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By John V. W. Reynders

Our entry into the World War suddenly brought home to us in a startling way the vital importance of manganese. Since the war, much has been written and said upon the subject of manganese and a great deal of time and money have been spent in attempts to find an adequate substitute for this metal in the manufacture of steel; none has been found. It is true that ways are known by which it is possible to make small amounts of good steel without manganese, but taking into consideration the diminishing quality of iron ores and fuels as well as the increasing exaction of specifications for finished products, it may safely be assumed that, high-grade manganese ore will be more and more a necessity in the production of steel as time goes on. Taking world resources as a whole it may be well to point out that the problem of obtaining needed supplies of manganese from a strictly commercial viewpoint is now less serious than it was before the war. Formerly it was feared that world resources of high-grade manganese ore might be exhausted in a relatively short time, but, largely as a result of the stress laid upon the importance of manganese during the war, the world's available supply of high-grade manganese ore has been greatly augmented by new discoveries and fuller development of previously known deposits. Sources of Production Russia alone, of countries producing the major part of the world's stee1, has within its geographical boundaries sufficient manganese to supply its needs. The domestic production of England is inadequate and English requirements for high-grade manganese are supplied principally from India. France also draws largely upon India, as it depends upon foreign sources of supply except with respect to a small tonnage of silico-manga-nese and silico-spiegel produced in the Hautes-Pyrénées. Germany and the United States likewise depend upon foreign sources of high-grade ore, though each possesses comparatively large reserves of ferruginous manganese ore and manganiferous iron ore. At present the world demand for high-grade manganese ore is met with ease by the production of Russia, India, Gold Coast and Brazil.

Jan 1, 1927

By Marius S. Darrow, William B. White, Rustum Roy

The PbS-PbTe systen has been studied by quench-ing and D.T.A. techniques f?om 400' to 1150°C. Runs were made in evacuated silica tubes so that all equilibria are at the vapor pressure of the system. Lattice parameters of the quenched salnples , measured by X-ray diffraction, show a complete crystalline-solution series existing over a narrow temperature range between approximately 805" and 871°C. An exsolution dome extends from a maximum of about 805"C (approximately 30 mole pct PbTe) to 1 and 96.5 pet PbTe at 400°C. A narrow melting region, deternined by D.T.A., extends form 918c (mp PbTe), The shapes of the liquides and solidus curves imply the existence of a minimum at 871°C at approximately 65 pct PbTe. THe exact composition of the minimum could not be established due to the very narrow two-phase region. At compositions containing less than 50 pet PbTe, liquidus temperatures begin to increase, while the solidus remains almost flat to about 15 mole pet PbTe before beginning to vise toward the mp of PbS (1075 C). LEAD sulfide and lead telluride are isostructural (NaC1 type) semiconductors whose electrical and optical properties have been extensively studied and used in recent years. If appreciable crystalline solution exists between these compounds, the variation of physical properties with composition could be of interest. The purpose of this investigation was to determine the extent, if any. of crystalline solution, and to obtain the phase diagram for the system. To the knowledge of the authors, only three studies of the system PbS-PbTe have been reported, and, in chronological order, each investigation found an increasing amount of crystalline solution. In 1956, Yamamoto reported finding no evidence of crystalline solution between the compounds. Sindeyeva and Godov-ikov,' in 1959, found very limited crystalline solution. but only under conditions of excess tellurium concentration. Finally Melevski s3 investigation in 1963 indicated that one solid phase exists in the region from PbS to 7 pct PbTe and from 82 pct PbTe to PbTe at 886'C, with an eutectic at 55 pct PbTe at that temperature. Detailed data on the solvus boundary were not given. EXPERIMENTAL EQUIPMENT AND MATERIALS Commercially produced PbTe and PbS powders were used as starting materials. Batches of specific mole percent composition were accurately weighed and mixed in a plastic bottle, in a shaker mill. An analy- sis of impurity content is given in Table I for pure PbS and PbTe and for two randomly selected batches after the powders were mixed. Individual samples, ranging in weight from 0.2 to 0.5 g, were sealed in evacuated silica tubes which had been thoroughly washed and rinsed with acetone and distilled water. Thus all data taken were at the pressure of the system. Subsolidus relations were studied down to 400°C by heating the samples in a vertical tube furnace for 24 hr. The sealed tubes were quenched in water with quench time from the hot zone not exceeding 1 sec. Temperatures were measured by a chromel-alumel thermocouple and controlled to 53°C for most runs. The number and composition of phases present were determined from powder X-ray diffraction patterns taken at room temperature on a Norelco diffractome-ter, using silicon as an external standard. Above 850°C quenching techniques were, in general, found to be unsatisfactory, and differential thermal analysis (D.T.A.) was used to determine melting relations. The evacuated tubes were recessed about 1 cm at one end to accommodate the differential thermocouple. Al203 was used as the reference material in a similar tube containing the other side of the differential couple. For temperature measurements, a separate thermocouple was placed in the recess of the tube containing the sample to be measured, thus providing an opportunity to obtain thermal, as well as differential, analysis. All thermocouples for these measurements were Pt-Pt 10 pct Rh. Temperature and differential curves were recorded separately on synchronized strip-chart recorders. Thermocouples and recording equipment were calibrated using NaCl and gold standards, using the melting points 801" and 1063 C, respectively, which span most of the temperature range of interest. Heating and cooling rates generally were from 4 to 7°C per min. It was found, in fact. that rates ranging from 1.5 to 25°C per min did not significantly change the data obtained.

