth permanent magnets. Commercial grade rare earth magnets There are only a few common types of rare earth magnets that are considered in the circuit design for magnetic separators. Early rare earth magnets of commercial significance (introduced in 1970) consisted of the first generation of sintered SmCo5. The energy product of these magnets ranged up to 23 MGOe, which provided the initial impetus to the field of high-energy permanent magnets. Although these magnets did not produce the extremely high magnetic field strengths of current rare earth magnets, they were relatively temperature stable. Containing 66% Co, they are the most expensive of the basic commercial rare earth permanent magnets. Their use is limited today because they are being replaced by second and third generation rare earth permanent magnets.

Jan 1, 1995

By J. Chipman, N. J. Grant, E. C. Roberts

An equilibrium study was made of the distribution of chromium and oxygen between liquid iron, containing less than 1 pct Cr, and simple slags of the CaO(MgO)-Si02-FeO-Cr& type in the temperature range 1526&apos; to 1734OC. The effects of slag oxidation, temperature, and basicity were observed. IN spite of the fact that chromium is one of the most important alloying elements in steel, and exists in almost all steels as a significant residual element, little research has been done to determine its behavior in basic steelmaking processes. Considerably more work has been done under silica-saturated acid slag conditions. Korber and Oelsen,&apos; Herasymenko,&apos; and others have generally agreed that in acid steelmaking practice the chromium in the slag behaved as if it were present as the chrom-ous ion (CrO). Work by Hilty- ir, high chromium slags also indicated that chromium may exist as CrO. In basic slag systems no equilibrium data exist. Based on individual studies of basic open hearth and electric furnace practice, Bardenheuer," Rock-rohr,% nd HauckQ oncluded that: 1—chromium recovery increased with decreasing basicity, and 2— chromium recovery increased with increasing temperature, although the effect was small. In similar studies Yavioskii and Dzemyen&apos; concluded that: 1— slag FeO is the most important variable, 2—the basicity of the slag has no effect on chromium recovery, and 3—slag viscosity is not high even when 20 pct Cr,O, is present. Lapitskii\ oncluded that chromium recovery improved as the basicity of the slag decreased and increased with increasing manganese in the metal. Regarding the effectiveness of CrZ08 as a base or acid in basic slags, both Kristofferseno and Trojer" reported that Cr,08 was an acidic component requiring neutralization as 2CaO-Cr,O,. Experimental Procedure The experimental apparatus and procedure used for the present research were similar in most details to those used by Winkler and Chipman" and were described in detail by them. A magnesia crucible was used, holding 60 to 80 lb of Armco iron which was decarburized with hydrogen to about 0.010 pct C. Since all the metal samples solidified without gas evolution, this carbon level was assumed not to be significant. Synthetic slags made by mixing pure oxides were used throughout the study. Temperatures were measured by means of calibrated W-Mo thermocouples and were checked by Pt-Pt-Rh thermocouples. The range of temperatures covered in this study was from 1526" to 1734°C. The chromium content of the iron was in the range 0.032 to 0.82 pct, although the bulk of the tests showed 0.04 to 0.2 pct. The slags were of the CaO(MgO)-SiO,-FeO-Cr,O, type in which the Cr,O, content was from about 2 to 20 pct, although most of the slags showed from about 2 to 10 pct. The FeO range was from about 10 to 65 pct. CaO and SiO, were in the range of about 5 to 45 pct each, yielding a rather wide range of basicity values. The first 12 heats were made without a sulphur addition, and with only 30 min allowed for slag-metal equilibrium to be reached. In previous research it had been shown that less than 30 min was adequate to achieve equilibrium in slags free of Cr2O8.11,14.15 A study of the present data indicated that some of the tests may not have reached equilibrium in this time; accordingly four additional heats were made in which at least 1 hr was permitted for equilibrium to be reached. For reaching

Jan 1, 1955

By Herbert H. Kellogg

Graphs representing the standard free-energy of formation as a function of temperature for 21 fluorides are presented, along with estimated values for the standard free-energy of formation of 20 atedadditional fluorides. A few of the many possible uses of these data in metallurgical calculations are discussed, including the fluorination of oxides, sulphides, metallurgicaland chlorides, and the reduction of metal fluorides. RECENT papers which have presented free-energy data for oxides, sulphides, chlorides, carbonates, sulphates, and silicates in the form of free energy vs. temperature plots,1-5 have found important uses in teaching and metallurgical development work. This method of presentation of thermo-dynamic data serves to make available in readily usable form thermodynamic constants which are scattered throughout the literature, and to show by graphical means the stability relations which exist between the compounds of a given type. It is certainly desirable to have these free-energy-temperature diagrams for as many types of compounds as are of present or potential use in metallurgical processes. Thus, even though there are but few uses of metallic fluorides in extractive metallurgy today, the potential uses of fluorine processes are of great importance and serve as the principal justification of this paper. Recent developments in the production of fluoro-carbons have resulted in vastly improved methods for the production and handling of fluorine and corrosive fluorides, with consequent reduction in costs.".&apos; The extractive metallurgist should no longer overlook possible fluorine processes when development of a new process for a relatively high unit-price metal is being considered. In a previous paperv he author outlined in some detail the importance and use of free-energy data in metallurgical calculations and also discussed the properties of a standard free-energy vs. temperature diagram. The same method of presentation is adopted in this paper, and the reader is referred to the earlier work for explanations of the use of free-energy data. Thermodynamic Data This paper presents standard free-energy vs. temperature diagrams, Figs. 1 and 2, for those fluorides for which the major thermodynamic constants are known. In the calculations of the standard free-energy of formation (AGO), values of the enthalpy of formation at 298°K (?Ho,) were taken from "Selected Values of Thermodynamic Constants"8 most of the values of standard entropy at 298°K (S°298) were taken from "Selected Values"," but in a few cases the values given by Kelley9 ere preferred; data for the Phase changes came from "selected Values" and several of Kellley&apos;s publics- tions;0-12 and most of the specific-heat data were taken from Kelley.l0 The appendix gives a detailed list of the sources of the data. As explained in an earlier paper,6 he accuracy of some of the standard free-energy relationships is not high. An error of +1 kcal at 1000°C is expected in most of the curves of Figs. 1 and 2. The error may be as high as +3 kcal in some of the curves. Rather than attempt to estimate the reliability of each curve, the source of the data used is reported in the appendix, and the reader may compare these data with newer values as they become available. Figs. 1 and 2 fail to show values for the fluorides of many important metals. In most cases this is because the entropy of the metallic fluoride is unknown. For preliminary calculations it is often useful to have available the best estimate of an unknown datum, rather than no information at all. With this in mind, Table I lists estimated standard free-energy values for a number of important metallic fluorides not included in Figs. 1 and 2. The values reported in Table I were, calculated by Brewer et al.13 and are based on estimated entropy values. The estimated uncertainty of the values for each fluoride were calculated from the uncertainty values given by Brewer1&apos; for ?H°, and the entropy function.

