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By R. J. Franklin, G. W. Beckman, D. Warren, E. Both, J. F. Libsch

BINARY and ternary alloys of iron, nickel and cobalt respond to annealing in a magnetic field by a characteristic change in the shape of their hysteresis 100p.l,2 An increase in retentivity and a decrease in coercive force produced by the magnetic treatment cause the hysteresis loop to approach the appearance of a rectangle. Materials with a rectangular hysteresis loop have made possible the contact-rectifier³ and have greatly improved the performance of pulse transformers4 and magnetic amplifiers." In the best material presently available for these applications, a 50 pct nickel-iron alloy," the desired characteristics are achieved by aligning the preferred crystallographic directions of magnetization along the rolling direction of the tape. The objective of the present study has been to produce rectangular hysteresis characteristics in materials with inherently high saturation. Iron-cobalt alloys, exhibiting saturation values up to 24,000 gausses' appeared to offer promise for the magnetic annealing technique, because they remain magnetic to very high temperatures,8 exhibit favorable magnetostriction properties: and show zero crystal energy at 42 pct cobalt.10 Among the ternary iron-cobalt-nickel alloys,7,11 response to heat treatment in a magnetic field is unfortunately limited to alloys having rather low saturation values.' It appeared interesting nevertheless, to study a series of compositions connecting the optimum composition (50/50) of the binary iron-cobalt system with the "Perminvar" composition (30 pct Fe, 25 pct Co, and 45 pct Ni). Very recently, R. Smoluchowski and R. W. Turner," have shown that under certain circumstances magnetic annealing can produce oriented recrystallization. A combination of this technique with the domain orientation utilized in the present study might well result in further improvements. The advantages of the powder metallurgy technique in preparing magnetic alloys for study have

Jan 1, 1951

By B. R. Palmer, G. Gutierrez B., M. C. Fuerstenau

Selective flotation in nonmetallic systems is often complicated by the presence of iron-bearing silicates occurring as gangue. Minerals such as augite, diopside, hornblende, and tourmaline respond readily to flotation under the same conditions as ore minerals. Mechanisms by which these minerals respond to flotation with anionic collectors must be established if selective separations are to be made in these systems. It was the objective of this investigation to determine the mechanisms involved in the flotation of two pyroxenes, augite and diopside, with potassium oleate. Experimental Materials and Methods Pure potassium oleate, prepared by neutralization of oleic acid with KOH, was used as collector, while reagent-grade HC1 or KOH were used for pH adjustment. Conductivity water, made by passing distilled water through a mixed-bed ion exchange column, was used in this investigation. Two pyroxenes, [ ], were involved in this work. One member of this class of minerals was augite and was found to contain 3.3% calcium, 4.6% iron, and 9.6% magnesium. The source of this mineral was Tillamook County, Ore. The other pyroxene involved was diopside which contained 8.3% calcium, 2.7% iron, and 7.6% magnesium. The source of this sample was Bancroft, Ont. Microflotation experiments were conducted with a Hallimond cell. Mineral samples were ground dry and sized to 100 x 200 mesh. One-gram charges were conditioned for 3 min in the presence of various additions of potassium oleate. Flotation was conducted for 1 min with a nitrogen flow rate of 50 cm3/min. The electrophoretic mobilities of these two minerals were measured with a Zeta Meter in the absence and presence of [ ] salts and in the presence of an indifferent electrolyte, NaC1, added to maintain ionic

Jan 1, 1978

By Stanislaus Skowronski

THE melting of cathode copper, usually containing 99.98+ per cent. Cu, would appear to be a simple matter. Owing to the well known affinity of copper for sulphur, however, so much sulphur is absorbed by the copper during the operation that a long and expensive refining process is required to remove it, and the final product is inferior in purity and lower in electrical conductivity than the original cathode copper. The furnace operation, as now conducted, includes the following stages: 1. Charging the cathodes into the furnace. 2. Melting the cathodes. 3. Oxidizing period-saturating the copper with cuprous sub-oxide and bringing the metal to the condition known as "set copper;" this is now done by blowing air into the molten bath of metal. 4. Reduction period, otherwise known as "poling," whereby the oxygen previously added is removed by covering the molten bath completely with coke or charcoal and introducing large poles of green wood; this reduces the cuprous sub-oxide, bringing the copper to the "tough pitch" stage ready for casting. 5. Casting Period. Many experiments have been made to obviate the long periods of oxidation and subsequent reduction, with no success. While the copper first, cast will be good, as indicated by the set surface of the bars, it is impossible to hold it to the "tough pitch" condition, and long before the whole charge has been poured the copper will become "overpoled," entailing numerous difficulties. Sulphur has always been blamed by the furnace men as the reason why this refining process is necessary, yet the literature on the subject does not sufficiently emphasize how small a proportion of sulphur will ruin copper for practical purposes.

Jan 3, 1918

By B. H. Bergstrom

The Gaudin-Meloy1 size distribution equation requires the evaluation of two constants, xo and r. The common log-log representation of a screen analysis as cumulative weight percentage passing versus size, readily yields the required constants as illustrated for curves A and B in Fig. 1. The 100% passing (y = 1.0) size is simply x,. If the straight portion of the curve be extrapolated to the 100% passing (y=1.0) abscissa, the intercept is the Schuhmann size modulus, k. The ratio of xo to the size modulus, k, is r as shown: The Gaudin-Meloy equation requires that the slope, a, of the size distribution approach unity in the finer sizes, as is the case for curves A and B. Often distributions are better characterized by slopes other than unity. The schuhmann2 equation is able to represent these distributions if the upper portions of the curves are ignored. Empirically, the Gaudin-Meloy equation can be modified to yield slopes other than unity by writing it as Here, a is the familiar Schuhmann slope, and xo is the 100% passing size. The value of r is still given by Eq. 2. Eq. 4 with its easily determined constants is more versatile than either the Schuhmann or the Gaudin-Meloy equations, since a wide variety of size distributions can be closely described. It is easier to fit than the Rosin-Rammler3 equation, and has the advantage that the top size, x,, is finite. REFERENCES A. M. Gaudin and T. P. Meloy: Model and a Comminution Distribution Equation for Single Fracture, AIME Transactions, 1962, Vol. 223, pp. 40 to 43. R. Schumann, Jr.: principles of comminution, I., size Distribution and Surface Calculations, AIME Technical Publication No. 1187, 1940. P. Rosin and E. Rammler: The Laws coverning the Fineness of Powdered Coal, J. Inst. Fuel, 1933. Vol. 7, p. 29.