Jan 1, 1967

By E. N. Skinner, Arthur Philliops

During the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson' who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.01; per cent at 1500ºC. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000ºC. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hemitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of mini-tie concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicro-scopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941

By E. N. Skinner, Arthur Philliops

During the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson' who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.01; per cent at 1500ºC. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000ºC. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hemitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of mini-tie concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicro-scopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941

By William Rawles

THIS report is the first of a series planned by The Mineral Inquiry, organized by the American Institute of Mining and Metallurgical Engineers to make factual studies of the world's mineral resources in their political and international relations. The efforts of The Inquiry are directed toward filling certain notable gaps in available information, without duplication of many other investigations touching this field which are being conducted by other organizations, public and private. Much of its work is indirect-suggesting topics for study by other individuals and organizations and aiding in their planning and correlation. The present report is designed to show the nationality of the commercial control of mineral resources, in addition to the geographic distribution of production by nation-in other words, the overlapping of political and commercial control. Detailed accuracy cannot be claimed for the figures presented. For some companies division of ownership by nationality has been very difficult to ascertain, as many companies are reluctant to dis-close the extent of their holdings in other corporations, and the impossi-bility of tracing all stock ownership is obvious. Also there are frequent changes in the distribution of stock control. The percentages given rep¬resent only the participation that has been identified definitely, even though it is known in some cases with fair certainty that larger interests exist, as, for instance, American participation in foreign chromite companies. In bringing together these figures we have had the cordial co-operation of the United States Bureau of Mines, the United States Geological Survey, the Mineral Division of the Bureau of Foreign and Domestic Commerce, the Brookings Institution, and of many specialists connected with the mineral industries covered. The report does not cover the entire list of minerals. Coal, although it is, one of the most important minerals, was omitted because not more than one or two per cent of the world's production comes from mines that are owned by companies foreign to the countries where the coal is produced. Others, such as gold, are omitted because sufficient data have not yet been accumulated. It is hoped that some of these may be covered in subsequent reports. It is not our purpose here to discuss the significance of the figures sub-mitted, but only to point out the general nature of the problems on which they have a bearing.

Jan 1, 1933

By C. H. Mathewson, J. A. Collins

The process of plastic extension of face-centered cubic single crystalline rods is so well understood, since the notable studies of Taylor and Elam,1 that the change in orientation of any crystal by slip and rotation may be predicted from the measured elongation. It is customary to assume a very homogeneous deformation, wherein gliding lamellar arc free to rotate so that their slip direction continually approaches the axis of the rod, until a second slip system comes into operation; whereupon conjugate slip proceeds quantitatively to an end adjustment with the [121] direction in the axis of the rod. This process has been checked in malty face.-centered cubie materialsand and readily permits the preparation of specimens that have been subjtvted to various determinable amounts of shearing action. It is elearly of interest to study in such measurably strained speeimens the, development of a recrystallized structure on annealing and if possilble detect the source of nuclei from which the new crystals grow. Strain-:~nneali~ig experiments of this charactcr have been performed by others but not in detail sufficient to permit a study, for example, of the number of recrystallized grains vs. the amount of shear. In the experiments now reported, this was done with a wide variety of orientations covering nearly the entire range of slip on a single system and corresponding to amounts of shear (ratio of shearing distance to distance between lamellae at the conclusion of a test of from 0.08 to 0.57. A particular point wa-made of determining the crystallite rotation, or small angular range. assumed by the octahedral slip plane after these various amounts of shear. The, mechanism of reerystallization and the magnitude and effeet of recovery on the recrystallization process was investigated.