Jan 1, 1952

By A. K. Mukhopadhyay, B. Sikdar, V. P. Arora

Introduction During the past several years, persistent concerns about an economic slowdown in India have tempered capital-expan¬sion plans. This has encouraged companies to find methods of increasing the capacity of existing production equipment. One of the more cost-effective methods of increasing produc¬tion capacity without major capital investment is to improve equipment maintenance to prevent needless machine down¬time. This can have a significant financial impact because of reduced maintenance costs and increased machine availabil¬ity. The maintenance program employs different techniques, but the analysis of the vibration behavior of machine compo¬nents to assess their condition was found to be the most accurate technique for monitoring various machine disorders. A dragline that handles overburden in open pit mines is one of the more capital-intensive pieces of production equip¬ment. It is imperative that the machine be run at its optimum capacity under the prevailing environmental conditions. Condition monitoring of the various components of the dragline through vibration analysis not only improves the machines availability but also ensures a long operation time free from sudden failure. This paper describes the application of vibration monitor¬ing and analysis techniques to assess the components of a W2000 dragline. The paper reveals that condition monitoring through vibration analysis can be as valuable in failure prevention as it is in failure analysis. Finally, the paper presents an approach to a knowledge-based expert system to the quick and correct diagnosis of mechanical faults in a dragline. Equipment A dragline is an intermittent-discharge-type excavator having a long boom at one end. Unlike other excavators, the bucket is not rigidly held by the frame structure. In favorable geomining conditions, the intensive operation of these exca¬vators is the least-expensive means of overburden removal. The basic working elements of this equipment are the hoist system, the crowd and retract system, the wing mechanism and the propel mechanism. The walking dragline is accepted as the most economical machine for stripping overburden at depths of up to 60 m (200 ft). They are electrically powered and the various motions are effected by individual drives. The Ward-Leonard system is used to provide the optimum flexibility in controlling different dc-drive motors. To mini¬mize the cost of mineral extraction, the largest such machine in India has a 24-m3 (850-cu ft) bucket with a boom length of 96 m (315 ft). Draglines are very costly, and considerable financial penal¬ties may arise from sudden stoppages due to component fail¬ures. Thus, operational reliability is of the greatest importance. Active measures are now being taken to minimize downtime by adopting condition-based maintenance techniques. Though a number of techniques come under this scheme, it has been observed that assessing the health of the dragline by measuring vibration is the best method of determining the dynamic behavior of its various rotating components to avoid any catastrophic failure. Based on criticality, the vibration-behav¬ior of the following components are studied: • motor-generator unit, • exciter unit, • hoist motor-gearbox unit, • hoist drum-gearbox unit, • drag motor-gearbox unit, • drag drum-gearbox unit and • swing motor unit The approach Increases in the vibration levels in different subsystems of the dragline were observed due to the presence of faults such as unbalance, misalignment, looseness and bad bearings. A vibration behavior study included the measurement of vibra¬tion level, trend analysis of time-domain vibration signals and vibration frequency analysis at bearing points of the components. A vibration meter, a vibration analyzer and a data collector are used. Vibration-level measurement. When the dragline was assembled and put into operation for the first time, vibration data were collected to generate baseline data for the equip¬ment (based on International Standard ISO 2372). After¬wards, the vibration levels were recorded regularly using a vibration meter. The measurements were taken at all bearing

Jan 1, 2000

By J. R. Lucas, H. E. Rutherford

The primary objective of this research was to evaluate the feasibility of ultrasonic testing for the purpose of analyzing the structure and properties of rock material. A secondary objective of this study was to determine experimentally the elastic wnstants of various rock specimens with the use of ultrasonic equipment. Elastic constants can definitely be determined quickly and accurately by ultrasonic investigation. With proper equipment there are indications that ultrasonic waves could be utilized in the detection of flaws, such as fractures and planes of weakness, measurement of thickness, and the study of structure of rock material. Ultrasonic principles have been applied in many industries for the purpose of determining the structural characteristics of various materials. The principal applications of interest here are detecting flaws, measuring thicknesses, and determining elastic constants. The main advantage of ultrasonic analysis is that it is nondestructive. It also has extreme sensitivity, high penetrability, good accuracy, rapid response, and the necessity to have access to only one side of the specimen. These various applications and advantages lead one to think that ultrasonic principles might be applied to rock material in situ for purposes of analyzing its structural characteristics. Therefore, the primary objective of this research was to evaluate the feasibility of ultrasonic testing for the purpose of analyzing the structure and properties of rock material. A secondary objective of this research was to determine experimentally the elastic constants of various rock specimens with the use of ultrasonic equipment. The term ultrasonics is given to that branch of acoustics dealing with periodic sounds whose fre- quencies are above the audible range or above approximately 15,.000 to 20,000 cps. The first practical production of this high frequency sound was made possible after World War I due to developments of electronically controlled sound wave sources. At the present, the maximum practically attainable ultrasonic frequency is approximately 1000 megacycles per sec. Sound waves of sufficiently high frequency can be made to travel in a beam with little spreading. Therefore, such a beam can explore a material and detect nonhomogeneities in it by reflection. This is the principle of the ultrasonic reflectoscope invented by F. A. Firestone&apos; in 1942. An ultrasonic beam, on pulse-penetratink a solid material medium, produces an echo when it strikes a flaw which has different acoustical properties than the surrounding medium. This echo can be detected by the same transducer which sends out the original pulse. This principle is the basis of the important industrial techniques of nondestructive ultrasonic testing of metals and other solid material. Later developments in the field of ultrasonic testing of solid material have been mostly improvements in equipment and instrumentation. To date, most of the industrial applications of ultrasonic analysis of solid bodies have been in the aircraft, electrical, and nuclear energy fields on the nondestructive testing of metal. The one solid material similar somewhat to rock material, upon which some work has been done to apply ultrasonic testing techniques to study structural integrity, is concrete. Jones and Gatfield3 briefly summarize this work on concrete. Their basic conclusion was that the strength of concrete was a function of the change of the longitudinal sound wave velocity in the concrete. Only recently has any extensive study been made to apply ultrasonic testing techniques to rock material. Lutsch studied rock material by an ultrasonic pulse method to determine the extent and degree of fracture of rock faces. Lutsch states that the number of observed reflections is a measure of the degree of fracture and that only ultrasonic waves are able to detect fractured zones subjected to high pressure. Suzuki, Sasaki, and Siohara5 studied the characteristics of the sonic wave in rock for propagation over a wide range of wave lengths. They indicated that, in rock, the propagation constant and attenuation of the

