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By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By C. W. Sherman, N. J. Grant

The correlation of the high temperature chemical properties of slag-metal systems with some easily measured property of either slag or metal at room temperature has been the goal of both process metallurgists and melting operators for many years. There are several rapid methods for estimating various constituents in steel in addition to the conventional chemical methods which are quite fast, but these do not reveal the nature of the slag as a refining agent, which is of primary interest to the steelmaker. Furthermore, there are several methods for examining slag, the three principal ones being slag pancake, petrographic examination, and the previously mentioned chemical analysis. The main objection to the last two is the lime required to make a satisfactory estimate of the mineralogical or chemical components. The objection to the first is the inadequacy of the information obtained. A new technique has been developed by Philbrook, Jolly and Henry1 whereby the properties of slags are evaluated from an aqueous solution leached from a finely divided sample of slag. It is known that the pH or hydrogen ion concentration (of saturated solutions that have dissolved certain basic oxides, notably calcium oxide) will indicate a pronounced basicity. Philbrook, Jolly and Henry devised the pH measurement technique in order to supply open hearth operators with a fast, reasonably accurate method of estimating slag basicity. They offered the method as an empirical observation and made no claims as to its theoretical justification. The results were presented as an experi-metally observed relationship which applied over an important range of basic open hearth slags. They found that, in plotting the measured pH against the basicity, the best relationship existed between the pH and the log of the simple V ratio, CaO/SiO2. Extensive investigation also showed that there were several variables in the experimental technique that influenced the results and necessitated following a standard procedure to obtain reproducible pH readings. These variables were: 1. Particle size of the slag powder used. 2. Weight of sample used per given volume of water. 3. Time of shaking and standing allowed before the pH was measured. 4. Exclusion of free access of atmospheric carbon dioxide to the suspension. 5. Temperature of the extract at the time the pH was measured. In subsequent investigations of the pH method by Tenenbaum and Brown2 and by Smith, Monaghan and Hay3 the general conclusions of Philbrook's work were reaffirmed. It was the object of the present investigation to extend the technique to a point where it could be used to evaluate slags of all types. Experimental Results PARTICLE SIZK OF SLAG POWDER A large sample of commercial blast furnace slag of intermediate basicity (V-ratio 1.15) was selected for the study. The slag had been put through a jaw crusher until all of it passed through a 20 mesh screen. Five fractions of this crushed material were separated, -20 to +40, -40 to +60, -60 to +100, -100 to +200, and -200 mesh. A representative sample of 0.5 g was removed from each fraction and the pH determined using the method of Philbrook. Check pH analyses on the sample fractions varied due to the different amounts of shaking. To eliminate this variable, a mechanical shaker was employed. In order to know the exact time of contact between the slag and water, it was found necessary to filter the extract at the end of the shaking period. Using the mechanical shaker and a filtering apparatus, similar runs were made on the five fractions for contact times of 5, 10, 20, and 40 min. Random checks gave reproducible results within 0.02 pH. The data are plotted in Fig 1. It can be seen from the plot that each slag fraction is hydrolyzed to an extent that is roughly proportional to the surface area exposed to the water. The (—100 to +200) mesh material changed very little in pH after 10 min. shaking time. The curves are symmetrical and lie in proper relation to one another. The —200 mesh curve appears to be somewhat flatter than the others, but this can be attributed to the portion of very fine material that is not present in the other fractions. The closeness of the (-100 to +200) mesh curve to the —200 mesh curve and the fact that a —100 mesh sample would contain amounts of slag down to 1 or 2 microns in diam were considered sufficient reasons for selecting a —100 mesh sample as representative of the whole sample of slag for the purposes of this investigation.

