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By D. M. Blacknall, N. N. Winogradoff, E. W. Williams

Low-temperature measurements of photolumines-cence were used to evaluate the progvess in materials development. Variation of the impurity type, impurity concentration, and method of growth were used to clarify the chemical origin of defects in GaAs. Melt-g~ozun, epitaxial vapor-, and solution-grown samples were studied. A comparison of measurements at 77" and 20°K shows that more defects can be observed at the lower temperature. Th'vee residual defects were identified in relatively pure GaAs. These were: silicon, copper, and a gallium vacancy-donor complex. Solution growth from a gallium solution inhibits the formation of the latter two. Eleven defects were studied and the "optical" activation energy of some of these, namely, silicon, cobalt, and chromium, has not been reported in the literature before. THE discovery of the injection laser in 1962 prompted extensive measurements of the photoluminescence of GaAs. The measurements were made at 77°K on GaAs doped with shallow impurities at various doping levels and compared with electroluminescence1'2 and absorp- tion data.374 In addition, lower-temperature studies were made on relatively pure GaAS' and on GaAs doped with oxygen,5'" manganese,' and copper.' The observation of defects* in GaAs with photolu- *The word "defects" ~efers to both chemical impurities and native defects. minescence at low temperatures makes photolu mines-cence an invaluable tool in evaluating the progress in materials development. The only previous evaluation was done at 77°K when solution-grown and melt-grown GaAs were compared.O No identification of defects was made but it was shown that some of the deep-level luminescence seen in melt-grown GaAs was absent in solution-grown GaAs. The present work extends the comparison of preparation techniques to lower temperatures and to a study of epitaxial vapor-grown GaAs. It is particularly valuable for thin epitaxial layers since they cannot be analyzed by conventional analytical techniques. In addition, by varying the impurity type and impurity concentration the chemical origin and nature of defects in GaAs was demonstrated. Eleven defects were studied in all. Three of the defects were identified as residual defects which often contaminate GaAs prepared from the melt and the vapor. Only one such defect was observed in GaAs grown from a gallium solution and this was identified as silicon.

Jan 1, 1968

W. 0. HOTCHKISS, * Madison, Wis.-It was fortunate, in a way, that this subject of income taxation came up during the war when the government could appeal, on the basis of patriotism, to men of large, business experience to undertake the work of formulating this matter and practically donate their services. At any other time the government would have been unable to secure the necessary number of men of like ability. There is one thing that must not be forgotten. In all cases, except the very largest and most important, the application of this income tax law to a mine is going to be made by clerks whose salaries are fixed by a Congress that appropriated a half billion of dollars for a war purpose and provided that $4000 should be the highest salary paid in the adminis-tration of that great sum. The Congress of the United States unfor-tunately seems almost entirely unaware of the fact that men of ability and experience are worth money and must be paid adequately if proper public service is to be secured. While the formulation of the broad plans for administering the law have been in the hands of. men of unusual ability, we have the future to guard, and, if possible, the mining industry should see to it that the Internal Revenue Department is permitted by Congress to pay salaries that will enable it to secure men of the ability and experience necessary to insure proper consideration of the industry. Another fact to which I would call attention is the difference between the business and the economic, or economists', points of view as to what a mine is. The economists have properly, from their point of view, classed a mine as a wasting asset, but the average metal mine is not a wasting asset if it is a real mine. The economists are correct in a broad sense in that every ton of ore taken out diminishes the orebody by that amount. When it comes to the consideration of an individual mine from the business standpoint, the future of that mine rests on unfore-seeable events-the discovery of new orebodies or the development of old bodies beyond the point of probable expectations. Every going mine must develop new ore each year to replace that extracted, and, .during all but the last one or two years of its activity, actually does so. Instead of being a "wasting asset" such a mine, from the practical stand-point which must control valuation, is an "increasing asset." From

Jan 12, 1919

By H. H. Uhlig

Soon after general use of stainless steels began, it was observed in practice that certain combinations of factors tended to induce corrosion by pitting. For most applications this was a serious drawback, not so much because the structural properties of the metal were impaired but because of the rapidity with which heavy sections of the alloys were penetrated by small elongated pits. These pits seemed to initiate readily in oxidizing metal salt solutions like ferric chloride and in chloride solu-tions like sea water. It was observed that in sea water pitting was more frequent in stagnant or polluted waters than in highly aerated, moving waters. The steels in these chloride solutions were observed to be sensi-tive to long contact with material such as sand grains or attached bar-nacles. At points of attachment or contact it was not uncommon to discover initiation of corrosion. Pits once begun at contact faces were observed to grow rapidly, usually elongating phenomenally in the direc-tion of gravity until the metal was perforated. Hydrochloric acid and other nonoxidizing acids, on the other hand, were observed to corrode stainless steels generally; the weight losses often were higher, but the penetration less than for the pitting type of corrosion. The causes of pitting, a type of corrosion recognized as character-istic not only of stainless steels but of many additional metals and alloys, are important in corrosion studies. A possible explanation bears prac-tical significance, for once it is known why pits begin where they do and continue to grow after initiation, intelligent direction can be given to diminishing corrosion. This can be done either by some alteration in the composition and treatment of the alloy or by some alteration in the environment. It appears foremost in importance to discover the nature of pit foci, for if initiation of pits can be discouraged their growth will be no longer a factor to be considered. In a multi-component alloy containing many impurities normal to production of such an alloy, each of which may play a part in pitting, and whose corrosion resistance is sensitive to heat-