Jan 1, 1962

By Robert E. Bush, E. S. Mardock

The object of this paper is to report recent developments in the quantitative interpretation of radioactivity logs. The use of reference lines is described in the application of the new zero radioactivity reference line for the determination of neutron derived porosities is discussed. Illustrated examples are shown of logs from the reef limestone of the North Snyder Field and from the Lansing-Kansas City limestone of central Kansas. A method of using an interrelation factor calculated from the neutron and gamma ray curves, called the neutron Productivity number, for the estimation of productivity from sandstone formations is discussed. When used in a relative manner the neutron productivity number has aided in Predicting whether a given zone will produce gas or liquid or whether it is too shaly to produce. Examples of logs from wells in the Freites District, Venezuela, and in East Texas are shown to illustrate the application of the neutron productivitv number. INTRODUCTION The petroleum industry was introduced to some of the preliminary results of investigations into the quantitative interpretation of radioactivity logs in October, 1949." It was stated at that time that the methods presented were entirely relative because they involved the use of reference points obtained from the radioactivity log, i.e., shale reference lines, dense zone reference lines, or a combination of both shale and dense zone reference lines. These relative methods offered many advantages to the industry in interpreting radioactivity logs in terms of porosity with particular application to limestone and dolomite reservoirs. However, these relative methods did not offer the wide range of applicability desired because the esta1)lishment of reliable reference points from shale in some areas were difficult. It was recognized that a more reliable mean; of establishing reference lines was vitally needed. Such a method is now available through the introduction of an instrumeutal zero device. It is the purpose of this paper to discuss the application of this new zero reference to the quantitative interpretation of radioactivity logs. Previously all applications of quantitative interpretations of radioactivity logs have been made in limestone reservoirs with little or no emphasis placed on sandstone reservoirs. A brief resumé of investigations into the quantitative interpretation of radioactivity logs in sandstone reservoirs is presented here. This discussion deals primarily with the interrelation of the gamma ray and neutron curves and the response of the latter to the density of the fluids filling the pore space in relatively homogeneous sandstones of uniform porosity. The authors believe that the methods presented herein are only applicable locally to specific fields and reservoirs, and that they probably do not offer a wide range of applicability. However, tile authors believe that the wider use of the new instrumental zero references in sand areas will reveal more information about the specific response of the gamma ray and neutron curves to changes in lithology and saturation. Two applications of quantitative interpretation using the new instrumental zero references are presented. Examples are given which show the comparison of logs and porosity in the limestones and dolomites of West Texas and Kansas. Logs of wells in &apos;Venezuela and East Texas are compared with the drill stem test data, production data, etc.. to illurtrate the interrelation of the gamma ray and neutron curve: and the rise of methods involving these interrelations to determine certain saturation variables. THE QUANTITATIVE APPLICATION OF RADIOACTIVITY LOGS TO LIMESTONE AND DOLOMITE RESERVOIRS Tile theoretical basis for the gamma ray and neutron curves has been discussed elsewhere.9 he method of recording the logs and apparatus involved has also been thoroughly covered and will not be discussed here.&apos;."".&apos;" It has been shown that the neutron curve responds exponentially to liquid filled porosity over the 1 1/2 to 35 per cent

Jan 1, 1951

By J. L. Wyatt

THE smelting of ilmenite to produce a slag rich in titanium, with pig-iron as a byproduct, introduces new concepts in electric smelting metallurgy. Titanium slags are characterized by low electrical resistance, thereby requiring a different type of electric furnace operation, and power supply sources substantially different from those encountered in normal steel melting and siliceous ore smelting furnaces. This paper describes special apparatus for determining specific electrical resistivity of titanium slags, and reports the values obtained on slags encountered in the process of smelting ilmenite ores. In an induction furnace under conditions approximating normal furnacing operation, 25 general heats and 6 special standardization and comparison heats were run. Results indicate relatively low resistivity. Resistivity depends primarily on slag composition, and, to a lesser degree, on temperature. During the summer of 1947 a cooperative project between the National Lead Co. and the Bureau of Mines was conducted at Boulder City, Nevada, in the Electrometallurgical Laboratories of the Bureau. The project involved smelting of ilmenite ores in electric furnaces, and has been reported in detail.&apos; The author participated as a member of the staff of the National Lead Co. during the entire campaign. One outstanding characteristic of the titaniferous slags, their apparently excellent and variable electrical conductivity, was considered sufficiently important to warrant further study. Although little electric smelting of iron ores has been done in the United States, a certain amount of information is available for comparative purposes. Personal experience in smelting siliceous iron ores in electric furnaces furnished further information for comparison. In general, silicate slags are relatively poor conductors of electricity. Current flow during smelting operations may be maintained through a floating layer of coke on top of the slag bath, or through a bath of molten iron, beneath the slag. Silicate slags are not sufficiently conductive to furnish a path for current passage when normal furnace voltages are used. Experimental smelting of a silicate iron ore was undertaken for comparative purposes. A fluid melt was not obtained until the FeO content was reduced to 15 pct. The resistivity increased as the FeO content decreased, FeO compounds being the most conductive of the various oxides in such a normal slag system. The converse appears to be true in slags containing large percentages of TiO2. It has been found that titanium slags become molten with FeO percentages in excess of 30 pct, and that the conductivity becomes generally better as the FeO con-tent of the slag diminishes. This phenomenon was demonstrated in the furnacing operations at Boulder City. During the initial smelting period furnace electrodes could be held immersed several inches in the slag, with tap selectors set for a no-load voltage of 70 v. As the FeO content decreased, the furnace electrodes would "walk up," until at one point in the process the tips would break the surface and arc on top of the slag. This was undesirable since direct arcing caused losses of important flux additions. The slag compositions under study at that time were such that losses due to surface arcing sometimes caused viscous slags to be formed. Forcing the electrodes into the slag bath by manual control to prevent surface arcing resulted in excessive power input and lack of control. Suitable low voltages were not available. Measurement of the electrical resistivity of titanium slags at various operating temperatures and slag compositions was undertaken. It was believed that this information would be of use in the design of electric furnaces suitable for smelting ilmenite, with voltages, electrode sizes, and electrode spacing adapted specifically to titanium slags.

