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By C. S. Roberts

The creep mechanism and kinetics of fine-grained magnesium have been studied over the temperature range 200&apos; to 600°F. As a result of a photographic study of microstructural changes, transient and steady-state creep components have been correlated with slip, subgrain formation, and cyclic deformation at the grain boundaries. THE approach of this research has been the blend of a quantitative study of the creep strain of polycrystalline magnesium as a function of time, stress, and temperature with direct microstructural observations of the operative deformation processes. The validity of the conclusions is dependent on the condition that the microstructural changes seen on the polished surface qualitatively represent those occurring in the bulk of the metal. The work was intended as much to lay a background to a study of highly creep-resistant magnesium alloys as to provide a description of the behavior of the base metal itself. The spectroscopic analysis of the electrolytic magnesium used in this study is as follows: Al, 0.009 pct; Ca, <0.01; Cu, 0.0011; Fe, 0.021; Mn, 0.012; Ni, 0.0004; Pb, 0.0012; Si, <0.001; Sn, <0.001; and Zn, <0.01. The impurity level is approximately that of commercial magnesium alloys. The original ingot was melted under Dow type 310 flux and cast as a 3 in. diam billet. It was extruded into 1 in. flat stock under the conditions: billet preheat 800°F (1 hr), container and die temperature 800°F, speed 3 ft per min, and area reduction ratio 45:1. The extrusion process was chosen in preference to rolling and recrystallization because it allowed easier grain size control from specimen to specimen. The grains of the extruded metal were fairly equi-axial and uniform in the size range of 4 to 6 thousandths of an inch. The preferred orientation of basal planes about the transverse direction was determined by an X-ray diffraction surface reflection method. A beam of filtered copper radiation was directed at an angle of 17" to both the transverse direction and the surface yet perpendicular to the extrusion axis. Analysis of the (002) diffraction arcs in the resulting photographic patterns gave an approximate intensity distribution along the great circle which extends through the center of the basal plane pole figure and to the extrusion axis poles. Successive layers of metal were removed by macro-etching between exposures. The extruded texture is relatively sharp, but the most significant point is the position of the maximum basal plane pole density and its variation with depth below the surface. Fig. 1 shows that this maximum is rotated 15" from the normal at the surface toward the extrusion direction. Such an inclination has been reported for extruded 1 pct Mn and 8 pct A1-0.5 pct Zn alloys.&apos; The inclination decreases until the maximum splits at about 0.025 in. depth into two elements of equal and opposite rotations from the ideal. The double texture persists to as great a depth as was experimentally convenient to examine. It probably continues to the very center of the extrusion. There is no great change in the sharpness of the individual elements of the texture with depth. A plate of metal about 0.015 in. thick at the surface of the extruded stock was produced by etching. A transmission diffraction pattern was made for the purpose of determining any preferred orientation of a direction in the basal planes. Relatively uniform {loo) and {101) rings were produced. There is little tendency for parallelism of a given direction in the plane with the projection of the extrusion axis on it. The creep specimens were machined from 6¼ in. lengths of the extruded stock. Creep was measured on the reduced section, ½x1/8X2¼ in. long. This section was electropolished on one side for the studies of microstructural changes during creep. An orthophosphoric acid-ethyl alcohol electrolyte was used under the conditions recommended by Jacquet.² Hand polishing was used for previous mechanical preparation. Electropolishing was continued until all mechanical twins had been removed. The electro-polished surface was protected from oxidation during creep testing by a thin layer of silicone oil. All micrographs were taken at room temperature on conventional metallographic equipment and after removal of the oil film. The creep tests were performed with machines which have been described in detail by Moore and McDonald." Five testing temperatures, 200°, 300°, 400°, 500°, and 600° ±3°F were used. Difference in temperature between the two ends of the specimen reduced section was 2°F or less. The testing was done at constant load. Strain readings were taken as frequently as necessary to develop usable creep curves. Tensile Creep vs Time, Stress, and Temperature A definition of terms is necessary. Whenever successive sections of a creep strain-time curve show decreasing, constant, and increasing slope with time they will be termed primary, secondary, and tertiary

Jan 1, 1954

By W. D. Robertson, Raymond C. Boettner

A study was made of the change in density during the first (transient) and second (linear) stages of the creep curve of polycrystalline copper as a function of 1) stress, 2) temperature, 3) plastic strain, 4) impurity and atmosphere effects, and 5) structure, including single crystals. Voids were not observed in single crystals strained 15 pct at 500°C, or in a polycrystal-line aggregate produced by recrystallizing a single crystal, within the limit of sensitivity, Ae/e = 1 x 10-4. It appears that voids are heterogeneously nucleated at grain boundaries by an insoluble phase, or phases, which can be removed by directional solidification. The principal controlling mechanism of void growth appears to be condensation of vacancies at grain boundaries. Vacancies are transported to a boundary and condense as a consequence of the tensile stress component across the boundary, which depends on the orientation and configuration of the boundary plane and on boundary shear across ledges and other irregularities. The ultimate source of vacancies is the free surface and diffusional transport is by way of the boundary plane. PREVIOUS investigations have dealt with the nucle-ation of voids at grain boundaries under creep condition~&apos;-~ and with the connection between grain boundary voids and subsequent brittle fracture.5-7 Growth of voids during the creep process, particularly in the transient and linear stages of creep, has not been studied with the same intensity. Therefore, it seems pertinent to investigate the process of void growth with respect to the related creep curve, and the morphology of growing voids with respect to the structure.