Jan 1, 1940

By R. I. Garrod, R. A. Coyle

The shapes and positions of X-ray reflections from specimens of copper, steel, and aluminum alloy haue been examined in the elastic and plastic ranges both while the specimen was under stress and in the unloaded condition. For the aluminum alloy the shape was unaltered by the application of stress either within the elastic limit or in the plastic range provided that no additional plastic strain was induced. In copper the broadening accompanying plastic deformation was very slightly reduced when the specimen was unloaded. A similay but more marked elastic component of broadening was also found for steel, but in this case below the yield stress. Line profiles corrected for instrumental and particle-size broadening indicate very large internal stresses in local regions of the plastically deformed metals. The results are discussed in terms of a recent suggestion that the heterogeneous dislocation distribution between the cells and their boundary walls plays a major role in the peak shifts and broadening of the X-ray reflections. STUDIES of the X-ray line profiles from strained polycrystalline aggregates concentrate usually on one or the other of two main parameters: a) the displacement of the peak of the intensity contour from its position for a strain-free aggregate, or b) the shape of the profile. From peak shifts data can be obtained either on the relation in both the elastic and plastic ranges between applied external stress and average lattice strains in a given (hkl) direction, or, alternatively, on the residual lattice strains which are present after a plastically deformed specimen is unloaded.' On the other hand, the shapes of the broadened profiles from cold-worked metals can be analyzed to separate the broadening produced by small particle size and by heterogeneous lattice strains.' In this paper the terms "size broadening" and "strain broadening'' are used in the general sense adopted by warren.' In the past, apart from two early qualitative observation, it has been customary to examine only the movements of the peaks of the profiles while the specimen is actually under load, since the line broadening induced by plastic strain remains after removal of the external stress. Consideration of the implications of existing data of this type suggests, however, that fruitful additional information on a number of fundamental aspects might be gained by careful examination of whether the X-ray line profile is in fact different in the loaded and unloaded states of the specimen. By taking advantage of the sensitivity and convenience of modern diffractometer techniques it is possible to explore with relative ease the magnitude and importance of any elastic effects which may be superimposed upon the well-known permanent changes in profile. The main aim of the work to be described was thus to investigate this point for typical metals and alloys. For this purpose annealed specimens were extended first elastically and then plastically and the positions and shapes of X-ray reflections were recorded. Initially it was anticipated that prime interest would center on observations within the plastic range; it has been found, however, that small changes in profile sometimes occur both before and after the nominal elastic limit of the material is reached. It is shown that the results obtained have important implications in relation to the structural changes and processes associated with deformation. I) EXPERIMENTAL To enable the diffraction lines to be recorded while the specimen was under uniaxial-tensile stress, a small hydraulic testing machine was designed and constructed for direct attachment to the goniometer of a Philips diffractometer. The specimens, which were machined from 1/2-in.-diam rod and had a central rectangular section 3/8 by 1/16 in. over a gage length of 1 in., were held in the machine by split collets mounted in grooves in the cylindrical ends of each specimen. No special precautions were taken to ensure precise axiality of loading. Constant oil pressure was maintained by a lever and weights system and transmitted to the loading rig by flexible pipe. The actual load on the specimen was measured by a load cell in the machine to an accuracy of * 1 pct. To enable smooth X-ray profiles to be obtained the specimen and machine were oscillated continuously during recording through *7-1/2 deg about the normal half-angle position of the goniometer. The three materials chosen for the investigations were high-purity copper as representative of a ductile fcc metal, a low-carbon steel for a bcc metal, and an aluminum alloy as a material in which the proof stress/ultimate strength ratio is high. Details are as follows. a) Copper. 99.999 pct purity. After machining the specimen surface was polished mechanically and

Jan 1, 1964

By H. E. Cline

Calculations of the formation and growth of faults caused by a variation in lumellar widths were made for a two-dimensioml three-plate problem. The angle between the a-ß boundary and the growth direction was allowed to vary and the time evolution was studied using a quasisteady state approach. At spacings smaller than a critical spacing given by X V = AO variations in the larrlellar widths grow in time to produce faults that coarsen the structure, while at spac-ings larger than this critical spacing, variations in the lamellar widths decay in time. If small plates are introduced into the structure they may grow only at large spacings to refine the structure. The time evolution and shape of faults were calculated for the three plate-problem and then the three dimensional problem and rod-like eutectic were qualitatively discussed. UNDERSTANDING of the mechanism by which the spacing of directionally solidified eutectics is determined may allow one to control their structure better. Steady state solutions for the growth of lamellar structures have been found for a range of lamellar spacings A and growth velocities V. To obtain a unique solution for the isothermal growth of pearlite, Zener1 assumed that growth occurs at a maximum velocity, while Tiller2 assumed that a eutectic alloy, grown under an imposed velocity, will choose a spacing corresponding to minimum undercooling. These assumptions are equivalent and have been referred to as "extremum growth". The extremum condition predicts the observed relation between velocity and spacing as given by V = constant [I] but does not provide a mechanism for changing the lamellar spacing. Jackson and Hunt3 calculated the interface shape by using solutions to the diffusion equation for a planar interface and a relation of the interface composition to the local curvature. If the spacing is much larger than the extremum spacing, the interface breaks down catastrophically to form forked plates. However, the catastrophic breakdown cannot account for the small adjustments in spacing that must occur in practice..3 Direct observations during the growth of organic eutectics4 and the Pb-Sn eutectic5 show that spacing changes occur by the formation of faults. A fault in a plate-like eutectic is the edge of a plate. Once the faults form, they may move to make small adjustments in the spacing.6,3 The motion of faults intersecting the growing interface was shown by an approximate analysis to give Eq. [I].6 A perfectly regular lamellar structure should be able to persist over a range of lamellar spacings. However, during growth small perturbations in the structure may occur. If the amplitude of the perturbation increases in time the structure is unstable, while if all possible perturbations decrease in time the structure is stable. In a previous paper7 variations in the shape of the solid-liquid interface were considered, while this paper considers only variations in lamellar widths while maintaining a macroscopically planar solid-liquid interface. Previously, theories of lamellar growth1"3 have artificially contrained the growth to give a regular periodic structure. To allow for a variation in spacing, the three phase intersections and groove angles were allowed to change with time as determined by assuming local equilibrium. THREE-PLATE PROBLEM Since the spacing changes in eutectics by local formation of faults,4'5 it is suggested that local variations in spacing are responsible. The interaction between neighboring plates will be greatest because they have the smallest diffusion distance. For simplicity, as a nearest neighbor approximation, a three-plate problem will be considered, as illustrated in Fig. 1. The structure consists of a periodic array in which all the plates are allowed to vary in width. As in steady state growth it is assumed that the average composition in the solid remains constant. A variation in plate widths, that maintains the composition in the solid, was introduced by making the first a-phase plate thinner by an amount A, keeping the width of the second B-phase plate constant, and increasing the width of the third a-phase plate. If the structure were not perturbed, as in the regular two-plate problem previously described,' then the groove angles at the three-phase junctions are the equilibrium angles, 0, and ? B, and the solid-solid boundary is normal to the interface. In the three-plate problem with a variation in plate widths the phase boundaries are assumed to be related to the three-phase junction by equilibrium angles, but the a/B boundaries may be rotated by an angle 0 from the growth direction. The angle H be-tween the tangent to the a/B boundary and the growth direction may vary during growth and determine the —> — — —.A_ Q-0 / 0 x, X2 Fig. 1—Schematic of the three-plate problem showing a variation in the spacing and the effect on the angles at the three phase intersections.

