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By P. M. Blair, D. W. Peaceman

The shape and position of the gas-oil transition zone during downdip displacement of oil by gas has been calculated using flow equations which include the effects of gravity, relative permeability, capillary pressure and compressibility of the fluids. The calculations treat the problem in two space dimensions, and results are compared with data from a laboratory model tilted at 30° and 60° from the horizontal on displacements near and above the maximum rate at which gravity segregation prevents channeling of the gas along the top of the stratum. The good agreement between calculated and experimental results demonstrates the validity of the tecbnique as well as that of the flow equations. INTRODUCTION Knowledge of the fluid distribution and movement in an oil reservoir is important in producing operations and estimation of reserves. The history of the oil industry has included steady progress in improving the accuracy of calculations which provide the required knowledge. The earliest method of calculating reservoir performance consisted of material-balance equations based on the assumption that all properties were uniform throughout a reservoir.l For many reservoirs such a simple formulation is still the most useful. However, when large pressure and saturation gradients exist in a reservoir, the assumption of uniform values throughout may lead to significant error. To reduce these errors, Buckley and Leverett2 introduced a displacement eqation which considers pressure and saturation gradients. Methods available at that time permitted solutions to the Buckley-Leverett equation in one space dimension; these solutions have been very useful in solving many problems related to the production of oil. However, the one-dimensional methods are not adequate for systems in which saturations vary in directions other than the direction of flow. An example of such a system is the case of gas displacing oil down a dipping stratum in which the gas-oil contact becomes significantly tilted. Of course, the Buckley-Leverett displacement method cannot predict the tilt of the gas-oil contact. Recent improvements3,4 of the one-dimensional Buckley-Leverett method achieve some success in predicting the tilt of the gas-oil contact at sufficiently low flow rates. However, at rates high enough that the viscous pressye gradient nearly equals or exceeds the gravity gradient, even these improved one-dimen,sional methods incorrectly predict the shape and velocity of the contact. Further progress in estimating such fluid movements in a reservoir appears to require consideration of the problem in more than one space dimension. The recent two-dimensional method of Douglas, Peaceman and Rachford5 appears adaptable to calculate changes with time of the saturation distribution in a vertical cross-section of a reservoir. The movement of saturation contours should represent the moving fluid contacts and include the effects of crossflow due to gravity, as well as variations in the rock and fluid properties. The nonlinear nature of the equations used in the method has prevented proof of the validity of the solutions. Douglas, Peaceman and Rachford made some comparisons with experiment but did not include cases in which gravity was important nor cases involving displacement by the nonwetting phase.For these reasons, a test of the two-dimensional method for a case in which these factors are included would be very desirable. The test selected was a comparison of calculated results with those from a carefully controlled laboratory experiment on a model with measured physical properties. The model selected was one in which gas displaced oil down a tilted, rectangular sand pack. The model can be thought of as representing a vertical cross-section taken parallel to the dip of a reservoir. The displacement thus simulates gas displacing oil downdip that might result from gas-cap expansion or gas injection. This report outlines the calculation method used

By J. L. Lytton, T. E. Tietz

The recovery of flour stress of recrylstallized are-cast molyhdenum after 10 pet prestrain at 150°C was studied for recovery temperatures of 725o 801o and 901oC. The yield phenomenon observed after recovery was such that the yield drop diminished and disappeared as recovery proceeded. A fractional flow-stress recovery parameter fr, was developed and it was shown that, independent of recovery ternperatzwe, equal f, values of about 0.16 produced superposition of stress-strain curves except for the initial yield phenomenon. The activation energy for low degrees oj recovery was found to he 32,600 cal per mole, in close agreement with a reported valzie for difjzdsion of carbon in molybdenum. For values of fr greater than about 0.15 where recovery was thought to predominate over strain aging, the activation energy varied from 43,600 to 82,500 cal per mole and increased with increasing recovery and recovery temperature. A 10 pet pre-strain shifted the ductile-brittle transition temperature, as indicated by tensile elongation, from 10°C. to about -22"C. A 100-hr recovery anneal at 801oC was shown to shift the transition temperature to about —5oC, the major shift occurring during the first hour of recovery. ThE recovery of cold-worked metals is accompanied by changes in the arrangement of the dislocations generated during cold work. In recent years, the use of transmission electron microscopy has allowed direct observation of some of the dislocation configurations formed, such as "tangles", networks, cells, subboundaries, and loops. These observations have recently been reviewed by Keh and Weissmann.' Accordingly, some understanding has been gained concerning the nature of the dislocation rearrangements involved. The relationship between recovery and the decrease of mechanical strength, however, has only recently been explored. Previous efforts of the authors were directed toward investigating the decrease of tensile flow stress of aluminum and Al-1 pet Mg during recovery2 and the effects of concurrent elastic and plastic strain on the flow-stress recovery of aluminum.3 In addition, an investigation of the effect of four different solute additions on the tensile flow-stress recovery of aluminum has been made.4 Many important metals, however, have the bee crystal structure, e.g., iron, molybdenum, tungsten, vanadium, columbium, tantalum, and chromium. These metals might be expected to behave differently during recovery from those with other crystal structures for two reasons. First, the previous and present investigations of aluminum and its alloys have shown that tensile flow-stress recovery is strongly affected by foreign atoms in the lattice. In the bee metals, interstitial impurities are usually present and might be expected to have various effects upon both flow behavior and recovery. For example, heterogeneous yielding might occur during prestraining. The diffusion of these interstitials can also relock dislocations during recovery so that a yield point might be obtained upon restraining (strain aging). Second, some of the bee metals (e.g., iron, molybdenum, and tungsten) undergo the familiar structure-sensitive ductility transition and exhibit brittle fracture at suitably low temperatures. It is of considerable interest to determine the effects of recovery on the transition temperature of such metals. The purpose of the present investigation was to extend our knowledge of flow-stress recovery to the bee metals and to study the effects of recovery on the ductile-brittle transition temperature. Unalloyed recrystallized are-cast molybdenum was chosen as a test material, since it exhibits a well-defined ductility transition near room temperature. As in the previous studies, the degree of recovery was measured in terms of the decrease of tensile flow stress. Prestraining and restraining were carried out at 150°C to avoid the possibility of brittle fracture. EXPERIMENTAL PROCEDURE The are-cast molybdenum sheet used in this investigation was obtained from the Climax Molybdenum Co. of Michigan. It was 0.060 in. thick by 10

