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By H. W. Mead, C. E. Birchenall

SELF-DIFFUSION in pure gold has been studied by Sagrubsky,1 McKay,2 Gatos and coworkers,3,4 and Okkerse.5 Sagrubsky used a sectioning technique but reported results far lower than any of the others. The work seems to be carefully done, and it appears that a factor of 60 must have been omitted in his calculations or the units misstated by an equivalent amount. McKay used a surface activity method, and Gatos and Kurtz, following Gatos and Azzam, applied autoradiography to the measurement of activity on an oblique section through the diffusion zone. These two investigations agree well with each other but give results below those reported here. Okkerse employed a very careful sectioning technique. Chemical interdiffusion in Au-Ag alloys has been measured under several concentration conditions. Average values of the diffusion coefficient for the range of 0 to 18 atomic pct Au were obtained by Braune.6 since the diffusion coefficient probably varies markedly over this range, the values may not be too useful. Also, a plot of these data suggests that grain boundary contributions may have been appreciable at the lowest temperature employed. Ebert and Trommsdorf7 give average values for 0 to 9 atomic pct Ag, and Johnson8 reports average values for 45 to 55 atomic pct Au. Johnson also measured silver and gold self-diffusion coefficients in 49.2 atomic pct Au alloys, and self-diffusion in pure silver. The self-diffusion of gold in pure silver has been determined by Jaumot and Sawatsky.10 Other measurements which do not cover a range of temperature or are of low precision are not mentioned in this account since a review by Kubaschewski is available." This contribution reports diffusion coefficients for self-diffusion in gold, self-diffusion of gold in Au-Ag alloys, and chemical diffusion in Au-Ag alloys. Although it had been intended to obtain silver self-diffusion data in the alloys it now appears unlikely that these measurements can be done soon, so a table has been worked out for a self-consistent scheme of diffusion coefficients which should not be too far from the true values. Experimental Details Experiments on pure metals were conducted using fine gold of 99.99+ pct Au and silver of the same purity. Alloys were prepared by melting the two metals together in a graphite crucible in vacuo and allowing the slug to solidify in the crucible. After machining to a cylinder about 0.85 in. diam each slug formed one half of a diffusion couple. Compositions were determined later by analyzing chips taken from the extremities of the diffusion zones. The gold used in the preparation of alloys was sometimes pure gold but was normally either in the form of clean pickled alloy from previous experiments or gold recovered by oxalic acid precipitation from warm aqueous solution. Chips from the various stages of experimentation were dissolved in aqua regia and the solution taken to low bulk, diluted with water, and again taken to low bulk before diluting for the precipitation. This precipitated gold contained a small amount of silver as the only impurity detectable by spectrographic analysis. Disks for use in diffusion couples had opposite plane faces abraded on emery paper as far as zero grit, were annealed for 12 hr at 900°C in argon, and had one face of each disk polished to 000 emery paper. Radioactive gold was plated at about 2 ma per sq cm from a small volume of cyanide solution containing 1 mg of inactive gold as a carrier. Specimens , were freshly abraded on 4/0 emery paper immediately prior to plating. In the case of the active couples disks of a similarly prepared but unplated alloy or pure metal were placed on top and welded to the active disk. With the concentration couples disks of different compositions were welded. Welding was performed after a pressure of 5,000 lb had been applied at

Jan 1, 1958

By V.K. Zworykin

Throughout its development the science of electronics, like so many other branches of science and industry, has been indebted to the metallurgist. Metallurgy has provided the electronic engineer with conductors to furnish passage for electrons outside of his evacuated tubes: it has developed tungsten and tantalum wires for emitting electrons and various refractory metals and alloys suitable for electrodes, which receive them and guide them within the tube; finally it has supplied ferromagnetic materials both for shielding electronic apparatus from magnetic fields and for forming highly concentrated fields for deflecting electron . Today I hope to show you that electronics has not been altogether ungrateful for this assistance. More specifically, I wish to indicate the role that the electron microscope, a relatively recent product of electronic engineering, is playing even now in the study of metals. Every metallographer is aware that his standard metallographic microscope will not reveal structural detail involving separations smaller than a certain fraction —at the very best a tenth—of a micron. This limitation, he knows, is a consequence of the fact that the wave length of the light employed for forming the image has this order of magnitude. It is, thus, a property of all light microscopes. TO overcome it, a different imaging medium must be employed, The existence of such a medium became evident when it was demonstrated1 that electrons were affected by magnetic and electric fields with axial symmetry just as light is affected by glass lenses; these fields, or "electron lenses," curve the paths of electrons reaching them from an object located on the axis of symmetry in such a manner that, at some distance from the lens, a true image of the object is formed. Furthermore, although a wave length may . be ascribed to electron beams just as to light, this wave length is much shorter; for electrons accelerated through a difference of potential of 50 kilovolts, the wave length is only about one hundred-thousandth of that of visible light. Actually, the elcctron microscopes of today resolve detail one hundred times as fine as light microscopes; if the maximum useful magnification of the latter is taken to be a thousand, that of electron microscopes is one hundred thousand. The Electron Microscope Since electrons are readily scattered and absorbed by matter, specimens to be observed in the electron microscope must be prepared to be less than one micron in thickness; furthermore, the interior of the microscope must be carefully evacuated to prevent collisions between the clectrons and the molecules of the air. Finally, as already mentioned, the lenses are formed by axially symmetric magnetic or electric fields, and not by any material medium such as glass. Apart from these basic differences, the electron microscope closely