Jan 1, 1970

By P. A. Witherspoon, S. P. Neuman

Evaluating the permeability of a caprock overlying a potential gas storage reservoir is a very critical problem. Pumping water from the reservoir can be used as an evaluation tool in analyzing this problem. Fluid level changes that occur in the aquifer us well as in the caprock can be measured with appropriately placed wells. If the leakage of water from the caprock into the aquifer is considerable, the effects will be apparent in the aquifer. If the leakage is slight, however, it will not be possible to detect it with certainty from observations in the aquifer alone. Fluid level measurements in the caprock must be relied upon. and improved methods of analyzing such effects have been developed which are based on a theoretical analysis of fluid flow through a caprock of infinite thickness. An example applying these methods to field data is discussed. INTRODUCTION One of the most critical problems in evaluating an aquifer gas storage project is determining the tightness of the caprock overlying the formation to be used as the storage reservoir. A formation that has previously held oil or gas obviously has a suitable caprock, but an aquifer that contains only water gives no such assurance. A number of aquifer projects in the United States have been troubled by gas leaking out of the intended storage zone, and the ensuing difficulties have led to the development of new evaluation methods. One of these new methods is pump testing wherein water is removed from the aquifer at some controlled rate prior to injection of gas. This fluid withdrawal causes a pressure drop to move out through the aquifer for considerable distances in a matter of days or weeks. Depending on the properties of the caprock, a pressure transient can also pass upward (as well as downward) through the caprock layers adjacent to the aquifer. Thus, if the operator has placed observation wells at appropriate distances from the pumping well, the rapidity with which the pressure transients reach different points in the system can be used to investigate the fluid transport properties of both the aquifer and its caprock. The usefulness of pump testing has been recognized by groundwater hydrologists for many years as a means of determining the potential yield and properties of aquifers used in water supply They have introduced the term "leaky aquifer" for a system in which an aquifer is overlain (or underlain) by semipermeable caprock layers. The ease with which water leaks into the aquifer during pumping can, of course, be very beneficial in bringing additional water to the pumped well. Hydrologists have therefore devoted considerable attention to this prob-lem. From the gas storage standpoint, however, the tighter the caprock layers that overlie the intended storage reservoir, the better are the conditions for minimizing or eliminating any vertical migration of gas. Thus, after a suitable geologic structure has been found, the emphasis in aquifer storage projects is in determining that the caprock is tight. Attention has recently been focused on the use of pump testing as one approach to solving this problem.23,24 This paper presents a further development on evaluating the permeability of a slightly leaky caprock when the caprock is of infinite thickness. From the practical standpoint, this means that the caprock layers are thick enough that pressure transients do not reach the outer boundaries of the system during the pumping test. In a subsequent paper, an analysis of the case where the caprock is of finite thickness will be presented. PREVIOUS WORK ON LEAKY AQUIFERS Jacob" developed a partial differential equation describing the flow of water in an aquifer of permeability k that is overlain by a leaky caprock of permeability k'. Fig. 1 shows a schematic cross-section of the system under consideration. One of his principle assumptions was that if k > > k', the direction of flow is essentially vertical in the caprock and horizontal in the aquifer. Neuman19 confirmed the validity of Jacob's assumption using a mathematical model. Another assumption was that a permeable source layer overlies the caprock (Fig. 1) and is able to maintain a constant hydraulic head at the upper boundary of the caprock. By neglecting the effects of compressibility within the caprock, Jacob1* developed a solution for a bounded circular aquifer. Later, Hantush and Jacobx5 used the same assumptions to solve the case of an infinite radial aquifer that is pumped at a constant rate. Their solution may be expressed in di-mensionless parameters by