Jan 1, 1962

By G. R. Pickett

Examples are presented which show that the velocity~ amplitude, attenuation and apparent frequency of several acoustic waves can be recorded in the borehole. Examination of such recordings, termed "character" logs, indicates that the wave types observed include a refracted compressional wave and a wave which travels with formation shear velocity. Laboratory data are used to show that compressional and shear wave velocities are dependent on porosity, effective stress and lithology; but that the change in reciprocal velocity per unit change in porosity is larger for shear waves than for compressional waves. We, therefore, conclude that. the accuracy of porosity determinations can sometimes be improved by use of shear wave velocities, provided that the shear wave amplitudes are large enough to delineate the shear arrival from the preceding compressional arrival on the character log. Borehole data are presented which show that the difference between shear wave and compressional wave reciprocal velocities can be used to predict porosities. This is a refinement which may allow the prediction of porosities from single-receiver acoustic logs without introduction of errors from borehole fluid traveltimes. Laboratory and field data are presented to show that the relationship between compressional and shear wave velocities can be used to indicate lithology. An example is presented to show that fractures usually cause a greater reduction in borehole shear wave amplitudes than in compressional wave amplitudes, an effect which may offer a more reliable means of detecting fractures. The complexity of the borehole acoustic wave train can rake presently available cement bond logs highly sensitive to the gate and bias settings used. The character log offers a means to circumvent possible misinterpretations by recording all amplitudes, from which the interpreter can select the appropriate data for evaluating the cement bond. Character logs may also be used as a quality control for open-hole transit-time logs when existence of small compressional wave amplitudes interferes with the proper functioning of bias-controlled timing devices. Evaluation of the potential uses of character log data is not complete; but a character log presented in a form convenient for routine use would be a desirable addition to currently available logs. To summarize, possible applications for such a log in formation evaluation include the following (1) quality control of transit-time logs, (2) refinement of porosity predictions, (3) determination of lithology, (4) improvement of fracture detection and (5) improvement of cement bond evaluation. Suggestions are made regarding the requirements for a suficient but practical character log for routine use. INTRODUCTION Acoustic logs have become a widely used porosity tool in formation evaluation. In addition, there is a growing application of acoustic logs in cement bond evaluation and fracture detection. These applications have mainly involved the use of logs of first-arrival transit times and amplitudes and have not included detailed studies of the complete signal. The purpose of this paper is to show that significant benefits in formation evaluation can be gained by a more complete use of the acoustic wave train generated in the borehole by an acoustic logging tool. We hope that this discussion will also stimulate further development of logs suitable for routine use so that these benefits may be realized. Examples of acoustic wave train logs, termed "character" logs, are presented to show that several identifiable acoustic waves are present in the borehole. The measurable characteristics of these acoustic waves and some of their relations to formation properties of interest are also discussed. The more obvious potential uses of character logs are listed, and some suggestions are made regarding the requirements for a sufficient but practical character log for routine use. CHARACTER LOGS Some 10 years ago, Vogel&apos; and Summers and Broding&apos; noted that the signals received uphole from an acoustic logging tool located in a borehole had a number of interesting characteristics. The logging tool consisted of two or more pressure transducers spaced on an acoustically insulated body (Fig. la). One of the pressure transducers was used as a transmitter to generate pressure waves in the borehole fluid. The other transducer served as a receiver to detect any pressure waves reaching it in the borehole. The receiver then converted these pressure waves to electrical signals which were transmitted to the surface and displayed on an oscilloscope as a record of time vs receiver-signal amplitude. Fig. lb is a schematic representation of a typical record. The interesting characteristics seen in the earlier&apos; and subsequent experiments were (1)

By L. Delisle

This work represents the first step of an attempt to test the applicability of the electron microscope to the study of subgrain structures in copper. Observations on annealed and deformed single crystals and polycrystalline samples of copper are described. IN the course of study of the structure of fine tungsten wires and tungsten rods with the electron microscope, well defined subgrain structures were observed. The size, size distribution, and orientation uniformity of the etch figures varied widely in different samples. Figs. 1 and 2, electron micrographs of a tungsten wire and of a tungsten rod, respectively, are illustrations of the difference in size and size distribution of the etch figures in different samples of the same metal. The observed differences, as pointed out in a previous paper,&apos; appeared to be related to the heat and mechanical treatments of the samples. They were also consistent with the results reported in the literature on the mosaic structure of metals.&apos; For that reason a program of research was initiated in an effort to obtain more systematic evidence of the possible relation of heat and mechanical treatments to the subgrain structure of metals as observed in the electron microscope. The purpose of this paper is to present observations made on the effect of cold work on the subgrain structure of copper. Procedure Starting Materials: Copper was the metal studied because it can be obtained in a high degree of purity, much information is available in the literature on its properties and its response to cold work and heat treatment, it shows no allotropic change, and it is sufficiently hard to be handled without great difficulty. Two groups of specimens were used: 1—single crystals cast from spectroscopically pure copper and 2—polycrystalline samples of oxygen-free high conductivity copper. Single crystals were studied because it was hoped that the elimination of a number of variables, such as grain boundaries, orientation differences, degree of purity, would simplify the problem and perhaps permit a better understanding of the phenomena that would be observed. The polycrystalline samples were designed to give a general picture of the changes considered. The single crystals were made of copper which analyzed spectroscopically to better than 99.999 pct Cu. They were cast in vacuum, by the Bridgman method, in crucibles made of graphite with a maximum ash content of 0.06 pct. The mold design is shown in Fig. 3. It permitted casting crystals of the size and shape required for the experiments, so that the danger of introducing cold work in the original samples by cutting or other machining would be eliminated. The polycrystalline samples were pieces, 3/4 in. long, cut from a rod of oxygen-free high conductivity copper, % in. in diameter. A flat surface, 1/4 in. wide, was milled along the rods, polished, and etched. The samples were then annealed in vacuum at 850°C for 1 hr. Polishing and Etching: Work previously done on tungsten,&apos; polished mechanically and etched chemically," had shown that: 1—the general appearance of the etch figures of a given sample was not altered by repeated polishings and etchings under similar conditions; 2—variations in the time of etching and the concentration of the etchant changed the definition of the etch figures, but did not alter their general size nor orientation distribution within the limits of observation. Further work confirmed the reproducibility of the subgrain structures observed in, 1—single crystals and polycrystalline samples of copper when polishing and etching were repeated under similar conditions, and 2—specimens of tungsten and polycrystalline copper when electrolytic polishing and etching were substituted for mechanical polishing and chemical etching, respectively. On the strength of these observations, it was felt that, if conditions of polishing and etching were kept constant, changes observed in the subgrain structure of a sample upon deformation and annealing would be attributable to such treatments. For that reason the conditions of polishing and etching were kept as constant as possible. The single crystals were polished electrolytically in a bath of orthophosphoric acid in water, in the ratio of 1000 g of acid of density 1.75 g per cc to 1000 cc of solution, under a potential drop of 1.6 to 1.8 V. Electrolytic polishing was selected to prevent the formation of distorted metal in polishing. The same samples were etched by immersion in a 10 pct aque-