Jan 1, 1967

By H. F. Yancey

THE jig may be termed the standard coal-washing machine. Although exact figures on the relative tonnages of coal treated by the various coal-cleaning processes are not available, it is known that a large part of all the coal given special cleaning treatment is handled by jigs. This wide use of the jig warrants a special study of its performance. In this paper are presented the results of an analysis of work done by a three-compartment jig in treating bituminous coal from the Thick Freeport bed in Allegheny County, Pa. Certain systems of washing coal require sizing before washing, while others treat unsized coal. The prevailing practice, however, for the preparation of coking coal from the more easily washed coal is to treat an unsized or natural feed at about -1 in. size and smaller. Under such conditions, the minimum size of particle that is beneficiated has long been and is still a matter of discussion and conjecture. In a careful laboratory investigation Jüngst1 concluded that the practical limit of settling of fine coal is reached at from 0.02 to 0.008 in. On the other hand, Hancock2 has found that single-compartment jigs, used in preparing coal for the domestic market, usually allow most of the heavy (refuse) particles smaller than 1/4 in. to go into the washed coal. He also states that it is impossible with the ordinary coal jig to make any noticeable improvement in the quality of the coal finer than 20 mesh (about 1/30 in.). Because of its importance in coal cleaning, the work described in this paper was undertaken for the purpose of obtaining information on this subject, as a part of the general coal beneficiation program being carried out by the Bureau of Mines.

Jan 4, 1925

By H. C. Vacher

THE limiting concentrations of carbon and oxygen which may co-exist at equilibrium in liquid iron are important in determining the degree to which liquid steel may be refined before it is deoxidized. Most refining processes depend upon the oxidation of a highly carburized iron which invariably results in contaminating the steel with oxygen. The oxygen .thus introduced presents many problems to the refiner, who in turn has attempted to rid the steel of this impurity by deoxidation with elements such as manganese, silicon and aluminum. The importance of the limiting concentrations of carbon and oxygen is accentuated in view of a number of recent researches which have indicated in many instances the existence of relations between oxide inclusions and dissolved oxygen and physical properties and chemical behavior of steel. The determination of the equilibrium concentrations of carbon and oxygen existing in iron under steelmaking conditions is obviously of fundamental importance. It has been generally assumed that the product of the equilibrium concentrations of carbon and oxygen in liquid iron is a constant and that this product is directly proportional to the carbon monoxide pressure in equilibrium with the liquid iron. Herty1,2 has computed values for this product based on open-hearth data which are all in the neighborhood of 0.01 to 0.03 (per cent. FeO X per cent. C) for temperatures in the vicinity of 1550° to 1600 C. and one atmosphere pressure. Kinzel and Egan3 have attempted to determine the value of this product by exposing liquid iron to carbon monoxide at one atmosphere pressure. The value reported by them was 0.0005 at 1550°. C. In. order to apply certain equations to the rate of carbon elimination in the open-hearth process, Feild4 found it necessary to assume. a value of 0.0102 at 1580° C. for this

Jan 1, 1931

By W. C. Shanks

Seventeen deeps, which contain hot or cold brines and/or metalliferous sediments, have been discovered in the axial rift zone of the Red Sea. Metalliferous activity results from the unique geological setting of this incipient ocean basin: oceanic crust intruding in a central rift zone flanked by thick evaporite sequences. Brine pools tend to occur in structural depressions where- transform faults intersect the spreading axis. The most significant metalliferous occurrence is in the Atlantis II Deep, which contains approximately 227 Mt (dry weight) of metalliferous sediment which averages 1.04% Zn and 0.28% Cu. Higher potentially economic grades (3-6% Zn, 1% Cu, 50 glt Ag) occur in the Southwest Basin of the Atlantis II Deep, comprising total metal tonnages of 1.7 Mt Zn, 0.4 Mt Cu, and 5000 t Ag. The Pre-Pilot Mining Test conducted in 1979 raised 15 000 m3 of mud by a slurry process and demonstrated the feasibility of mining, concentration by froth flotation, and tailings disposal at sea. A Pilot Mining Test is scheduled for 1983-1984. The metalliferous discoveries in the Red Sea provide a model example of deep marine mineral exploration. Detailed mapping of bottom bathymetry and brine-interface reflectors using a high-resolution narrow-beam echo sounder has been the most effective exploration tool in the Red Sea. Followup coring has discovered additional metalliferous deposits in basins without present-day brines, and potential exists for additional discoveries. Geochemical exploration using heavy metals values in sediments (iron, manganese, zinc, copper, and mercury) and sulfur isotope values of sulfides are considered to be the most promising techniques for discovery of currently inactive deposits. Positive sulfur isotope values in the range I to 17 are an indication of hydrothermal sulfides in the Red Sea, and there is considerable contrast from back- ground bacteriogenic sulfides ( - 10 to - 45).