By R. J. Quigg, G. S. Doble

Commercial stress -relieved TD Nickel bar was shown to retain room- and elevated-temperature tensile strength after exposure up to 2501°F. Cold swaging increased both room -temperature and 2000°F tensile strength. After annealing at 2500°F the strengthening due to swaging was retained at 2000°F hilt eliminated at room temperature. Annealing produced changes in hardness and X-ray half peak width indicating the presence of recovery processes as 1071° as 1000°F but no recrystallization of swaged material was noted at any temperature. In contrast to swaging, rolling induced a recrystal-lized structure after annealing. The tensile strength of this recrystallized structure was comparable to the cold-worked condition. High-temperature tensile properties of as -received bar were highly anisotropic with the transverse tensile strength being one fifth the longitudinal value. The aniso-/ropy is affected by working direction and may he partially reversed by changing the direction of metal flow. The divergence in tensile strength, beginning above 550°F or- approximate one third the absolute melting point, is strain-rate dependent. T D Nickel is a commercial dispersion-hardened alloy containing 2 vol pct thoria. The dispersion, consisting of spherical particles 0.030 to 0.050 in diameter with an interparticle spacing of less than 1 is reported to maintain stable properties up to 2400°F.1 This stability of second phase results in maintenance of elevated-temperature strength at higher temperatures and longer times than normal nickel-base superalloys.2 The purpose of this paper is to describe the effect of various mechanical working operations on the strength and microstructural stability of TD Nickel bar. MATERIAL AND PROCEDURES All material used in this study was commercial TD Nickel bar. This material is produced by a chemical process which results in a nickel powder containing a dispersion of thoria particles. The powder is then pressed, sintered, extruded, and subsequently worked to bar stock. Three starting materials from three separate lots were used: as-extruded bar. 1-in.-diam stress-relieved bar, and 1/2-in.-diam stress-relieved bar. Since TD Nickel bar stock is cold-worked without a recrystalliza-tion anneal, the accumulated deformation or degree of cold work in these materials increases as the bar diameter decreases. Some of the 1/2-in.-diam bar was swaged to 1/4 in. diameter at room temperature in order to produce an as-worked condition for comparison with the stress-relieved stock. Tensile testing was performed on an Instron Tensile Tester at a constant crosshead speed of 0.020 in. per min. The 0.2 pct offset yield strength was measured from the load-crosshead movement plot. Specimen gage dimensions were 0.080 in. in diameter by 0.40 in. in length, producing a strain rate of approximately 0.050 min-1. Specimens were tested in air and heated within a resistance-wound furnace controlled to ±5°F. A 15-min soak at temperature was employed before testing. Samples were heat-treated in air and specimens machined after exposure with sufficient material removed to eliminate any surface contamination. X-ray line breadth was determined from a diffractometer scan of a transverse face of a bar using copper K, radiation. Metallographic preparation utilized standard mechanical polishing with Carapella's etch. Specimens for electron microscopy were electropolished in a 1:7 sulfuric/methaol solution and chromium-shadowed collodion replicas prepared. RESULTS AND DISCUSSION I) Effect of Elevated-Temperature Exposure on the properties of TD Nickel. The effect of various elevated-temperature exposures on the room-temperature tensile strength of TD Nickel is shown in Table I. In the unexposed condition the tensile strength, reduction in area, and hardness all increase with increasing accumulated deformation while the elongation decreases. After exposure at 2500°F the strength of all three materials decreases to about 65,000 psi and the elongations increase slightly. The apparent increase in strength of the 1-in. bar after a 2000°F treatment is probably experimental scatter. These results indicate that the room-temperature strengthening due to additional deformation is annealed out upon elevated-temperature exposure. In contrast to the room-temperature data, the 2000°F tensile strengths increase in order of increasing deformation even after exposure. Although some loss of strength occurs after exposure, much of the effect of working is still maintained at 2000°F. The room-temperature hardness after various

Jan 1, 1965

By R. E. Steiner, A. F. Weinberg, R. J. Van Thyne

Uranium solubility in molten bismuth was determined in the temperature range 350" to 600°C, varying from 0.09 wt pct to near 2 wl pct, respectively. Zirconium and magnesium, simulated fission products, and sodium were found to increase or decrease uranium solubility in bismuth in the temperature range 370° to 420°C, depending upon the addition or temperature. Data were obtained by both chemical analysis of samples obtained by filtration from saturated melts and by measurement of the variation of electrical resistance with temperature. IN a study for the United States Atomic Energy Commission, a Liquid Metal Fuel Reactor Experiment (LMFRE) was proposed in which a solution of uranium dissolved in molten bismuth served as both the fuel solution and the primary coolant. It was proven necessary to add other elements to this solution for certain desirable properties: 1) zirconium acts to prevent reaction of the fuel solution with the graphite core (which would result in the formation of uranium carbide) and also to inhibit mass transfer of iron and chromium from the walls of the reactor tubing to cold spots resulting in blockage; and 2) magnesium acts as a deoxidant and prevents loss of uranium. In addition to these intentional additives, other elements entering the solution are: 1) fission products which are a by-productof reactor operation, 2) sodium (the secondary coolant) through possible small leaks in the heat exchange system, and 3) iron and chromium from the container walls. Each of these elements may affect the solubility of uranium in the fuel solution. Since the concept of this reactor is based upon a liquid solution, the relatively low solubility of uranium in bismuth will dictate the minimum temperature at which the reactor heat exchanger can be operated. The solubility of uranium in liquid bismuth and the effect of some additives on this solubility have pre- viously been investigated1-' (more recent results6" became avaliable after initiation of this investigation). However, some discrepancies between the various results have been noted, and also the cumulative effect of the several additions or impurities was not known. This investigation was commenced to obtain definitive results. MATERIALS Analyses of the materials used are presented in Table I. Although ostensibly of extreme purity (99.999 wt pct), the bismuth was found to contain a significant amount of impurities, probably oxides. Except for determination of the binary system, Bi-U, prior to use all bismuth was hydrogen-refined and