Jan 1, 1943

By V. K. Zworykin

Throughout its development the science of electronics, like so many other branches of science and industry, has been indebted to the metallurgist. Metallurgy has provided the electronic engineer with conductors to furnish passage for electrons outside of his evacuated tubes: it has developed tungsten and tantalum wires for emitting electrons and various refractory metals and alloys suitable for electrodes, which receive them and guide them within the tube; finally it has supplied ferromagnetic materials both for shielding electronic apparatus from magnetic fields and for forming highly concentrated fields for deflecting electron . Today I hope to show you that electronics has not been altogether ungrateful for this assistance. More specifically, I wish to indicate the role that the electron microscope, a relatively recent product of electronic engineering, is playing even now in the study of metals. Every metallographer is aware that his standard metallographic microscope will not reveal structural detail involving separations smaller than a certain fraction —at the very best a tenth—of a micron. This limitation, he knows, is a consequence of the fact that the wave length of the light employed for forming the image has this order of magnitude. It is, thus, a property of all light microscopes. TO overcome it, a different imaging medium must be employed, The existence of such a medium became evident when it was demonstrated1 that electrons were affected by magnetic and electric fields with axial symmetry just as light is affected by glass lenses; these fields, or "electron lenses," curve the paths of electrons reaching them from an object located on the axis of symmetry in such a manner that, at some distance from the lens, a true image of the object is formed. Furthermore, although a wave length may . be ascribed to electron beams just as to light, this wave length is much shorter; for electrons accelerated through a difference of potential of 50 kilovolts, the wave length is only about one hundred-thousandth of that of visible light. Actually, the elcctron microscopes of today resolve detail one hundred times as fine as light microscopes; if the maximum useful magnification of the latter is taken to be a thousand, that of electron microscopes is one hundred thousand. The Electron Microscope Since electrons are readily scattered and absorbed by matter, specimens to be observed in the electron microscope must be prepared to be less than one micron in thickness; furthermore, the interior of the microscope must be carefully evacuated to prevent collisions between the clectrons and the molecules of the air. Finally, as already mentioned, the lenses are formed by axially symmetric magnetic or electric fields, and not by any material medium such as glass. Apart from these basic differences, the electron microscope closely

Jan 1, 1943

By Harry M. Mikami, A. Gene Sidler

Chemistry of the evolution of materials in contact with copper converter tuyeres is delineated by means of analyses of periodic punch rod samples taken during a converter cycle. Lining samples from known peripheral and end locations from three converters were investigated chemically and petrographically. One set of eight specimens representative of all lining parts was removed for study before completion of the campaign. Purely surface removal by slag action is minor. Slag filling of interconnecting cracks extending to the hot face results in a "stoping'' action which shapes the hot face contour and is a significant factor. Major wear mechanism is believed to be copper metal slabbbing caused by metal first penetrating joins and invading fractures or impregnating brick structure laterally from the joints. Importance of lining design and joint fit are emphasized. New laboratory tests are indicated. In the copper converter, molten matte, which is essentially a solution of iron and copper sulfides, is blown with air to produce blister copper. During the first stage of the process the FeS component is oxidized to SOz and FeO, the latter combining with a siliceous flux to form a predominantly ferrous silicate slag. Successive increments of matte and flux are charged, blown, and skimmed of slag until sufficient CuzS ("white metal") has accumulated. This white metal is then blown to copper metal in the final or blister-forming stage by the oxidation of sulfur to SOz and the reduction of combined copper to metal. The reactions of both stages are exothermic so provide the required heat. Temperature is controlled by cold scrap copper, flue dusts, smelter reverts, and so forth. Considerable vari- ation in practices occur depending on the type of converter, grades of the matte and flu, and other factors. Lathe and Hodnett's' survey of world converter practices gives much information on these variations and their effects on the refractories. Principles of converting chemistry are presented by Newton and wilson,' Ruddle,' and schuhmann. Most copper converting occurs within the temperature range 2100" to 2370°F although individual smelters report1 ranges from as low as 1700" to 2240°F to a high of 2200" to 2400°F. Temperature intervals reported from beginning to end of blow varied from 45" to 540°F. Average temperature range was 2030" to 2260°F and the average interval 250°F During the matte-blowing stage varying amounts of magnetite (FeO.Fe,O,) are formed in the slag as suspended crystals and also the liquid portion of the slag will contain, in addition to ferrous silicate, some Fe20s which adds to the potential magnetite formation if the temperature falls. This is a component of the so-called "dissolved magnetite" often referred to in the literature. Although the slag may contain minor amounts of CaO, A1209, MgO, and alkalies, the principal components are Fe0-Fez03-SiO,. The phase equilibria relationships of this system have been elucidated by Muan~ and Schuhmann, et a1.' These data and estimates of converting atmospheres by schuhmann4 are useful tools in studying slag behavior. It would appear that in many cases reported magnetite contents of slags are apparently higher than actually is present at operating temperature. This is probably because much of it is formed during slag solidification. The quaternary systems which have Mg-0,1,0,' and addition to iron oxides and silica are also of interest in considering the reactions of the slags with basic refractories. The formation of magnetite has an important interrelationship throughout the pyrometallurgy of copper (Mossman,' Gronningsater and Drummond," Ruddle,' Elwood and Henderson") but its presence in the converter particularly relates to operating efficiency and lining life in certain instances. Archi-

Jan 1, 1963

By David, Cole

THE years 1914-15-16 were a pioneering period in mining, milling, and copper metallurgy generally. It was uncertain just what path the crushing, grinding, and concentrating processes would take. This situation was quite embarrassing to the directors of some of our large porphyry properties, then being equipped for production. Inspiration had already made several designs for its proposed 15,000-ton concentrator, incorporating in them the latest devices developed in the art of gravity concentration, only to have the work vitiated by the rapid march of events. In a little improvised plant, built on ground that is now in the crater of subsidence over the Inspiration- Miami orebodies, flotation was being experimentally ' applied to Inspiration ore by Minerals Separation engineers in 1914, with results indicating that this process would be of major importance in the concentration of the sulfides. How best to apply it, and especially how to crush and grind the ore to the very much finer sizes required for the new process, was a serious question, properly to be answered only by doing it, in full- sized machines, under regular 'operating conditions.