Jan 1, 1954

By R. M. Jorda

The mechanism of parafin deposition and prevention has been studied in the laboratory using an apparatus which provides a quantitative means of studying parafin deposition on metal and plastic surfaces. The amount, hardness, adhesion, per cent wax and mean molecular weight of parafin deposits appear to be governed by surface roughness alone, all other conditions being constant. Tests of various plastic coatings indicate that most smooth, nonparafinic plastics are capable of reducing parafin deposits in oil wells, but flexible, highly polar, nonparafinic plastics are more suitable for providing long term resistance to parafin deposition in oil wells if the flow stream contains abrasive materials. INTRODUCTION The problem of paraffin deposition is one of long standing in the oil industry.&apos; Crude oils often contain paraffins which precipitate and adhere to the liner, tubing, sucker rods and surface equipment as the temperature of the producing stream decreases in the normal course of flowing, gas lifting or pumping. Heavy paraffin deposits are undesirable because they reduce the effective size of the flow conduits and restrict the production rate from the well. Where severe paraffin deposition occurs, removal of the deposits by mechanical, thermal or other means is required, resulting in costly down time and increased operating costs. The troublesome paraffins are normal hydrocarbons ranging from approximately C15H38 to C38H78 mixed with small amounts of branched paraffins, monocyclic paraffins, polycyclic paraffins and aromatics.&apos; The amount of paraffins found in crude oils varies from less than 1 to more than 30 per cent. Many publications are available which deal with this problem, and perhaps the most significant findings in recent literature are contained in a publication by Hunt3 ho developed the "cold spot tester", a really useful means of investigating paraffin deposition. Hunt&apos;s observations led to many generalized conclusions concerning the effect of surface roughness on paraffin deposits. He ascertained that there was an observable qualitative correlation between the severity of paraffin deposition and the roughness of the surfaces which he tested (cold rolled steel, stainless steel and several plastics). Because of the number of meaningful observations made by Hunt, his cold spot tester was modified somewhat and extensive tests were per- formed to study the quantitative relationship between surface roughness and the physical and chemical nature of paraffin deposits. LABORATORY TEST PROCEDURES The cold spot test apparatus consists of a flat circular plate mounted on a curved tube and positioned in a vessel containing a wax-oil solution (Fig. 1). The apparatus is arranged so that the temperature of the central portion of the circular plate can be varied by means of a circulating liquid stream; the test equipment includes provisions for maintaining a constant wax-oil solution temperature and stirring speed. In the paraffin deposition studies, the modified cold spot tester was used as follows. The cold spot probe consisted of a flat circular plat 2 in. in diameter and 1/8-in. thick positioned in the wax-oil solution kept at constant temperature. As in Hunt&apos;s earlier experiments," a cold liquid was circulated through a tube connected to the circular plate so that the liquid impinged on one side of the plate cooling the plate from the center outward, causing paraffin to deposit on the side of the plate exposed to the wax-oil solution.

Jan 1, 1967

By H. T. Sumsion, A. U. Seybolt

The results of an investigation of vanadium-rich V-O solid solutions are presented, indicating the structure and lattice parameters of two solutions, a and ß, and their approximate temperature-composition existence. The a solution is the terminal body-centered cubic one, and contains up to 3.2 atomic pct 0. The ß solution has an ordered body-centered tetragonal structure, is formed at 1270°C, and exists from about 15 to 22 atomic pct 0. From the evidence available, the various phase boundaries have no appreciable temperature dependence. Evidence has been found for a polymorphic transformation in pure vanadium at 1550°C. IN an earlier investigation&apos; dealing with the preparation of pure vanadium by calcium reduction of the oxide, it was found that small amounts of oxygen drastically reduced the ductility of the metal. Because this effect was so marked, it was decided to make a study of the solubility of oxygen in solid vanadium. This report deals principally with this solubility and the nature of the phase relationships in the vanadium-rich region, particularly at temperatures below 1300 °C. However, during the investigation enough data on the V-0 system were obtained to make it appear worthwhile to present a tentative phase diagram up to the composition VO. The only significant prior work found on this system are the contributions of Klemm and Grimm,&apos; and Mathewson et al.3 Klemm and Grimm prepared a wide range of V-O compositions by powder techniques including the compositions VO.l, VO.2, VO.3 and VO4 (9.1, 16.8, 23, and 28.6 atomic pct 0, respectively). The first three compositions were found to consist of a body-centered tetragonal solid solution, while the last also showed lines of VO (NaCl structure). They found that the parameter c, increased and the parameter a, decreased with increasing concentration of oxygen. For their composition VO.27, or about 16.8 atomic pct O, they cite the values a, = 2.948A, c, = 3.53A, and c/a = 1.2. Klemm and Grimm made no attempt to determine the solid solubility limit nor to construct a phase diagram. They did, however, give some data on the homogeneity range of VO, and they proposed a structure for the body-centered tetragonal solid solution; these points will be taken up later. Materials and Preparation of Samples The vanadium used in this investigation was prepared in the laboratory by the method previously mentioned.&apos; A typical analysis is as follows: Fe, 0.007 pct; Si, 0.02; Ca, 0.06; C, 0.224; O2, 0.044; N,, 0.0017; H2, 0.003; and V, 99.34 ±0.3 (assay). The vanadium assay is probably low by about the error given. The impurities total about 0.36 which, if subtracted from 100, gives a purity of about 99.6. At the time material was being prepared for this work no suitable technique was available for melting vanadium without appreciable contamination. The procedure adopted therefore was to cut the calcium-reduced regulii into slices which were then rolled to strip about 0.025 in. thick for oxygen diffusion. Pieces of rolled vanadium of approximately 0.025xY4xl in. and weighing about 0.3 g were suspended in a vertical fused-silica tube which was part of an ordinary gas absorption apparatus. The silica tube was heated by an electric resistance-tube furnace which could be raised around the silica tube or lowered away from it as desired. This apparatus had no novel features which require detailed description. Other than the silica tube and furnace, it consisted of a glass system evacuated by a liquid nitrogen trapped mercury diffusion pump, a mercury-operated gas burette, a McLeod and a Pirani gage, and a mercury manometer. It was also equipped with suitably located stopcocks for isolating various parts of the system; the vacuum ordinarily attained was between 10" and 10-6 mm of mercury. Oxygen generated by decomposing MnO2 was passed through anhydrous magnesium perchlo-rate before introducing it into the gas burette and thence to the absorption chamber.