Jan 1, 1983

By A. J. Chellew, Robert Condit

THE Company maintains a port agency at Antofagasta for dispatching copper and also for receiving from ocean vessels the vast variety of materials and supplies required at the plant. Copper shipments from the oxide plant refinery to Antofagasta amounted to 162,000 metric tons during 1951, while incoming freight totalled 175,000 metric tons. Electrolytic market copper in various shapes is currently loaded at the plant upon 20 or 30-ton cars of the meter-gage Antofagasta-Bolivia Railroad, to be transported a distance of 165 miles to the company's yard at Antofagasta. Here it is unloaded by cranes at the rate of about 175 tons per hr. Copper not scheduled for immediate shipment is stocked in tiers within the yard, but most of it is reloaded and sent to port works or a wharf serving lighters. Some of the vessels entering Antofagasta tie up at the port works, while others anchor inside the breakwater. In the latter case, all of the loading into the hatches is from 50-ton lighters towed to the vessel. When the vessel is at the dock, about half of the copper is loaded by port works cranes and the other half is loaded by ship's tackle from lighters. Fuel Oil Requirement Expands One of the innovations caused by the construction of the sulphide plant has been the necessity to provide facilities at Antofagasta for receiving and storing greater quantities of fuel oil than in recent years. From here it is loaded into tank cars for transportation to Chuquicamata. The older installation consisted of a 10-in. submarine pipe line, heating, and pumping facilities, a 67,500-bbl storage tank, and railroad loading rack, located at Antofagasta's northern limits. Two new tanks, of 80,000 and 30,000-bbl capacity respectively, have now been added and a second submarine pipe line will shortly be installed. Fuel oil requirements for the sulphide plant are estimated at 39,000 bbl per month, in addition to which 9000 bbl per month are required for the operation of the oxide plant. The company has a special lighter which is used by its diver for connecting the oil line with the oil tanker when disembarking oil, this lighter also being used for inspecting and overhauling buoys, as well as for recovery of bars of copper which are sometimes dropped into the bay when loading vessels during periods of rough weather. Transport of oil to Chuquicamata is by 76 tank cars of, 20-ton capacity and 20 of 30-ton capacity, all assigned to the company's fuel oil shipments excepting six for Diesel oil and one for gasoline. Incoming Freight Other freight received by the port agency has been averaging about 4800 metric tons per month of operating supplies for the oxide plant (renewals of equipment, spare parts, lubricating oils, and greases, etc.), some 1900 metric tons per month for the company stores, and about 6000 metric tons per month of materials and equipment for the construction of the sulphide plant. The greater part of these shipments (particularly the operating and construction supplies) originate from abroad, and must be handled through the Chilean Customs. Hence the company maintains a Customs storage warehouse (goods pending appraisal of Customs duties) in addition to its other storage facilities at Antofagasta. Not the least of the Port Agency's duties is to meet air and steamer passengers en route to Chuquicamata and to arrange for their trips up the hill. Landing in a strange country with a strange language, the first impressions of a new employee might otherwise be indeed confusing when facing Antofagasta's unique setting of brown barren hills.

Jan 1, 1952

By J. E. Warren

To clarify the specific questions raised by J. E. Warren's discussion, the following remarks are offered. 1. It is correct that stratification is assumed in the application of the statistical zonation technique, but this does not constitute a limitation. If, in fact, the reservoir is not stratified the zonation technique will show it. The reservoir is then considered as one zone with a particular distribution of permeabilities. 2. The statistical zonation technique was intended as wells may not be an adequate measure of the lateral permeability changes; e.g., if the data presented in Table A-4 of the subject paper are evaluated on the basis of two crossed classifications with interaction, the variation between zones is significant with a probability greater than .99; however, the variation betwen wells is also significant with a probability greater than .87. It is apparent that the technique suggested by the author can be generalized to provide a powerful method for describing petroleum reservoirs. This generalization can be achieved by treating the core data as a two-way classification to determine the between-zones and the between-wells variations; then, the build-up permeabilities can be analyzed, perhaps on at least-squares basis, to establish the probable distribution of the permeabilities within the zones associated with the individual wells. an additional tool for the reservoir engineer to use together with other techniques and all available information. If pressure build-up permeabilities are available, they should certainly be included. Pressure build-up tests were not available for the reservoir considered in the paper. 3. The proposed correlation of zones between adjacent wells was the best of the techniques that I examined. It is not so much a "measure" as an indication of lateral permeability changes, regardless of whether they are seemingly random or form an obvious trend.

By H. L. Shergold, O. Mellgren

Concentration of fine quartz particles at the iso-octane/water interface has been investigated under different conditions of pH and dodecylamine concentration. The results obtained from the related studies on the effect of amine concentration and pH on the interfacial tension, adsorption density, electrokinetic potential, contact angle, and concentration of the various amine species in the system are presented. A good correlation was obtained between these different variables. It is well-known that very fine mineral particles are difficult to float in conventional flotation machines. Flotation rate studies have revealed that the rate of flotation of fine mineral particles is much smaller than that of coarser size fractions. The theories accounting for this behavior have been discussed by Arbiter and Harris1 and also Meloy.2 Theoretically, a hydrophobic fine particle might never make contact with a bubble because of the presence of an energy barrier in the vicinity of the air/water interface.' This energy barrier will have electrostatic, hydrodynamic, and Van der Waals force components. It was thought that by using an oil phase instead of air the energy barrier would be decreased so that fine particles could be concentrated at the oil/water interface more readily than at the air/water interface. The technique used involves dispersing the fine particles in water, containing the appropriate chemical reagents, and injecting a fine dispersion of iso-octane oil droplets into the pulp. After vigorous conditioning, the pulp is passed into a separating column where the oil droplets coated with a layer of mineral particles rise to the surface to form a separate layer. Air is introduced into the base of the separating column to ensure that heavy agglomerates of oil and particles report with the organic layer. This technique has been described previously4 and adopted by Lai and Fuerstenau5 who studied the alumina-dodecyl sulfonate system. The interfacial phenomena in the system composed of hematite, water, and iso-octane in the presence of sodium dodecyl sulfate have been studied and the results reported" earlier. This paper describes the results obtained from investigations into the interfacial phenomena in the quartz/water/iso-octane system in the presence of dodecylamine. The technique used in measuring the interfacial tension, electrokinetic potential, contact angle, and adsorption density were similar to those described previously? Materials Selected pieces of a high purity natural quartz, from the Isle of Man, were crushed in a laboratory jaw crusher and pulverizer. The — 52+72 mesh size fraction was retained and leached with successive washes of hot concentrated hydrochloric acid to remove iron impurities. When no iron was detected in the solution by ammonium thiocyanate, the quartz was washed thoroughly with distilled water until the conductivity of the wash water assumed that of the distilled water. Samples of 25 g of the —52+72 mesh quartz were ground for 5.25 min in an agate vibratory mill. The ground product was 100% —44 m and 57% —10 am, as determined by the Andreasen pipette. The specific surface area of the sample used for the adsorption and flotation tests was 0.94 sq m g-l. This corresponds to a mean particle diameter of 2.4 am. The —44 am quartz sample was stored under vacuum in the presence of silica gel crystals. For the contact angle determination between the three phases, quartz, iso-octane, and water, a piece of the natural quartz was ground into a block about 15 mm long, 15 mm wide, and 5 mm thick. One surface of the block was then polished by successively finer grades of silicon carbide "paper." The final polishing was conducted with alumina on a "hyprocel" paper. The polished quartz specimen was cleaned using nitric acid and ethyl alcohol followed by a wash with distilled water and then stored under distilled water. This pro-