Jan 1, 1964

By P. Chiotti, J. T. Mason

Thermal, X-ray, metallographic, and resistivity data were obtained to establish the phase diagram for the Yb-Zn system. Six intermetallic compounds and five eutectics have been identified. The compounds position at 695°C. No evidence for the compound YbZn,, was observed. Whether this compound is stabilized or inhibited by small amounts of impurities is uncertain. SEVERAL aspects of the Yb-Zn system have been reported in the literature. Much of this work deals with the crystallographic identification of some of the compounds. The YbZn compound has been reported by Iandelli and palenzonal and the YbZn, structure and thermal data for the composition range between YbZn and Yb3Znll have been reported by Michel et al. A compound of uncertain stoichiometry in the range 60 to 68 wt pct Zn with a cubic structure has been reported by Kuz'ma et aL4 The YbzZn17, YbZn,,, and YbZn13 compounds have been reported by both Kuz'ma et a1 and Iandelli and Palenzona.' YbnZn17 has also been identified by Laube. This investigation was undertaken to establish the phase diagram of this system. Ytterbium in many respects behaves as an alkaline earth rather than a rare earth metal6 and it is of interest to note the resemblance between the Yb-Zn system, the Ca-Zn,' and typical rare earth-zinc systems.g'10 MATERIALS AND EXPERIMENTAL PROCEDURES The materials used in this investigation were Ames Laboratory ytterbium and Bunker-Hill slab zinc, 99.99 pct pure. Analyses of the ytterbium showed 38 ppm Ta, 82 ppm 0, and 15 ppm N with Ca, Cu, C, Mg, Al, Si, Cr, Fe, Ni, Sc, Y, Er, Tm, and Lu all less than 50 ppm. The ytterbium was dehydrogenated by heating in tantalum under vacuum for 8 hr at 900°C. The metal was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys in the composition range between ytterbium and Yb2Zn17. With higher zinc concentrations the tantalum was penetrated by the alloy and failed after several days at temperatures of 600" to 700°C. Approximately 20 g of zinc and ytterbium metal were sealed under argon in *-in.-diam tantalum cruci- bles equipped with thermocouple wells. The crucibles were in turn sealed in stainless-steel jackets. The alloys were equilibrated in an oscillating furnace and given various heat treatments in a soaking furnace. The steel jackets were removed and differential thermal analysis data were obtained under an atmosphere of argon. The thermal analysis apparatus was calibrated against the melting points of pure zinc, aluminum, silver, and copper and found to give thermal arrests within 1°C of the accepted melting temperatures for these elements. The thermal analysis apparatus has been described in an earlier paper.g Alloys were further heat-treated as necessary and subjected to metallographic examination and X-ray diffraction analysis. Most alloys were etched with Nital (0.5 to 10 pct nitric acid in alcohol). EXPERIMENTAL RESULTS The results of the thermal analysis are summarized by the points on the phase diagram, Fig. 1. Six compounds and five eutectics were observed. The eutectic temperature and compositions in weight percent zinc are 491°C and 12 pct, 645°C and 32 pct, 687°C and 54 pct, 742°C and 67 pct, and 750°C and 77 pct. The compounds YbZn, YbZn2, Yb2Zng, Yb2Zn17, and YbZnll melt congruently at 650°, 751°, 75Z°, 754", and 755"C, respectively. The compound Yb3Znll undergoes a peritectic decomposition at 695°C. The transformation and melting temperatures for the ytterbium were observed to be 797" and 817°C. re-

Jan 1, 1969

By F. A. Crossley

The additions: o, Sn, Zr, Cb, Mo, and V were studied for their effects on the a/a + Ti3A1 boundary of Ti-A1 base ternary alloys. These additions were chosen because of their importance to commercial titanium alloy practice—oxygen as the major impurity (in terms of influence on mechanical properties) and the others as major alloying additions. The composition and temperature ranges of investigation varied according to the system as shown in Table I. The principal means of investigation was light-microscopy. The basis of the ternary studies was the recently determined titanium-rich end of the Ti-A1 system.' MATERIALS, METHODS, AND PROCEDURES Ingots were prepared in 15 g size for all alloys except those of the Ti-Al-Mo and Ti-A1-V systems which were prepared in 20 g size. These alloys were prepared from high-purity, electrolytically refined titanium obtained from the Bureau of Mines, Boulder City Metallurgical Laboratory, Boulder City, Col., and Chicago Development Corp., Riverdale, Md., for the 15 g and 20 g ingots, respectively. The alloying additions were obtained from commercial sources, and were at least of 99.9 pct purity, except the V-15 wt pct A1 master alloy for vanadium additions. This alloy was of 98.2 pct purity; the major impurities were 0.37 wt pct Fe and 0.38 wt pct Si. The ingots were prepared by multiple melting in a nonconsum-able-electrode arc furnace. The ingots were covered with Markal coating "CR-T22" (Markal Co., Chicago) to protect them from scaling. Markal coating is applied as a slurry of solids in a volatile carrier liquid. The coated article is air dried. Upon heating to the hot working temperature the coating fuses to form a glassy, protective film. The ingots were heated to 1000°C and rolled to 0.16 in. thickness, reheating after each pass. The glassy film was removed by sand blasting. Ten mils were removed from all surfaces by grinding and/or pickling (3 pct HF, 30 pct HN03, balance water). Grinding was always followed by pickling to remove traces of the grindmg medium. Hydrogen removal was accomplished by vacuum annealing at 1000°C for 2 hr to a final pressure of about 0.02 µ Hg. This was followed by annealing in evacuated Vycor bulbs (800°C, 2 hr, ice brine quenched (IBQ)) in order to maximize ductility. The materials were then lightly pickled and cold rolled to 0.12 in. thickness or cracking, whichever occurred first. After rolling, 1/2 by 1/4 in. specimens were cut for the equilibration anneals given in Table 11 and carried out as previously described.1 Final polishing of the specimens for metallographic examination was done by electrolytic means. Specimens were first examined without etching under bright field and polarized light illumination, for this is the only means of detecting the "two-phase" phenomenon.1,2 The term "two-phase syndrome" refers to Ti-A1 al-loys which appear on the bases of their chemical, phys-ical, and mechanical properties, to be two-phase, but are actually single phase and inhomogeneous in composition. Since processing and heat treatment of the alloys of the first group were completed before the two-phase syndrome was discovered, a number of the specimens were found to exhibit this phenomenon—80 pct of those of the Ti-Al-Zr system, 5 pct of those of the Ti-Al-Sn system, 30 pct of those of the Ti-Al-Zr system. The affected specimens were homogenized by heating above the ß transus temperature and quenching. The heat treatment and working schedules to accomplish this are given in Table 111. After rolling, specimens were pickled (3 pctHF, 30 pct HNO3 in water) to remove 1 to 2 mils from the