Jan 1, 1940

By J. A. Collins, C. H. Mathewson

The process of plastic extension of face-centered cubic single crystalline rods is so well understood, since the notable studies of Taylor and Elam,1 that the change in orientation of any crystal by slip and rotation may be predicted from the measured elongation. It is customary to assume a very homogeneous deformation, wherein gliding lamellar arc free to rotate so that their slip direction continually approaches the axis of the rod, until a second slip system comes into operation; whereupon conjugate slip proceeds quantitatively to an end adjustment with the [121] direction in the axis of the rod. This process has been checked in malty face.-centered cubie materialsand and readily permits the preparation of specimens that have been subjtvted to various determinable amounts of shearing action. It is elearly of interest to study in such measurably strained speeimens the, development of a recrystallized structure on annealing and if possilble detect the source of nuclei from which the new crystals grow. Strain-:~nneali~ig experiments of this charactcr have been performed by others but not in detail sufficient to permit a study, for example, of the number of recrystallized grains vs. the amount of shear. In the experiments now reported, this was done with a wide variety of orientations covering nearly the entire range of slip on a single system and corresponding to amounts of shear (ratio of shearing distance to distance between lamellae at the conclusion of a test of from 0.08 to 0.57. A particular point wa-made of determining the crystallite rotation, or small angular range. assumed by the octahedral slip plane after these various amounts of shear. The, mechanism of reerystallization and the magnitude and effeet of recovery on the recrystallization process was investigated.

Jan 1, 1940

By Patrick H. O’Neill

FUNDAMENTALLY a dredge designed for operating under arctic conditions and particularly when the temperature is below freezing is not greatly different than one for use in more moderate climates. Because of the accumulation of ice it is necessary to design suspension units to carry an increased weight when ice forms on the digging ladder or stacker. Winch room and house must be made with double walls and insulated. The dredge must be heated either by steam or by circulating warm air electrically heated. The stacker must be covered and heated to avoid having the drive units frozen tight. Actually the worst trouble that might develop in a stacker, because of cold weather, is the freezing of spilled material and ice accumulation on the head pulley and the underside of the belt. For this reason, stackers are completely enclosed and the pan kept open to get rid of any spilled material and to prevent overloading. Since the stacker is the most vulnerable place on a dredge in cold weather, heat is turned on there long before it is necessary any other place on the dredge. The principal points of interest in' connection with dredging, under subfreezing conditions, concern the preparation of the ground being dredged and the frozen ponds. In the interior of Alaska, and also in the Yukon territory of Canada, most of the gold bearing gravel deposits are permanently frozen and they are also covered by variable thicknesses of fine grained sediment, locally called muck. The better pay areas in this frozen ground have generally been worked by the earlier miners who sank shafts to bedrock in the frozen ground, then drifted in four directions and dug out the areas between the drifts as they re- treated toward the shaft. They thawed only the area they were excavating, doing so with steam from wood-fired boilers, and hoisted pay gravel to the surface for subsequent washing.

Jan 11, 1954

By C. C. Henning

In any line of human activity logical handling requires an amount of attention to each phase that is in keeping with the importance of that phase. In the complex and rapidly changing field of modern ferrous metallurgy it is difficult to allot the proper degree of attention to the various subjects, and it is not surprising that one or more subjects of major importance should for a time be neglected. Bessemer steel is a good example of a neglected subject. It is largely taken for granted, inferior physical quality is assumed for it, and there is a • lack of interest in its technical development and commercial application. Availability of supply is limited. In spite of this technical indifference, limited source and lack of commercial exploitation, bessemer steel constitutes a large volume of tonnage in daily use. There is a fairly prevalent idea even among technical people that bessemer steel survives mostly because of low cost and by reason of a dwindling residue of applications sufficiently common to permit of its use. The difference in cost between bessemer and open-hearth steel is governed largely by the relative cost of manufacture of pig iron and the market price of steel scrap. During the past four years there have been long periods of time during which the price of steel scrap was low enough so that open-hearth steel was considerably lower in manufacturing cost than bessemer. As to application, it may be pointed out that thousands of tons of this material in the form of bessemer screw steel are applied for moving parts in automotive and other equipment. Some forging work and considerable heat-treating, particularly carburizing, is performed on this grade. From an economic standpoint the most effective contribution of bessemer steel lies in its free machining qualities. It is by far the freest

Jan 1, 1935

By C. C. Henning

In any line of human activity logical handling requires an amount of attention to each phase that is in keeping with the importance of that phase. In the complex and rapidly changing field of modern ferrous metallurgy it is difficult to allot the proper degree of attention to the various subjects, and it is not surprising that one or more subjects of major importance should for a time be neglected. Bessemer steel is a good example of a neglected subject. It is largely taken for granted, inferior physical quality is assumed for it, and there is a • lack of interest in its technical development and commercial application. Availability of supply is limited. In spite of this technical indifference, limited source and lack of commercial exploitation, bessemer steel constitutes a large volume of tonnage in daily use. There is a fairly prevalent idea even among technical people that bessemer steel survives mostly because of low cost and by reason of a dwindling residue of applications sufficiently common to permit of its use. The difference in cost between bessemer and open-hearth steel is governed largely by the relative cost of manufacture of pig iron and the market price of steel scrap. During the past four years there have been long periods of time during which the price of steel scrap was low enough so that open-hearth steel was considerably lower in manufacturing cost than bessemer. As to application, it may be pointed out that thousands of tons of this material in the form of bessemer screw steel are applied for moving parts in automotive and other equipment. Some forging work and considerable heat-treating, particularly carburizing, is performed on this grade. From an economic standpoint the most effective contribution of bessemer steel lies in its free machining qualities. It is by far the freest