Jan 1, 1931

By P. S. Kotval, H. Hahell

PRECIPITATION of M23C6 carbides at grain boundaries in austenitic steels and nickel base superalloys has received considerable attention. Hatwell and Berghezan,1 in a study using carbon extraction replicas, observed that dendritic growth of the M23C6 carbide phase occurred at grain boundaries in austenitic steels. Merrick and Nicholson2 have observed that in thin foils of "Nimonic 75" alloy the precipitation of M23C6 carbide was discontinuous at grain boundaries. Lewis and Hattersley3 have suggested that the type of M23C6 precipitation observed in Ni-Cr austenites represented the early stages of discontinuous precipitation. In a more recent study, Singhal and Martin4 have concluded that grain boundary M23C6 precipitation involves the migration of an austenite grain boundary by a mechanism very similar to that proposed by Tu and Turnbull.5 Tu and Turnbull's suggestion essentially involves grain boundary migration under the driving force arising from the difference between the surface free energies of the opposite sides of the plate. Thus, Singhal and Martin's observation4 implies that the first stage of discontinuous precipitation has taken place and that the grain boundary has provided a diffusion short circuit for the sub-stitutional solute atoms (principally chromium) which assist the preferential growth of the M23C6 plate in contact with the grain boundary. However, no evidence of the characteristic cellular morphology typical of discontinuous precipitation was found in Singhal and Martin's studies. Presumably, this is due to the low volume fraction (i.e., low supersaturation of solute) of the precipitating carbide reported by Singhal and Martin.4 Recently, Raymond6 has studied precipitation of the M23C6 carbide in Incoloy alloy 825 and shown that the growth of this phase is perpendicular to grain boundaries at 1400°F and in the plane of the grain boundary at 1700°F. The former aging condition resulting in discontinuous or "cellular" precipitation. Raymond has suggested an explanation for this behavior based on the relative rates of chromium diffusion by volume and grain boundary diffusion at the two different aging temperatures. In the course of a recent investigation on precipitation behavior in several ' strengthened superalloys, precipitation of M23C6 carbide at grain boundaries was studied. Under conditions of a high degree of supersaturation, the M23C6 carbide precipitates in the discontinuous or cellular morphology in Waspalloy (Ni-18.51 Cr-2.0 Fe-3.53 Mo-1.16 Al-2.78 Ti-0.09 C). This note presents electron microscopy observations of this mode of precipitation and its effect on mechanical properties. Specimens of Waspalloy after "solution" heat treatment at 1950°F show essentially single phase matrix with a few residual particles of "primary" MC carbide. In normal commercial heat treatments, precipitation of Ni3(Al,Ti) ordered fcc r' phase occurs throughout the matrix and M23C6 precipitates as globular particles at the grain boundaries. In these commercial heat treatments the degree of supersaturation during precipitation is low. However, if specimens of Waspalloy are quenched from the solution heat treatment temperature of 1950°F and then aged at an aging temperature where the degree of supersaturation is high, discontinuous precipitation of M23C6 occurs. Figs. 1 and 2 show thin foil micrographs of Waspalloy, solution heat treated at 1950°F, water quenched, and aged at 1292° and 1598°F, respectively, for 500 Fig. 1—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 500 hr at 1292°F. Magnification 15,500 times. Fig. 2—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 114 hr at 1598° F. Magnification 13,000 times.

Jan 1, 1970

By M. Cohen

THERE seems to be a natural urge for the human mind to wonder about the beginning of things. When an explosion occurs, we immediately inquire "what set it off?" If a person contracts a disease, we are likely to ask "how did it happen?" On a much loftier plane, when we reflect about the universe, there is the inevitable question "what, or rather Who, started it all?" In principle, these varied queries have at least one attribute in common: they are attempts, whether earnest or casual, to search out the origin of events in nature. Accordingly, they involve not only scientific, but philosophical and even re1igious matters of deep concern. It is evident that, in a broad sense, the phenomenon of nucleation is enmeshed in this enticing concept of "the beginning", but we must extract the scientific component of the problem for our present purposes. Nucleation, as in the case of phase transformations, is best regarded from the standpoint of kinetics. There are then two main steps, which may come in either order: (a) Experimentally, one attempts to measure the frequency with which transformation centers spring into existence; and (b) theoretically, one seeks a model that will account for this observed birth-rate. Temperature, composition, strain, and prior history are some of the important variables that must be considered both experimentally and theoretically when dealing with nucleation in the solid state. Such interaction of theory and observation is an integral part of science in general, but it is particularly significant in the nucleation problem because the very beginning of a phenomenon invariably occurs on too localized a scale in both space and time to be detected with available techniques. Thus, there is little hope of making direct measurements on the nucleus during its birth or to ascertain the exact nature of the process; one can only infer the details of nucleation from the model whose predicted behavior seems to harmonize best with the measured rate of nucleation and its dependence on known parameters. In the field of solid-state nucleation, both theory and experiment call for much ingenuity, but somehow the conceptual schemes have spawned faster than they can be tested by observation. This is not to say that there are many basically new ideas in modern nucleation theory; rather, as we shall see, it is because the required fine-scale measurements are of immense technical difficulty. Quite likely, some of the nucleation models existent today have survived only because of the latitude permitted by meager data. There is great need to bring theory and experiment into better balance in this important area of physical metallurgy. Although one can

Jan 1, 1959

By Charles B. Forgan

THE Stan Trg ore body now being exploited by Trepca Mines, Ltd., originated by the metasomatic replacement of limestone and consists mainly of an intimate mixture of sulfides associated with little admixed gangue. The chief sulfides are galena, marmatite, pyrite, and pyrrhotite. Geological structure, embracing both igneous and sedimentary agencies, exerts important control on ore deposition and presents many features of great interest. Geological Formations and Intrusives Stag Trg Series-The dominant formation is the Stan Trg series, which