Jan 1, 1970

By G. H. Enzian

THE effects of phosphorus and nitrogen on the properties and behavior of low carbon steels are important considerations to both the manufacturer and the user of such material. For one thing, these two elements are the principal points of distinction between the chemical compositions of Bessemer and open-hearth grades. Further, open-hearth steels themselves may vary considerably in nitrogen content depending on the raw materials and ..practice used. In addition, appreciable amounts of rephosphorized open-hearth steels are being used at the present time in some low alloy, high strength grades and in certain other cases. For these and other reasons, it was felt desirable to obtain more complete knowledge of the effects of simultaneous small variations in phosphorus and nitrogen content on such properties of low carbon steel as tensile strength, impact toughness, sensitivity to cold work, and strain aging. A long range investigational program designed to furnish such information, was carried out, and the present paper summarizes some of the data currently obtained. General Discussion The strengthening effect of relatively small amounts of phosphorus in steel has been recognized, and to some extent utilized, for many years. A number of investigators have pointed out, from time to time, that under proper conditions of control, phosphorus can be a useful alloying element in low carbon steels.1-3 Nevertheless, in spite of the volume of data on the subject, the use of phosphorus for this purpose has always been handicapped by widespread feeling that its presence makes the steel brittle, difficult to cold work, and unreliable at low temperatures. This belief on the part of some steel users is not entirely justified in many cases, and often stems from early experience with acid Bessemer steels which have appreciably higher phosphorus (and nitrogen) contents than basic open-hearth grades. Nitrogen in steel, and its effect on properties, has also received considerable attention in the literature.4 In 1906, Braune5 ascribed the brittleness of Bessemer rails to the nitrogen content, and proposed a schedule of nitrogen limits for steels for various uses. This was one of the first papers to recommend directly the use of nitrogen content as a quality control measure, but it did not meet with much favor or support; as a matter of fact, the Jernkon-toret was rather sharply criticized for publishing the paper. In the intervening years a number of papers have been published on the subject of nitrogen in steel. As a result, it is now generally recognized that nitrogen can have an important effect on the properties and behavior of steel and that the presence of this element should be considered in any systematic study of factors affecting steel quality. In 1932, Graham6 introduced the concept that the quality of various steels could conveniently be evaluated and compared in terms of "sensitivity", which was defined as "the characteristic reaction rate of a piece of steel toward brittleness or hardness." This concept formed the basis for a broad research program into factors causing variations in the quality of commercial steels. At an early stage of this work, it became apparent that the observed effect of either phosphorus or nitrogen on the sensitivity of steel depended, in no small measure, on how much of the other of these two elements was also present. Indeed, the combined effect of phosphorus and nitrogen in steel may often be more important than the specific effect of either. With a few exceptions, it is not possible to predict accurately the effect on steel properties of a change in the amount of either phosphorus or nitrogen in the steel without also specifying the approximate amount of the other element. It seems desirable, at this point, to discuss briefly the distinction between strain-sensitivity and strain aging as used in this paper. In the early stages of its development, the work-brittleness test7 (which will be described in more detail later) was used

Jan 1, 1951

By R. T. DeHoff

In any structural transfortnation which is driven by surface tension, the geometric variable of fimdamental importance is the local value of the mean surface curvatuve. Acting through the suvface free energy, this quantity determines the magtnitude of both the pressure and the chemical potential that develops in the neighborhood of an arbitrarily curved surface. A metallographic method which would permit the quaniitatiue estinzation of this propevty is of fundarnerztal irztevest to studies of such processes. In the present paper, it is shoun that the average value of the mean surface curvature in a structuve can be estimated from two simple counting measuretnents made upon a vepresentative metallograpIzic section. No simplifyirlg geonzetric assurmptions are necessary to this deviuation. It is further shoum that the result may be applied to parts of interfaces, e.g., interparticle welds in sintering, or the edge of growing platelets in a phase transformation, without loss of validity. In virtually every metallurgical process in which an interface is important, the local value of the mean surface curvature is the key structural property. This is true because the mean curvature determines the chemical potential of material adjacent to the surface, as well as the state of stress of that material. The theoretical description of such broadly different processes as sintering,1,2 grain growth,3 particle redistrib~tion4,5 and growth of Widmanstatten platelets8 all have as a central geometric variable the "local value of the mean surface curvature". The tools of quantitative metallography currently available permit the statistically precise estimation of the total or extensive geometric properties of a structure: the volume fraction of any distinguishable part:-' the total extent of any observable interface,10,11 and the total length of some three-dimensional lineal feature:' and, if some simplifying assumptions about particle shape are allowed, the total number of particles.'2"3 The size of particles in a structure, specified by a distribution or a mean value, can only be estimated if the particles are all the same shape, and if this shape is relatively simple.14-16 The relationships involved in converting measurements made upon a metallographic section to properties of the three dimensional structure of which the section is a sample are now well-established, and their utility amply demonstrated. In the present paper, another fundamental relationship is added to the tools of quantitative metallography. This relationship is fundamental in the sense that its validity depends only upon the observation of an appropriately representative sample of the structure, and not upon the geometric nature of the structure itself. It involves a new sampling procedure, devised by Rhines, called the "area tangent count". It will first be shown that the "area tangent count" is simply related to the average value of the curvature of particle outline in the two-dimensional section upon which the count is performed. The average curvature of such a section will then be shown to be proportional to the average value of the Mean surface curVature of the structure of which the section is a sample. The final result of the development is thus a relationship which permits the evaluation of the average value of the mean surface curvature from relatively simple counting measurements made upon a representative metallographic section. The result is quite independent of the geometric or even topological nature of the interface being studied. QUANTITATNE EVALUATION OF AVERAGE CURVATURE IN TWO DIMENSIONS The Area Tangent Count. Consider a two-dimen-sional structure composed of two different kinds of distinguishable areas (phases), Fig. l(a). If the system is composed of more than two "phases", it is possible to focus attention upon one phase, and consider the remaining structure as the other phase. The reference phase is separated from the rest of the structure by a set of linear boundaries, of arbitrary shapes and sizes. These boundaries may be totally smooth and continuous, or piecewise smooth and continuous. An element of such a boundary, dA, is shown in Fig. l(b). One may define the "angle subtended" by this arbitrarily curved element of arc, dO, as the angle between the normals erected at its ends, Fig. l(c). Now consider the following experiment. Let a line be swept across this two-dimensional structure, and let the number of tangents that this line forms with elements of arc in the structure be counted. This procedure constitutes the Rhines Area Tangent Count. Suppose that this experiment were repeated a large number of times, with the direction of traverse of the sweeping lines distributed uniformly over the semicircle of orientation.' Those test lines which ap- proach from orientations which lie in the range O to O + dO form a tangent with dA; those outside this range do not, see Fig. l(c). Since the lines are presumed to be uniformly distributed in direction of traverse, the fraction of test lines which form a tangent with dA is the fraction of the circumference of a semicircle which is contained in the orientation range, dO; i.e., vdO/nr or dB/n. If the number of test lines is N, the number forming tangents with dA is N(d0/n). Since each test line sweeps the entire area of the sample, the total area traversed by all N test lines is NL2. The number of tangents formed with dA, per unit area of structure sampled, is therefore