Jan 1, 1935

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-'. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.' and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner's3 data for cation self-diffusion, D:, using Wagner's theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner's data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-' at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By R. R. Goddard

By use of the frequency response method with a radioactive tracer, it was possible to determine fluid dispersion and distribution in a natural consolidated and an unconsolidated medium. Measurements were made in a linear flow system at oleic saturations of 69 per cent in the consolidated medium, and 100 per cent in both media. Dispersion and distribution were obtained by measuring the amplitude attenuation and the phase velocity of sinusoidal waves with a dual monitor apparatus. The gamma ray emissions permitted in situ measurements at any distance along the porous samples. One result of importance was that the effective diffusivity increased as the wave length increased. As a consequence, a dispersion coefficient appropriate for the injection of large slugs might exceed the value measured by use of small slugs. Since flow models based solely on fluid velocity and an effective diffusivity coefficient imply that the diffusivity should be independent of frequency, such representations were not adequate for the data of this study. A comparison was made with a capacitance model of porous media with deadend PVs, but even this model was not completely adequate. By using attenuation and phase velocity data, fluid dispersion can be predicted without postulating a differential equation satisfied by the tracer concentration, thereby eliminating the need of a complicated model to represent dispersion. INTRODUCTION The flow of similar miscible fluids through a porous medium can be fairly adequately described by two parameters: the average fluid velocity and the effective diffusivity.1-3 It has been pointed out recently, however, that significant discrepancies exist between this representation and the experimental data.4-7 An improved agreement can be obtained by introducing additional parameters based on the concept of dead-end pores. The purpose of the present investigation was to find out whether the frequency response method could be used to measure the relevant parameters. The method was used in the following form. A stream of fluid was flowed at a constant rate through a sample of porous material and the concentration of a radioactive tracer in the fluid was varied sinusoidally at a fixed frequency. The effects of flow through a porous medium are a decrease in the amplitude of the concentration wave and an increase in the velocity of the peaks of the waves above the average velocity. Attenuation and phase veIocity of the waves were measured as a function of frequency and fluid velocity. The simple two-parameter model implies that the diffusivity should be independent of frequency. Data reported in this paper show that the diffusivity decreases as the frequency increases. Hence, as shown also by many others, the two-parameter model is not completely adequate. Coats and Smith 5 used two additional parameters in their model: the volume of the dead-end pores and the rate of mass transfer between dead-end pores and the flowing stream. Their capacitance model of a porous medium containing some stagnant fluid, to which transfer occurs by molecular diffusion, did not explain the dispersion results of either the present study or of theirs. Instead, the capacitance effect can be better described as the result of extreme velocity variations within the pores of the medium, with transfer between the velocity zones by convection. EXPERIMENTAL PREPARATION OF POROUS MEDIA Data reported here were obtained with a natural Berea sandstone, and with two packings of 20/25 mesh sand. Pertinent information about these media is listed in Table 1. The sandstone core was first sealed with a non-

Jan 1, 1967

By Munroe F. Warner

As originally built, the plant of the American Zinc and Chemical Co. at Langeloth, Pennsylvania, was based upon the Joplin and Wisconsin fields as primary sources of zinc ores, the ores being the then normal jig and table concentrates. Construction incorporated standard Matthies-sen and Hegeler kilns without regenerators. With the development of differential flotation, zinc concentrates produced by that process became the basis of operation. These concentrates were very fine, upwards of 90 per cent passing a 300-mesh screen, and had a comparatively low fusing point with marked caking and crusting characteristics. Difficulties and losses quickly developed. In roasting, the ore went through a decidedly fluid state, and spills became serious. Caking and crusting on hearths was severe and dust losses throughout became intolerable. Acid recoveries dropped from the normal ton-for-ton level to 0.85 tons per ton of ore, and choking of Glover towers and acid lines became a problem. In 1926 and 1927 a two-unit sintering plant was built and placed in operation in accordance with the Baelen process for finishing desulphuri-zation with admixture of carbon. This had its beneficial effect in smelting, but the other problems remained. The problem presented was the roasting of Pecos flotation concentrates at the rate of 200 tons daily to a sulphur content suitable for finishing in the sintering plant. Specifications had to be governed by the existing acid plant of four chamber sets built in units of two, rather widely separated, and the sintering plant built in the space between the existing pairs of kilns, of which there was one on the center line of each of the four chamber sets. The problem contained elements of pioneering and experimentation. A thermal analysis and heat balance clearly demonstrated a possibility of accomplishing autogenous roasting, well worth the attempt, because of high fuel costs and resultant economies in operation of the acid plant due to decreased gas volumes and a consequent release of capacity for increasing acid production, a problem also faced.