Jan 1, 1950

By C. L. Berrien

Many fires have occurred in the mines of Butte in recent years, and while all have been of a serious nature, simply because they were mine fires, six of them have been especially dangerous in respect to loss of life and property, and the expense of extinguishing or controlling them. It is not my intention to discuss the relative merits of methods used in fighting these different fires because the conditions under which they occurred varied in each case, and it was not always advisable to expend the large sum of money necessary to actually extinguish them if they could be bulk-headed off from the rest of the mine. It is needless to say that everything possible has been done to check all fires at the beginning, but without success in some cases; and it has then become necessary to bulkhead all connections to them, in which state several now exist. The mine fires of Butte, or fires in any mine, may be divided into two classes, namely: Those occurring in accessible workings, and those occurring in inaccessible workings; because these two conditions govern to the greatest extent the methods of fighting fires. Accessibility and inaccessibility in the case of mine fires concern not only new open workings and old closed workings, respectively, but also the condition of the ventilation in and about those places. When a fire is accessible at the start it should not be difficult to confine it to a small area and extinguish it in a relatively short time, but when it is impossible to actually reach a fire in old filled, abandoned workings, or there is no opening by which the gases may be conducted away from the fire zone, then the time consumed in changing those conditions permits the fire to increase to such an extent that it is a long, hard fight to overcome it. These different conditions have been met in Butte, and of the six fires of serious proportions the Steward mine fire and the High Ore-Modoc mine fire were in new accessible workings and were extinguished in a month or so. The Anaconda mine fire, the Leonard-Minnie Healy mine fire, the West Colusa mine fire, and the Mountain View mine fire, were all inaccessible. The Anaconda mine fie started about 25 years ago and though safely bulkheaded is still active. The Leonard-Minnie Healy

Jan 1, 1916

By J. E. Strassner

Oilfield emulsions are stabilized primarily by film-forming asphaltenes and resins containing organic acids and bases. Adding inorganic acids and bases radically changes the physical properties of these films and their emulsion-stabilizing properties. Interfacial films show one of three different physical characteristics when retracted in pendent drop tests. These compressed films have rigid, soap-type or minimum film properties depending on the quantity of asphaltenes and resins in the crude oil and on the pH and composition of the brine. There exists for each crude oil-brine system an optimum pH range over which the adsorbed film exhibits minimum contracted filtn properties. In this range, intmfacial tension is high — frequently near its maximum value — indicating the absence of highly surface-active specier; crude oil-brine emulsions generally show minimum stability; and surfactant requirements for breaking these emulsions are significantly reduced — sometimes no surfactant is needed. About two-thirds of the world's crude oil is produced as emulsions that must be treated (demulsified) to be marketed.' Approximately three-fourths of all domestic crude oil produced must be treated. The percentage of crude requiring treatment increases as fields become older and more water is produced. Demulsification most frequently is attained through use of surfactants, heat and electric treaters. It is estimated that over 75 percent of all oilfield emulsions are broken by chemicals generally containing alkylene oxide condensates. Although acids and bases are known to affect emulsion stability:-' they rarely are used in the oil field except in batch treatment of the most severe emulsions. Nevertheless, pH adjustment by using acids or bases in demulsification has some advantages over other methods. Mainly, it is cheaper. Acids and bases frequently are cheaper to use than surfactants, or can appreciably reduce the amount of surfactant required for demulsification. Secondary advantages are that less oil is lost by emulsi-fication into the aqueous phase, and that less corrosion is encountered when the optimum pH is basic. Limitations to the use of pH include (1) use in brines containing high concentrations of reactive ions, (2) closer supervision for pH control than is required for surfactants and (3) need for corrosion protection when the optimum pH is sufficiently acidic. These factors indicate that the economics of pH con trol in demulsification will be maximized when relatively large treating facilities are needed, when relatively large surfactant concentrations are required to break an emulsion, when a relatively low concentration of the aqueous phase is emulsified in the oil and when the emulsified aqueous phase contains relatively low concentrations of reactive ions. Because there are no broad guide lines for using pH control in breaking oillield emulsions (and because the limited guides available are highly specific and frequently contradictory), this paper will attempt to clarify the principles involved in using acids and bases to break emulsions. These principles also should be useful in refinery separations and in other oilfield applications where stable or unstable petroleum emulsions are involved. Principles of Emulsion Stability Oilfield emulsions generally occur as water droplets dispersed in oil (w/o) and occasionally as oil droplets in water (o/w). These emulsion droplets are usually in the 0.1- to 10-micron range. However, more coarsely dispersed water droplets frequently are present in the emulsion. Pure hydrocarbons and water will not form stable emulsii except in extreme dilutions where the large distance brtween droplets inhibits coalescence. An emulsion breaks because interfacial tension acts to minimize the surface area of the dispersed drops by coalescence. However, emulsions can be stablized for long periods of time by the presence of a third phase that adsorbs at the oil-water interface and inhibits coalescence of the dispersed phase."' Emulsions generally are stabilized by (1) repulsive charges on the surfaces of the dispersed phase and (2) adsorbed films that, being preferentially wetted by the continuous phase, act as a physical barrier to inhibit contact between the dispersed droplets. Both these factors generally are important in stabilizing and in breaking o/w emulsions. However, repulsive charges are less effective in stabilizing w/o emulsions which generally are stabilized by adsorbed films.V or this reason the nature and importance of these films at oil-water interfaces were examined closely; as will be shown, pH changes were found to affect the films significantly, and this work led to laboratory tests of pH- adjustment in emulsion breaking. This paper will present evidence to show that emulsions are stabilized primarily by films that form around droplets