Jan 1, 1962

By Allan Martin, R. A. Swalin

Diffusion rates of manganese, aluminum, titanium, and tungsten in nickel were measured at temperatures between 1100° and 1300°C. Activation energies, Q, and values of the frequency factor, Do, were calculated for each system. Values of Q were found to be within 15 pet of that for self-diffusion of nickel in agreement with present theories of diffusion. ONE of the most interesting problems in diffusion concerns factors governing the order of diffusion coefficients of various solutes in a common solvent metal at low solute concentrations. An early suggestion by Rhines and Mehl' was that diffusion coefficients might each approach that of the self-diffusion coefficient of the solvent itself. Later Thomas and Birchenall' pointed out correlations between the order of the diffusion coefficients and the freezing point depressions of the solvent by the various solutes. Other correlations have been sought. To settle this question it seems likely that much more data will be needed and, in particular, data collected at low solute concentrations. This type can be obtained by special analytical techniques as well as by use of radioactive tracers. The following study was made of diffusion of manganese, aluminum, titanium, and tungsten in a common solvent, nickel, at relatively low solute concentrations: 1—Production of alloys of nickel with manganese, aluminum, titanium. and tungsten at concentrations of the order of 1 atomic pet. 2—Use of pressure-welded diffusion couples in cylindrical form. 3—Diffusion anneals in the temperature range of 1100" to 1300°C. 4—Lathe sectioning of the diffused couples. 5—Spectrophotometric analyses of lathe turnings for the solute being studied. 6—Calculation of the diffusion coefficient for each of the solutes as a function of temperature. 7—Interpretation of results with current theories of diffusion. Experimental Work Materials—Two types of nickel were used in this research. The grade designated as Vacuum melted Mond nickel was used for all diffusion systems except the Mn-Ni system for which the Vacuum melted electrolytic nickel was used. Analyses of the two grades are given in Table I. The manganese used in making alloys was 99.9 + pet pure, aluminum 99.99 pet pure, titanium 99.9 pet pure, and tungsten of C.P. grade powder. Alloys used in this investigation were prepared by melting in vacuo or under a low pressure of argon. After melting, all heats except those of nickel-manganese were poured into a cylindrical copper mold 3 in. long and 1 in. ID. In the case of nickel-manganese, the alloys were solidified in the melting crucible. For nickel-aluminum heats alumina crucibles were used and for all other heats, zirconia crucibles.

Jan 1, 1957

By R. S. Dean

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

Jan 1, 1944

By David W. Kennedy, Stephen P. Harrison

In the past few years, a new system has been developed for ventilating longwall panels in some gassy coal mines in the Northern West Virginia area. This system utilizes a five or six foot diameter air shaft to ventilate a group of three or more longwall panels dependent on conditions. This shaft exhausts all the air needed to, ventilate the active longwall and adjacent gob areas. By law, this bleeder fan can handle double the maximum methane concentration allowed in a normal return air course. As a result, the methane that must be diluted by the primary ventilation circuits is reduced. This new ventilation system was first conceived by mine management as a means of coping with a sudden shift in production mode that occurred a few years ago. Formerly, production often consisted of room and pillar mining with continuous miners. The high methane liberation rate was handled by driving entries around a large block of coal prior to mining. This isolated the future mining area from the adjacent coal seam and allowed a major portion of the trapped in situ methane to bleed off. Also, these bleeders served to exhaust return air from the mining area. Once the bleeders were established, productive mining could start. When the decision was made to shift production mode from continuous miners to longwall mining, some of the bleeders did not encompass large enough unmined areas under the old ventilation system to initiate longwall production. Also, many other established continuous miner section bleeders were either improperly positioned or too restricted for longwall ventilation. Unfortunately, standard bleeder development can take up to two years' time. In order to eliminate the old style bleeder system and maintain or increase the margin of safety for ventilation, the bleeder shaft system was conceived. With this system, the only entries developed are those necessary for the longwall, significantly reducing the production delay. In this area, the Pittsburgh #8 coal seam dips to the northwest. As a result of this dip, the bleeder shaft is constructed in the northernmost set of tailgate entries. In this manner, groundwater accumulations can be pumped to the surface and bleeder entries kept dry. During the initial longwall entry development, the bleeder fan can be used to ventilate entries adjacent to virgin coal where significant methane liberation often occurs. Once longwall production starts, the bleeder shaft exhausts the entire air quantity necessary to safely ventilate the longwall. As the bleeder entries deteriorate, the air quantity and pressure characteristics must be increased. The extreme flexibility of the centrifugal fan used at the surface allows the air quantity and pressure to be adjusted without stopping the fan. This improves safety by decreasing the possibility of a methane buildup resulting from the fan being out of service. The bleeder shaft system of ventilation, developed by mine management in Northern West Virginia, can provide a safe means for effectively ventilating longwall panels in excessively gassy mines. This system should be considered where mining conditions are comparable.