Jan 1, 1954

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&apos;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 F. A. Schaufelberger

METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.&apos; Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on page 545. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.&apos;s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.&apos; The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited3 to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SO2,4 which may lead to contamination with sulfur, or C0,5 which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents,7 which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere.&apos; It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution composition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.&apos; It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farben10 claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic, antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373ºC), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred, probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By A. E. Blakeslee

Morphological and electrical properties of GaAs epitaxial layers are influenced not only by changes in the nominal substrate orientation but also by small amounts of misorientation from the exact crystal planes. Deviations up to 5 deg from {11IA}, {11IB}, and (100) planes were investigated. Growth rates increase progressively with angle, approximately I u per hr per deg. Size and density of growth pyramids fall off with increasing angle, but other effects that are deleterious to the surface may occur which are heightened by increased misorientation. Carrier concentration decreases and electron mobility consequently increases as the angular offset increases, except in the case of strong compensation, where the mobility trend is reversed. It has long been known that changes in the crystallo-graphic orientation of the substrate may cause pronounced effects on the morphological properties of vapor grown semiconductor films. Reports of orienta-tion-dependent growth rates and surface characteristics are as old as the literature on epitaxy itself. shawl has recently published a comprehensive study of the dependence of growth rate on substrate temperature and orientation in epitaxial GaAs. It is also well-known that misorienting the substrate surface a few degrees away from the nominal low-index crystal-lographic plane often produces a much smoother epitaxial surface. This was reported by Tung2 for silicon, Reisman and Berkenblit3 for germanium, and by Kontrimas and Blakeslee4 for GaAs, and use is commonly made of this fact in the semiconductor industry to help guarantee smooth vapor deposits. The effects of substrate orientation on the carrier concentration and mobility of vapor grown GaAs were first documented by williams5 in 1964 and have been observed by several other authors since then,6,7 but no one has yet reported a careful study of how small changes influence these properties. We have made such a study and have found that sizable differences in growth rate, morphology, carrier concentration, and mobility can indeed be observed for epitaxial films grown on substrates that are oriented by progressive small increments away from the exact crystal plane. EXPERIMENTAL Early in the investigation an arsine synthesis system of conventional design8 was employed to produce growths on {111A}-oriented GaAs substrate crystals. In that early work, pronounced effects on carrier concentration and electron mobility were observed as a function of slight misorientation from this low index plane. That observation led to the more careful study that is reported here. An AsC13 system, differing in major aspect from those commonly in use today9 only in that the reactor is vertical rather than horizontal, was used for the detailed study. The gallium source was at 900°C and the substrates were at 750°C. The flow rate of pal-ladium-diffused H2 through the AsCl3 bubbler was 200 cu cm per min, and the flow rate of bypass H2 was also 200 cu cm per min. The substrates consisted of chro-mium-doped semiinsulating GaAs to facilitate elec-trical evaluation of the overgrowth by means of Hall and conductivity measurements on conventional eight-legged Hall bridges. They were misoriented by 0 to 5 deg from the {111A}, {111B}, and (100) planes, toward the (100) from the {111A} and {111B} and randomly toward the <111A> or <111B> from the {loo). The crystals were oriented for sawing by the Laue back-re-flection technique, which is good only to about ±1/2 deg; but after polishing or sometimes after epitaxial growth the wafers were checked by a diffractometer technique which is accurate to about * 0.1 deg. After lapping, the wafers were polished with NaOCl after the technique of Reisman and Rohr,10 and just before use they were cleaned in NaOC1, thoroughly rinsed with de-ionized water, and blown dry with nitrogen. Each run employed four wafers, each misoriented by differing amounts from one of the three major faces, and at least two runs were made for each orientation. The runs were continued long enough to provide at least a 15-µ or thicker layer. SURFACE MORPHOLOGY The appearance of all the films that were grown in a given run always changed from wafer to wafer as a function of increasing misorientation, but not always in the same regular fashion. At least three different trends were observed. These are more easily seen than described, and reference to the series of photo-

Jan 1, 1970

By R. E. Zinkham

An investigation has been conducted to compare short transverse and longitudinal fatigue and fracture properties in 4.25-in.-thick, high strength aluminum alloy plates. One plate was produced using standard rolling techniques while the other was pre.forged before rolling. Little difference was shown in fatigue strength of longitudinal specimens taken from mid-thickness of the plate. Howeuer, in the short transverse orientation fatigue strengths at 107 cycles were about 25 and 50 pct less, respectively, for the preforged and standard rolled plate. Differences in fatigue strengths were attributed to grain size and shape as well US orientation of constituents. Fatigue crack propagation rates and fracture toughness were compared at three different stress intensity (K) levels, using a constant compliance, double cantilever, wedge-shaped specimen. In a given plate, comparable fatigue crack Propagation rates were observed in the longitudinal (i9W) and short transverse (TW) orientations. Somezuhat gveater rates were observed in the short transzerse (TR) orientation. The preforged plute gave a lower rate for all three directions. Considerable secondary cracking developed, at times, over portions of the fatigue crack in both plates, particularly at the lower stress intensity levels in the short transverse specimens. Micro structure revealed constituent stringers as possible causes of the crack branching. Fracture toughness was considerably less in both plates in the short transuerse orientation. It is concluded that preforging not only improved directional tensile properties but also the fatigue and fracture properties in general. On occasion, aluminum plates have been milled away for hinges or bolted connections and stressed through the thickness or short transverse direction. Little or no information is available concerning fatigue characteristics or fracture toughness in this loading orientation in aluminum plate, or of the effect of fabrication on these properties. It was the intent of this project to examine, develop, and apply a unique specimen that has been advocated by others to study the fatigue characteristics and fracture toughness of two differently fabricated high strength aluminum plates. Linear elastic fracture mechanics criteria may be applied to the specimen so that the fatigue crack propagation rate and fracture toughness data may be of use for design or inspection applications. Fatigue characteristics are generally measured in the longtudinal or long transverse direction, where fairly large specimens such as center notched panels,&apos; are usually employed. Limitations are evident due to plate thickness, however, in the type and size of specimen that may be tested in the short transverse direction without extensions. Therefore, a specimen that is to be loaded in this direction should, for convenience, be compact. The general type of fatigue crack propagation specimens discussed and employed herein meet this requirement. These specimens are commonly called double cantilever beam specimens and lately "crackline-loaded edge-crack specimens".2 They may vary from a slope of zero (parallel-sides) to a wedge shape, the type employed herein. In general for most specimens the stress intensity KI at the tip of a crack is a function of the load, P and crack length, a. Some varieties of the wedge shaped specimen, however, give essentially a constant stress intensity KI over a considerable range of crack length.&apos; This feature can be a valuable asset in fatigue crack propagation experiments because the stress-intensity can be controlled simply by controlling the load without regard to crack length. MATERIAL AND METHODS Material. A standard rolled (light pass reduction) and a ~reforged and rolled (heavy pass reduction) plate of 7179-T651 material were used for the evaluation. The chemistry, processing history and average tensile properties are shown in Table I. Specimen Selection and Preparation. The specimen selected for the generation of fatigue initiation or S-N data was an axial tension type and is shown in Fig. 1. Specimens were taken from mid-thickness in the longitudinal and short transverse directions from both plates. Specimens were polished with 500 grit paper in a direction parallel to the loading axis. For the fatigue crack propagation tests, the specimen shown in Fig. 2 was used. This is similar to a specimen that has been employed by Mostovoy3 for fracture toughness studies on 7075-T6 aluminum alloy. It also fortuitiously agrees quite well with the dimensions of a specimen for which Srawley and Gross2