Jan 1, 1968

By J. E. Miller, W. E. DeVaney, L. Stroud

During a recent phase study of a natural gas, two stable equilibrium liquid phases were observed at temperatures below —200°F and pressures above 200 psi. This paper reviews the published literature on the occurrence of multiple equilibrium liquid phases and presents analytical data for the vapor and two equilibrium liquid phases of the liquefied natural gas at five experimental conditions. In addition, data for 30 conditions of two-phase equilibria are included. INTRODUCTION The low-temperature phase behavior of gases, most of which contained helium, has been investigated in the laboratories of the Helium Activity for many years. Since 1952, experimental studies of these systems have been continuous as part of the research program at Amarillo, Tex. Because of their value to private industries interested in participating in the Helium Conservation Program, several "Open File" reports containing phase equilibria data for heliurn-bearing natural gases have already been released by the Helium Activity. A paper containing information on the general phase behavior, operating criteria and extensive vapor-liquid data for two helium-containing systems was recently published.2 Additional publications presenting experimental data on the phase relationships of various gas systems are now in process and will be available in the near future. PREVIOUS EXPERIMENTAL WORK Although the formation of multiple liquids has been reported for various systems, to our knowledge this paper is the only substantiated evidence of a vapor-liquid-liquid equilibria in a naturally occurring gas. In 1940, Vink, Ames, and others13 reported the presence of two liquid phases in a hydrocarbon system consisting of mixtures of crude oils, solvents and natural gas. Eilerts and co-workers; published data on the recombined fluids from a gas-condensate well. This condensed gas, containing approximately 76 per cent methane and 24 per cent ethane-plus, exhibited two distinct liquid phases. Weinaug and Bradley 14 observed "unusual" phase behavior in a reservoir mixture. These workers postulated that the anomalous phase behavior was due to the "imminent formation of a second liquid phase". Botkin, Reamer, Sage and Lacey 1 studied two California crude oils that exhibited multiple phases. Kohn and Kuratal0 recently reported two equilibrium liquid phases in the methane-hydrogen sulfide system. Roof and Crawfordl1 and Eakin, et a16 also have reported experiments with binary systems that formed two stable equilibrium liquid phases. APPARATUS AND PROCEDURE A U. S. Bureau of Mines Phase Equilibrium Apparatus was used in conducting this study. The apparatus and procedures employed in its operation have been previously described3 and will not be repeated in detail ill this report. Briefly, the apparatus consists of a windowed cell which can be maintained within ±0.5°F for temperatures between room temperature arid -320°F. Pressure within the cell can be maintained within 0.1 per cent of gauge reading up to 800 psig. Equilibrium vapor and liquid samples are obtained in special containers4 for analysis by a mass spectrometer. Although the accuracy of the analyzer is about ±0.1 mol per cent, the reproducibility of the phase-equilibrium apparatus is considered relatively poor. Values reported from methane and nitrogen are considered accurate to ±l.0 and ±0.6 mol per cent. Data for ethane-plus in the vapor are accurate within 0.2 mol per cent; liquid-phase data for this aggregate compolnent are accurate within 1.5 mol per cent. For helium in the vapor phase, the analytical data are accurate within 0.2 mol per cent; liquid-phase analyses for this component were obtained by the charcoal adsorption method described by Frost8 and are accurate within 0.006 mol per cent. All of these references to the accuracy of reported values are conservative estimates based upon a statistical treatment of reproducibility data obtained with the apparatus.

By Robert E. Green, Kenneth Reifsnider

A microscopic X-ray diffraction technique was employed for the simultaneous study of the behavior of several families of lattice planes, whose local orientatiotz changes are manufestations of internal distortions resulting from specimen deformation. Photographs taken using aluminum were single crystals 1/64 in. In diam are presented which illustrate the appearance of various types of deformation- or growth- induced structural variations. Slip and lattice bending were detected in tensile tests for strains as small as 0.1 pct. Evidence of deformation bands, lineage structure, and void formation wns also shown. AmONG the most important methods of studying internal stresses in metals is the utilization of various X-ray techniques. The general subject of X-ray metallography has been treated in a most excellent manner by Taylor,1 and the use of X-rays for the direct observation of imperfections in crystals has recently been reviewed in an article by Newkirk2 and in the book edited by Newkirk and Wernick.3 Since the inception of metallographic X-ray analysis, there have been numerous technological developments and refinements, each with its particular advantages and disadvantages and, acrording to these, its particular applications. X-ray diffraction techniques can be divided into two general categories, that of X-ray diffraction microscopy and that of X-ray diffraction macroscopy. In the former are included such methods as those of Berg-Barrett, Lang, and Schultz2,3 which are concerned with microscopic imperfections such as dislocations. The second category includes all work concerned with the study of the condition of a crystal lattice structure as indicated by the marroscopic detail in its diffraction patterns. An example of this is the study of the diffraction manifestations of inhomogeneous plastic deformation as manifested by formation of deformation bands and inhomogeneous lattice rotations. The method used in the present investigation was an X-ray diffraction macroscopy technique. The geometry and analytical aspects of the method were similar to those of Julien and Cullity.4,5 The source was collimated with a single slit in a manner simi- lar to the "parallel beam'' method of Barth and Hosemann6 except that a continuous spectrum of radiation was employed. The apparatus produced large-beam transmission Laue patterns of thin cylindrical aluminum-wire crystals, which were deformed either in tension or torsion. Although the conventional X-ray target and interposed slit were not capable of the high resolution obtainable with a fine-focus X-ray source as employed in a microfocus apparatus, resolution was a secondary consideration in our technique, and was sacrificed to obtain sufficient intensity along a sizable length of the specimen. By using a grid indexing technique similar to that of Barth,7 we were able to study several diffraction lines from various planes simultaneously. The results of these tests give additional information with regard to the inhomogeneous deformation of single crystals, and the indexing procedure used provides a correlation between portions of the test specimen and portions of a diffracted beam. EXPERIMENTAL TECHNIQUE The experimental arrangement used is shown schematically in Fig. 1. A source of continuous X radiation from a vertically mounted Machlett X-ray tube possessing a copper target and operated at 20 kv and 10 ma was passed down a horizontal lead tube 80 cm long which terminated in an adjustable vertical brass slit. The slit opening was adjusted to correspond with the diameter of the test specimen. In front of the brass slit it was possible to place a screen wire mesh, one horizontal strand of which was a lead wire which served as a fiduciary mark, the screen itself serving as an indexing system as will be described later. Behind the screen was the test specimen which consisted of an aluminum single crystal wire 1/64 in. in diameter and 3 in. long. These 3-in.-long crystals were cut from

Jan 1, 1965

By F. W. Jessen, N. Lamont

The effect of an existing fracture or joint plane, which may exist in a rock, on the extension of a hydraulically induced fracture through the rock has been investigated in the laboratory. By use of a series of models made from various outcrop rocks, the width and orientation of existing fractures do not alter the extension or direction of the hydraulic fracture. The results, which conform quite well with the Grifith theory of failure, are illustrated by a series of photographs of the various models. INTRODUCTION The process of hydraulic fracturing has been widely used in the oil industry since its introduction in 1948 and has made possible the production of many reservoirs which would have been uneconomical prior to this process. Numerous studies of the mechanics of the process2-h nd of the effects of oriented fractures on recovery'.' have appeared in the literature. The increased recoveries led to attempts to predict the orientation of hydraulic fractures at the wellbore and to the development of methods to control this orientation. Field tests have been devised"." which indicate the validity of theoretical predictions of fracture orientation at the borehole. The direction of extension of hydraulic fractures from the borehole has not received much attention since most studies have predicted, at least implicitly, that a fracture will continue in the same plane unless a change of state of stress in the rock occurs. Since such predictions are based on the assumption of rock homogeneity, the effects of rock heterogeneities are left unknown. Most sedimentary rocks are composed of layers which reflect the changing depositional conditions of geological time. In addition, the more competent rocks frequently are fractured and jointed as the result of structural deformations or tectonic movements. Evidence of such joint systems exists in many surface outcrops, and it can be assumed that similar systems occur in many subsurface rocks, although the individual joints may be rather tightly closed due to overburden forces. This paper investigates the effect that an existing fracture in a rock would have on the direction or orientation of an extending or advancing hydraulic fracture when it intersects the existing fracture. The study was conducted on small rock models under triaxial stress conditions. The results indicate that an existing fracture will have little effect on the hydraulic fracture. THE MODEL STUDY The rock model represents an elemental portion of the earth containing an existing fracture which is located at some distance from a borehole from which hydraulic fracture is being extended. A generalized view of a model is presented in Fig. 1. The models were constructed from cement blocks and natural rocks. The various materials tested and some of the physical properties are listed in Table 1. The rocks were cut into rectangular blocks with dimensions of 11/2 X3Y2 X4 to 8 in. An initial slot was cut into the end face of each block along the longitudinal axis normal to the top face. The slot was filled with plastic aluminum along its outer edge to a depth of 1/16 in. A hole of 3/8-in. diameter was drilled into the sealed slot at the center of the end face to serve as an entry port for the fracturing fluid. Existing fractures of various types were simulated in the models. A "hairline" fracture with essentially zero width was created by cutting the model into two parts with a diamond saw and replacing the two parts together along the cut. A finite-width fracture was created by placing a layer of sand grains between the two faces of the cut just described (see Fig. 12). A large open fracture (similar, perhaps, to a vug) was created by cutting the model in two parts and removing a portion of the downstream block to a depth of % in. See Fig. 13. For a fourth