Jan 1, 1969

By John Griffen

DURING the past year, purchases of coal-preparation equipment and the discussions and plant-scale tests conducted indicate that much attention is being given to better recoveries of coal by preparation plants and improved quality of the finer sizes to widen their market. In the anthracite regions the new equipment was predominantly for the cleaning of the steam sizes, much of it for treating No. 4 and No. 5 buckwheat. The units installed were largely coal-washing tables, Hydrotators, and Menzies cone separators.

Jan 1, 1944

By S. W. Zehr, G. S. Murty, W. A. Backofen

AN observation by Squires, Weiner, and phillipsl has stimulated interest in a mechanism of deformation at high temperature (above -0.5 of the absolute melting point) that is not usually thought to be involved in the creep of metals. They found precipitate-free or "denuded" zones along grain boundaries normal to the stress axis in tensile specimens of a hydrided Mg-1/2 wt pct Zr alloy after slow straining at 450° and 500°C. Their suggestion that the zones were a result of directional diffusion of magnesium atoms was supported with calculations from Harris and Jones2 which also tended to identify the process as Nabarro-Herring (N-H) creep3,4—a process that is characterized by Newtonian viscosity, with stress (o) directly proportional to strain rate (C), and one that proceeds by lattice diffusion. Material transport by diffusion along grain boundaries is an alternative basis for Newtonian viscosity, as demonstrated by Coble,5 and is favored over N-H creep for fine grain size and lower temperature.6 In either case, the strain rate sensitivity of flow stress, defined as m = d log o/d log E (which commonly appears in the empirical a = KEW), is unity. The experiments to be described here gave metallo-graphic indications of diffusional creep which were no less clear than those just cited, but the associated m (as measured by the method of Ref. 7) was much more like that of a Bingham material. For true Bingham behavior, (a — ao) E, where oo is an initial yield stress. Therefore, even if flow after yielding should occur by diffusional transport, m must increase from 0 as < is raised to reach unity only in the limit as One result is that the resistance to tensile necking conferred by Newtonian viscosity is lost, which would become increasingly apparent through the formation of more sharply defined necks as 6 is lowered. That trend appeared in these experiments. Most of the work was done on an extremely finegrained alloy of magnesium with -6 wt pct Zn and ½ wt pct Zr (Mg ZK60); the initial mean-intercept grain diameter, L, was 0.55 µ. Shown in Fig. l(a) is a germanium-shadowed carbon replica of the surface of a specimen that was coated with silicone oil,* heated to 270°C under a helium atmosphere, and then stretched locally -200 pct at an initial E = 3.3 x 10-5 sec-1. Under

Jan 1, 1969

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.&apos; is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By Strathmore R. B. Cooke, Iwao Iwasaki, C. S. Chang