Jan 1, 1951

By M. C. Fuerstenau, J. J. Fitzgerald

Aluminum silicate hydrosol synthesis and characterization are discussed. Plausible polymeric aluminosilicate species are presented together with their effect on electrokinetics of selected minerals and flotation response of various ores. The addition of aluminosilicate hydrosol to porphyry and oxide copper ores and to a tungsten ore resulted in enhanced flotation recoveries ranging from about 1.5 to 5 percent. A significant portion of the nation&apos;s mineral resources are presently lost in the form of particles with very fine grain size. In the case of copper, for example, approximately 225 million tons of ore are concentrated by flotation per year in the United States. Total losses from porphyry ores are generally 15 to 20 percent with half of these losses being finely-divided copper sulfide minerals which do not respond to flotation. The additional 5 to 10 percent loss is the result of copper oxide minerals which are not floated. The losses of copper sulfide minerals are thought to be due in part to the lack of appropriate dispersion of the finely-divided solids less than 20 microns in size. To effect dispersion in flotation systems, sodium silicate is commonly added. Enhanced dispersion effectiveness is achieved when polyvalent metal salts are combined with sodium silicate. Since originally described by Patek (1), numerous workers have explored the utility of metal silicates. Makrousov (2), Belash et al. (3), and Eigeles (1950) (4) showed the applicability of these reagents to calcite/apatite and fluorite/calcite ores. Mercade (5, 6) reported depression of calcite in the presence of 3.33/1 mole ratio Al/Si hydrosols prepared from Type N sodium silicate (Si02/Na20 ratio 3.22/1) and 1% A12(SO4) 3•18H20 solutions. He importantly observed that the colloidal precipitates did not play a significant role in dispersion and depression but that the soluble species were responsible for this action. Patented work by this author described metal silicates used to depress calcite in scheelite flotation using 1% metal salt (FeSO4•7H2O, CoSO4•7H2O, etc.) and 5% Type N sodium silicate solutions to produce hydrosols with Si/Fe or Si/Co ratios of 8.79/1. Aluminum (III) ion systems were less effective as depressants than the iron and cobalt systems. Yang (8, 9) has studied metal silicate sols for use in the flotation of lithium and ultra-fine hematite ores. Using 10/1 Si/Fe mole ratio hydrosols prepared from 2% ferric nitrate, Fe(NO3)3.9H20, and 5% Type N sodium silicate solutions, solutions, he showed that the hydrosols either modify the slime particle surfaces or are adsorbed on the slime particles preventing anionic collector adsorption. In a subsequent patent, Yang also reported the use of these hydrosols as dispersants for beneficiation of lithium ores. Recent studies of aluminum silicate hydrosols in the flotation of chalcocite, chalcopyrite and scheelite have been reported using Si/Al dispersants prepared from 5% Type N sodium silicate and 0.1 M aluminum chloride (A1C13.6H20) solutions. Dispersant properties were shown to be dependent upon the method of synthesis, supernatant pH, and the hydrosol Si/Al mole ratio. Polymeric soluble species in these hydrosolsupernatants have been proposed as the active dispersant species. Aluminosilicate hydrosols are synthesized by the general reaction scheme presented in Figure 1. Commercial sodium silicates are available with ratios of SiO2 to Na20 of 1.60-3.25. The sample which is most frequently employed is Type N whose ratio of Si02/Na20 is 3.22/1.00. Gel filtration chromatography and NMR studies have shown that these sodium silicates contain numerous species of molecular weight from 325-2,000 gm/mole. Monomeric, oligomeric and higher molecular weight linear polymeric arrangements of these structures are found in these solutions.