Jan 1, 1936

By R. L. Schmidt, J. D. Verhoeven

The diffusion coefficients and electrotralzsport mobilities of aluminum, gallium, and arsenic have been determined in molten germanium with the capillary reservoir technique. The diffusion coefficients are slightly higher than those determined by the solidification technique of Brirton et a1.1 It was found that aluminium and gallium migrate to the cathode in molten germanium) whereas arsenic migrates to the anode under an electric field. A possible technique for producing p-n junctions by means of electric field freezing is discussed in view of the experimental data. In the past decade or so the literature has abounded with articles concerning the solid-state properties of the semiconducting elements germanium and silicon. It is surprising by comparison how little has been published concerning the liquid-state properties of these materials. In the production of doped germanium or silicon the diffusion coefficient of the dopant in liquid germanium or silicon is an important quantity. Yet, to the best of our knowledge, no one has ever made a direct measurement of the diffusion coefficient of solutes in either molten germanium or silicon. A number of authors'-4 have determined some diffusion coefficients by the indirect technique developed by Burton et al.1 This technique appears to give numbers of the correct order of magnitude but it does depend upon a number of assumptions in the analysis and also requires prior knowledge of the viscosity of the melt. In the present work a more direct measure of the diffusion coefficients of arsenic, gallium: and aluminum in molten germanium has been made. It has been shown independently by two groups of authors5, 6 that, when an electric current is passed through the interface of a solidifying metal containing an impurity, the resulting electrotransport in the liquid boundary layer at the interface offers a mechanism for control over the redistribution of the impurity accompanying the solidification. These authors show that the degree of control is proportional to the mobility, U of the impurity atoms in the liquid boundary layer, where the mobility is defined as the drift velocity relative to the solvent per unit electric field. In principle the results apply to the solidification of a doped semiconductor and offer an interesting technique for control of the doping of a semiconductor. In the present work the mobilities of aluminum, gallium, and arsenic were determined in molten germanium in order to evaluate the potential usefulness of electro-transport as a technique for solute control when applied to the solidification of doped germanium. EXPERIMENTAL PROCEDURE Both the diffusion coefficients and the mobilities were measured using high-purity alumina capillaries and a resistivity technique for analysis. A schematic diagram of the electrotransport apparatus is shown in Fig. 1 and the details of the cell design are shown in Fig. 2. For the mobility experiments electrical contact with the bottom of the capillary was made with graphite, as shown in Fig. 2. In order to prevent electrical contact with the melt the graphite was coated with a thin layer of alumina using a plasma spray torch. The cell assembly, a graphite electrode, and another assembly containing two blank capillaries were fastened to the lavite disk shown in Fig. 1. To make a run the system was evacuated and the doped germanium was outgassed at the operating temperature of 1030°C. The cell and blank capillaries were then submerged beneath the melt and a slightly positive pressure of helium was introduced to fill them. After passing current through the cell for a given time the cell and blank capillaries were raised from the melt and the furnace was shut off. The temperature of the cells dropped below the freezing point of germanium within 1 to 2 min after the furnace was shut off.

Jan 1, 1968

By M. P. Tixier

In several log interpretation methods, water saturation is evaluated by use of the ratio of the readings of a short spacing resistivity device and a long spacing resistivity device plus information on the mud filtrate and connate water resistivities, which is often derivable from the SP. These methods are valid over a certain range of conditions, usually specified by moderate invasion and R.. greater than R,. Since these methods involve no explicit evaluation of the formation factor, F, the saturafiion so found may be used in the standard Archie equation to derive a computed formation factor which, as a check, may be compared with the formation factor known from other independent measurements. Discrepancies in the two values of formation factor generally indicate that the ratio method is not within its range of applicability. If the computed F is too low, the corresponding S, is too low; if the computed F is too great, the corresponding S, is too great. By means of this "porosity balance" check, and some knowledge of the probable conditions of invasion, the interpretation can often be improved. The poqosity balance check is discussed for the cases of the Induction-Electrical Log Interpretation Method, the Rocky Mountain Method, and the R.,/R, Method. For the first method, a discussion is also given for the case of shaly sands. INTRODUCTION Al though many logging tools are available to obtain a practical value of porosity, the only logging method reflecting the water saturation is electrical logging. Water saturation is commonly computed from electrical log data by means of the basic Archie formula, Where F is the formation factor, R, the resistivity of the formation water, and R, the true resistivity of the formation. One difficulty in this procedure is a possible error in the evaluation of R, from the logs— for example, in the case of very deep invasion. There is no possibility, inherent in the procedure, which would provide a check of the accuracy of R, and, hence, of the computed saturation. Other approaches have been proposed which are based essentially on the ratio of the readings made with two dzerent devices: one device, with a short radius of investigation, provides a value close to the resistivity of the invaded zone; the second device, with a long radius of investigation, gives a value close to the true resistivity of the bed. By these methods, the determination of saturation is made independently of any direct knowledge of the formation factor. Therefore, if the formation factor (or porosity) is known from other sources (core analysis, neutron log, MicroLog . . .), it becomes possible to take advantage of this additional information in order to check the value of saturation derived from these latter methods. Inasmuch as this proposed check procedure relies on a knowledge of the value of formation factor or porosity, it has been deemed appropriate to call this verification a porosity balance. The purpose of this paper is to discuss the principle and the application of the porosity balance, depending on the method of interpretation being used. Basis of the Method There are in existence three interpretation methods by means of which the water saturation can bc found without a knowledge of the formation factor (or porosity). As just stated, they are based on the fact that the ratio of the two resistivities (one measuring the resistivity close to the hole, the other measuring the resistivity far from the hole) is independent of the formation factor since it affects the two resistivity measurements in the same way. Chronologically, the resistivity ratio methods are: (1) the Rocky Mountain Method, which has been used since 1943 and was explained in a paper in 1949;' (2) the R../R, Method or Shaly Sand Method, presented in 1954, which permits the calculation of the water saturation in both clean and shaly sands2; and (3) the Induction-Electrical Log Method, presented in 1957 for the interpretation of the induction-electrical log combination." Each method requires certain definite conditions in order for the interpretation to be reliable. The porosity balance method will let us know whether these conditions are fulfilled. In clean formations we know that the fundamental Archie relation (Eq. 1) must always be verified. This relation can be rewritten:

By A. F. Brock

The cut-and-fill mining methods in use in the mines of The International Nickel Company of Canada Limited, at Falconbridge Nickel Mines Limited, in the Sudbury District, and at McIntyre Porcupine Mines Limited in the Porcupine District, are typical of the general cut-and-fill practice in both the base-metal mines and the gold mines in the Province of Ontario. The following pages describe the methods in use. HORIZONTAL CUT-AND-FILL STOPING Horizontal cut-and-fill stoping, as practiced in the mines of The International Nickel Company of Canada Limited, falls into two main classifications: (I) transverse cut-and-fill stoping, where ground conditions or wide ore bodies make it necessary to establish narrow stopes and pillars across the width of the ore body; (2) longitudinal cut-and-fill stoping where ore body widths and ground conditions allow safe mining of the full width of the ore body. Transverse Cut-and-fill StopiNg General Stoping Layouts Stope and Pillar Widths.—For transverse stoping, experience has indicated that narrow stopes and pillars, 27 ft. 6 in and 22 ft., respectively, are most satisfactory. These width are multiples of 5 ft. 6 in., which is the center to center dimension of a standard square set. Thus any stope, or block of stopes, can be readily converted from cut-and-fill to square set-and-fill if ground conditions should warrant such a change. Formerly, pillars were established 16 ft. 6 in. wide, the equivalent of the width of three square sets, with the intention of extracting the pillars by mining an overhand slice one set wide and an underhand slice two sets wide. However, subsequent experience proved that a two-set overhand slice is so much more efficiently mined than a one-set slice, and 22-ft. pillars have been made standard. Chutes.—The stope chutes are established on the longitudinal center line of the stopes and are spaced at 22-ft. centers from footwall to hanging wall. The footwall chute is usually from 5 to 10 it. from the footwall of the stope. It is offset where necessary at an angle of 52° and vertical chutes are carried from the offset at 22-ft. centers. In sections of the ore body where a flat hanging wall would cut off hanging-wall chutes within a few cuts of the sill, it has proved to be more economical to use temporary chutes or slushers, or both, for these first few cuts, rather than to el permanent chutes at the hanging wall.

Jan 1, 1946

By Augustus Locke

The paper has two parts: the field argument and the microscopic argument. The field argument indicates that either the deep chalcocite has replacea sulfide of extraordinarily easy replaceability or it is hypogene. The microscopic argumentindicates that this sulfide, if it existed, must have been hypogene bornite; that this bornite must so excel known bornite in replaceability as to constitute a new variety; that the existence of this new variety is wholly unsupported by evidence; and that the deep Butte chalcocite is therefore hypogene. IN 1900, when the public first heard of "secondary enrichment" the Butte chalcocite seemed clearly supergene. Mining, through successive regions of leached capping, bonanza sulfide, and sulfide less rich, had paused at lean bottom levels which, though chalcocite-bearing, suggested the waning of copper. The deepest chalcocite, at 1500 ft., was yet too shallow to disturb the supergene hypothesis. But, with deeper mining, lean levels yielded to fat ones. Here and there they showed, within the same vein, an inverted distribution, chalcopyrite above and chalcocite below. To the miners' astonishment, they carried chalcocite, unaffected by cross faults, on an independent course to the depth of 2500 ft. The pattern of ore distribution, hitherto revealed only in fragments, was now appearing in perspective, and, in the depth of the chalcocite, was beginning to make Butte differ from all districts where the chalcocite is indubitably supergene. The idea of hypogene origin at length came into favor; by 1913, when Sales1 advocated this origin, the argument had become a powerful one. This argument rested on field evidence; but, already, there was beginning to emerge microscopic evidence not included in this arugment. Especially pertinent was the proof that (1) The deep chalcocite lies in-mixed with bornite, often microscopic; (2) the deep chalcocite often replaces bornite; and (3) replacement of bornite by chalcocite is accom-

Jan 3, 1924

By H. H. Kellogg

A model of the slag-fuming process for recovery of zinc oxide fume from lead blast furnace slags, adapted to solution by a digital computer, is presented. The model incorporates the variaticm with time of the following: the fuming of zinc and lead, the change in the ferrous-ferric ratio in the slag, the transfer of sulfur to and from the slag, the temperature of the liquid slag, the temperature of the gases and fume which exit to the flue, the heat losses to the water jackets, and the amount of frozen slag on the water jackets. The assumptions which underlie the model-some of which are but crude approximations—are discussed. Despite some obvious shortcomings, the model simulates faithfully many of the important features of practical slag-fuming operations. The behavior of the model is compared with the operation of the American Smelting and Refining Co. fumzace at El Paso, Tex. The model is used to predict the effects on performance of changes in the coal rate, the temperature of the secondary air, and the composition of the coal. THE fuming of lead blast furnace slag for recovery of zinc oxide is standard practice today, and it has been the subject of several previous attempts at mathematical process analysis.'-' The mathematical process model described in this paper incorporates many of the features from the earlier studies, but it is a far more complete and realistic representation of the commercial process in that the following additional features have been included: the fuming of lead as well as zinc; the transfer of sulfur between slag and gas; the addition of slag feed in batches, over a period of time; tapping of the final slag over a period of time; the change of slag temperature with time. The additional features of the present model add greatly to the mathematical complexity, but this difficulty has been obviated by programming the model for solution by a digital computer. The IBM 7094 computer solves the model for one operating cycle of the fuming furnace in less than 1 min. It is doubtful if the same calculations could be completed with the aid of a desk calculator in less than a month. The computer program, written in the Fortran IV language, is too lengthy for presentation here.* Instead, this paper As shown in the sections which follow, it does simulate with remarkable faithfulness most of the known behavior of the industrial process. On the other hand, the model contains several gross simplifications of both the chemistry and heat balance, necessitated by the lack of more exact knowledge. In addition to these known weaknesses, it is not unlikely that those more intimately acquainted with industrial practice than the author will find other additions to or modifications of the model which will improve its utility and reliability. CHEMISTRY In brief outline, the present model treats the fuming furnace as two units, A and B, in series. In A the batch of slag reacts with the continuous stream of air (primary and secondary) and fuel injected at the tuyeres, to produce a stream of hot, reduced gases containing zinc vapor. The zinc content of both the slag and the product gas changes with time because of the batch nature of the process. Unit A is called the "lower furnace" in this paper; physically, it is considered to be that part of the fuming furnace which lies below the charge port. In B, the "upper furnace", the product gas from A is burned with the stream of "tertiary" air, to produce zinc oxide fume. The performance of B also depends on time because of the time dependence inherited from the product gas of A. The rate behavior in the lower furnace determines the important features of the process—the rate of elimination of zinc and lead from the slag, and the amount of fuel required for this purpose. Bell, Turner, and peters' published the first useful model of the lower furnace. They employed the assumption that, at any instant of time, the slag and reduced gas reach a state of equilibrium, according to the reactions: They cited only indirect evidence in support of their assumption of slag-gas equilibrium, yet several more recent laboratory studies of the activity of zinc oxide in slags4-8 have produced evidence which supports their view. On first acquaintance it seems unlikely that a high-output "rate" process like slag fuming would even approach an equilibrium state. The author, in an earlier study,' established, however, that the gas-slag interface in a fuming furnace was capable of such high mass-transfer rates that a close approach to equilibrium between gas and slag was quite probable. In devising the present model it was decided to assume a state of equilibrium between slag and gas at the outset, and then to modify this assumption as necessary in order to make the model agree with the be -havior of the actual process. Up to this time the assumption remains a part of the model, since no behavior