The effects of aeration on an aqueous suspension of pyrrhotite were studied and their results correlated with flotation tests using xanthates as collectors. The effects of copper activation and of pH variation were determined and possible mechanisms postulated. PYRRHOTITE has long been considered a gangue mineral to be eliminated as tailing in the treatment of various sulphide ores. However, in recent years the world-wide lack of sulphur resources has called attention to this mineral as a potential source of both sulphur and iron. Its importance as an economic mineral, however, has not been particularly emphasized. For this reason very little is known about its response to flotation, except that it can be depressed easily in alkaline circuit, by long aeration,1,2 addition of oxidizing agents,3 or by starch.&apos; The object of this work was to study the floatabil-ity of pyrrhotite. This includes the effect of oxidation by aeration, of copper activation, and of change in pH. Preparation of the Pyrrhotite Sample: It was desirable that the highest grade of pyrrhotite obtainable be used for this experiment, since the presence of other minerals could affect the surface properties.5 However, no pyrrhotite was available as crystals, and massive deposits of hydrothermal origin commonly contain considerable amounts of chalcopyrite. Pyrrhotite concentrate was, therefore, prepared from a sulphide deposit occurring near Aitkin, Minn. The deposit is of pyrometamorphic nature consistirlg mainly of pyrrhotite and pyrite with graphite, silicates, and carbonates as gangue. The ore, already crushed through 3 mesh when received, was screened at 65 mesh and the undersize discarded. The oversize was crushed through rolls, and then stage-ground dry in an Abbe porcelain mill, the —65 mesh portion being screened out after every 15 min of grinding until all the material passed through this size. The ground product was then concentrated with a drum-type dry magnetic separator. The rougher concentrate was cleaned twice and then demagnetized. The final product was split in a Jones splitter and stored in air-tight bottles. Microscopic examination of the concentrate showed that it was relatively clean and free of pyrite, locked particles, and gangue. By means of the krypton gas adsorption method," the specific surface was determined to be 3000 cm2 per g. The chemical and screen analyses of the final concentrate are given in Tables I and II respectively. It is a well-recognized fact that the oxidation of some sulphide ores during stockpiling, grinding, and conditioning affects their flotation behavior. The problem of oxidation may become serious in the case of pyrrhotite, since this is known to be more easily oxidized than many other sulphides. To ascertain the extent of oxidation, an experiment was carried out by aerating an aqueous suspension of pyrrhotite with air, oxygen, and nitrogen as follows. A 300-g sample of pyrrhotite in 2700 ml of water was agitated and simultaneously aerated in a Fager-gren-type laboratory flotation machine. A Precision wet test meter was connected to the air inlet valve, the flow rate of the gas being kept constant at 0.3 cu ft per min throughout the experiment. Samples of approximately 30 ml each were taken from the cell at 0, 4, 10, 20, 35, 60, and 90 min. After the pH was taken, each sample was filtered and the filtrate was analyzed for total iron and sulphur. The iron was determined colorimetrically by the thioglycolate method using a green filter.&apos; The filtrate was oxidized with bromine to convert all of the soluble sulphur compounds into sulphate and this was determined with a Parr turbidimeter." When aeration tests were made in alkaline circuit, calcium hydroxide or sodium hydroxide was added at regular intervals to maintain a constant pH. A similar procedure was followed in an experiment to determine the abstraction of copper. ion by pyrrhotite. In this case various quantities of cupric chloride were added. The filtrate from each sample taken was analyzed for copper, total iron, and sulphur. The carbamate method with a green filter was used for the copper analysis,&apos; since this method could tolerate a considerable amount of iron in the solution. A pneumatic cell, made from a 350-ml fritted glass Buechner funnel, was used for this experiment. The detail of the assemblage has been described elsewhere." In the present work a stainless steel baffle was inserted in the cell. This baffle overcame the tendency for the coarse pyrrhotite particles to be swirled around the wall of the cell and thus fail to collect in the froth. A 50-g sample of pyrrhotite was added to the cell which contained 260 ml of water. When pretreat-ment of the sample was desired, reagents, such as activator and pH regulator, were then added and the pulp was conditioned for a specified conditioning time. Prior to the addition of the collector approximately 15 ml of the solution were removed for pH measurement and for iron and sulphur analyses. Copper when used as activator was also determined. Collector and frother were then added and the pulp was conditioned for an additional 2 min. Air was admitted to the cell and the froth removed. The separation required from 4 to 6 min, depending on the characteristics of the froth. The float and non-float products were filtered, dried, weighed, and assayed for iron.