Jan 1, 1989

By R. S. Rickard, M. C. Fuerstenau

Anodic polarization curves for iron dissolution and cathodic polarization curves for copper deposition and ferric and hydrogen ion reduction were studied. These results were used to predict the relative rates of the reactions: The rates of the first two reactions were found to be first order with respect to the reacting ion, and the rale-controlling step was diffusion of the ions to the callzode surface. The rate of hydrogen ion reduction in an oxygen-free solution is dependent on the reciprocal of the square root of the hydrogen ion activity. In solutions containing oxygen, the rate of hydrogen reduction becomes dependent on the square root of the partial pressure of oxygen. At equal concentrations copper precipitation occurs about twice as fast as ferric ion reduction. In an air-saturated solution containing 0.01 M cupric ion at pH 2, the rate of hydrogen ion reduction zs about 10 times slower than that of copper precipitation. At pH values below 3, the rate of hydrogen reduction in oxygen-free solutions is very slozu. COPPER cementation has been utilized industrially for many years as a means of recovering copper from aqueous solutions. There are many different types of cementation plants, but all simply provide a means of contacting iron with relatively dilute copper solutions. In the past little or no attention has been paid to rates or mechanisms of the reactions involved. As a result, this and other studies&apos;-3 have been undertaken recently to establish the important parameters in this system. The reactions involved in copper cementation by iron are: Since transfer of charge is involved in every case, these reactions should be considered from an electrochemical point of view. In any electrochemical system involving electrolytic conduction, passage of electrons necessitates ion transfer to the respective electrodes according to Faraday&apos;s law. The current in the system will be proportional to the rate of ion transfer, and, therefore, when the current in the galvanic cell is known, the rates of the reactions involved can be determined. Galvanostatic electrode measurements5" are applicable for these electrochemical studies, in that with this technique polarization curves (current density vs electrode potential) are established by impressing a constant current through an electrode and measuring the electrode potential. Once the current density, electrode potential, and reacting area are known for each reaction in this cementation system, the rates of the iron-consuming reactions can be determined. EXPERIMENTAL MATERIALS Several metal electrodes were used in this investigation; they are shown in Table I. Solutions were made with reagent-grade salts and conductivity water. Air, nitrogen, and oxygen were employed. All of these gases were saturated with water and degreased prior to use. EXPERIMENTAL PROCEDURE The experimental work was divided into two general areas. The first area involved galvanostatic measurements, which were used to determine the rates of reactions as a function of various parameters. The second area comprised actual cementation experiments to check the rates predicted from the electrode measurements. Galvanostatic Electrode Experiments. Polarization curves were obtained using a standard galvanostatic technique5&apos;= with the apparatus shown in Fig. 1. The various electrode polarization experiments were run the same way except for changes in solution composition, polarity, and type of measured electrode. The general procedure involved the following steps: 1) a solution was made 0.5 M in sulfate ion and to the desired cation concentrations; this solution was placed in a constant-temperature bath and saturated with the desired gas; 2) the electrodes were cleaned and placed in the electrode holder; 3) the previously cleaned apparatus was assembled and immersed in a constant-temperature water bath (temperature controlled to ± 0.05"C); 4) the electrode was then positioned; the solutions were introduced, and the polarization meas-

Jan 1, 1969

By James N. Grassby

Metal production has traditionally been a cyclical industry. 1977 in the base metals industry has highlighted that fact with a steady decline in the market place for base metals. Corporate aggregate planning is based on good forecasting and when changing conditions make that forecasting inaccurate, alternate analysis of schedules must be accomplished quickly. The computer is the only medium powerful enough to answer management&apos;s questions within an acceptable time frame. Worldwide communications networks now make it possible for the many multinational mining companies to arrive at coordinated corporate production plans based on similar basic data from several producing divisions. The Ontario Div. of Inco Metals Co., a unit of Inco Ltd., encompassed during 1977 14 producing mines, 2 nonproducing mines, 1 nonproducing open pit, 5 flotation mills, I smelter, 2 nickel refineries, 1 copper refinery, and an iron ore recovery plant. Several new mines are under development. Mine production approximates 63 500 tpd (70,000 stpd) from some 1000 workplaces. The need for longrange mine planning and scheduling is obvious and until recently has been satisfied by manual methods. However, while manual methods are often quite practical for a small number of mines, or for mines with relatively short lives, or for mines with only one mining method, the situation in the Ontario Div. is too complex and long-term to allow effective, timely planning by such methods. In 1967, a year after the first computer was installed in the division, work was begun on the computerization of the more than 30,000 borehole logs kept in the mines exploration files with a view to speeding up the assessment of mineral resources. Also in 1967 one of the first substantial systems developed on the main business systems computer was the monthly scheduling of development and production for all mines. This system encompassed tons productions per workplace, feet development per workplace, auxiliary and service activities and the requisite labor for each of these. These two dates are mentioned to show that concurrently with the acquisition of computers in the division there was an early understanding of the importance of automating mine scheduling and planning and of the potential for effective and useful computerization of such activities. In 1970, a pilot program was developed in one of the mines containing a large number of workplaces (350) to schedule the production on a network basis. Varying degrees of interest were shown by the individual mine engineers based on the complexity of the production planning problem at each mine. In an evolutionary process, mines were added to the system as its value became obvious in terms of time saving, flexibility, and accuracy. In 1975, the central mine engineering department decided that the system should be extended to all mines so that a complete division-wide long-range scheduling system would be available upon which to base development and production planning. This system would use basic ore data, allow the addition of scheduling commands, and calculate a schedule for the life of the mine. Many reports could be produced for each mine and all-mine summaries would also be available. The significance of the system can be stated in one phrase-speed, accuracy, and flexibility. Whereas in the past a long-range all mines schedule might have been done once a year, taking from two to three months, now it can be done in a day. The chief mines engineer can incorporate changes in input data and external constraints and call for a "new look" at the long-range schedule to assist him and mines production management in their decision-making processes. Using previous manual methods this could not be done quickly enough to be useful.