Jan 1, 1937

By A. Kelly, S. Sato

Tensile tests have been performed on aluminum single crystals of 99.99 pct purity at 196°K. The resolved shear stress when the stress-strain curve becomes concave to the strain axis depends on orientation, being always higher for crystals with an initial orientation close to the sides of the unit triangle. Observations have been made, with the optical microscope, of the appearance of slip lines on polished surfaces of the crystals. Particular attention has been paid to the first appearance of cross-slip. It is confirmed that marked cross-slip is first seen when the stress-strain curve becomes concave to the strain axis. Measurements are reported of the lengths of the slip lines observed on top and side faces of the crystals at various stages of the deformation. The lengths of the slip lines vary inversely as the flow stress for all crystals, independent of crystal orientation. From measurements of the lengths and separations of the slip traces it is possible to estimate the number of dislocations which are annihilated at each cross-slip site. It is concluded that the annihilation of screw dislocations of opposite sign is the most important cross-slip process occurring. FRIEDEL1 recently pointed out that the stress-strain curve of many pure metals of face-centered-cubic structure can be considered as composed of three stages. Plastic flow commences with a region showing a small rate of hardening which is approximately linear. This has been called "easy glide*. It is followed by a region of more rapid hardening in which the slope of the curve is again approximately constant and this, in turn, is superseded by a final part of the curve which is concave to the strain axis. Following Diehl2 we may designate these regions as stages I, II, and III respectively. The onset of stage 111 occurs at lower stresses at higher temperatures. The appearance of the slip lines formed during these various stages has been described by a number of workers?-5* The object of the present work was to make detailed observations of the lengths and separations of slip lines for a number of crystals of different orientations deformed at the same temperature and strain rate. Although much previous work has been published on the deformation of aluminum single crystals the importance of measurements of these quantities has only recently been realized—they are essential for experimental tests of recent theories of work hardening.' 9 In aluminum, deformed at room temperature, stage 11 of the stress-strain curve is very weakly marked, as the stress for the onset of stage 111 is attained soon after the end of easy glide. In the present experiments it was decided to use a temperature lower than room temperature so that stage II of the curve was better developed. However, at temperatures as low as 90°K slip lines are not measured easily with the optical microscope.5 For this reason 1960k was chosen as a suitable temperature. Even at 1960k however, stage III of the curve commences at glide strains of 6 to 10 pct and hence

Jan 1, 1960

By James O. Lewis

Gravity drainage is the self-propulsion of oil downward in the reservoir rock. Under favorable natural and operational conditions, it has been found to effect recoveries comparable to water displacement. With modern technical knowledge, the operator can often make a choice between dissolved gas drive, water drive and gravity drainage as the principal recovery agent in a reservoir. It is desirable that the opeator be able to determine which of the three agents will be most effective under each set of conditions. So far, gravity drainage has received less consideration than the other two. In this paper. an endeavor is made to set forth some of the principles of gravity drainage, to point out the types of reservoirs favorable for it, and to show how it may be applied in them. Field examples are described and discussed. Introduction Since early in the history of the oil industry, it has been recognized that gravity is one of the three important natural forces for expelling oil from the reservoir rock. As knowledge of the technology of oil recovery progressed, ideas changed with respect to the relative importance of the three forces and with respect to the manners in which they functioned. For a time, disproportionate emphasis was placed on the importance and function of gas and the need for conserving gas pressures. More recently, disproportionate emphasis has been placed on encroaching edge water. Only lately has there been evidence that the function and importance of gravity was to receive due consideration. Study of this neglected phase of oil recovery is needed to round out our knowledge of reservoir behaviors and to gain a balanced viewpoint of the interplay of forces that may operate in varying importance in reservoirs. The purpose of this paper is to discuss mainly in a qualitative way, the functions of gravity, to present some concrete instances where it has been important and to raise some questions that should be investigated further. Oil-recovery Agents The important natural agents for effecting oil recovery that may be originally available in a reservoir are gas, both dissolved in the oil and free in gas caps, encroaching edge water and gravity. Each of these agents can act in a dual capacity—physically to overcome the surface energies that hold the oil within the pores and mechanically to overcome viscous . resistance and to propel the oil through the porous reservoir rock to the wells. Advancing edge water displaces the oil from the pores and lifts it updip to structurally lower wells. Gravity drains the oil from the pores and flows it downdip to the wells. Gas displaces oil from the pores, entrains it in the gas stream and flows it to the wells, but gas in solution also affects the physical properties of the oil and thus can influence oil recovery by the other agents, whether or not the mechanical energy in the gas is utilized. Of the two functions of these agents, the more important is the ability to dis-