Jan 1, 1955

By Edwin B. Wilson, Joseph W. Leonard, Richard W. Borio

preparation of specification coals for the utility industry is approached from the standpoint of a cooperative effort with the power company to assure that the shipped product will be a noncorrosive coal. Selective mining, coal preparation, the use of additives, and coal blending are mine-site techniques proposed as means for upgrading corrosion-retarding constituents of utility coals (CaO and MgO) while, at the same time, reducing the concentration of those constituents of coal (Na20 and K,O) which cause corrosion. Data obtained from large-scale boiler testing in combination with bench-scale physical and chemical tests are used as a basis for the formulation of mine-site procedures to improve coal combustion utilization. Electric power generation remains the greatest market for coal in the United States. A major reason for this strong market has been the ability of the coal industry to supply a superior product for combustion while maintaining competitive prices. Now that the coal industry is engaged in intensive competition with nuclear power for future energy demand, it becomes ever more imperative that superior coal products are produced. One important problem when burning some coals is a liquid phase corrosive attack on boiler tube metal in the superheater and reheater areas of the furnace where steam temperatures may exceed 1050°F. In addition to causing power outages and high maintenance costs, corrosion is a continuing barrier to the future development of more efficient steam cycles which permit lower generation costs when using coal. Research methods of the past which have been directed at finding solutions which could be applied at the power plant site have been only partially successful and are generally costly. This paper contains a suggested --method of corrosion control through investigation of the problem at the source of the trouble—the coal supplier facility. It is proposed that mine-site pre-ventative procedures be considered as an effective means of cooperative corrosion control between the power company and the coal supplier. Economic justification must be applied to the individual situation. This paper is based on recent work by Combustion Engineering, Inc. and the Coal Research Bureau of West Virginia University under a contract from the Department of the Interior Office of Coal Research.&apos;,&apos; Results which are of importance to this discussion may be summarized as follows: 1) The alkali minerals of coal (Na2O and K2O), as measured by an acid leaching process, can be related to corrosion rate in utility boilers. As these constituents increase in a coal product, its corrosiveness can be expected to worsen. 2) The alkaline-earth minerals contained in coal, reported as total CaO and MgO reduce corrosiveness 2s their concentration increases. 3) Naturally occuring, alkaline-earth-bearing materials, such as limestone and dolomite, may be added to a coal to reduce its corrosiveness. 4) Coals with very low iron contents tend to be less corrosive. These results provide the groundwork for examination of the system of operations which occur at the supplier facility from the seam face where mining is begun to the point of loading for shipment. The Mining System Fig. 1 is a cross section of one of the typical coal seams (designated coal A) that was boiler tested during this research program. This seam is overlain by material which consists primarily of a gray-black shale. In the lower third of this seam, there exists a thin rock parting of less than 4 in. in thickness which is consistent throughout the seam. The floor material is fireclay. In order to examine mineral distribution throughout this particular seam, the Coal Research Bureau collected a