By Heribert Wiedemeier, Ali Khan

The tetnperature-conposition phase diagram of the syste,n MnS-CdS has been investigated over a range fro)n 600° to 1000° C. The small degree of solid solution on the MnS rich slde cornpared to the large CdS rich single-plzase region could be esplained by the difference in strzrctures of the cotnponents and the relative sizes of the metal ions. The change in lattice parameter as a function of cot)zposition is linear atzd jollous Vegavd's rule within experittzental limits of error. Mns and CdS have gained considerable attention in recent years because of their interesting solid state properties. In order to investigate such properties and thermodynamic quantities of mixed compositions of transition metal chalcogenides, it is necessary to establish their phase diagrams. Two earlier publications are concerned with the MnS-CdS system. Schnaase' found complete miscibility when MnS and CdS were co-precipitated in aqueous solutions at room temperature. However, there is evidence that the mixed crystals were not stable over the entire range of composition. roger's' investigation of the ternary system ZnS-CdS-MnS at 900" C indicates a solution of 48 mole pct MnS in CdS. During the course of this work which covers a temperature range from 600" to 100O° C, emphasis has been placed on the use of high-purity materials and well-defined modifications of starting products. EXPERIMENTAL Starting Materials. The stable green modification of MnS with NaCl structure was prepared by direct fusion of the elements and by chemical transport reaction. Stoichiometric amounts of manganese of 99.99+ pct purity and of sulfur of 99.999 pct purity from Gallard-Schlesinger Corp. were sealed in an evacuated quartz tube at a pressure of 10"5 mm Hg and annealed for 48 to 60 hr at 800°C. The quartz tubes used throughout this work were outgassed under high vacuum at a temperature of 90OU to 1000° C for 12 to 18 hr. For the synthesis of MnS by chemical transport3 stoichiometric ratios of elemental manganese and sulfur and small amounts of iodine were sealed under vacuum in a quartz tube, which was placed in the temperature gradient, 900/800-C, of a two zone furnace. Single crystals of MnS in form of platelets and octahedra were deposited at the cooler end of the tube. The manganese content was determined by EDTA titratin. A typical result of several analyses was 63.05 pct Mn which agreed well with the computed value, 63.14 pct. Commercially available CdS of 99.9+ pct purity, a mixture of the cubic and hexagonal forms, was converted into the hexagonal high-temperature modification by annealing CdS under vacuum in quartz tubes at 700° C for about 36 hr. As a second method, cadmium sulfide was transported in a temperature gradient, 70O° /650" C, with in vacuo sublimed iodine from the hot to the cooler zone of the tube. Large sized crystals in form of hexagonal columns and some platelets were obtained. An average result of the cadmium analysis by EDTA titration4 was 77.93 pct in good agreement with the computed value, 77.81 pct. Only the NaCl modification of MnS and the wurtzite modification of CdS were used for the solid solutions. Preparation of Solid Solutions. Finely powdered MnS and CdS samples were thoroughly mixed in molar ratios and compressed into pellets of about 6 mm diam and 2 mm in height at a pressure of approximately 13,500 atm.

Jan 1, 1969

By E. P. Whittemore

Experience with the ASC multipoint gas lift system was obtained in Colonia zone of the West Montalvo field near Oxnard, Calif. The wells in this pool produce from depths varying from 10,500 to 12,000 ft. Oil gravity is generally 14 to 15' API with a few extremes of 12 and 20" API. Some salt water is produced which causes some very viscous emulsions. Viscosities at 150F (which is the approximate wellhead temperature) vary from 5,000 to 100,000 SSU. Most of the production is by gas lift, although a few wells are produced by rod and hydraulic pump. About half of the gas-lift wells are on continuous flow and the remainder are on intermittent lift using large, ported, pilot-operated valves for single-point transfer of gas from casing to tubing. Gas-liquid ratios vary from about 6 to 10 Mcf/bbl of gross fluid lifted. Wells are produced to a 450-psi trap system. The following remarks will be confined to intermittent lift only, since this is the type of lift which has been achieved with the ASC valve system. The maximum gross fluid which has been produced by single-point intermittent lift is about 350 B/D in 3-in. tubing and 200 B/D in 21/2-in. tubing with gas-liquid ratios of approximately 7 to 9 Mcf/bbl. Some design changes could reduce this ratio. The ASC multipoint system has provided production as high as 480 BOPD in 21/2-in. tubing with gas-liquid ratios just under 4 Mcf/bbl. To be able to apply the multipoint system, it is recommended that a detailed explanation be obtained concerning transition-point pressure and stabilizer setting—what its significance is to the string design, how it may work for or against the operation of the well, how it is related to tubing sensitivity and how it affects the unloading operation. The unloading operation may only be of academic interest in a technical paper, but to the production foreman, unloading and setting the valves in operation is a very real problem and should be understood in detail. One item touched lightly in the paper was the unloading valve. This valve controls the maximum pressure at which the well can be operated. When lifting heavy viscous fluids, it is most important to set this valve for the maximum possible realistic operating pressure at the surface. If the well lifts easily, it is simple to set the ASC valves at a lower operating pressure and the unloading valve will remain closed; but if the well happens to be heavier to lift than anticipated, it may be desirable to operate on the unloading valve itself and use all the energy obtainable at the bottom of the hole. In the Colonia pool very heavy wet-gas gradients are experienced due to the viscosity of the liquid and the dense mist which is left behind a slug of fluid. There are many combination strings of 3- and 21/2-in. tubing. This aggravates the wet-gas gradient problem and provides wet-gas gradients of about 50 to 70 psi/1,000. An advantage which multipoint lift has provided is increased slug efficiency through better maintenance of pressure under the slug and decreased fall back as the slug passes up the tubing. By using multipoint injection, wet-gas gradients have been reduced to about 30 psi/1,000. This has reduced bottom-hole operating pressure and given a production increase. The ASC valve is not a simple device. It's operation is difficult to understand, and it must be understood to be used efficiently in gas-lift design. Operating problems are difficult to diagnose—whether they be caused by the fluid lifted, valve malfunction, lift gas rate, or operating pressure. Calculations and reasoning are required to find out what is causing the problem. Inherent in the ASC valve is the inability to create large pressure differentials across a slug. Large differentials may be required to overcome the inertia of very viscous fluid as it is being accelerated in the bottom of the hole. This is tied back to the design of the unloading valve and is one reason for the importance of setting the unloading valve for the highest possible operating pressure. ~u; to the narrow spread the ASC valves provide, it is impossible to cycle slower than about 24 cycles/day on choke control. If small production of 150 BOPD and less is expected, a surface time-cycle controller will be required if the most economical operation is to be achieved. To achieve a satisfactory operation, the operator must keep a record of any changes made in the operating pressure of the ASC valves. Anything which may cause changes in casing pressure in excess of the stabilizer setting will change the valve operating pressure, and if this is not noted from daily inspection of the well casing-tubing pressure recorder charts, the operator will lose control of the well. Significant results can be achieved using ASC valves; however, considerable knowledge is required to design with them, and attention to detail is required for satisfactory field operation.