Jan 1, 1944

By James O. Lewis

Gravity drainage is the self-propulsion of oil downward in the reservoir rock. Under favorable natural and operational conditions, it has been found to effect recoveries comparable to water displacement. With modern technical knowledge, the operator can often make a choice between dissolved gas drive, water drive and gravity drainage as the principal recovery agent in a reservoir. It is desirable that the opeator be able to determine which of the three agents will be most effective under each set of conditions. So far, gravity drainage has received less consideration than the other two. In this paper. an endeavor is made to set forth some of the principles of gravity drainage, to point out the types of reservoirs favorable for it, and to show how it may be applied in them. Field examples are described and discussed. Introduction Since early in the history of the oil industry, it has been recognized that gravity is one of the three important natural forces for expelling oil from the reservoir rock. As knowledge of the technology of oil recovery progressed, ideas changed with respect to the relative importance of the three forces and with respect to the manners in which they functioned. For a time, disproportionate emphasis was placed on the importance and function of gas and the need for conserving gas pressures. More recently, disproportionate emphasis has been placed on encroaching edge water. Only lately has there been evidence that the function and importance of gravity was to receive due consideration. Study of this neglected phase of oil recovery is needed to round out our knowledge of reservoir behaviors and to gain a balanced viewpoint of the interplay of forces that may operate in varying importance in reservoirs. The purpose of this paper is to discuss mainly in a qualitative way, the functions of gravity, to present some concrete instances where it has been important and to raise some questions that should be investigated further. Oil-recovery Agents The important natural agents for effecting oil recovery that may be originally available in a reservoir are gas, both dissolved in the oil and free in gas caps, encroaching edge water and gravity. Each of these agents can act in a dual capacity—physically to overcome the surface energies that hold the oil within the pores and mechanically to overcome viscous . resistance and to propel the oil through the porous reservoir rock to the wells. Advancing edge water displaces the oil from the pores and lifts it updip to structurally lower wells. Gravity drains the oil from the pores and flows it downdip to the wells. Gas displaces oil from the pores, entrains it in the gas stream and flows it to the wells, but gas in solution also affects the physical properties of the oil and thus can influence oil recovery by the other agents, whether or not the mechanical energy in the gas is utilized. Of the two functions of these agents, the more important is the ability to dis-

Jan 1, 1944

By Gordon E. Agar

Several correlations have been proposed to relate energy consumption and size reduction in comminution, and although these are arrived at from different starting points, it is postulated that they are all statements of the same basic concept. To test this postulate, the dry ball mill grindability of langbeinite was determined, and the results were analyzed according to the various methods. An examination ' of the energy-particle size relationships proposed in the recent past revealed that they had much in common. In fact, the conclusion was tentatively drawn that these expressions were essentially the same, even though they were arrived at from quite different basic premises. The equations attributed to Charles2 and Holmes3 were shown to re- duce to the same single equation, W - A K-3, and the simulated continuous test used by Maxson et al.4 was shown to give the best experimental value of the required empirical parameter, ß. Furthermore, the size distribution parameter a in the Schuhmann equation, y - (x/K)2, was shown to be equal to ß in many cases. The kinetic approach used by Arbiter and Bhrany5 should give the same results as the Maxson test procedure; however, the batch operation used by Arbiter and Bhrany could not produce data that would be as precise as the simulated continuous technique. To test the validity of these conclusions, the simulated continuous method was used to obtain data on the dry grinding of langbeinite. The results are discussed in terms of the various equations and approaches. APPARATUS AND MATERIAL A ball mill with internal dimensions of 17.5 cm (6 7/8 in.) in length by 19.4 cm (7 5/8 in.) in diam was loaded to 50% of its volume with balls 3.2 cm in

Jan 1, 1969

By C. C. Furnas, T. L. Joseph

It is well known that particles of different sizes are not distributed evenly throughout the average charge in an iron blast furnace. Just how great the disparity in particle size in different parts of a single plane in a furnace may be is indicated by the results of some recent investiga-tion1,2 conducted by the Bureau of Mines on a furnace operating on Lake ores. The wide variations found in gas velocity, gas composition, and temperature from the periphery to the center of the upper charge column were caused by the great variation in particle size of the raw materials used and were also greatly influenced by the methods of charging. This paper summarizes the results of an investigation of the influence of different methods of charging and of the treatment of raw materials upon the size distribution of the solid particles in the blast furnace. A more complete report will appear later as a Bureau of Mines technical paper. Importance of Gas-solid Contact One of the authors has pointed out in a previous report? that the operation of the blast-furnace process is entirely dependent on contact between the gas stream and the solid particles in the stock. The gas stream carries the necessary heat as well as the carbon monoxide molecules that do the work of rednction. In the parts of the furnace in which there is little or no contact between the gas stream and the solids there can be little work of reduction. Obviously, the part of the apparatus that is not doing the work for which it is intended is inefficient; the ideal condition is one in which all portions of the stock column are