Jan 1, 1982

By Ernest F. Burchard

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

Jan 1, 1931

By P. H. Lindon, J. C. Billington

Fe-O melts containing 0.045 pct 0 were deoxidized with Mn-Si-A1 alloys. Product compositions were reluted to the melt and alloy compositions and were found to be most sensitive to the aluminum content of the alloy. Low residual oxygen contents could be obtained when aluminum oxide was present in the Products because of the reduction of silica and manganese oxide activities. Flotation of the Products from a quiescent melt was followed both by analysis of the oxygen content and metallographic measurement of inclusion concentration. MnO-SiO2-A12O3 products were found to float most rapidly when their composition was such that their viscosity may be expected to be low. Changes in the particle size distribution indicates that particle coalescence occurred and differences in the degree of coalescence are thought to be responsible for the different flotation rates observed between products 0f differing composition. Measured flotation rates were slower than those Predicted from a model based on Stoke's Law, although alumina flotation might be reasonably accounted for by this model. Interfacial effects between oxide particles and the melt are believed to be responsible for the discrepancy. It has been recognized that deoxidation products constitute a large proportion of the nonmetallic inclusions present in killed steel. The amount of oxide inclusions which originate as deoxidation products depends largely upon three factors. These may be summarized, according to P16ckinger1 as: 1) Amount of primary products remaining in the steel prior to cooling. 2) Residual dissolved oxygen content of the steel after deoxidation. 3) Amount of secondary products, formed during cooling and solidification, which remain entrapped in the solid steel. In a well-deoxidized steel containing residual aluminum and/or silicon, the equilibrium dissolved oxygen content is usually very low and so the maximum amount of oxide which may be produced as secondary deoxidation products is small in comparison with the amount of primary products. It may be seen, therefore, that the amount of indigenous nonmetallic inclusions may be minimized if a low dissolved oxygen content is achieved by deoxidation and if the primary deoxidation products are efficiently removed. Oxides which originate by reaction of the metal stream with the atmosphere during teeming are not considered in the present study. It is known that two or more deoxidizers may result in a lower equilibrium oxygen content when used in conjunction with one another than when any of the individual deoxidizers are used alone. Equilibrium studies by Hilty and crafts2 and by Bell3 have shown that manganese increases the effectiveness of silicon as a deoxidizer, and Walsh and Ramachandran4 relate this to a reduction in the activity of silica in the products as the manganese :silicon ratio in the steel increases. It was also shown by Herty's work on deoxidation of steel by silico manganese alloys,5 that there existed an optimum ratio of manganese to silicon which gave a minimum inclusion content. This ratio was in the range 4:l to 7:l and the (FeO-MnO-SiO2) products formed by such deoxidation practice were found to lie in a composition range having very low liquidus temperatures (1170 to 1250°C approx). The optimum manganese:silicon ratio was then explained by postulating that these fluid products were able to coalesce and that the larger particles formed floated out of the steel very quickly as predicted by Stoke's Law. The present work examines the effectiveness of various Mn-Si-A1 alloys as deoxidizers and their effects on the composition and removal of primary deoxidation products from a quiescent melt. EXPERIMENTAL TECHNIQUE Approximately 250 g of prepared Fe-O alloy, containing 0.045 to 0.055 pct O, were melted in an alumina crucible and deoxidized at 1550°C by plunging a thin steel cartridge containing the deoxidizer below the melt surface. A high frequency induction furnace supplying current at 8.5 kHz was used to heat a graphite susceptor, the interior of which had been machined to give a wall thickness of 0.85 in. to form a receptacle for the alumina crucible. The iron melt was essentially quiescent as the induced current was concentrated at the external surface of the graphite susceptor by the skin effect. A nonoxidizing atmosphere was maintained over the melt by passing a continuous stream of argon through the lid of the susceptor. The melt temperature was measured before deoxidation, and again at the end of an experiment by means

Jan 1, 1970

By E. W. Davis

IF the tonnage of merchantable iron ore remaining in the Lake Superior district is divided by the average of the annual shipments for the past 20 years, it will be found that this ore supply will be exhausted in approximately 35 years. This computed exhaustion period would be an indication of the future activities of the iron-mining industry if it were not for the fact that merchantable ore is being manufactured from low-grade ore, of which there is an almost inexhaustible supply in the Lake Superior district. It is true that at present only the simplest of these low-grade ores are being concentrated to any considerable extent, but progress is being made with the treatment of the more complex ores, and now, in addition to 20 washing plants on the Mesabi Range, three plants are equipped with jigs for the treatment of ore that cannot be concentrated simply by washing. The latest addition to the ore-treating plants of the Mesabi Range is a magnetic roasting and concentration plant at Cooley, Minn., in which ore that cannot be concentrated either by washing or by jigging is roasted to the magnetic state and concentrated on magnetic separators. This plant is beginning its third season of operation, and while it is too soon to make definite predictions, there are strong indica-tions that this new process may make commercially possible the manu-facture of high-grade, merchantable iron ore from large quantities of low-grade ore now considered worthless. After the iron oxide contained in an ore has been converted to mag-netite, almost any desired grade of concentrate can be produced, using magnetic-concentration equipment of the types now in general use for the concentration of the natural magnetites of New York, New Jersey and Pennsylvania. The conversion of hematite (Fe2O3) to magnetite (Fe3O4) is easily accomplished by heating the ore to a dull red tempera-ture in a reducing atmosphere. The reaction is slightly endothermic, and while it requires 200 B.t.u. to heat to 900° F. one pound of hematite ore containing 45 per cent Fe, it requires only 100 B.t.u. to convert the oxide into magnetite. In the laboratory, using small quantities of ore, this conversion is very simple, but large furnaces suitable for commercial

Jan 1, 1936

By O. George Specht, Carl A. Zapffe

In recent print, some remarkably contradictory statements have appeared regarding the importance to be attached to sponge Iron,1-6 a metallurgical commodity whose history goes back at least to the time of Diodorus Siculus in the fourth century B.C. This disagreement, however, expresses the lack of a satisfactory method for producing sponge iron rather than defection in the commodity. The blast furnace is admitted to have certain inherent disadvantages, such as a general unsuitability for magnetite and the heating and blowing of vast quantities of undesirable nitrogen, so that a workable sponge-iron process remains attractive. In this respect, low-temperature gaseous reduction shows especial promise; but confusion persists regarding the factors involved. The present paper, therefore, has three principal divisions: (I) an exhaustive examination of all previous work on low-temperature gaseous reduction, (2) experi- mentation on the reduction of a magnetite with hydrogen, and (3) development of certain thermodynamic relationships in reduction, with a summarized depiction of the factors in the general process. PREVIOUS INVESTIGATIONS Gaseous media used in the reduction processes under discussion can be classified in three types: (I) H2, (2) CO, and (3) other gases. In the second, the CO is often admixed with H2. The third principally comprises hydrogeniferous gases, such as natural gas and producer gas, and in addition includes chlorine. Because hydrogen therefore features in all three, a study of hydrogen reduction based on investigations using pure hydrogen alone may be incomplete. The present paper reviews the three groups of investigations in the listed order, paying particular attention to hydrogen reduction. For the benefit of future workers, an exhaustive bibliography has been prepared and similarly classified. Group I: Reduction with Hydrogen Equilibria Although the present problem is specifically one of kinetics, a first consideration is the equilibrium of the system, since the reactions to be studied comprise that equilibrium, and their direction and end points are defined by it. The historic development of these researches is interesting and informative.