Jan 1, 1965

By M. V. Lowry

This paper outlines the economic considerations that led to the recent installation of a thickener at St. Joseph LeadCo.'s Balmat, N.Y. mill. To incorporate storage of concentrates, they decided upon a single, unusually deep tank to be used for both storage and thickening. The abnormally high rake lift required was achieved by the novel feature of having the entire drive platform raise and lower. Initial operating problems are described along with the satisfactory solutions. Total costs for concentrate handling before and after installation of the storage thickeners are compared. In Northern New York State, the St. Joseph Lead Co. conducts a 2100 tpd zinc mining and milling operation at its Balmat Plant. Conventional crushing, grinding, and flotation is used to produce a zinc concentrate. For 32 years, from 1930 through 1962, the plant operated with the concentrates going directly from flotation to the filtering, drying, and loading facilities. All of the concentrate handling equipment, therefore, had to operate 24 hrs per day. It also had to accommodate wide fluctuations in tonnage, due to variations in the grade of ore. Many problems were thereby encountered in filtering and drying, but it was never concluded that the cost could be justified for installing a conventional, large diameter thickener. Finally, in 1963, they installed an unconventional thickener that is unusual in several respects. The tank depth is 16 ft instead of the normal 8 ft. The rakes are raised and lowered by having the main drive gear located on a movable platform. Automatic controls are programmed to raise the drive platform and rakes during one shift of storage. During the next two shifts of withdrawal, the controls are programmed to lower the drive platform and rakes. After three years of operating this unique storage-thickener, the conclusion is that a correct choice was made from several alternative schemes for storing concentrates. The various considerations involved in the final selection will here be analyzed, and the design features and installation details will be de- scribed. Operating problems and modifications made to the equipment will next be considered, and finally the effects upon filtering, drying, and loading will be reported. SELECTION CONSIDERATIONS Even without a thickener, concentrate handling had become reasonably efficient at the Balmat Mill by the year 1962. A tonnage that varied between 6 and 25 tph was being handled fairly satisfactorily. The filter cake moisture of 8%% seemed quite respectable, except that two large filters were usually in service. Three filters often had to be operated in order to prevent excessive filter overflow with consequent loss of values. This situation occurred when zinc concentrates from flotation exceeded 20 tph and when filter cloth blinding developed. Over the years, numerous small improvements had been effected, such as: selection of a filter cloth with better flow characteristics; addition of flocculant to the filter feed; and, in 1953, the smallest of three drum filters was replaced by a five disc, 8' 10" diam filter with a bottom agitator and snap blow. As another example of fairly efficient operation, the oil-fired dryer was doing a seemingly satisfactory job of further reducing the moisture content to an average of 3%. However, there were often considerable dust losses when the tonnage suddenly dropped off to 6 tph. At high tonnage rates, the resulting high moistures of 4% and 5% caused difficulties due to concentrates sticking and freezing in chutes leading to the box car loaders. (Drying of concentrates is justified because of the high freight rate for the long shipping distance to the company owned smelter at Josephtown, Pa. near Pittsburgh.) It was long realized that installation of a thickener would permit the subsequent steps of concentrate handling to proceed more smoothly and would alleviate the problems existing in the filtering, drying, and loading operations. It was also realized that even a slightly lower filter cake moisture could mean considerable savings in fuel oil. However, all these factors were never quite sufficient to warrant the expense of a thickener until three more considerations were added to the picture. First, the advent of flocculants meant that a thickener of relatively small area could now be considered. Secondly, a complete renovation of the zinc flotation circuit was made between 1957 and 1961. The

Jan 1, 1967

By Ralph Hultgren, Prodyot Roy

Manganese vapor pressures from 1250° to 1500°K were measured by conventional Knudsen and torsion-effusion methods in twelve Fe-Mn alloys with compositions from 9 to 80 at. pct Mn. The Knudsen re-sults agveed approximately with previous measurements found in the literature which indicated the solutions were nearly ideal. However, except for the higher manganese compositions, the initial torsion readings indicated much (up to 50 pct) higher vapor presszcres than the Knudsen method. These high readings decreased steadily with time. The results are interpreted as due to depletion of surface concentration of manganese during evaporation. Thus the initial torsion readings are the most nearly correct and Knudsen methods on alloys are to be regarded with suspicion unless it can be demonstrated that diffusion rates are rapid enough to replenish surface concentrations depleted by evaporation. For the lowest manganese contents and highest temperatures, depletion causes initial torsion readings to be too low. FEW thermodynamic data are available for alloys of the high-melting transition metals due primarily to experimental difficulties at the high temperatures involved. Measurement of vapor pressure is one of the most promising techniques to be applied to this problem. From the vapor pressure of a component of an alloy phase, its activity or its partial molar Gibbs energy can be directly calculated. From measurements over a sufficient range of temperatures and compositions the partial and integral Gibbs energies, enthalpies, and entropies may be determined through Gibbs-Duhem integration. For solid phases of variable composition, which commonly are found in alloys, measured vapor pressures are low because of depletion of the surface concentration of the more volatile component as it is selectively vaporized. Diffusion from the interior tends to restore the depleted concentration. The seriousness of the effect depends on the relative rates of diffusion and vaporization. Although depletion has been recognized as a factor,' direct measurements of its rate are lacking and quantitative estimates of its effect on measurements are uncertain. In the present work the vapor pressures above a series of Fe-Mn alloys have been measured by the torsion-effusion method. This method permits a measurement of the vapor pressure of manganese as soon as the sample comes to temperature and continuously throughout the run. The rate of decline of the apparent vapor pressure measures the rate of depletion and the torsion reading at zero time should be correct. At high manganese concentrations (70 and 80 at. pct Mn), the torsion reading remained nearly constant; surface depletion was negligible. There was a slow drop in measured pressure due to bulk loss of manganese from the sample. However, for lower manganese contents, especially at high temperatures, the depletion effect was considerable and the apparent vapor pressure decreased steadily with time. For these alloys the Knudsen method should give pressures which are too low. The measurement of pressure in the Knudsen method cannot be made until enough manganese has been vaporized to be weighable. The Knudsen result is therefore an integrated average between the initial and final vapor pressures. To verify this, conventional Knudsen measurements were also made with results in approximate agreement with previously published Knudsen measurements for these alloys. As expected, for the lower manganese contents the initial torsion readings of pressure were as much as 50 pct higher than the Knudsen. THE APPARATUS The apparatus, shown in Fig. 1, is capable of operating to temperatures up to 2000°K. A vacuum of 5 x 10"6 mm Hg can be maintained. Temperatures were measured to +3° by a W-Re thermocouple placed in the dummy cell, N. The torsion cell consisted of two alumina crucibles with holes in their covers. They were placed in the molybdenum holder shown suspended from the torsion wire. Rectangular torsion wires (1 by 4 mm) were found to have superior sensitivity and less residual distortion than circular (2-mm-diameter) wires. The precision of angular measurement was found to be *0.025 deg; the variation is no doubt due to temperature fluctuation and vibration. For the Knudsen experiments the alumina cell was set on the support, N. SAMPLE PREPARATION 800-g samples were prepared by melting together electrolytic iron and electrolytic manganese and pouring the melt into a water-cooled copper mold. Melting and pouring were done under a helium at-