Jan 1, 1929

By R. W. Carpenter, J. C. Ogle

It is possible, by using pack-rolling instead of conventional rolling, to reduce a number of metals to thicknesses of 2µm or less. Such thinfoils are generally made at room temperature without intermediate annealing. In addition, pack-rolled foils fail by developing pinholes at thicknesses near 2µm instead of developing the shear cracks usually observed in cold-rolled ductile metals. This paper presents the results of a general investigation of the deformation substructure and texture developed in copper and iron pack -rolled from 130 to about 2µm thickness. Electron microscopy showed that in both metals a fine (0.2 to 0.5?µ m) deformation subgrain structure formed during pack-rolling; in neither case was this substructure grossly different from substructures formed during conventional rolling. The deformation texture formed in pack-rolled iron was quite similar to usual bcc textures; however, in the case of copper, the cube texture was stable during pack-rolling and the normal copper deformation texture was unstable. It is shown analytically that the constraining pack induced a large hydrostatic pressure in the foils during pack-rolling. The pinhole failure mechanism is attributed to the presence of the large hydrostatic pressure during pack-rolling; this strongly suppressed the growth of shear cracks. The stability of the cube texture in copper is also probably due to the unusuul stress distribution developed during pack-rolling. EXPERIMENTS at several laboratories have shown that very thin foils of the common structural metals and many of the rare earths can be made by "pack-rolling". 1-3 The technique was originally developed to make specimens for nuclear scattering experiments and foils for X-ray filters. It is also useful for making experimental laminar metallic composite bodies and foils thin enough for direct examination by ultra-high voltage electron microscopy without the need for special thinning techniques. Pack-rolling in the present context means a three-layer pack, with the material to be rolled into foil comprising the center layer. The outer two layers, which constrain the foil during reduction, are ordinarily austenitic stainless steel. Typically, a 130 µm (0.005 in.) metal strip can be reduced to a final thickness of 2 µm or less by this process. This is accomplished at room temperature, without intermediate annealing. It has been observed that foils produced by this process do not exhibit at any stage of their reduction the severe work-hardening found in strip rolled by conventional cold-rolling methods. Neither is the failure characteristic the same."&apos; Conventionally cold-rolled ductile metal strip fails by developing shear cracks on planes whose normals nearly bisect the angle between the rolling direction and normal to the rolling plane; these are planes of maximum shear stress. In pack-rolling this mechanism has not been observed; failure occurs by the formation of pinholes on the foil surface (penetrating the foil). If pack-rolling is continued the hole density increases. These differences in behavior imply the existence of appreciably different substructure in pack-rolled foils compared to substructure in conventionally rolled material, or perhaps that the geometry of pack-rolling has an effect on the foil behavior. This paper describes an investigation of deformation substructure and texture in some specimens of pack-rolled copper and iron, and some considerations of the stress distribution in the foils during rolling that result from the geometry of pack-rolling. EXPERIMENTAL DETAILS Three different materials were used for pack-rolling in the present work: soft copper sheet (99.8 pct Cu, 0.03 pct 0, electrolytic tough pitch) and two types of iron, Ferrovac E* and Armco iron. Each was "Crucible Stccl Co. initially in the form of 130 µm annealed strip with grain size ranges of approximately 10 to 40 µm. The initial texture of the copper (determined as noted below) was the normally observed cube type (001)[100]; there was evidence of a small amount of material in the cube-twin orientation reported by Beck and Hu.4 The initial texture of the Ferrovac E was similar to that reported for recrystallized iron by Kurdjumov and sachs,5 who list the principal orientations as {111}<112>, {001}<110> 15degfrom RD and a weak component {112}(110) 15 deg from RD. The starting texture of the Armco iron was not determined. Pack-Rolling Procedure. A four-high mill was used for all specimens. The work roll and backing roll diameters were 1.625 and 5.25 in., respectively. The peripheral roll speed of the work rolls was about 2.5 in. per sec. All foils were initially reduced from 130 to 100 µm by conventional straight rolling and then inserted into a pack, without any intermediate annealing, for further reduction. The pack consisted of an 0.033 in. (838 µm) thick 3 by 6 in. polished sheet of austenitic stainless steel, folded to make a 3 by 3 in. jacket. After folding, the jacket was given a small reduction to close the fold tightly before insertion of the foil. During pack-rolling a constant change in roll spacing was made every third pass. The roll-spacing change corresponded to a 5 pct reduction in thickness for a new pack. This approached a 10 pct reduction when the pack had decreased to about half its original thickness. At this point the deformed pack was discarded and a new one