Jan 1, 1979

By Samuel Tescher

The operation of gaseous mines is a problem, due to the fact that we have not only the ordinary mine accidents to guard against, but have also the ever present menace of a mine disaster involving a large number of human lives, and the destruction of valuable property. In looking over the reports of mine disasters throughout the country in the past several years, we find that methane gas, coming in contact with an ignition agency of some kind, has been the source of at least 75 per cent of our mine explosions. Coal dust, of course, plays its part in propagating the explosive action throughout the mine workings and rendering it more violent and destructive; nevertheless, the initial ignition of a body of explosive gas-sometimes of very small volume-has been the primer for the large majority of our mine disasters. We find also, that the places of initial ignition are most frequently found at the working faces, or in close proximity thereto. This is mainly due to the following reasons: First-The working faces are, as a rule, the places where methane gas is most freely generated. Second: They are places that are most poorly ventilated. Third-They are the places where ignition agencies are most frequently found. The sources of ignition, as a rule, consist of naked lights, the shooting -of shots, defective flame safety lamps, and electrical arcs. The problem, then, in the operation of gaseous mines, is primarily to so ventilate the working faces that an explosive mixture is not likely to occur, and to endeavor to keep away from the working faces all sources of ignition. To do both of these things may seem impossible. Nevertheless, by working along both of these directions, a great many disasters can be avoided. The efficient ventilation of the working faces is paramount. By efficient ventilation, we mean the continuous passing of large volumes of air at the working faces. This can only be accomplished by adequate ventilating equipment, capable of being driven by at least two independent and distinct sources of power, together with large, clean, straight air courses which are free of short turns, constructed areas, and leaky doors and stoppings. In other words, furnish a suitable course for its travel through the mine. Many of us sharpen our pencils and rack our brains to properly estimate the proper size pump and pipe equipment that may be needed to handle a certain amount of water. We estimate the size of copper conductors to a nicety. We immediately rush to repair leaks in our water, compressed air or electric lines. But how many of us give serious thought to the travel of the air through our mines, the health and safety-giving fluid on which so much depends! In driving air courses, a certain economical cross-sectional area should be adopted and maintained as standard. When turns are necessary, they should be made with long radius curves, and the cross-sectional area should be increased on the curves. All entry stoppings should preferably be built of monolithic concrete, with suitable hitches into floor and ribs, and after the concrete has set, they should be examined and leaks due to shrinkage and settling should be eliminated. Overcasts and their approaches should have cross-sectional areas larger than the entries leading to them, to allow for the sudden change of direction, bearing in mind that air wants to travel in straight lines. In the early development of a property, ample provision should be made in the size of the main entry pillars to allow for the driving of additional

Jan 1, 1925

By T. L. Fritzlen

Extrusion of aluminum alloys in this country is performed mainly by direct extrusion, therefore this paper is confined only to factors affecting the rate of extrusion by this method. Many factors affect the rate of extrusion of aluminum alloys. It is the purpose of this paper to present a discussion on the factors that are subject to technical control. Most of them are closely related, so that a clear-cut distinction between them is rather difficult. However, an attempt will be made to evaluate the effect of each factor separately, as far as possible. The most important factors only will be considered, and these will be discussed in detail under three general headings: (I) characteristics of the equipment, (2) size and structure of the ingot, and (3) temperature of ingot, cylinder, and other parts. It is a well established fact1 that the pressure and the speed of extrusion are related and are exponential functions of one another. Therefore, whenever a certain condition tends, for instance, to increase the pressure required for extrusion, it will reduce the extrusion speed if the pressure is maintained constant. For this reason, in this paper the effect of various conditions is expressed either in regard to their effect on the pressure required or the extrusion speed. Another established fact is the relation- ship between the temperature of the material being extruded and the pressure required to extrude. According to Schi-shokin,= this relationship is of the exponential type, and as the temperature is increased the pressure required is decreased. It would seem from the preceding that the greatest rates of extrusion can be obtained by the use of higher temperatures. However, as is well known, other factors intervene to limit the rate of extrusion of aluminum alloys when increasing the temperature. These factors will be discussed in detail later. Characteristics of the Equipment The capacity of the press determines * the maximum unitary pressure that can be applied for any given cylinder diameter. Pressures used for extrusion of aluminum alloys range from approximately 50,000 lb. per sq. in. to 150,000 lb. per sq. in., dependent upon the alloy and the size of the shape extruded. Higher pressures could be used to advantage, but existing steels limit pressures employed in the production of extrusions. Numerous mechanical characteristics of the extrusion press affect extrusion rate. The most important characteristics of the press itself are: (I) sensitivity of the main pressure valve and accuracy of pressure gauges, (2) accuracy of equipment to heat the cylinder uniformly and to control cylinder temperature, and (3) accuracy of means of measuring the speed of extrusion. The variables subject to control during the extrusion operation are pressure, temperature, and speed, and it is evident that the preceding characteristics

Jan 1, 1946

By D. W. Evans

Mine subsidence problems due to coal extraction have occurred in a number of areas throughout the United States. Depending on the local geology, the depth of the mined seam, the type of mining method employed for extraction, and other related factors, subsidence can result in anywhere from slight displacements to a total loss of ground. These conditions can have serious consequences on the health and safety of the people living above the mined areas. A number of methods exist to provide support for the ground overlying mines. All of these methods employ some mechanism for providing additional support to either the roof of the mine or the sides of the pillars. Since failure usually occurs due to overburden stresses which are transmitted to the roof and pillars, these methods employ techniques to counteract stresses induced due to the coal extraction. The applicability of any particular method will depend on the availability of backfill material, the areal extent of the affected area, and of course, the cost. The primary use of coal ash for subsidence control has been as a backfill material for the stabilization of large areas. Large scale backfilling projects for subsidence control have been performed in Rock Springs, Wyoming, Wilkes-Barre and Scranton, Pennsylvania, and in Fairmont, West Virginia. Some of these projects have utilized sand, as well as, coal ash as backfill material. Much of the backfilling work performed in the United States has been done in an effort to control mine subsidence in abandoned mines. South Africa, on the other hand, has used backfilling extensively both for ash disposal and to increase extraction in active mines. The utilization of repetitive fill and mine techniques has resulted in extraction increases of as much as eight percent in shallow mines and as much as twelve percent in deep mines.(1) The coal ash injection system which can be used for backfilling depends largely upon whether the mine voids are dry or submerged. For dry mines, hydraulic or pneumatic conveyance systems can be used, while submerged mines are limited to backfilling by hydraulic methods. The use of coal ash as a backfill material has a number of advantages, such as: 1. Coal ash is available in areas throughout the United States and in many instances is conveniently located near areas requiring backfilling. 2. Coal ash is available in significant quantities since many coals when burned will result in about 15 to 30 percent ash by weight. 3. Coal ash as backfill is, in many instances, the most economical alternative fill material. Due to the costs associated with above ground disposal, power companies will often times give the material away to lower their overall operating expenses. 4. Coal ash is usually pozzolanic in nature, that is, this material results in cementitious bonding within the backfilled matrix of material.