Jan 1, 1971

By H. L. Lovell, L. H. E. Weyher

Cyclones have been used successfully in the mineral industries to solve solid-liquid as well as solid-solid separation problems in the processing of fine particles. Substantial information is available about the operation of cyclones as thickeners, classifiers, and concentrators using a dense medium. However, very little is known about the operation of the cyclone as a fine coal concentrator not using dense medium. This application of the cyclone, namely to wash fine coal in water, requires that classification phenomena be minimized in order to arrive at an effective separation of the high density ash and sulfur-bearing mineral particles from the low density coal particles over a wide particle size range. The authors have investigated the role of feed pressure, orifice diameters, and vortex-finder length in the cyclone washing of fine coal (--1/4 in.) in water. The results of this investigation show that cyclone washing of fine coal in water is an effective unit operation particularly capable of reducing the inorganic pyritic sulfur content. The combination of hydrocyclones with complimentary equipment such as Sieve bends, shaking tables, and flotation units appears to be especially promising and may ultimately yield fine coal processing systems that could approximate the high recovery efficiencies of today's coarse coal cleaning circuits. In the future, fine coal beneficiation can be expected to receive even greater research emphasis as a result of increasing sulfur restrictions on all major coal markets. In a previous paper, work, conducted at the Pennsylvania State University, on the hydrocyclone washing of fine coal was discussed.' The initial evaluation based on that wo-rk demonstrated the feasibility of hydrocyclones as fine-coal cleaning devices, and in that previous paper selected test data were presented that showed in principle how product yield and assay respond to variations of the major cyclone operating variables. The present paper reports in greater detail on the findings and presents a comprehensive evaluation of the data as follows: (1) Hydrocyclone throughput rates were related to feed pressure and other variables by regression equations. These equations are compared with other capacity-vs.-pressure drop expressions taken from the literature on classification cyclones. (2) The flow ratio was found to be the most important variable for the separation of the solids. Control of this ratio through various cyclone operating parameters is discussed. (3) The data on the product yield as well as the ash and sulfur assays from the tests were evaluated by means of correlation and multiple regression analyses. Because size-classification phenomena cannot be suppressed completely in hydrocyclone washers, product yield and assay data are regressed against cyclone operating variables separately for different size classes. These equations then reveal how the interactions of the cyclone operating variables vary in terms of the separation for different size classes. (4) Density partitions from additional tests were analyzed by supplementing product-size analyses with sink-float analyses of the separated product size classes. The evaluation of these data show how classification phenomena affect separation by density. The results demonstrate in particular the feasibility of the hydrocyclone washer for removing pyritic sulfur from fine coal. In addition to these specific findings, the investigation points up the value, in general, of using hydrocyclone washers in combination with unit operations such as screening, table concentration, and flotation. In order to make optimum use of the hydrocyclone washers and work out the most effective combination of unit operations, it is important to have careful flowsheet analyses corresponding to the given feed and product requirements. Analyses of this kind are now possible by means of computer simulation of flowsheets and other operation research tools. INTRODUCTION Before proceeding with the detailed treatment and evaluation of our results, it will be useful to review the fundamental aspects of cyclone separators and also restate the experimental procedures and data handling employed in these studies. Review of Cyclone Fundamentals: AS shown in Fig. 1, the basic components of cyclones commonly used

Jan 1, 1970

By Seymour G. Epstein

Using a modified capillary-reservoir technique, electromigration of dilute solutions of silver in liquid bismuth has been measured with relatively good precision. The effects of experiment duration, temperature. current density, and silver concentration have been investigated. Chemical diffusion coefficients of silver in liquid bismuth were also measured at temperatures ranging from 300°to 600°C. The effective valence of silver in bismuth was calculated as a function of temperature from a comparison of electric mobilities and diffusion coefficients. In an alloy containing 1 wt pct Ag, the electric mobility of silver increased from 1.65 x X sq cm per v-sec at 300°C to 2.38 x 10-4at 600°C; the diffusion coefficient in-creased from 3.0 to 17.5 x 10-5 sq cm per sec over the same temperature range. Calculated values of effective valence decreased from 0.28 at 300°C to 0.10 at 600°c. ALTHOUGH there has been considerable progress in the theoretical treatment of electron-transport properties in liquid metals, the mechanisms of mass-transport phenomena in liquid metals are still not clearly understood. This is especially true for the case of electro migration, alternatively termed elec-trotransport or electrodiffusion, which is mass transport induced by an applied electric field. A thorough knowledge of the mechanisms governing electromigration will considerably aid in understanding the electronic state of an impurity atom in a liquid metal. Electromigration has been long observed and studied in liquid metals and alloys. However, no satisfactory theory to explain the observed effects has been developed. The disparity in the present theoretical treatments, summarized by Verhoeven,1 has been attributed to the difficulty in describing the momentum transfer between electrons and ions and to the lack of precise measurements in liquid metals, especially at elevated temperatures. Prior to the last decade most of the electromigration studies were qualitative, in that only the direction of migration of alloy constituents was determined with any degree of reliability. These results have been summarized by schwarz,2 who was able to measure the electric mobility of several elements in mercury. More recently electromigration in liquid metals has been measured by a variety of techniques, with a varying degree of success. Mangelsdorf3,4 made precise measurements on dilute amalgams at room temperature, using a technique relating changes in composition to changes in alloy resistivity, but was unable to make measurements at elevated temperatures. Using a modification of this technique, Verhoeven and Hucke5 measured electromigration and resistivities in liquid Bi-Sn alloys. However, the resistivity technique is not sensitive to small composition changes and is impractical for very dilute alloys. Verhoeven and Hucke6 also measured electromigration of several solutes in liquid bismuth by adapting the capillary-reservoir method for determining diffusion coefficients in liquids. The reported precision of these measurements was poor, however, primarily due to the large uncertainties in the chemical analyses to determine concentration changes. Belashchenko7 has summarized the recent Russian investigations of electromigration, many of which, however, are of questionable accuracy. The present study was initiated to develop an experimental technique which would be both versatile and sufficiently sensitive to yield precise measurements of electromigration of solutes in dilute metal alloys at elevated temperatures. Using this technique, a comprehensive study of silver in liquid bismuth was made to determine the effects of experimental variables on the apparent electric mobilities. Chemical diffusion coefficients of silver in liquid bismuth were also measured over the same temperature range for comparison with the electromigration data. EXPERIMENTAL TECHNIQUE Electromigration Measurements. Electromigration of silver in liquid bismuth was measured by the capillary-reservoir technique, similar to that used by Verhoeven and Hucke,6 but modified to yield more