Jan 1, 1971

By Graham Bright

THE rapid increase in reliability, the low cost f operation, the ready application of safety devices, and the growing availability of central-station power have made the question of installing a hoist of the electric type no longer debatable. Where adequate electric power is available, there are few cases where it would be advisable to install a steam or air hoist. The type of electrical equipment depends largely on the nature of the power supply, its capacity, and the form of the power contract under which power is purchased. In a large majority of cases, the available electric power is alternating current, three phase, 60 cycles. There is, however, considerable 25-cycle power in use; and in a few instances constant voltage direct current is the only power available for a small or an occasional medium-size hoist. Where a new hoist is to be installed, the designer of the mechanical parts can readily take care of the maximum stresses likely to be imposed by the&apos; motor. Where the hoist is already installed and operated by steam or air and it is desired to substitute an electric motor for the engine, a careful check should be made to determine the advisability of using the old mechanical parts. In most cases it is better to install a complete new hoist than to attempt to use old mechanical parts. A steam engine has a definite maximum torque, which the hoist has been designed to withstand, while a motor may be able to deliver momentary torques beyond the strength of the mechanical parts of the hoist. The selection of the proper type of electrical equipment can only be made after complete information is obtained and certain calculations made to determine the capacities required. There are several methods used in making hoist calculations, but no matter what method is utilized a fair degree of familiarity with hoists and hoisting conditions is necessary before an intelligent analysis and proper selection can be made.

Jan 9, 1921

BARBOUR, PERCY E., Deputy Supt., (Captain), New York State Troopers; Captain, 22nd Regiment, N. Y. N. G. BARLING, 1i. B., 1st Lieutenant, Engineer Officers&apos; Reserve Corps. CHAPMAN, R. H., Major, Engineer Officers&apos; Reserve Corps. DUNN, THEODORE S., 1st Lieutenant, Engineer Officers&apos; Reserve Corps. DWIGHT; ARTHUR S., Major, Engineer Officers&apos; Reserve Corps. FORBES, CARROLL R., Captain, Engineer Officers&apos; Reserve Corps. GOODSPEED,. G. E., JR., 1st Lieutenant, Engineer Officers&apos; Reserve Corps.

Jan 7, 1917

By Frank C. Aplleyard

The two calcium sulfate minerals-gypsum and anhydrite-occur in many parts of the world, and gypsum has long been of economic importance in the family of industrial minerals. Gypsum, the dihydrate form of calcium sulfate (CaSO4•2H2O) and anhydrite, the anhydrous form (CaSO4) are frequently found in close association, and it is seldom that a calcium sulfate deposit will consist exclusively of one mineral or the other. Although known gypsum deposits are extensive, anhydrite makes up the largest part of total calcium sulfate reserves. However, it has very minor economic use, and most of the following discussion will be devoted to gypsum. Calcium sulfate is one of the principal constituents of evaporite deposits, and when pure, has the following composition: [Sulfur Combined Lime Trioxide Water (CaO) (SO,) (H2O) Gypsum 32.6% 46.5% 20.9% Anhydrite 41.2% 58.8% -] Deposits of pure gypsum or of pure anhydrite which are large enough to be considered commercial have never been found because of both the metastable relationship between the two minerals, and the presence of impurities such as calcium or magnesium carbonates, chlorides, other sulfate minerals, clay minerals, or silica. As a result most mine production of gypsum will range between 85 and 95% pure. Often it is used as mined, although in certain cases, one or more forms of mineral beneficiation are employed to upgrade the product. End Uses The largest use for gypsum is based upon the unique property which calcium sulfate has of readily giving up, or taking on, water of crystallization. With the application of a moderate amount of heat in a process known as calcining, gypsum is converted to plaster of paris (the hemihydrate of calcium sulfate, CaSO4 ½ H2O) which when mixed with water will set or harden as the calcium sulfate returns to the dihydrate form. This semifinished product, usually called stucco, is then manufactured into a large variety of plasters, wallboard, and block for construction use, or into plasters for industrial applications. About 75% of the gypsum used in the United States is calcined for these purposes. Uncalcined uses of gypsum are principally as a retarder for portland cement, as a soil conditioner, as a mineral filler, and other minor industrial applications. About 25% of the gypsum mined in the United States goes into these markets; however, in less developed countries where construction and other industrial uses may be quite limited, the use of uncalcined gypsum for portland cement retarder may well be the dominant-if not the only-market for the mineral. It has often been noted that calcium sulfate constitutes the world&apos;s largest reserve of sulfur, and minor use of both anhydrite and gypsum has been made to produce sulfuric acid or other sulfur compounds such as ammonium sulfate. However, because sulfur is readily available at lower cost from other sources, use of calcium sulfate has been limited to only a few locations where it could compete economically. No such use is reported in the United States at this time. Mineralogy Anhydrite, CaSO4 because of its geologically rapid conversion to gypsum, and relatively high solubility (about 0.2 g per 100 g H2O) is not often found outcropping in climates wet enough to support abundant vegetation except on steeply dipping slopes or other places where hydrated material is continuously removed. Anhydrite rock is most often light to bluish gray in color, and under the microscope, varies