Jan 1, 1947

By Robert A. Rapp, Jan E. Verfurth

From the measurement of internal-oxidation band widths in Ag-In and Cu-A1 alloys, products for the solubility No and the diffusivity Do of oxygen in silver and apparent NODo products in copper have been obtained over a range of temperature. The NODO products for silver are in agreement with the product of the individually determined No and Do values of Eichenauer and Müller. Although interstitial diffusion of oxygen in silver is expected, the temperature-independent factor Do of the diffusion coefficient does not agree well with the theory of Wert and Zener. For Cu-A1 alloys internal oxidation does not follow the expression derived for ideal kinetics, since the apparent NODo product calculated from internal-oxidation measurements is a function of the alloy content in the specimen. Thus, unequivocal values for No or DO or even the product NODO in copper are not available from the literature. RELIABLE values for the saturation solubility NO and diffusivity DO of oxygen in fcc metals are lacking and difficult to determine, partially because internal-friction measurements are not applicable. Permeability experiments and Sieverts7-type adsorption -desorption methods3 have met with difficulty; however, Eichenauer and Müller4 have recently reported on the solubility and diffusivity of oxygen in silver as determined by the latter technique . Rhines, Johnson, and Anderson,5 and independently Meijering and Druyvesteyn,' introduced the possibility of deriving values for the product NODO in a metal from measurements of the widths of internal-oxidation zones (subscales) formed during the internal oxidation of alloys. In addition to these authors, several other investigators7-9 have made such measurements in various silver and copper alloys at various temperatures, mostly using me- chanically polished specimen surfaces. The purpose of this investigation was to determine over a range of temperature the calculated products NODO in silver and copper from systematic measurements of the widths of internally oxidized zones in Ag-In and Cu-A1 alloys, using specimens with electro-etched surfaces. Consider the internal oxidation of a dilute solid-solution alloy in which the base metal is not oxidized. If diffusion of oxygen is the rate-controlling step, then the depth 5 of the internal-oxidation zone is given by where y is a dimensionless parameter and t the oxidation time. Based on the solution of the diffusion equation, wagnerl0 has shown that under certain conditions several mathematical simplifications may be used in the evaluation of y, so that Eq. [I] may be expressed for the case that y « 1, and y(Do/DB) 1, where N(so)the is the equilibrium solubility (mole fraction) of oxygen in the solvent metal for the given oxidizing atmosphere, is the mole fraction of the solute metal in the bulk alloy, 4 is the diffusivity of the solute in the base metal, and v is the ratio of oxygen atoms to solute atoms in the precipitated oxide BO,. Rearranging Eq. [2] Maak' has derived an expression analogous to Eq. [3] for the case that an external-oxide scale, in addition to an internal-oxidation zone, is formed. For this combined external and internal oxidation for the case that 5/2 where 5 is the distance of the internal-oxidation front from the original external s.urface, and X is the distance of the external oxide/metal interface from the original external interface. The function F is defined by the expression

Jan 1, 1964

By W. A. Forbes

PAGE Introductory............357 ReasoNs for Gas Cleaning.........358 First Methods of Separation of Dust.......359 Amount of Dust Produced by the Blast Furnaces of the United States Steel Corporation During 1912.....359 Dust Content in Blast-Furnace Gas.......360 Primary Cleaning. Dry Cleaning: General Remarks..........360 Braasert- Witting Whirler........362 Brassert Modifications of Brassert-Witting Whirler....363 Dyblie Whirler..........363 Remarks on Efficiency of Dry Cleaning......366 Wet Cleaning: Zschocke System..........367 Duquesne Tower..........367 Bian Gas Washer..........369 Final Cleaning. Wet Cleaning: Theisen Gas Washer.........371 Theisen Disintegrator Gas Washer.......372 Schwerz-Bayer Disintegrator Gas Washer..... 374 Fowler & Medley Vertical Gas Washer......376 Feld Gas Washer..........377 Reco Centrifugal Gas Washer........379 Sepulchre Gas Washer.........381 Dry Cleaning: Halberger-Beth Gas-Cleaning System......382 Smith.Bagley Gas-Cleaning System,......384 Howard Dust Separator.........387 Possible Separation of Dust by Electrical Precipitation ... 389 KapnOGraph............389 Methods of Determining DUst in Gas.......389 Advantages of Clean Gas.........393 Introductory. During the early stages of blast-furnace practice. the gas formed in the furnaces by the combustion of the coke used in smelting the ores was allowed to escape into the atmosphere. The light furnished