Jan 1, 1967

By J. L. Moriarty, Irving Johnson, H. M. Feder

The crystallization of ternary alloys has been studied as a coprecipitation phenomenon by measuring the substitutional carrying of trace metals with CeCd11 precipitating from liquid cadmium. The Doerner-Hoskins logarithmic distribution law has been found to apply in all cases; the coprecipitation coefficients obtained were: 1.48 (La), 1.06 (Th), 0.63 (Pr), 0.24 (Gd), 0.17 (Sm), 0.13 (U), 0.10 (Er), 0.09 (Sr). Li, Na, K, Ba, Y, Sc, and Zr were not measurably carried. It has been observed that coprecipitation was most extensive for those tracers which form with cadmium an intermetallic compmdnd isostructural with CeCd11 or closely related thereto. For these tracers an inverse relation between Solubility in cadmium and coprecipitation coefficient was noted. THE partition of impurities between the liquid and solid phases of a metal or a congruently melting intermetallic compound has been extensively studied by the methods of zone melting.' However, when the composition of a liquid alloy and of the solid phase crystallizing from it differ grossly, partition of an impurity cannot be investigated in this manner. Partition of the impurity under equilibrium conditions may be studied by investigation of the appropriate phase diagram and partition under nonequi-librium conditions may be studied by observation of coring in the solidified alloys.2 The nonequilibrium case is of special interest in metallurgical practice because many complex alloys are cooled too rapidly to permit the uniform diffusion of impurities throughout the crystallizing phase(s). With this in mind, the present study was undertaken to obtain quantitative data on the phenomenon of coprecipitation via substitutional solid solution in certain metallic systems. It will be noticed that rather than adopting metallurgical ter- minology we have chosen to refer to the partition of impurities during alloy crystallization as coprecipitation.3 In the terminology of coprecipitation the impurity is referred to as the tracer and the precipitating phase as the carrier. From aqueous solution, coprecipitation may occur as a result of adsorption on the surface of the carrier, by occlusion of the liquid within the crystals, or by solid solution of the tracer in the carrier. By slow cooling of liquid metallic solutions it is relatively easy to form large, regular crystals of the carrier; the effects of adsorption and occlusion may be minimized and the influence of substitutional solid-solution formation may be made to predominate. Previous studies of the crystallization of some intermetallic compounds4 and of copper, silver, and gold5 have shown that the coprecipitation or partition behavior of trace metals is entirely analogous to that observed in aqueous systems when ionic substitution occurs, e.g., coprecipitation of Ra++ with BaSo4. The precipitation of CeCd11 from liquid cadmium was chosen for study. This choice was influenced by the following consideration. If the relative atomic sizes of the tracer atom and the atom for which it substitutes determine the tendency to coprecipi-tate, then a lattice having a substitutional site of well-defined size would be desirable. In CeCd116 (structure type cubic BaHg117) the cerium atom is completely surrounded by a cage of twelve nearly equidistant cadmium atoms. Thus, atoms much larger or much smaller than cerium should be poorly accommodated in this cage. The choice of a lanthanide central atom allowed the testing of the size hypothesis with a number of lanthanide tracers which differed in size but not in valence or electro-negativity. EXPERIMENTAL The general technique of this investigation was to prepare a slightly undersaturated solution of carrier in liquid cadmium to which a tracer was added. The concentration of tracer was always so low that saturation over the entire temperature range investigated was never exceeded. The solution was cooled in a stepwise fashion. After each step a por-