Jan 1, 1970

By David C. Russell

The Department of the Interior used to be a quiet, noncontroversial, almost boring agency. It, after all is the fifth oldest of the Departments, and as an old line Federal agency it has studiously performed its preservation and resource management functions in a caretaker mode--though some would say more "undertaker" than "caretaker"--locking up the body and soul of America piece-by-piece. Yes, quiet, serene. That is until Jim Watt showed up. And we have all seen that version of Mt. Vesuvius which resulted--only it was the environmentalists who blew their tops. Ronald Reagan chose Jim Watt as Secretary of this fine old agency to prove that one-third of our Nation&apos;s land and over a billion acres on the Outer Continental Shelf can work for this Nation. At the foundation of President Reagan&apos;s charge to Secretary Watt is a belief in the tenets of the free enterprise system, and in the individual freedoms upon which this country was founded. There are those who don&apos;t share this belief in democracy and free enterprise, and those who believe this 205 year experiment called the United States of America will fail. Nikita Krushchev said "we will bury you"--obviously he didn&apos;t agree with our system. An Italian sociologist, Franco Ferrorotti, said bureaucratic stagnation will kill capitalism. Certainly we have all felt the ravages of bloated bureaucracies. Perhaps one indicator in the United States is the Federal Register, that daily compilation of Government&apos;s largesse. In 1970, 20,000 pages of the Federal Register were published. A decade later, in 1980, that volume had quadrupled to 80,000 pages. The Federal bureaucracy can stagnate from excessive budgets as well. The Interior Department spent $60 million on administering Federal coal leasing in 1981. That&apos;s nearly two bits a ton for every ton of coal leased in 1981. You wouldn&apos;t stay in business very long if your administrative overhead on inventory was that outrageous. But the pessimism of our critics is apparent from more than red tape and bloated budgets. For decades America has been fasting--consuming too little of America&apos;s wealth of minerals, subsisting instead on a diet heavily reliant upon mid-east oil, with little emphasis or concern for inventorying and developing domestic energy and mineral resources. Economics--yes. But short-term, short-sighted economics. Excessively dependent upon foreign imports, of oil, cobalt, chrome and other strategic minerals, the U.S. measures its time before another embargo--or fallen Shah, or Soviet manipulation, or Saudi shift, or, as we witnessed in Egypt, assassination--an untimely loss to mankind and efforts to bring peace to the troubled mid-east. These disruptions, in addition to their tragic human tolls, impair the free world&apos;s security. Huge chunks of the United States have been locked away in dozens of single land use categories in the name of conservation, with only the foggiest idea of what resources might be denied the American people-and this at a time of unacceptable levels of energy and strategic mineral imports. More than half and perhaps two-thirds of all Government-owned lands are totally withdrawn from or severely restricted to development under the mining and leasing laws. We must continue to rid Government of the overly zealous restraints which have been keeping us from drawing upon that which can help restore our economy and national security. When we assumed responsibility, the United States was dependent on foreign sources for about 40 percent of its oil. In 1981, our oil import bill was approximately $83 billion--nearly 17 times what it was in 1972. Our reliance on foreign sources for essential minerals is even more disturbing. We must look to other countries--some unfriendly, some unstable--for 22 of 36 strategically critical minerals. Yet the energy resources on federal lands which are owned by the American people could meet our needs for centuries if properly managed. Eighty-five percent of the crude oil yet to be discovered in America is likely to come from public lands, as will 40 percent of the natural gas, 35 percent of the coal, 80 percent of the oil shale, nearly all of the tar sands, and substantial portions of uranium and geothermal energy. Our vast hardrock-mineral wealth includes untapped deposits of essential elements we now import, such as chromium, copper, platinum, and cobalt. The obvious question is, if these abundant resources can help to revitalize our economic strength and to preserve our national security, why aren&apos;t we using them to better advantage? To a large extent, the answer can be found in past decisions to restrict public access to the federal estate, thus deferring to us or our successors the tough decisions that flow from Congress&apos; mandate to provide for environmentally responsible development of America&apos;s energy and mineral treasures. Here is the legacy this Administration inherited: In January 1981, 7 years after the onset of the Mideast oil embargo: ---Less than 15 percent of federal onshore lands were under lease for oil and gas development; ---No oil and gas leases had been issued in Alaska for 15 years;