Jan 1, 1982

By M. B. Ramachandra Roa

This paper records the results of the earth resistivity surveys made in the Godavari River in connection with the Ramapadasagar project. After describing the topographical and geological features of the area, the results of the investigation at the several sites have been mentioned. Further, a detailed account has been given of the resistivity methods adopted, the apparatus used and the interpretation of the curves. The resistivity measurements carried out over the water course have been specially outlined, and a review of the verification of the electrical indications by drilling in a number of cases, has also been presented. Introduction The Government of Madras has under consideration the Ramapadasagar project which is estimated to cost some Rs.660,-000,000 (about two hundred million dollars). The most essential feature of this project is the construction of a high dam across the Godavari near Polavaram for impounding the waters of this great river of South India, whose maximum discharge is 2 million cu secs in flood time. It is estimated that when the proposed reservoir is constructed, about one million tons of rice could be produced annually under irrigation. To those who have had any acquaintance at all with the recent distressing famine conditions which India has passed through and is still undergoing, the Lounteous effects which this project will bring about to the country in the future, are obvious. In the region of the proposed reservoir, the river flows for several miles through a hilly tract, hemmed in between flanks of hard, solid rock; but the river bed is mostly sandy. A few bore holes put down in this sandy bed touched rock at a depth of 180 to 200 ft. The river bed is about jo ft above the mean sea level (m.s.l.) and the bedrock was found at —125 to —160 ft m.s.l. The crest of the dam is proposed at +162 ft m.s.l. The proposed dam mould therefore be about 120 to 130 ft above the river bed, and the foundations would have to reach down nearly zoo ft below the bed at the deepest part. A number of alternative sites were proposed for investigation, and it became necessary to quickly ascertain the bedrock topography at these sites. Dr. M. S. Krishnan,* who was consulted in the matter, furnished a detailed account of the geological features of the region and suggested a geophysical investigation which the writer carried out from February to April 1944, employing solely the electrical resistivity methods. The total length of the survey lines for the electrical measurements amounted to 62,600 ft and the number of resistivity determinations was about 2500. Altogether nine alignments for the dam were inten-

Jan 1, 1949

By A. W. Jenike

A theory of gravity flow of bulk solids like ores, concentrates, coal is outlined and an example of design for unobstructed flow is given. Mass-flow and plug-flow patterns are defined and related to the geometry of the bin. The effect of these patterns on segregation, first in-first out flow, and caking is described. This paper is a report on the results from the AIME sponsored project "Flow of Bulk Solids" which was carried out under the author&apos;s direction at the Utah Engineering Experiment Station, University of Utah, during the period 1956-1962. The theory has been applied to the design of numerous industrial storage plants. A QUANTITATIVE METHOD OF DESIGN FOR FLOW There is hardly an industry which does not store and handle solid materials in bulk form. When the volume of the solids is large, gravity is invariably relied upon to cause the solids to flow out of storage, through channels and chemical reactors. Such materials as ore, coal, cement, flour, plastics, clay, soil, to which a general term of bulk solids is applied, flow by gravity or are expected to flow by gravity in thousands of installations and by billions of tons annually. The chemical and process industry depends on gravity flow of solids in process and out of storage. Mining relies on gravity flow in block-caving, in ore passes, as well as in storage and loading bins. Agriculture uses gravity flow in elevators, in feed plants, and in farm silos. In practice, satisfactory gravity flow is seldom attained. Such problems as doming, piping (rat-holing), lack of live capacity, segregation, deterioration in storage, harass industry. In spite of the universality of these problems, until recently, there has been no theory of solids flow, no method of predicting how a solid would behave, and how the channel, bin, or hopper should be designed. In the late nineteen forties and early fifties, the theory of plasticity came of age and simultaneously the computer became widely available. These two factors permitted the development of a theory of flow of bulk solids. The work was conducted during the years 1953-1961. In conjunction with the development of the theory a method to measure the flowability of solids was also developed1-7 and the theory was ap-plied to the design of ore pockets, storage plants,16 chemical reactors and adsorption columns. A comprehensive report of this work is given in a previous work." THEORY OF FLOW The most important question which a theory of flow has to answer is: what conditions need to be satisfied for a given solid to flow uniformly and without obstructions through a channel? First of all, the following observations are made:

Jan 1, 1967

By George A. Grandy, D. W. Fuerstenau

Simulation of nonlinear grinding systems is discussed in the context of the size-discretized batch-grinding model. A linear approximation of environment-dependent (or nonlinear) selection functions is postulated for systems which exhibit feed grinding orders less than unity. For this, a convex linear combination of zero and first-order selection function forms is used to obtain an analytical solution that can be used for simulation. An example in which marked nonlinear behavior occurs is rod-mill grinding. Accordingly, a series of grinding experiments was carried out in a batch laboratory rod mill to test these techniques; agreement between experiment and the model was found to be very good. Recently, significant progress has been made in the simulation of linear grinding systems by using a population balance mathematical model. Herbst and Fuer-stenaul presented a parameter estimation scheme that can be used with the size-discretized batch-grinding model, and Gumtz and Fuerstenau3 have extended these techniques to the simulation of locked-cycle grinding. Grandy et aL." summarized the simulation of linear systems and noted important alternate solutions to the batch-grinding equation. Kelsall et a1.&apos;-" discussed the dynamic simulation of linear batch grinding, as well as linear open and closed-circuit grinding. In all of these, the key word is linear, which certainly restricts the engineer trying to simulate a variety of grinding systems. This paper discusses an approach for the simulation of non-linear grinding systems, particularly those which exhibit grinding orders less than unity. Experimentally, dry rod-mill grinding is used to evaluate the technique presented. Batch Grinding Model The size-discretized batch-grinding model has been discussed in detail by Mika et al.&apos;.&apos; and by Herbst and Fuerstenau,&apos; and therefore, will only be briefly developed here. The model is formulated by making a differential mass balance of each size fraction in such a manner that the equation parameters are precisely defined in terms of selection and breakage functions,&apos; which can be either calculated&apos;.&apos; or estimated1 from experimental data. The model is phenomenological because it averages all stress-application events in the system and, therefore, does not distinguish the manner in which individual particles are stressed.&apos; For this average environment, the resistance of all particles in a size fraction to breakage is defined by that size-frac-tion&apos;s selection function; and when fracture occurs from an average event, the breakage product size distribution is defined again by that size-fraction&apos;s breakage function. The model is deterministic and is derived in terms of a continuous time variable and a discretized size variable,&apos; i.e., the n mass fractions associated with the n defined size intervals (see Table 1 for nomenclature).