Jan 1, 1964

By Charles E. Mann, Douglas J. Lootens, Rufino B. Bomasang

INTRODUCTION The economy of the Philippines, like that of many other developing nations, has been severely strained by the rapid escalation of imported crude oil prices over the past decade. In an effort to reduce its dependence on imported crude, significantly increased emphasis, both in the public and private sectors, is being placed on the rapid development of Philippine coal resources. This paper is designed to present an overview of the Philippine coal industry, its historical development, present status, and future potential. COAL RESOURCES AND RESERVES In 1977, a British consulting firm collated all available data on Philippine coal resources and estimated the total coals potential at about 0.9 to 1.4 billion metric tons (mt). In 1981, using more recent data the Philippine Bureau of Energy Development (BED) estimated the potential at 1.7 billion mt. The BED estimated the proven coal reserves at 257 million mt. These coal resources are scattered throughout the major islands comprising the Philippine archipelago. However, about 52 percent of the currently proven reserves are located in the tiny island of Semirara between the islands of Mindoro and Panay. About 25 percent is located in the Cagayan Valley in northeastern Luzon while 13 percent is located in Mindanao. The remaining 10 percent is scattered in the islands of Cebu, Samar, Mindoro, Negros, Polillo, Batan, and Catanduanes. The bulk of Philippine coal is sub-bituminous in rank. Some bituminous coal with coking properties has been reported in Malangas, Zamboanga del Sur in western Mindanao, and in Catanduanes, but the exact tonnages have not been accurately established. It is believed, however, to be at most 5 million tons. A little semi-anthracite coal exists in Malangas with the remaining unmined reserves estimated at a little more than one million tons. Table 1 shows the quality ranges of Philippine coal deposits.. Figure 1 shows the distribution of known Philippine coal resources PHILIPPINE COAL PRODUCTION In 1981, total coal production was 330,720 mt. Though modest by world standards, this was the highest production figure in Philippine coal mining history. This came from 25 mines, mainly small scale underground mines of capacities varying from 10 to 100 tons per day (tpd). The actual production capability was about 800,000 mt in 1981, but the producers had to scale down production to the level of local demand. Even then, some 50,000 tons of coal remained unused by year-end. The 1981 production came from the following areas: Cebu 224,751 mt (68%) Zamboanga del Sur 57,095 mt (17%) Semirara 13,222 mt (4%) Polillo 17,132 mt (5%) Cebu has always been the main source of Philippine coal production. Coal mining has been carried out in Cebu for the last 50 years, although it has been characterized by a very crude mining technology. Due to the limited size of coal deposits and complicated geology, however, Cebu's share of the total national production is expected to go down to only 10 percent by 1985. Except for Semirara's open-pit production, the balance of Philippine coal production comes from underground mines. These underground mines generally use room-and-pillar methods, except for those at Zamboanga del Sur and Polillo which use modified longwall methods patterned after those used in Taiwan. Due to the much higher mining recovery, most underground mines are now planning on switching to longwall. At Semirara, an open pit mine is now being developed for a one million ton per year capacity by 1984, and will then be the largest Philippine coal mine. While present earthmoving work is done with bulldozers, loaders, and trucks, the main coal extraction equipment will be bucket wheel excavators imported from Austria. PRESENT COAL UTILIZATION Existing coal production is sold mainly to coal- fired cement plants and power plants. The balance is sold to a sugar central, a coconut oil mill, a food processing plant, and two plants producing carbide and ferro-silicon alloys.

Jan 1, 1982

By J. S. Brown, A. G. Guy

With the exception of the work of Tammann and Hartmann,1 no published information has been found on the structural changes produced in eutectic structures as the result of heating following plastic deformation. In part this lack of information may be due to the fact that many eutectic structures contain an intermetallic compound as a prominent phase, and as a consequence have been considered to be unworkable. For example, Tammann and Hartmann were able to obtain useful data only on those alloys that they could greatly reduce in thickness by cold rolling. This restriction placed on the investigation of alloys containing intermetallic compounds has been largely removed by the work of Savitskii2 which showed that large deformations of such alloys can be produced by relatively slow compression at temperatures near the melting range. It was possible, therefore, to carry out the present work on a range of binary eutectics including one composed of two intermetallic compounds. The essential results obtained on the alloy systems studied are illustrated by the Pb-Mg eutectic containing 33.2 pct Mg, Fig 1. The cast structure, Fig la, was obtained by melting together magnesium of 99.8 pct purity and chemically pure test lead, casting into a heated, small steel mold, and furnace cooling in the mold from about the eutectic temperature. The fairly coarse eutectic structure thus obtained was too brittle to work at room temperature without cracking. Fig 16 shows the worked structure obtained by compressing a 1/2-in. cube 70 pct in about 15 sec at 550°F and then water quenching. The pronounced changes in the distribution of the two phases produced by heating the worked alloy at 850°F for 1 hr are shown in Fig lc. Recrystallization of both phases appears to have taken place, and the mechanical properties of the cast alloy must have been significantly changed by the working and heat treatment. Similar results were obtained with the Mg-59.5 pet Bi, Mg-36.4 pet Sn, Mg-65.4 pet Cu, and Bi-40 pet Cd eutectics, only the last of which could be worked at room temperature. Tammann and Hartmann reported a thickening and shortening of the needles of the eutectics which they heated about 10°C below the melting range for 1 hr after drastic cold rolling. They found the following eutectics, given the indicated amounts of reduc- tion, to have a granular structure after heat treatment: Sn-9 pet Zn (98 pet); Cd-82.5 pet Pb (60 pet); and Bi-43.5 pet Pb (90 pet). On the other hand the alloy Al-11.7 pet Si (60 pet) showed no change after heating. Tammann and Hartmann observed a distinct shrinking of the needles in unworked eutectics subjected to heat-treatment. In the present work inappreciable change in the eutectic structure was found on heating undeformed alloys. In summary, it appears that eutectic structures can be recrystallized into a "spheroidized" condition by heating near the eutectic temperature after severe deformation. If the eutectic contains one or more brittle phases the necessary deformation can be accomplished by pressing at high temperatures. It is reasonable to expect that this tendency towards equiaxed grains from the plate- or needle-like eutectic structure should be general since the energy relations and mode of growth in recrystallization are so different from those that hold for eutectic crystallization. References 1. G. Tammann and H. Hartmann: Ztsch. Melallkunde (1937) 29, 141-144. 2. E. M. Savitskii: Doklady Akad. Nauk S.S.S.R. (1940) 62, 349-351. Abstr. in Melal Prog. (July, 1949) 56, 126, 128.