Jan 1, 1965

By Robert E. Green, Robert A. Swanson

Ultrasonic attenuation and stress were measured simultaneously as a function of strain for aluminum single crystals tested in compression. The propagation mode and polarization of the ultrasonic waves were chosen with reference to the theoretical analysis presented in Part I. Good experimental agreement was found with this theory and with earlier experimental work in tensile tests. Support is given to the contention that ultrasonic -attenuation measurements are much more sensitive to the early stages of plastic deformation than are conventional stress -strain measurements. Dislocation meclzanisms are suggested which are compatible with both the present and the earlier experimental observations. A brief historical introduction of previous work concerned with the study of dislocation motion by ultrasonic-attenuation measurements has been given in Part I. The purpose of the present experimental investigation was to make use of the theoretical considerations from Part I in order to gain further knowledge concerning dislocation motions during plastic deformation. Emphasis was placed on the choice of propagation modes and polarization of the waves, such that interactions between these waves and dislocation movement on a specific slip system could be investigated. EXPERIMENTAL PROCEDURE Since the primary concern of this investigation was dislocation damping, other sources of damping were eliminated as much as possible. The test specimens were 0.5-in.-diam single crystals of 99.99+ pct pure aluminum grown from the melt by a modified Bridgman technique. Ultrasonic-attenuation measurements were made at a frequency of 10 megacycles per sec using a Style 56A001 Ultrasonic Attenuation Comparator manufactured by Sperry Products Inc. after a design by Chick, An- derson, and Truell.1 At this frequency the particle vibrations are essentially adiabatic and thermo-elastic damping should be absent. This frequency was selected since it was one of the frequencies used by Hikata et al.2 n conjunction with tensile tests on aluminum crystals, thus allowing direct comparison with this work. The use of quartz-crystal transducers insures that the amplitude of vibration is not sufficient to cause the break away of the dislocation loops from weak pinning points. The quartz-crystal transducers used all possessed a resonance frequency of 10 megacycles per sec and were thin circular discs 0.375 in. in diameter. X-cut crystals were used to generate the longitudinal waves and AC-cut crystals to generate the transverse waves. Aluminum was chosen as the basic material because it is a typical fcc metal whose deformation behavior is well-known and because the most recent work at the time the present research was initiated was that by Hikata et al. who used aluminum. The present tests were run in compression to see if such tests could be satisfactorily run in compression without being severely masked by grip effects.. A second reason was to compare the results in compression with those of the tension experiments of Hikata et at. Finally, shorter specimens could be run in compression with less over-all damping than in tension. All of the aluminum-crystal test specimens used were oriented for plastic deformation by single slip; i.e., they possessed the orientation having a maximum Schmid factor of 0.5. Because of the well-known time dependence 3 of plastic strain at constant stress, the test specimens were subjected to a quasi-static loading. Previous investigations4-' have indicated that attenuation after plastic deformation is also time-dependent, so any continuous loading of the specimen would show that changes in attenuation were also a function of strain rate. By loading the specimen to a given stress level and holding it constant until the recovery process was essentially complete, the time dependence was eliminated. The quartz transducer was permanently bonded to the aluminum crystal using Eastman 910 cement. Excess cement was removed from around the quartz with DMF (dimethyl formamide). Eastman 910 was found to be far superior for bonding, especially with regard to the shear-wave transducer, since it formed a solid bond which readily supports shear-wave propagation. The solid bond formed by the Eastman 910 cement also insured that the quartz

Jan 1, 1964

By Adrian C. Dorenfeld, Theodore Balberyszski, Strathmore R. B. Cooke

This paper reports results of studies of sulfidiza-tion of base-metal oxides and silicates with gaseous sulfur, hydrogen sulfide gas and pyrite and of their subsequent flotation with xanthate collectors. It has been established that a 100% conversion of the oxides of lead, zinc, copper and manganese into their respective sulfides is possible and is a function of reaction time and temperature. Sulfidization of chrysocolla (with malachite and azurite inclusions) resulted in a product containing covellite, chalcocite and digenite in proportions depending on conditions of sulfidization. Reacting cassiterite with gaseous sulfur, H2S or pyrite at various reaction temperatures resulted in its partial conversion to a tin sulfide. Flotation of the products of sulfidization indicated that their behavior is similar to that of natural sulfide minerals, the recovery being a function of the con-version of the oxides to their respective sulfides. The gradual depletion of high-grade sulfide mineral deposits has turned the attention of the mineral industry to the recovery of metals from the oxides and silicates. Anionic (fatty acid) and cationic collectors have in some cases made flotation of nonsulfides possible, although, in general, flotation of oxide ores is not as yet an economic process. Consequently, many attempts have been made to sulfidize the surface of the relevant oxide mineral and thus make it amenable to to In recent years, Bautista and sollenberger4 have investigated the conversion of a number of oxides to sulfides by reacting them with molten sulfur. This paper presents the results of .investigations carried out at the School of Mineral and Metallurgical Engineering at the University of Minnesota to study the flotation characteristics of some sulfidized minerals. It is divided into two parts: The first describes the sulfidization of a number of oxides and a silicate, and the second presents the flotation behavior of the products of sulfidization. SULFIDIZATION OF METAL OXIDES AND SILICATES Experimental Procedure: SULFIDIZATION WITH HYDROGEN SULFIDE GAS — Sulfidization with H2S gas was carried out in a horizontal tube furnace (Fig. 1). The temperature of the furnace was regulated by means of a Variac and determined with a chromel-alumel thermocouple. The constant temperature zone in the furnace was about 6 in. in length, and it was within this zone that the experiments were carried out. The gases employed were supplied from standard compressed gas cylinders, and passed through a glass-wool filtering tower before entering the Pyrex reaction tube. Gaseous products were bubbled through a water tower (used as a flow indicator) and excess H2S was burned off at the end of the outlet tube. Samples of reagents or minerals were placed in a 3-in. Alundum boat and inserted within the constant temperature zone of the furnace. Nitrogen gas (6 ppm O2 content) was passed through the tubes at room temperature to remove air in the tube, and continued to pass while the furnace was heating up. When the required temperature was reached, H2S was allowed to enter the tube and the supply of nitrogen was shut off. At the end of the reaction period, the reverse procedure was carried out, the samples being cooled to room temperature in a nitrogen atmosphere. The flow rate of H2S gas was maintained fairly constant in all experiments, although the rate was not determined. SULFIDIZATION WITH SULFUR POWDER - To study the sulfidization of minerals with sulfur (liquid or gaseous), samples of the mineral, together with a measured quantity of sulfur powder, were placed in a stainless steel (SS316) reaction vessel (Fig. 2). The reaction vessel was heated in a vertical resistance coil furnace, the temperature being regulated through a Variac. At the end of the experiment the vessel was cooled to room temperature before the sample was removed. Cooled products were leached with CS2 to remove any free sulfur. SULFIDIZATION OF TIN CONCENTRATES - Fifty gram samples of sulfidized tin ore were prepared by mixing -48 mesh Bolivian tin concentrate with -48 mesh Ottawa sand in various proportions and sulfi-dizing these samples with H2S in the horizontal tube