Jan 1, 1982

By R. E. Powers, E. H. Kinelski, H. A. Morrissey

A group of 17 American blast-furnace sinters, an American open-hearth sinter, an American iron ore, and a Swedish sinter were used to evaluate testing methods adapted to appraise sinter properties. Statistical calculations were performed on the data to determine correlation coefficients for several sets of sinter properties. Properties of strength and dusting were related to total porosity, slag ratio, and total slag. Reducibility was related to the degree of oxidation of the sinters. THIS report to the American iron and steel industry marks the completion of a 1949 survey of blast-furnace sinter practice sponsored by the Subcommittee on Agglomeration of Fines of the American Iron & Steel Institute. The use of sinter in blast furnaces, sinter properties, raw materials, and sinter plant operation have been reported recently.1,2 After preliminary research and study," test procedures were adapted to appraise the physical and chemical properties of sinter to determine what constitutes a good sinter. During the 1949 to 1950 plant survey each plant submitted a 400-lb grab sample to research personnel at Mellon Institute, Pittsburgh, Pa. A 400-lb sample was also submitted from Sweden. In addition, 2 tons of group 3 fines iron ore were obtained from a Pittsburgh steel plant. The following tests were performed on the iron ore sample and on the 19 sinter samples: chemical analysis; impact test for strength and dusting; reducibility test; surface area measurements, B.E.T. nitrogen adsorption method; S.K. porosity test; Davis tube magnetic analysis; X-ray diffraction analysis for magnetite and hematite; and microstructure. Results of these evaluations are discussed in this paper and supply a critical look at testing procedures used to determine sinter quality. Sinter Tests and Results Each 400-lb grab sample of sinter was secured at a time when it was believed to represent normal production practice at each plant. It was not possible to use the same sampling procedures throughout the survey; consequently samples were taken from blast-furnace bins, cooling tables, and railroad cars. These were very useful for evaluation of test methods, since they were obtained from plants with widely divergent operations. With the exception of Swedish sinter and sinter sample N, which were produced on the Greenawalt type of pans, all survey sinters were produced on the Dwight-Lloyd type of sintering machines. Sinters submitted for test were prepared in identical manner by crushing in a roll crusher (set at 1 in.), mixing, and quartering. To secure specific size fractions for tests, one quarter of the sample was crushed in a jaw crusher and hammer mill to obtain a —10 mesh size. The remainder was screened to obtain specific size fractions. The group 3 fines iron ore was dried and screened and samples were taken from selected screen sizes to be used for various tests. Prior to testing, each ore sample except the —100 mesh fraction was washed with water to remove all fine material and was then dried. This iron ore, a hematitic ore from the Lake Superior region, was used as a base line for comparing results of tests on sinters. The iron ore did not lend itself to impact testing, since it was compacted rather than crushed in the test, and no impact tests are reported. However, the iron ore was subjected to all remaining physical tests to be described. Chemical Analysis: Table I presents chemical analyses performed on the survey sinter samples. Included in this table are data obtained from determination of FeO and the slag relationships: CaO + MgO and total slag (CaO + MgO + SiO, SiO2 + Al2o3 + TiO2). The percentage of FeO was used as an indication of the percentage of magnetite in the sinter. It was believed that slag relationships could be correlated with sinter properties. During initial determination of FeO great disagreement arose among various laboratories, both as to the results and the methods of determining values. Table I lists the values of FeO resulting from the U. S. Steel Corp. method of chemical analysis,&apos; which reports the total FeO soluble in hydrochloric and hydrofluoric acids (metallic iron not removed) with dry ice used to produce the protective atmosphere during digestion. Use of dry ice was a modification required to obtain reproducible results. In this method, the iron silicates and metallic iron are believed to go into solution and are therefore reported as FeO. This is important, for in the study of the microstructure of sinters, glassy constituents suspected of containing FeO as well as crystallized phases of undetermined identity which may also contain FeO have been observed. Strength Test by Impact: In evaluating sinter quality, one of the properties stressed most by blastfurnace operators is strength. This strength may be described as the resistance to breakage during handling of sinter between the sinter plant and the blast-furnace bins. It is also the strength necessary to withstand the burden in the blast-furnace. After

Jan 1, 1955

By G. L. F. Powell

g samples of Cu-20 wt pct Ag alloy have been mdercooled to a maximum of 197°C by melting under a slag of commercial soda-lime glass in a vitreous silica crucible. No grain refinement of the primary copper was observed in samples undercooled to the maximum of 197°C. When the samples contained a small amount of oxygen, the copper dendrites were partially recrystallized at undercoolings greater than 97°C. In previous papers&apos;-3 reporting the grain structure of undercooled silver and copper, it was observed that grain refinement was dependent on both undercooling and oxygen content. Grain refinement occurred in undercooled silver when the degree of undercooling exceeded the range 153" to 175"C, while in Ag-0 alloys (0.12 wt pct) fine equiaxed grains were exhibited when undercooling was greater than 50°C. Similarly, copper samples undercooled as much as 208°C displayed fan-shaped growth from a single nucleation site, while the grain structure of Cu-O alloys (0.08 wt pct) was fine and equiaxed at undercoolings larger than 150°C. Thus the presence of oxygen greatly reduced the undercooling at which grain refinement occurred. It was also observed that the change in grain size resulted from recrystallization and was not due to an enhanced nucleation rate in the liquid-solid transformation. It is possible that the influence of oxygen on recrystallization is due primarily to its presence as a solute element. walker4,&apos; reported that, although a grain size change did not occur in pure nickel until the undercooling exceeded 150°C, small grains were observed in samples of Ni-Cu alloy solidified at small and large degrees of undercooling. Jackson et al.6 suggested that the fine grained structure of the Ni-Cu alloy resulted from the melting off of dendrite arms during recalescence. This remelting process may occur in alloys as a result of segregation during freezing which causes a variation in liquidus temperature from point to point within a dendrite. It was therefore decided to undercool copper with a metallic alloying element to ascertain whether the presence of a metallic solute would have a similar effect to oxygen in inducing grain refinement. A Cu-Ag alloy was chosen, since both metals had been shown to behave similarly on undercooling. The alloy Cu-20 wt pct Ag was selected since the eutectic constituent outlines the initial growth form of the primary copper, so that the as-frozen grain structure is not obscured if subsequent recrystallization occurs. This paper describes the results of undercooling experiments carried out with Cu-20 pct Ag samples undercooled to a maximum of 197°C and the effect of oxygen content on the grain structure of the undercooled samples. EXPERIMENTAL Melting was carried out in a small cylindrical resistance furnace using "fine" silver granulate and oxygen-free high conductivity copper. The procedure adopted was to melt the required quantity of silver in air in a clean vitreous silica crucible for approximately 15 min, freeze, and add granulated commercial soda-lime glass to form a complete surface slag cover, after which the sample was melted and frozen several times to reduce the oxygen content. The glass slag cover was approximately 3 in. thick. Pieces of copper (=50 g) were added to the crucible until the required quantity to make 350-g samples of alloy had been charged. Each piece was added quickly to the crucible which was held at a temperature slightly above the melting point of silver. The piece was quickly pushed beneath the glass to minimize oxidation and any oxide coating usually decomposed before the piece had settled down into the silver. After the full quantity of copper had been added, the melt was stirred with a silica rod to hasten homogenization and a Pt/Pt 13 pct Rh thermocouple enclosed in a vitreous silica sheath inserted for temperature measurement. Heating and cooling curves were recorded on a potentiometric chart recorder fitted with a zero suppression unit. The milli-voltage range of the recorder was adjusted so that temperatures could be read to 1°C. Heating and cooling curves were taken every hour until three consecutive readings gave the same solidus-liquidus range, consistent with the solidus-liquidus range for this alloy composition by reference to Hansen and Anderko.7 Metallographic examination of samples frozen at this stage, failed to show any variation in composition from bottom to top of the ingot. Consequently, it was considered that the melt was homogeneous at this stage and undercooling experiments were then car-