Jan 1, 1950

By Nicholas J. Grant, Olaf Troili, John Chipman

IN recent studies of the factors which affect the rate of desulphurization and its equilibrium, it became apparent that certain concurrent reactions were operative which had a significant effect on desulphurization. This is emphasized in the experiments of Hatch and Chipman1 and of Grant, Kalling, and Chipman' by the slow approach to a final state of equilibrium which is in marked contrast to the initial rapid transfer of sulphur from metal to slag. Since the removal of sulphur is of such profound importance in iron and steelmaking, it appeared necessary to investigate the reactions responsible for this behavior. It is now known that the presence of iron oxide in the slag interferes seriously with the principal reaction of blast-furnace desulphurization: CaO (slag) +-S + C - CaS (slag) + CO [l] The interfering reaction is most simply expressed as: CaS (slag) + 0 = CaO (slag) +-S 121 and a small concentration of oxygen (or FeO) is sufficient to hold a considerable amount of sulphur in the metal. It has been shown by Grant, Kalling, and Chipman2 that the addition of MnO to blast-furnace slag slows the removal of sulphur from the metal. This effect overshadows the contribution of MnO to basicity and is ascribed to its oxidizing power. It will be shown in this paper that SiO, also has sufficient oxidizing power to interfere with blastfurnace desulphurization. This is, of course, only one of its several effects. Primarily it is an acid and therefore reduces the concentration of excess lime. But when silicon is reduced to the metal the oxygen to which it was previously bonded becomes in part available for reaction 2. The proof of this statement is found in the following experiments. Experimental Procedure and Results Utilizing the same procedure and apparatus described by Grant, Kalling, and Chipman' five additional heats were made using slags IV and 11, the starting compositions of which were: slag IV—40 CaO, 10 MgO, 35 SiO,, 15 A1,0,; and slag 11—50 CaO, 10 MgO, 25 SiO,, 15 Al3O3. An important difference between these heats and those previously reported was that silicon to the extent of 1 to 4 pct was added to the present heats whereas the starting silicon content was formerly about 0.2 pct. Table I shows the slag and metal analyses for heats 82 to 87, and Table I1 shows the silicon addi- tions made to the charge. These additions are based on 400 g of metal and 400 g of slag. All heats had 1.65 400pct S charged before the cold slagadditions. The temperature was maintained at 1525°C. Rate of SiO, Reduction: Fig. 1 shows the silicon content of the metal in contact with slag IV at 1525°C as a function of time. Heat 70 from the work of Grant, afunctionKalling,of and Chipman is included as the lowest starting silicon. It will be noted that eeven with 4 pct Si in the starting metal, there is an increase in silicon content with time. Heat 84 is apparently approaching silicon equilibrium very slowly. Heats 70 and 82 with very much lower slowly.starting silicon show a more rapid initial rise in startingsilicon content but do not reach equilibrium during a long holding period. Fig. 2 shows 3 different initial silicon contents for Fig.2shows3differentheats 73 (from Grant, Kalling, and Chipman) 86 and 87, in contact with slag II, the most basic slag. Heat 73 is increasing in silicon with time, whereas heat 87 with an initial silicon content of 3.7 pct shows a decrease with time. Heat 86 shows a very close approach to equilibrium. The rate of transfer of silicon from slag to equilibrium.metal is very slow in all of those heats, even those which are initially far from equilibrium. ____

Jan 1, 1952

By R. L. Segall

AN unusual thermal etch figure in copper is described and an explanation in terms of twinning is suggested. A flat polycrystalline specimen of OFHC copper cut from a rolled sheet was electro-polished in orthophosphoric acid and annealed at 950°C in a vacuum of approximately 10-3 mm Hg for 2 hr. The specimen was found to be thermally etched, the markings on the surface being consistent with the assumption that they were the traces of the (111) planes which are developed preferentially because they have the lowest free energy. However, on one grain (the grain shown in Fig. 1) the traces formed an almost regular pentagon and at first sight it seemed unlikely that they could all be (111) traces. These traces were studied further because it was thought that they might be a type of growth spiral. A fringe pattern showed that this was not so, the grain being sensibly flat and the only features having steps were the striations and the faint curved line passing out from the center of the pentagons. To obtain some additional information, the specimen was deformed in tension. The effect of the stress was first to cause the appearance of lines running from the centers to the apexes of the pentagons and then to tilt the five segments so formed. At a much greater stress, appreciable slip appeared on the grain; these effects can be seen in Fig. 2. The micrograph was taken at a fairly late stage in the deformation and the tilting is quite marked. The magnification is the same as in Fig. 1, and although some slip can be seen it could be observed better by varying the illumination and using higher magnifications. In each segment of the grain, slip (which takes place on the (111) planes) was parallel to the side of the pentagon in that segment. The marked changes in direction of slip from segment to segment seemed to be incompatible with the presence of a regular array of subgrains. These results suggest that some of the five segments were twins. If this is so, since the twinning plane in copper is the (111) plane, the radial lines must be traces of the (111) planes on the surface. From the symmetry of the striations about the radial lines, these planes must be almost perpendicular to the surface. The angle between <III>directions in face-centered-cubic copper is 70&apos;32&apos;. If, in Fig. 3, OAB (triangle 1) is taken as matrix and OA, OB are (111) planes viewed edge on, then AB is in the correct direction to be the trace of either of the other two (111) planes on the surface. If triangle 2 is the twin (about the (111) plane perpendicular to the surface and containing OB) of triangle 1, then once again it can be shown that all lines are traces of (111) planes. Similarly, triangle 3 is the twin of triangle 2, 4 of 3, and 5 of both 4 and 1. (The sequence is, of course, quite arbitrary.) However, if this were the case there would be a discrepancy of 7&apos;20&apos; to be accounted for. It is suggested that the faint curved line passing outward from the center of the pentagon represents either a low angle boundary or a sixth small twin. The slight step shown by the fringes at this line might be an indication that the former is the case. This explanation does not account for the coincidence of obtaining a grain whose surface must be so close to (110) and obtaining the curious twinning described previously; it would be of interest to find a specific mechanism for this.