Jan 1, 1983

By L. G. Margolin

INTRODUCTION In this paper we derive an expression to predict the onset of growth of a crack in a quasibrittle material. We employ an energy criterion, which was first proposed by Griffith (1920), and is essentially equivalent to the first two laws of thermodynamics. The criterion is applied to the elastic-plastic crack of Olesiak and Wnuk (1968), which is a three-dimensional generalization of the Dugdale (1960) crack. Our expression for the onset of growth differs in several respects from a criterion based on a crack in a brittle material (i.e., using linear elastic fracture mechanics) . Furthermore, the new features are in qualitative agreement with the experimental data. Among these new features are 1) the dependence of the apparent surface energy, or critical strain energy release rate on crack size (the shape of the R-curve); 2) the effect of in-plane stresses (i.e., the stresses that do not lead to any traction on the crack faces) on crack growth; and 3) a brittle-ductile transition. The energy criterion, as a necessary condition for crack growth, rests on a firm theoretical basis. However, its role as a sufficient condition is less secure. Several alternate criteria have been proposed as necessary and sufficient conditions for the onset of crack growth. We will contrast several of these, including critical strain (Olesiak and Wnuk, 1968; Goodier and Field, 1963) and crack opening displacement ("COD", Burdekin and Stone, 1966) with the energy criterion. We will show that these alternate approaches are inconsistent with the energy criterion, in the sense of being necessary conditions, and so should be rejected as criteria for growth--at least for the elastic-plastic crack.

Jan 1, 1984

By C. M. Brown

Selection criteria for the instrumentation employed in semi-autogenous grinding circuits are reviewed. Instruments in use for grinding mill and related process equipment start- up, shutdown, protection, monitoring, control, and performance reporting functions are discussed with examples given of current industry practice. The quantity and type of instrumentation used vary from operation to operation, but today many semi- autogenous circuits are highly instrumentated, and employ automatic process control for both circuit stabilization and optimization of economic performance. Examples of analog and digital based control systems exist, and are described.

Jan 1, 1982

By AIME AIME

A COMMITTEE of the American Railroad Association, consisting of Samuel Rea, president of the Pennsylvania System, Chairman; F. D. Underwood, president of the Erie Railroad; A. T. Dice, president of the Philadelphia & Reading Railroad; E. J. Pearson, president of the New York, New Haven & Hartford Railroad; and C. H. Markham, president of the Illinois Railroad (who was represented at the meeting by J. F. Porterfield of his system), met at the headquarters of the American Institute of Mining and Metallurgical Engineers, New York, on April 6 to assist in the Coal and Coke Committee&apos;s attempt to solve the bituminous coal problem. There was a full discussion of the questions of seasonal freight rates and the purchase by the railroads during the slack months of their winter&apos;s supply of coal. As the question of fuel supply for the railroads is in the hands of the Railroad Association, as well as the coal operators, it was vital that it should be represented at this important conference. The situation from the point of view of the mine operators was presented very thoroughly. No seasonal rates were considered necessary for the year 1920, and, as this matter requires considerable thought, it will be given thorough study and worked out in detail at a subsequent meeting.