Jan 1, 1970

By L. M. Pidgeon, P. G. Thornhill

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,&apos;"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. lengtn of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of ¼ in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10o to 15oC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press Operating at a temperature of 140°C

Jan 1, 1958

By E. R. Russell, N. E. Richards

The current ejyiciency of aluminum cells was derived from the metal produced over a period of time and the theoretical faradaic yield. The difference in the actual amount of aluminum in the cathode at the beginning and end of the period must be determined. The weight of aluminum in the cathode was calculated from the dilution of an added quantity of impurity metal. Use of multiple indicator metals, copper, manganese, and titanium, demonstrated that the weight of aluminum in cells can be determined to within 1 pct with routine but careful chemical analyses. Over intervals of the order of 30 days, current efficiencies reliable to within 1 pct can be obtained. INVESTIGATIONS beginning with those of Pearson and waddington ,&apos; through the most recent published work of Georgievskii,9-11 illustrate the direct relationship between the composition of the anode gas and the applicability of analysis of anode gases to the control of alumina reduction cells. McMinn12 noted the lack of an independent method for measuring cell production efficiency over the short term. There is no doubt that changes in the current efficiency are immediately reflected in the composition of anode gases. However, the accuracy of faradaic yields calculated from gas analyses depends upon the degree of interaction between primary anode gas and Carbon.6 A conventional industrial practice of obtaining long-term current efficiency for production units from mass balances and quantity of electricity is generally insensitive to the impact of planned control of any one or more of the influential reduction cell parameters such as temperature, alumina concentration, and mean interelectrode distance. Consequently, there is a real need in the aluminum industry for a procedure to obtain the absolute cell current efficiency over a short term—10 to 30 days—both for the calibration of values obtained from gas analysis6 and for evaluating the effect of controlling specific parameters in the reduction process. The amount of aluminum produced may be determined by considering the cathode pool as a reduction of an impurity metal in aluminum. Analyses over a period will show a decreasing concentration of the impurity due to the accumulation of aluminum solvent. The increase in aluminum inferred from analyses is the amount produced by the cell during the period. Combining weights of the cell aluminum in the cathode at the beginning and end of a specific period, weights of aluminum tapped and the quantity of electricity passed during the interval will yield the current efficiency. Smart,I3 Lange;4 Rempel,15 Beletskii and Mashovets,16 and winkhaus17 have used dilution techniques to determine aluminum inventory in alumina reduction cells. A technique for determining the weight of aluminum in production cells by addition of small amounts of copper to the aluminum cathode was described by smart.13 The precision in values of the aluminum reservoir through dilution of copper in the cathode ranged from about 1 to 3 pct depending upon the quantity of copper added in the range 0.2 to 0.01 wt pct, respectively. Because the method appears so direct and apparently simple, one would not anticipate difficulties in application to industrial cells. The objective of this study was to resolve this problem associated with the trace metal dilution technique for determining the amount of aluminum in a cell. The approach in evaluating trace metal dilution as a basic factor in determining the weight of aluminum in the cell reservoir, and the absolute current efficiency of the Hall-Heroult cell, was to dilute more than one trace metal in the aluminum cathode so that we could discriminate among complications arising from physical mixing, the possibility of separation of intermetallic compounds, loss of the added elements, and chemical detection. EXPERIMENTAL METHODS These experiments are not complex but require standardized procedures. The technique involves addition of the trace metals to the cathode, knowing when these metals are homogeneously distributed in the liquid cathode, timing of the sampling, employing accurate and precise analytical methods, using reliable procedures for monitoring the amount of electricity passed through the cell, and accurate weighing of aluminum removed from the cell during the particular period. More accurate results might be obtained if the increment in concentration of the added indicator metals were of the order of 0.1 to 0.2 wt pct. The method must be applicable to production units and, hence, the contamination of the aluminum minimized. For this reason, the concentration of trace metals in the cathode was kept below 0.07 wt pct and generally at 0.04 wt pct level. Trace quantities of copper, manganese, titanium, and silicon are already present in virgin aluminum and are suitable as additives from electrochemical and analytical points of view. Concentration of silicon is quite dependent upon the characteristics of the raw materials and was not used extensively in this work. Chemical Analyses. All instrumental analyses require calibration against an absolute technique such as a gravimetric, volumetric, or spectrophotometric method which represents the ultimate in sensitivity, precision, and accuracy. On review, the best methods for copper appeared to be optical absorption without

Jan 1, 1969

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann&apos;s finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author&apos;s reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp u/RT, where u is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf&apos;s can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

By J. H. Wernick, D. Dorsi, K. E. Benson

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,&apos;"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. iength of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10O to 15OC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press operating at a temperature of 146°C