Jan 1, 1968

By E. P. Abrahamson, S. L. Lopata

A general relalionship between the amount of glide shear (due to slip) and the macroscopic shape change has been developed. Since the deformation can be large, finite strain analysis is employed. In this treatnzent, the shape change is expressed by a deforlnation gradient matrix, F - [axi/aXj/ where X and x refer lo the initial and final positions of a particle. This matrix is readily evaluated in termas of the amounl of glide shear, a , and the direction cosines of the slip-plane normal and the slip direction for a single active slip systena. In the case of deforma tion from slip on several systems, the product F(a) of the several deformation gradient matrices is first calculated. Then, by assuming that the final configuration is reached by a long series of small shears of magnitude a, occurring more or less alternately in the several slip sys- IN problems of crystal plasticity, it is often necessary to relate the amount of glide in the operating slip systems to the macroscopic strain components. This relationship is relatively simple when only small strains are considered. In this case the separate strain contributions from several slip systems are additive. Such a procedure is incorrect in the case of large plastic deformation. To the authors' knowledge, no general treatment of the latter problem has appeared in the literature. In specific instances, Mark, Polanyi, and schmid3 have derived the relationship between glide and axial elongation during tensile pulling of a single crystal when only one slip system is active. A similar relationship for duplex slip was worked out by v. Göler and Sachs.4 Taylor and Elam1 have also studied in detail problems of large plastic deformation. Due to uncertainties as to the slip systems at the time, ! terns, the final deformation gradient matrix can be obtained. Mathematically, the problem is reduced to finding the limit of F(aN as N — m while a — 0 in such a way that the Product Na = a finite conslant designatzng the accumulated amount of shear. It turns out that this limit is simply eafF1, where F, is the matrix whose elements are the coefficients of a in the F(a) twatrzx. Application is made of the present treatment to a fcc crystal of Permalloy compressed on the (110) plane and contrained to elongate in the [112] directzon. In addition, it is shown that one rnay readily obtain from the general analyszs the well-known formulas relating elongation, amount of glide shear, and amount of lattice rotation for crystals deforming by single and double slip under tension. however, they were mainly concerned with proving that slip occurs on {111}(110) systems in fcc metals. The present general treatment arose out of recent investigations of magnetic anisotropy in cold-worked Fe-Ni alloys6 as well as some related problems in strength anisotropy of single crystals.' Detailed application of the general analysis will be provided in the case of a Permalloy single crystal compressed on the (110) plane and constrained to elongate only in the [112] direction. It will be seen that, as expected, the small strain approximation leads to significant errors after moderate straining. It will also be shown that the present general treatment yields the formulas of Mark et al. and of v. Goler and Sachs in those specific cases. GENERAL CONSIDERATIONS Consider a homogeneous deformation in which a material point initially at moves to (xl,xz,x3), both positions being referred to the same set of Cartesian axes. Such a deformation can be