Jan 1, 1914

By K. G. Wikle, W. W. Beaver

A general survey of the mechanical properties of commercially pure beryllium fabricated from powder by vacuum hot pressing and other consolidation methods is presented. The effect of fabrication method, grain size, strain rate, and directionality upon both room and elevated temperature tensile properties is reported. BERYLLIUM metal, in spite of its rather restricted use, has been the object of attention for many researchers in the past half century. However, such work was performed on special experimental lots of metal made in small quantities by a variety of reduction methods. Not until 1946 was there a substantial production of beryllium metal, and not until 1950 was there a steady production of a commercially standard beryllium in the United States. This output was both the result of a requirement of the Atomic Energy Commission for a high grade beryllium of consistent quality and the development of a powder metallurgy process, by the Brush Beryllium Co., known originally as Process Q, which yielded a fine grained beryllium suitable for fabrication. Because this powder metallurgy product, known as QMV, superceded other types of metal made previously and represents the great majority of beryllium in use today, it seems worthwhile to present the results of studies on the mechanical properties of this metal as currently made. To the design engineer and the metallurgist, beryllium has extremely interesting properties. It is as light as magnesium alloys while having a stiffness modulus 40 pct greater than steel and a strength-weight ratio superior to titanium and aluminum alloys and aircraft steels. The melting point is high, 1287°C (2348°F), and it has good corrosion resistance both in air and water. Also, it is highly transparent to X-rays and has good heat and electrical conductivity (electric conductivity is greater than 40 pct of Cu). To the atomic energy program beryllium is considered a valuable material because of its low neutron-capture cross section and high neutron-scattering cross section which make it a good moderator and reflector for the lower velocity neutrons. A major technical difficulty limiting the use of beryllium, especially in structural applications, has been its notch sensitivity and consequent room temperature brittleness. Kaufmann, Gordon, and Lillie1 have reported their work on the mechanical properties of beryllium performed from 1946 to 1950. They studied the room and elevated temperature properties of cast and extruded beryllium and extruded electrolytic flake, Table I. Cast and extruded alloys of 85 to 99 pct Be were tested also. They found that extruded metal developed good strength and appreciable ductility in the extrusion direction and that thermal treatment and alloying provided little improvement in mechanical properties. They concluded that preferred orientation and fine grain size were the means of obtaining optimum tensile properties in beryllium. Other investigators have measured and commented on one of the most striking mechanical properties of beryllium, namely, its abnormally low Poisson's ratio.2 Udy, Shaw, and Boulger3 presented the latest published survey on properties of beryllium but their information is based only on published data available before April 1949 and cites little information on metal fabricated by powder metallurgy

Jan 1, 1955

By Charles S. Barrett, Herman F. Kaiser, Robert F. Mehl

The copper-silver system presents several points of special interest in the study of segregate structures. The system is simple eutectic, with limited solid solutions terminal with the pure component metals. The extent of solid solubility decreases with decreasing temperature for both the copper-rich and the silver-rich alloys, thus offering a possibility for the formation of Widmanstätten figures and also a possibility for aging after quenching. In contrast to the structures studied previously the structures in this system are unique in their origin, for one terminal solid solution will precipitate the other, and vice versa. In most of the other systems for which crystallographic data on the precipitation (or transformation) process arc available, either intermetallic compounds or intermediate phases partake in the decomposition process; the absence of such phases thus distinguishes this system. The lattice structures of the two solid solutions are identical in type, differing in lattice spacing by approximately 10 per cent; because of this it seems difficult if not impossible to predict on the basis of present theory either the outward form of the precipitate or the lattice orientation relationships between matrix and precipitate. The eutectic temperature in the copper-silver system' is 779" C. At this temperature copper dissolves 4.3 atomic per cent (7.0 weight per cent) of silver in solid solution; this solid solubility decreases to zero at room temperature.² Silver at the eutectic temperature rctains 14.0

Jan 1, 1935

By C. N. J. Wagner, E. N. Aqua

Dilute Fe-Si alloys (0 to 5 wt pet Si) were cold-worked by making filings at room temperatuve. The analysis of the broadening of the X-vay powdev pattern peaks yields anisotropic particle sizes normal to the (110), (100), and (112) planes which are a consequence of deformation faults (probability a) and twin faults (probability p). The combined fault probability (1.5a +ß) increases from 0.01 in pure iron to 0.02 in Fe-5 pct Si. The root mean square stvains vary with crystallographic ovientation due to elastic anisotropy of the alloys, and increase from about 0.0035 in pure iron to 0.005 in Fe-5 pct Si measured in the [100] direction. Assuming that deformation and twin faults occur with equal probability, the X-ray data would imply that the stacking-fault energy does not change upon alloying. THE crystallographic aspects of the plastic deformation of dilute Fe-Si alloys has been studied many times since the observation of glide band structures by Barrett et a1.l These glide bands were much straighter than the wavy bands observed by Gough2 in unalloyed iron nearly 40 years ago. This difference in the morphology of the slip band structure has been verified many times, most recently by replication electron microscopy3 and dislocation etch-pitting methods.4,5 These observed differences in deformation behavior have been considered to result from the degree of cross slip that occurs in pure iron and in the Si-Fe alloys. The lowered tendency for cross slip would result from a lowering of the stacking-fault energy of iron by the silicon alloying addition. Experimental evidence for this lowered stacking-fault energy in the Si-Fe alloys, obtained with transmission electron microscopy, is the observation of dissociated dislocations in Fe-6 pct si6 and Fe-3 pct Si alloys,7 and the observation of sharply defined cellular substructures in Fe-3 pct si6,7 compared to the more diffuse substructure in zone-refined iron.' The activation energy for recovery of cold work is greater in the Si-Fe alloys than it is in pure iron, indicating that cross slip has become a more difficult process.9 The purpose of this investigation is to determine the change in stacking-fault probability from the broadening of powder pattern peaks in dilute silicon-in-iron solid solutions, when cold-worked at room temperature. The knowledge of the stacking-fault probability and the dislocation density, both of which can be deduced from line-broadening analysis of two orders of reflections from (110), (200), and (112) planes, will permit us to calculate the change in stacking-fault energy upon alloying silicon into iron. Previous X-ray investigation of cold-rolled Fe-5 wt pct Si (100)[001 ] single crystals did not reveal any line broadening, whereas cold-rolled Fe-3.1 wt pct Si (001) [110] and (001)[100] single crystals10 showed line bro2dening as a consequence of small particle sizes (-200A) and root mean square strains (-0.25 pct), which are comparable to those found in cold-worked iron filings.11 EXPERIMENTAL PROCEDURE A series of five Fe-Si alloys containing nominally 1 to 5 wt pct Si and pure iron were cold-worked by making filings at room temperature. The actual silicon content deviated at the most by +0.1 pct which is of no significance in the present study. The carbon contents of these materials were less than 0.02 pct. The X-ray diffraction patterns were measured with molybdenum, cobalt, and iron radiation using a GE and a Philips diffractometer. The (110)-(220), (200)-(400), and (112)-(224) pairs of reflections were

Jan 1, 1968