Jan 1, 1971

By W. Bradley, R. G. Hall

This paper will attempt to show how a metallurgical problem at one California quicksilver mine was solved, and how the solution was applied successfully at another mine. The pronouns "we" and "our," as used below, refer &apos;0 the Bradley &apos;lining Co. of San Francisco. The term "concurrent firing" for the purpose of this paper can be defined as feeding and firing a a kiln at the same end—that is, of course, the upper end&apos; This is as opposed to "countercurrent firing," the orthodox method, in which a kiln is fed at the upper and fired at the lower end. The terms "quicksilver" and "mercury" are used interchangeably. Early References The earliest work on nonferrous metallurgy, we believe, was The Pirotechnia of Vannocio Biringuccio,l its first edition having been printed in Italy in 1540. Quoting from its chapter entitled "Concerning Quicksilver and Its Ore": Quicksilver ... is one of the gods and has divine strength in itself, and also, to the annoyance of the alchemists, it is winged. Hence, when it sees that it is in gravest danger, it loosens itself from . . . every bond . . . and fies away into the heavens, escaping from the hands of those who crucify it. Almost laughing, it leaves all its adversaries mocked and scorned, with their phials and filters empty . . . How thorough a job, under certain conditions, it can do of mocking its adversaries and leaving their phials and filters empty, was found out four centuries later at the Sulphur Bank mine, on the east shore of Clear Lake, in Lake county, California, The other mine mentioned in the title is the Reed, in Yolo County, California, 35 miles by road southeast of Sulphur Bank, Reed and Sulphur Bank ranked respectively Nth and seventh in U. S. production in 1943. The earliest direct reference we can find to furnacing troubles at these mines was by Thomas Egleston in 1890.2 Speaking of Sulphur Bank, Egleston says: of there is more sulphur than cinnabar in the ore, which is a detriment to both . . . making the sulphur impure, and rendering the cinnabar difficult to work on account of the soot. In some of the early . . . furnaces the accumulation of soot from the excess of sulphur has been known to penetrate as far as the fan blower at the end of the . . . condensers, and completely prevent its revolution. In order to get rid of the inconvenience of this accumulation . . . , as well as to get a commercial value from the sulphur, it (the sulphur) is now separated by steam and sold. It is claimed that the sulphur alone pays all the expenses of ... the mine. The mine was first worked for sulphur, and the cinnabar it contained was considered to be an inconvenience, and was carefully picked out and thrown away, as its richness and value were not

Jan 1, 1949

By E. A. Gulbransen, J. W. Hickman

ONE of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film A comprehensive program has been undertaken to study these phenomena This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C Before the introduction of the electron diffraction technique, it «as necessary to use either direct chemical analyses or X-ray diffraction analyses to determine the nature of the oxide film formed on the metal or alloy Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry In special cases the information obtained may be identical, but in general both view-points are necessary Much of, the early work was carried out on the oxidation of bulk samples where thick films were obtained The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses Although much useful information has been obtained in this manner, little could be learned about the character of the protective oxides during the period when the films were actually protective Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective LITERATURE The oxidation of iron has been extensively investigated by X-ray and electron diffraction Jackson and Quarrell1 found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe304, between 515° and 900°C the stable film was FeO Above the upper change point of iron the oxide was found to be Fe304 prom 400° to 515°C , FeO, Fe304 or a mixture of the two oxides was found Recrystallization of the air-formed film below 400° and above 900°C led to the formation of Fe304 In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described

Jan 1, 1946

By J. H. Brophy

Experimental evidence in recent years shows that nickel coated hydrogen reduced tungsten powder can be sintered to 98 pct of theoretical density at 1100°C. New data indicate that the sintering rate is the same for nickel contents ranging from 0.125 wt pct (mon-atomic layer) to 5.0 wt pct Ni coated on 0.561. tungsten powder. Nickel tungsten made by coreduction from oxides sinters in a kinetically similar way, but the rate tends to increase with higher nickel contents. The activation of sintering can be accomplished with a minimum amount of nickel if coated powder is used. Transverse rmpture strength was found to increase in specimens containing 0.25 pct Ni as density increased during the initial stage of the carrier-phase sintering process. Upon the onset of grain growth in the final stage, strength was found to decrease. With increasing nickel contents up to 4 pct, strength increased. Maximum strengths in three-point loading were observed at 73,000 psi for 0.25 pct Ni and 93,000 psi for 5 pct Ni. These were comparable to that of massive tungsten recrystal-lized in the presence of nickel and tested in the same way. The results were sensitive to the mode of powder treatment and ductility was negligible in all cases. The study and application of sintered bodies of nickel and tungsten is not new; however, the analysis of the mechanism by which small additions of nickel increase the sintering rate of tungsten promises to Contribute new information regarding sintering theory in general. Initial experimental evidence was presented by the authors showing that nickel-coated hydrogen-reduced tungsten powder may be sintered to 98 pct of theoretical density at 1100°C in 16 hr.&apos; Simultaneously, a kinetic analysis of the process showed that it took place in two distinct stages. In the first stage, nickel evidently served as a carrier phase through which tungsten atoms could move. This stage was kinetically similar to the &apos;solution-precipitationo step postulated when the carrier phase is liquid3 although in the nickel tungsten case, there is no evidence of the existence of a liquid phase either in equilibrium phase relationships or in mi-crostructures at the temperatures under consideration. In the present work, new data for nickel-coated tungsten powder are offered in support of the proposed mechanism, and a more explicit study of the second stage of densification is presented. Concurrently, the sintering kinetics of these coated powders are compared to Ni-W powder made by coreduction of oxides. In this way the present work can be compared to earlier results in nickel activated sintering of tungsten in which the coreduction process was emplyed. The ultimate utility of such an activated sintering process will be determined to some extent by the mechanical and physical properties of the final prod-

Jan 1, 1962