Jan 1, 1967

By A. R. Hendrickson, C. F. Smith

Hydrofluoric-hydrochloric acid mixtures have been successfully used to stimulate sandstone reservoirs for a number of years. Hydrofluoric acid (HF) has a specific reactivity with silica which makes it more effective than HCl for use in sandstone. Kinetics of the reactions of HF have been studied to determine the related effects of reservoir composition, temperature, acid concentration and pressure on the spending rate of HF. Secondary effects from by-product formation are noted and described. Predictions are made concerning the improvement in productivity resulting from HF treatment of skin damage. The kinetic order of HF reaction in sandstone was experimentally determined to be first order, i.e., the reaction rate is proportional to concentration. HF reacts faster on calcite than on clay, which, in turn, is faster than the reaction rate of HF on sand. Static conditions retard the HF reaction rate. As HF is forced into cores, there is a temporary reduction as a function of flow rate and acid concentration. Extensive deposition of calcium fluoride in acidized cores was not observed. Although some CaF, was defected, it was not considered a major source of damage in cores containing moderate amounts of carbonate. Other fluosilicates could be potentially more dangerous than CaF, in reducing permeabiliry. INTRODUCTION Hydrofluoric acid has been widely used in stimulation treatments since 1935, when mud acid was introduced to the petroleum industry. Originally, this hydrochloric-hydrofluoric acid mixture was intended to remove mud filter cake, but it has since been successfully applied to many other oilfield problems. Mud acid treatments have been unusually successful in sandstone reservoirs where hydrochloric acid is unreactive due to a lack of enough calcite in the formation. The relatively small amount of hydrofluoric acid present (2.1 per cent) reacts with sand grains, clays and traces of calcite which are generally present in sandstone reservoirs. Since hydrofluoric acid (HF) is the key to mud acid success, this research effort has been dedicated to gaining a more thorough understanding of the basic chemical and physical principles involved as HF reacts. Hydrofluoric acid's reactivity with silica makes it unique in application. Other mineral acids such as hydrochloric, sulfuric or nitric are unreactive with most silicious materials which comprise sandstone formations. A typical sandstone reservoir may contain 50 to 85 per cent silicon dioxide, more commonly called sand or quartz. Hydrofluoric acid reacts as follows: 4HF + SiO2 + SiFO + 2H2O The silicon tetrafluoride (SiF,) is a soluble gas, in some ways similar to CO2, and is capable of undergoing further reaction when held in solution by pressure. These reactions will be considered in detail later. Kinetics of the reactions of HF have been studied to determine the effect of reservoir composition, temperature and pressure on the spending of the acid. Secondary effects from by-product formation have been noted and described. The individual reactions of HF on quartz, glass and clay are reported. Mathematical correlations have been drawn, then applied to studies of HF spending in cores obtained from actual producing sandstone formations. The research reported herein is only the beginning of a continuing approach to better understanding and use of HF in petroleum reservoirs. THEORY AND DEFINITIONS Through the years, a concentrated effort has been made to understand the effects of many variables on hydrochloric acid (HCI) spending in limestone. Hendrickson el al., have given mathematical relationships for HC1 reactions which made possible the engineered approach to acidizing. The same variables—temperature, acid concentration, formation composition, pressure and permeability-porosity relationships—which affect HC1 behavior in limestone also govern HF behavior in sandstone. Insoluble by-products of HF reaction have been isolated and identified. Their effect on fluid flow has been measured under varying conditions in an attempt to evaluate the extent of possible damage and means of eliminating it. In general, HF follows the same reaction paths as HCI. It will react with limestone and dolomite with speed and ease. Thin sections of acidized cores show the reaction of HF with limestone or calcite faster than its reaction with either clay or sand. When HF reacts with calcite (CaCO,), theoretically, calcium fluoride (CaF2) is precipitated, and has been blamed as a major cause of reduced permeability. On the other hand, pH and pressure such as that encountered in an underground formation under acid treatment definitely retard CaF2 formation,' so the whole question of CaF, deposition in wells is a subject for study.

Jan 1, 1966

By Charles S. Barrett

THIS paper is a progress report covering metallographic applications of the electron microscope that have been made during the past year at Carnegie Institute of Technology. An account is presented of the techniques that have been most satisfactory, the difficulties encountered, the resolution obtained, and the peculiarities that have been noted in the microstructures. About 12m exposures have been made during the year on the instrument, which is an RCA type B2 transmission microscope,1 and a number of these have been selected to illustrate the results obtained. Prints are also included showing the common types of falsities-to borrow a term from the biological field, the "artifacts." In brief, the paper is a record of our attempt to determine the value of the electron microscope in the study of the structure of metals and alloys. n addition to comments on techniques and the quality of photomicrographs obtainable with them, the paper discusses the nature of the etch attack on a few metals, and the possible relation between the fine structure revealed by etching and the mosaic block structure of the grains. Since numerous papers and reviews are available on the subject of imperfection in crystals, the comments here may be very brief; in fact, are restricted almost entirely to points having to do with recent theories relating the strength of metals to imperfections and to spacings of slip lines. SPECIMEN PREPARATION AND PHOTOGRAPHS Mechanical polishing by hand was used throughout this work. Precautions that must be taken in microscopy at high magnification, which have been well explained by Vilella in his book on Metallographic Technique for Steel, are likewise important with the electron microscope. This applies particularly to the need for repeated polishing and etching (each successive polish becoming less severe and each etch lighter), since the final etch should in general be no heavier than is used for oil-immersion optical microscopy and in many instances should be much lighter (compare Figs. 6a and 7a, 6d and 7b). An extremely light etch, of course, is incapable of cutting through a flowed layer of appreciable thickness. Unquestionably it would be very advantageous in each instance to compare the structures obtained by electrolytic polishing with those obtained by mechanical polishing, but difficulties with the electrolytic method have prevented this in the following collection of prints. The choice of etchant is important, of course; for example, picral proved superior to nital for tempered martensite. With the exception of Figs. Ib and IC, the replicas used were of silica, deposited up0n polystyrene and floated from the polystyrene in ethyl bromide according to polystyrene in ethyl bromide according to the method of Heidenreich and Peck.2 The samples were mounted in Bakelite, polished and etched, then the polished Bakelite

Jan 1, 1943

By Alex Hay

THE Sydney coal field, the largest and most valuable in Nova Scotia, is situated on the northeastern coast of the Island of Cape Breton, extending from Mira Bay on the south to Cape Dauphin on the north, a distance of 30 miles, and has a general dip northeast under the sea. (Fig. 1.) The field embraces the mining villages of Morien, Birchgrove and Reserve and the towns of Dominion, Glace Bay, Waterford and Sydney Mines. The city of Sydney is situated about midway between the northern and southern extremities of the field and on the western fringe of the productive coal measures. Sydney harbor crosses the coal field, cutting off direct rail connection between Sydney Mines and the greater part of the field to the southeast. (Fig. 2.) The coal measures are exposed in the cliffs on the coast line, which rise to an average height of 30 ft., and are almost continuous throughout the length of the field. The portion of the coal field under land forms a small segment of a circle, the greatest distance from the coast landwards is 9 miles, and it occupies an area of 200 sq. miles. The greatest distance developed seawards from the shore by mining operations is 2 ¼ miles. The strata maintain a regularity of dip at this distance, proving a submarine area of about 70 sq. miles. How much further the coal field extends seawards is unknown, but the indications are that it extends far beyond the present economical working limit and in all probability there is a vast submarine coal field. The productive coal measures are of Carboniferous age, these being underlaid by beds of sandstone, locally classed as millstone grit, which define the southern limit of the field,, while a spur of syenitic hills cuts off the coal-bearing strata on the north. Two main anticlinal folds having a general course easterly divide the field into three basins named from north to south: Sydney Mines-Lingan, Glace Bay and Morien.