Jan 1, 1958

By J. E. Pavlick, A. G. Guy

The total creep of tin alloys containing antimony in solid solution was observed to decrease with increase in antimony content. However, near the solubility limit an anomalous maximum in deformation was. found, in agreement with similiar observations by Bochvar. IT has long been recognized that alloys may deform more rapidly under stress if there is a tendency for a phase change or other structural change to occur simultaneously. However, the phenomena involved are complex and in some instances the opposite effect, strengthening, may result.&apos; This area of research has not attracted much interest in the western world, and although Russian investigators have studied it for the past 15 years their work has not received due attention here. Recently diametrically opposing views on one aspect of this problem have been espoused by two Russian investigators, Kornilov and Bochvar. The question is this: in certain binary alloys tested in creep at the temperature where the solute is at the limit of solid solubility, does the incipient formation of the second phase strengthen or weaken the alloy? Korni-lov&apos;s arguments in favor of strengthening were presented at the 1954 Symposium at the National Physical Laboratory, =Creep and Fracture of Metals at High Temperatures.The most recent statement of Boch-var&apos;s theory of weakening is in Oding&apos;s new book on creep and rupture.3 Although Bochvar agrees that strengthening occurs in some alloy systems, he argues that in certain alloys an anomalous weakening is observed. However, the extensive work of Korni-lov&apos;s group on creep properties of alloy systems has not revealed any anomaly of this type, but instead has tended to refute Bochvar&apos;s theory. This clear-cut controversy offered a good opportunity for a simple experiment to resolve the problem. The experiment and its results supporting Bochvar are the subject of this paper. However, it will be helpful first to sketch the present status of the larger question of the effect of a phase change or other structural change on plastic deformation. PREVIOUS WORK One of the first researches in this area was by Pfei1,37 who investigated the creep resistance of an 80 Ni-20 Cr alloy containing varying amounts of titanium. He found that the resistance to creep increased rapidly as the solid solubility limit in the alloy at 775&apos;c was approached and slightly exceeded. With further addition of titanium the creep resistance decreased, presumably because of precipitation effects. Bochvar&apos;s first work in this field was a study in 1945 of "superplasticity" in zinc alloys containing 15 to 25 pct Al.4 He found that alloys quenched from about 400 had anomalously low hardness when tested below this temperature. The following year, in a paper on the dependence of mechanical properties on the composition and structure of alloys,5 he extended some observations of Kurnakov to predict that at high temperatures of testing the hardness values for solid-solution alloys might be lower than those for the component metals. He also pointed out the influence of changes in solidus temperature in affecting curves of hardness vs composition, and he

Jan 1, 1962

By R. Maddi, I. R. Kramer

The delay time for the initiation of slip was studied in single crystals of a brass, aluminum, and ß brass. A delay time for slip was found in ß brass when the specimens were tested below room temperature; however, one was not found for a brass or aluminum. A general theory for the existence of the brittle transition temperature is proposed. A LTHOUGH a considerable amount of effort has A been devoted to the study of the deformation and fracture of single crystals, the vast majority of the work was concerned with static tests or with tests carried out at relatively slow strain rates. The necessity for the study of a possible incubation time for slip becomes apparent when the various theories which have been postulated for the elucidation of the mechanism of slip are considered. The existence of an incubation period would strongly indicate that slip occurs by a process of nucleation and growth; whereas the absence of an incubation would present rather convincing evidence that slip occurs by a cataclysmic process. In addition to shedding light on the process of plastic deformation, an understanding of the early stages of plastic deformation may be helpful in finding an explanation for the brittle behavior of the body-centered metals under certain conditions. It is well known that these metals, such as iron, molybdenum, tungsten, ß brass, etc., will become brittle as the test temperature is lowered or the strain rate is increased. In spite of the fact that this subject has received considerable attention since the turn of the century, no adequate theory exists today which explains the phenomenon. In the ductile temperature range the metal breaks with a "fibrous" fracture after considerable slip has taken place. In the brittle temperature range the metal fails essentially by cleavage on the {loo) planes: however, some plastic flow is always present even in the most brittle fractures. It is possible, as will be explained later, to ascribe this brittle behavior to the length of the incubation time for slip. Clark and Wood,&apos; using polycrystalline metals, showed that a delay time existed for the yield point in mild steels and that the delay time depended upon the applied stress. These authors stated that the delay time was observed only with those materials for which the stress-strain curve showed a definite yield point. In their work only the mild steel specimens exhibited a delay time at the yield point, while the other materials studied-type 302 stainless steel, SAE 4130 normalized steel, SAE 4130 quenched and tempered steel, 24s-T aluminum—did not show a delay time. These authors&apos; in an extension of their work, found that as the temperature was lowered the delay time was increased. It is, then, the purpose of this investigation to measure or to set an upper limit on the delay time for plastic flow in single crystals of a brass, aluminum, and ß brass. The delay time will also be studied as a function of temperature. The incubation time may be measured by determining the length of time the specimen will support a stress without slip occurring when the stress is greater than the static critical resolved shear stress. In order to accomplish these measurements use was made of a pendulum which was so designed that a single crystal specimen could be placed at various positions along its length. When a pendulum is struck by another pendulum of the same length, an elastic wave is transmitted down the bar with the velocity of sound in the material and is reflected from the far end of the bar. The reflected wave then travels back and unloads the stress until it reaches the impacted end of the bar and the two pendulums separate. The length of time that the specimen is subjected to the stress is equal to the time it takes for the stress wave to travel twice the distance from the specimen to the end of the bar. The stress applied to the specimen is governed by the velocity of impact of the two pendulums. The stress at which the specimen first suffers plastic: deformation was determined in these experiments by examining the specimen under the microscope for the first appearance of slip lines and by measuring the residual strain after each impact. In these experiments the critical resolved shear stress was approached from the low stress side and no attempt was made to determine it exactly. To determine it exactly, it would have been necessary to find that stress at which slip would have just started. However, since the stresses were increased in rather small increments the critical stress is believed to be approached rather closely, as will be seen from the experimental results. The critical stress will be taken as the highest stress obtained before the onset of plastic deformation. The stresses

Jan 1, 1953

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was (&apos;Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970