Jan 1, 1970

By J. Nagy, D. W. Mitchell, E. M. Murphy

In 1957 research was initiated in the U.S. Bureau of Mines experimental coal mine near Pittsburgh, Pa., to study factors affecting foam generation and transport, to evaluate the effectiveness of high-expansion foam for controlling mine fires, and to develop techniques for applying the method under U.S. mining conditions. These investigations showed that high-expansion foam containing at least 0.2 oz of water per cu ft of foam is effective in controlling experimental underground fires burning coal, wood, and oil. Sometimes the fire was completely extinguished, but more often, it was brought under sufficient control to permit either a direct attack on the fire with a stream of water or loading of the hot material into cars. A progress report&apos; prepared in July 1958 summarized the initial achievements of the USBM experiments. Since then other phases of the foam-plug method for attacking fires have been studied in the laboratory and in the mine. Previous studies by British engineers&apos; of the foam-plug method for fighting mine fires indicated that high-expansion foam was effective in controlling experimental timber fires in an underground passageway. Their subsequent workx-1 pertained to the practical aspects of fighting large fires within a mining area with a foam-plug. CONTROLLING EXPERIMENTAL FIRES In the USBM tests foam was formed by spraying a dilute solution of a foaming agent on a metal or cotton net of 1/8 to 1/4-in. mesh. Air passing through the continuously wetted net forms bubbles of 1/2 to 11/2-in. diam and produces a honeycomb of foam that fills the passageway. Under the ventilating-air pressure, this light-weight plug moves forward through the passageways, around sharp corners, and over obstacles. as illustrated in Fig. 1. High-expansion foam was transported to a wood fire, an oil fire, and 13 coal fires. Figs. 3 and 4 show a typical coal fire before and after attack with foam. In 12 of the 15 experiments the fire was brought under control when the water content of foam was 0.2 oz or more per cu ft. A fire was considered controlled when the flames were quenched and observers could cross the area without wearing breathing apparatus or protective clothing. In the other three experiments, conducted when the water content was less than 0.2 oz per cu ft of foam, the flames were retarded but the fire was not controlled. Coal fires have been attacked successfully by foam introduced at points varying from 155 to 1010 ft from the fire. The time of burning in coal beds 10 in. thick ranged from 11/2 to 5 hrs or more. Most of the experimental fire beds were 15 ft in length. However, in one experiment a floor fire 25 ft long and 5 ft wide was constructed $5 upwind from another fire 15 ft in length; in another instance, the fire was 100 ft long and 5 ft wide. Foam was applied to the fires for periods ranging from 7 to 36 min. The time required for foam application depends on the extent of the fire, time of burning, water content of foam, foam velocity, and degree of fire control desired. In addition to the coal fires, foam was transported to a fire covering 45 sq ft, produced by 15 gal of oil burning in metal trays on the floor. The foam extinguished the oil fire in about 1 min. In one other test, the burning of 1100 lb of dry sawmill slabs stacked in open cribs 4 ft high and 16 ft long was brought under control by foam in 2 min. Composition of Gases in Return Air: In several of the experiments samples of the return air from fire zones were collected; composition of the atmosphere before, during, and after foam application was then determined. Because of condensation in the relatively cool sampling tube, the amount of water vapor was not determined. Analyses showed that concentration of carbon dioxide and combustible gases increased as the foam began passing over the fire. This resulted from the decrease in the volume of air when foam generation started and from the formation of gases when water reached the fire.* The quantity of gases generated would not be greater than that from an equivalent amount of water applied directly to the fire. The highest total concentration of combustibles (CO, CH1, and H2 mixture) obtained during the experiment was about 2 pct; this occurred 6 min after foam reached the fire. This atmosphere was nonex-plosive, but calculations show that if the air flow were reduced to about 5 fpm and if the rate of gas liberation from the fire remained constant, the mixture would be explosive. The use of foam on a fire in all probability would affect the normal ventilation of a mine. If the mine is gassy, this factor must be carefully considered before the foam is applied. APPLICATION OF THE FOAM-PLUG TECHNIQUE IN MINES Equipment and procedures for applying the foam-plug methods must be adapted to the prevailing conditions at a particular mine. Some factors to be considered in developing equipment are: size or extent of the mine, dimensions and number of entries, ventilation system, mining methods, haulage facilities, availability of water, amount of methane liberated, and existing fire-control apparatus. • In most experiments the initial air velocity of 200 fpm decreased to 50 to 100 fpm as the foam plug increased In length.

Jan 1, 1961