Jan 1, 1929

By A. K. Snelgrove

This symposium is designed to marshal a state-of-the-art account of approaches and solutions to problems arising out of waterlogging and salinization in the world's largest irrigation system which was dismembered by legal beheading of the Eastern Rivers under the lndus Waters Treaty of 1960. In this introduction, the geological and historical backgrounds of surface waters and groundwaters in the Indus Basin are presented with a summary of remedial measures undertaken and proposed to combat waterlogging and salinization. At a time when water-resource planning is proceeding on a continental scale, a study devoted solely to the Indus River Basin may seem to require an apologia. None is offered, however, for three major reasons: (1) Although the Indus is a single river basin, it is one of great magnitude and importance. The Indus River, which comes from Himalayan sources to form part of the great Indo-Gangetic Plain drainage system, is vital to agriculture and hydroelectric power in the thickly populated northern subcontinent of Indo-Pakistan. (2) The Indus has become a plexus of extraordinary problems since the dismemberment of the world's largest irrigation system of which it was a part. The break-up of this system occurred with the legal beheading of the Eastern Waters under the Indus Waters Treaty of 1960. (3) Th River Basin has been the target of a Herculean effort to contain the twin encroachments of waterlogging and salinization that now threaten it with a shortage of fresh water. The British irrigation system of barrages and canal on the Indus was a venture admirable in conception. Unfortunately, it is now a legacy burdened with unwanted consequences due to interference with the hydrological regimen, particularly the rise of water table occasioned by leakage. To cope with this situation, there has been a possibly unprecedented concentration of domestic and international engineering and scientific talent on the Indus and its problems (about a score of organizations by recent count). To marshal a state-of-the-art account of their approaches and solutions is the purpose of this Symposium. The coordinated effort now being made on a variety of fronts under the general supervision of West Pakistan Water and Power Authority (WAPDA) is directed toward the modification and control of interactions and relationships between geological materials — soils, water and its salt balance, and air —in what has been termed a huge "underground lake" in an alluvial basin. The problem is an intriguing one in that a highly complicated case history of river-course changes visible in the present surface must be projected downwards through Recent and Pleistocene sediments in order to decipher the environmental controls of deposition in terms of vertical and lateral variations in lithology and patterns. Such studies must be extended to compaction, deformation, and fabrics of the alluvium. Geohydrology is often defined as groundwater hydrology. As employed herein, it includes the distribution, quality, and behavior of surface and subsurface waters, including their evolution, vagaries, and geological, climatological, and botanical milieux." GEOGRAPHY The Indus (Sanskrit, Sindhu = river) rises at nearly 17,000 ft above the sea in the glaciers on the northern slopes of Kailas Parbat, Tibet. It is about 1800 miles long and has a total drainage area estimated at 372,000 sq miles. The average discharge is 196,000 cfs at mouth. Leaving the Plateau of Tibet, the river flows at a level which is miles above the sea, and in places miles below Himalayan peaks, in a structurally controlled northwestward course. Joined in this course by six tributaries and swollen by the melt waters of giant glaciers, it swirls about the base of the famous

Jan 1, 1970

By Clark A. Sumner

An apparatus for agglomerating fine particles was developed in 1969 as a joint effort of Stauffer Chemical and O’Brien Industrial Equipment. Commercial sized units were built for agglomerating home dishwashing detergents. Recently, as a result of further pilot development, variation of bed depth and cage configuration has resulted in a means of controlling the amount of internal classification from a minimum, producing small agglomerates, to a maximum, producing compact rounded agglomerates. Little or no external classification of discharged agglomerates is needed. At maximum internal classification the agglomerates roll on a bed of fine particles rather than the shell resulting in increased agglomerate size.

Jan 1, 1977

By Howard I. Smith

THE mineral trona was discovered on Government land in 1938, about 18 miles west of the town of Green River, Wyo., in the core of the John Hay, Jr., well, a test well drilled for oil by the Mountain Fuel Supply Co. in sec. 2, T. 18 N., R. 110 W., sixth principal meridian. Although no oil or gas was reported, the drilling led to a discovery of great potential economic importance and exceptional scientific interest. Trona is a relatively rare mineral found at various places in playa deposits but not previously found at any great depth. It is composed of hydrous sodium carbonate and sodium bicarbonate (Na2CO3.NaHCO3.2H20). Pure trona contains the equivalent of 70.35 per cent of sodium carbonate. Total sodium computed to carbonate times 1.42 equals the percentage of trona in the absence of other sodium carbonate minerals in the sample. ANALYSES Two short pieces of core sent to the author a few days after the completion of the Hay well were analyzed by R. C. Wells[t] and found to be exceptionally pure trona. A brief article on this discovery has already been published.1 Arrangements were then made through W. T. Nightengale[$] for the author to inspect and sample the core. The company log of the well included notations of sodium salt crystals from a depth of 1190 to 1820 ft. Not being able to identify all the minerals present, the author selected several specimens of the core for petrographic examinations and sampled the sections of trona for analysis. J. J. Fahey, of the Geological Survey, examined the specimens and reported most of the crystals to be a new anhydrous sodium carbonate and calcium carbonate mineral (Na2CO3.2CaCO3), which he named shortite,2 after Maxwell N. Short.* He analyzed the samples of trona, with the results shown in Table I. [ ] In addition to the 10 ft. I in. of trona in the first section, it is reasonable to assume that the 9 ft. 8 in. for which no core was available for sampling is either mostly trona or some other soluble salt, but it should not be included in calculating reserves. In the part of the core between 1590 ft. 3 in. and I600 ft. 4 in. the material insoluble in cold water, amounting to about 5 per cent, was estimated petrographically to contain 70 per cent clay, 25 per cent shortite, and 5 per cent pyrite. ACCOMPANYING MINERALS Fahey later secured about 600 ft. of the core for a detailed examination and study

Jan 1, 1942