Jan 1, 1958

By A. J. Sedriks

ALTHOUGH the occurrence of a readily visible tarnish on the stress-corrosion fracture surfaces of titanium alloys tested in oxygenated nitrogen tetrox-ide solutions has been reported,&apos; the possibility that the formation of this tarnish is a requirement for cracking to proceed does not appear to have been considered. It has been proposed that failure occurs in this system as a result of some electrochemical-mechanical process.2 However, recent studies3-6 of the stress-corrosion cracking of a brass in certain ammoniacal solutions, which also cause visible tarnishing, have led to the view that failure occurs by the repeated formation and fracture of a brittle surface film of cuprous oxide. The purpose of this note is to point out the similarities which exist between the tarnish which forms on a brass and that found on titanium alloys failed in nitrogen tetroxide, and to suggest, by analogy, that a similar tarnish-rupture mechanism may be operative in the latter case. The titanium alloy selected for the present study contained 5.2 pct Al, 2.5 pct Sn, 0.025 pct C, 0.16 pct Fe, 0.014 pct N, 0.012 pct H, 0.07 pct 0, and 0.002 pct Mn by weight. Vacuum-annealed alloy strips measuring 4 by 0.25 by 0.04 in. were used to prepare self-stressed test specimens. Each specimen was made from two strips by bending the end portions and spot welding them together to produce curved sections of uniform bending stress. (The exact details of preparing such specimens have been described by Lisagor el al.7) The curvature in the strips determines the ma-magnitude of the outer fiber stress, which in the present specimens was 100,000 psi (yield stress = 120,000 psi). The specimen surface in the spot-welded end regions was shot-peened to induce compressive stresses and thereby eliminate the possibility of stress-corrosion cracking in these regions. The test environment was nitrogen tetroxide, initially containing 99.5 pct N2O4, 0.1 pct H2O, and 0.08 pct C1, through which oxygen had been bubbled for 30 min. During testing the tetroxide was subject to an oxygen pressure of 250 psi. The duration of the test was 96 hr, and during this time stress-corrosion cracks propagated through some 50 pct of the thickness of the specimens. After testing, the tarnish was liberated from the fracture surface by immersion in a methanol-5 pct bromine solution, and then examined by electron dif- fraction and transmission electron microscopy using a JEM-7 electron microscope. The possibility that the bromine solution had affected the structure of the tarnish was investigated by an "in silu" examination of the stress-corrosion fracture surface using a reflection electron diffraction attachment designed for handling bulk specimens. Typical areas of the tarnish liberated by the me-thanol-bromine solution are shown in Fig. 1. Fig. l(a) reveals that the tarnish consists of individual platelets, and from Fig. l(b) it can be seen that the platelets are joined together to form a semicontinuous film, the boundaries of the titanium substrate grains being retained in the tarnish. Electron-diffraction patterns taken from these areas exhibited diffraction spots typical of a monocrystal. The diffraction pattern shown in Fig. 2 was taken from the central area in Fig. l(n). Monocrystal patterns obtained from areas containing numerous individual platelets can only be explained by assuming that their growth is governed by the titanium substrate (i.e., their growth is epitaxial). In other areas, the tarnish had folded over or became mechanically damaged, and these areas gave diffraction patterns consisting of "spotted" rings, enabling interplanar spacings of the tarnish lattice to be determined. These spacings, measured using a

Jan 1, 1968

By A. Hamilton Garner

The occurrence of oil seepages in Venezuela has been known since the early days of Spanish occupation. It was not until 1912, however, that any serious exploration work was undertaken. In that year, the Caribbean Petroleum Co., then a subsidiary of the General Asphalt Co., employed a large staff of geologists to make a systematic survey of large areas in eastern and western Venezuela, selecting the most desirable localities out of the immense area covered by the Valladares concession. This preliminary work was completed in the fall of 1913, and in February, 1914, the company completed its first commercial well at Mene Grande. Development work has progressed slowly, for various reasons, but petroleum in quantity has been encountered in nine widely separated localities. The Mene Grande field has been put on a producing basis and approximately 4,000,000 bbl. of oil is being shipped annually. Increasing quantities of oil are now being drawn from El Mene and La Rosa. In the light of these developments, the world&apos;s need for oil reserves, and the proximity of Venezuela to the United States, American capital is being attracted more and more to Venezuela. Although considerable careful geological work has been done in Venezuela by the various oil companies now operating, most of the data is buried in the company files, and the published literature has been extremely meager. The most valuable contribution to date has been a map and report by Jahn, which, as it was printed in Spanish, is not generally available to the American oil public. Venezuela, located in the northwestern part of South America on the Caribbean Sea, lies between l° and 12° north latitude. Its principal

Jan 1, 1925

By Ernest F. Burchard

The Pao deposits of iron ore are in the State of Bolivar, Venezuela, near Upata, about 30 miles south of the Orinoco River and 90 miles east of Ciudad Bolivar. They were discovered 4 or 5 years ago and have not yet been developed to the stage of mining. In March-April, 1929, the writer devoted a week to the examination of these deposits. The maps, drill records and chemical analyses presented herewith were derived from original sources, and the field photographs were made by the writer. The petrographic and metallographic data are from notes by C. S. Ross and M. N. Short, of the U. S. Geological Survey, who have kindly collaborated in these special phases of the study. The Iron Obebodies Topography and Accessibility The deposits are in a region of low mountains representing northern outliers of the Guayanan Highlands. These mountains reach altitudes of 1800 to more than 2000 ft. above sea level, as determined by aneroid barometer. The iron ore is found on mountain crests that reach altitudes of 1915 to 1930 ft., and may be followed down precipitous slopes for 200 • to 300 ft. or more. The greatest vertical range in outcrop is nearly 400 ft., and drilling has indicated that the ore extends to this depth below the surface in one place, at least. The superior hardness of the iron ore accounts for the preservation of the local mountain crests with the intermediate valleys eroded in softer granitic rock. The deposits of iron ore are reached by a private road for automobiles branching northeast from the Ciudad Bolivar-Upata road, a distance of about 12 miles. This road was used in 1928-29 by trucks for transportation of food and camp supplies, gasoline, drilling equipment, etc., but was not suitable for the transportation of iron ore. Between Ciudad Bolivar and the iron-ore area the western two-thirds of the automobile road passes through nearly level, open country known as the savanna, largely used for grazing cattle. About 96 km. (60 miles) east of Ciudad Bolivar at

Jan 1, 1931