Jan 1, 1920

By M. E. Wadsworth

The chief value of a paper like this consists in its statistical tables, putting on record material useful to future inquirers. The data here given have been compiled from time to time as far back as 1874, and subsequently brought up to date. Much of the data could only be procured by personal inspection of the catalogues, as for example those relating to the Lawrence Scientific School, which were taken at that time from the catalogue of Harvard University, on file in the University Library, by the present writer, then an instructor in that institution. These tables of statistics were first prepared for publication by the present writer in 1888-1890 and published in his "Report to the Board of Control of the Michigan College of Mines " (Michigan Mining School) for 1886 to 1890. Later they were revised, enlarged and brought down to date in his reports to the same Board for 1890-92; and since that time they have been, at his request, revised, greatly enlarged and kept up to date by Mrs. Frances H. Scott, the efficient Librarian and Secretary of the Michigan College of Mines. Great credit is due to her for her devotion to this work and her untiring efforts to have the statistics complete as far as possible. The accompanying running commentary is given simply as a string to hold these statistics together, and in order to call attention to a few points. In compiling any tables like those accompanying this paper, one is confronted by serious difficulties, some of which render these results only approximate. In order to insure greater correctness and fullness in the statistics to be published the writer&apos;s reports for 1890-92 were sent to the president of every college, university, and technical school in the country, so far as known. Accompanying this was a personal letter which asked of each one his aid in correcting any errors, and in giving fuller statistics. But relatively few answers were obtained, and subsequently from one to many letters have been sent to each institution not formerly reply-

Jan 1, 1898

By S. R. du Toit, W. J. Oberholzer, M. I. Watson, D. G. Krige

The objectives, essential features and implications of the &apos;random&apos; and &apos;deterministic&apos; types of ore value surfaces are examined as well as the basic requirements for a satisfactory prediction model. The &apos;random&apos; method used on the South African gold mines and based on observed auto-covariance patterns is briefly discussed as well as its justification in preference to the &apos;deterministic&apos; approach. Various mathematical models for auto-covariance patterns are examined for the one-dimensional case. It is also shown that these patterns as estimated for ore values in certain mines agree closely for various sizes of ore unit. In two case studies the variations in gold, uranium and ore thickness covariance patterns are examined and compared with certain geological features established independently from sedimentological studies.

Jan 1, 1969

By R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of the gaseous, topo-chemical reduction of porous hematite spheres. Gas-solid reduction is permitted at each of three advancing interfaces and is controlled by a complex series-parallel sequence of chemical and transport steps. Despite the fact that transport resistances are significant to the advance of each interface, little deviation from linear advance is predicted for the first 98 pct of reduction. Calculations to predict the movement of magnetite /wustite interface by a solid-state diffusion mechanism have been incorporated into the earlier dense-pellet model.&apos; The porous-pellet model is found to give a better description than the dense-pellet one for McKewan&apos;s measurements2 of interface movements in dense polycrystalline hematite reduced in hydrogen-water vapor mixtures. THIS paper reports a continuation of work"3" directed toward the better understanding of gas-solid reactions and the development of mathematical models that may be helpful in the design or control of ore-reduction processes. Laboratory studies of the reduction of single oxide samples in tube furnaces normally employ an abundant excess of pure reducing gas. Reduction may appear to be adequately described by a model assuming gas-solid reaction solely at the iron/wustite interface.&apos;&apos;&apos; However, when iron ore is reduced in either a fixed bed or an efficiently operated counter-current column, there are portions of the bed where the partially spent gas is no longer capable of reducing wustite to iron. Nevertheless, the formation of the intermediate reaction products, wustite or magnetite, can and does continue. In order to account for this aspect of the reduction of beds of particles, three semiempirical mathematical models were devised.&apos; One of these was for the limiting case of completely dense particles, and two alternatives were provided for porous particles. For purposes of the analysis, a dense pellet was defined as one in which the wustite and magnetite layers were impervious to the reducing gas when the atmosphere was capable of forming iron. In a porous pellet, the intermediate product layers were assumed to be sufficiently permeable to allow reducing gas to penetrate beyond the iron/wustite interface to form wustite and magnetite by removal of oxygen as a gaseous product rather than by a solid-state redfiction mechanism. Further progress required a better understanding of the reaction of the individual particles with the gas stream. A comprehensive mathematical treatment was developed&apos; to describe the continually changing interplay of transport and reaction steps

Jan 1, 1967