Jan 1, 1969

By H. W. Schadler

The superplastic behavior of low carbon and manganese bearing steels has been evaluated. The results of elevated-temperature stress-strain rate and elongation tests are reported which indicate that high strain rate sensitivity (>0.5) and adequate elongations are achievable in ultrafine-grained steels 1 to 2 p, but at strain rates which are not commercially attractive. It has been demonstrated that the fine grain size is retained after long times and high strains if the temperature is kept within the range of the two-phase (a + ?) field. INTEREST in superplasticity has been stimulated by the desire to: 1) understand the origin of, and mechanisms responsible for, the large uniform elongations observed, and 2) exploit this property for commercial advantage in metal forming operations. Although the Zn-22 wt pct Al alloy presently being studied as a model material1-5 may find application in sheet forming and extrusion, the potential of super-plasticity should best be realized in large tonnage materials, such as steel and aluminum alloys. The degree of superplasticity in low-carbon and manganese-bearing steels has been evaluated. The results of elevated-temperature stress-strain rate and elongation tests on ultrafine grain size material are reported. Avery and Backofen6 and Hart7 have shown that geometrically stable flow leading to extensive uniform elongation in the tension test is associated with high values of the strain rate sensitivity, m, defined: Lozinsky had reported that titanium and zirconium experience permanent deformation if subjected to a constant load and cyclic heating through the temperature range of the phase transformation. Although strain rate sensitivities in excess of about 0.2 had not been reported previously for steel, permanent deformation had been observed11-13 in a wide variety of steels subjected to a constant load and cyclic heating through the temperature range of the a-? phase transformation. Thus by analogy, steel could be expected to exhibit high strain rate sensitivity but only in the a + ? condition. High strain rate sensitivity has been observed at 650°C (a + Fe3C), but not reported as such, by Bailey, Dickenson, and pearson14 in 1931 at a strain rate of about 10-9 per min. It then remained to determine whether high tensile elongations would be observed in a rate-controlled test at constant temperature and at what strain rate strain rate sensitivity values greater than 0.5 would be observed. Since previous experience8 had indicated the importance of fine grain size to realizing high m at reasonable strain rates, it was first necessary to produce an ultrafine grain size and then keep the grains from growing during the test. The results of this investigation show that fine grain size can be readily produced16 and maintained by restricting the temperature of testing to below the ? transus. Further, superplasticity (high m and large uniform elongation) is observed. However, the strain rate range is only marginally useful for commercial forming operations with the finest grain size produced. MATERIAL The material investigated initially was a 1.9 wt pct Mn, 0.42 wt pct C, hot-rolled bar previously used by Low and Turka1015 and available in the laboratory. The 0.500-in. round was cold-rolled to a 0.090-in. flat, annealed for 4 hr at 850°C in argon, air-cooled, and cold-finished to 0.050 in. Subsequently, four additional steels of the compositions given in Table I were investigated to explore the effects of manganese, carbon, and test temperature on the observed stress-strain rate behavior. These steels were melted under argon, cast to 0.75 by 2 by 5 in. slabs, hot-rolled at 850°C, surface-finished to 0.13 in., and cold-finished to 0.050 in. Sheet tensile specimens 0.200 in. x thickness with 1- or 2-in. gage length were cut parallel to the rolling direction. Table I also includes the nominal transformation temperatures for the AISI 1340 and the four experimental steels. EXPERIMENTAL PROCEDURE Production of Fine Grain Size. Ultrafine grain size (1 to 5 p) was considered essential for this studv. Grange16 has described two techniques for producing

Jan 1, 1969

By E. R. Buchanan, R. E. Reed-Hill

Cylindrical magnesium single crystals were deformed in torsion. The axis of torsion was the basal pole. Five crystals were deformed to different strains between 0.08 and 1.03 and then sectioned in order to determine their dislocation densities using the transmission electron microscope. The work hardening rate of all specimens was at least an order of magnitude higher than that normally associated with easy glide in a tension test and comparable to that obserzed in stage B of a tension test. The correspondence between stage B in a tension test and the initial stages of a torsion test is believed to result from the fact that in both cases deformation occurs in a structure containing roughly equivalent densities of the dislocations associated with the three basal slip vectors. THERE are three basic ways of changing the shape of a crystal using slip dislocations. The crystal can be sheared along a slip direction in a slip plane; it can be bent about an axis in the slip plane normal to the slip direction; and, if the slip plane contains multiple slip directions, it can be twisted or rotated about the slip plane normal. Of the three processes, generally known as translational, flexural, and rotational slip, only rotational slip has not been extensively investigated. The object of the present research was to obtain basic information about this phase of crystalline plasticity. This paper is concerned with some aspects of the stress-strain curves obtained by twisting magnesium crystals about their basal poles. Magnesium was selected for four reasons. One, its recovery rate at room temperature is relatively low. Two, single crystals may be easily grown. Three, at room temperature the critical resolved shear stress for basal slip is about two orders of magnitude lower than that for nonbasal slip, so that rotational slip might be expected to occur primarily by basal slip. Finally, relationships between flow stress, shear strain, and dislocation density have been determined for tensile deformation of magnesium crystals,' thereby providing a basis of comparison for the torsional results. EXPERIMENTAL PROCEDURES Crystals were grown from 0.5 in. diam extruded sublimed magnesium rod furnished by the Dow Chemical Co. who reported that it contained in weight percent less than 0.0003 Al, 0.01 Ca, 0.01 Cu, 0.0012 Fe, 0.001 Mn, 0.0005 Ni, 0.003 Pb, 0.001 Si, 0.01 Sn, and 0.02 Zn, with the balance magnesium. All crystals were grown in a dried argon atmosphere using Jill-son's2 modified Bridgman technique. Two different methods were used to obtain crystals with the basal plane normal to the specimen axis. These included direct growth from seeds of the proper orientation, and spark machining (trepanning) of 0.5 in. diam cylinders from larger (1.5 in. diam) randomly grown crystals. The crystals thus produced were polished in a 20 pct HC1 water solution and then etched in a 1 pct HC1 water solution to develop etch pits lying in rows parallel to the basal plane trace. The crystals were then revolved about their axes on the stage of a low-powered microscope. Torsion specimens were prepared only from those crystals whose axes were normal to the rows of etch pits. It is estimated that this simple orientation method was accurate to about 51 deg. 1.625 in. long cylinders were next cut from these selected crystals and then acid machined in a 20 pct HC1 water solution into torsion specimens with a 1 in. long by 0.30 in. diam reduced gage section. Following this, they were annealed in air at 400°C and furnace cooled to room temperature. The specimens were given a final polish in a 10 pct HC1 water solution, rinsed in ethanol, dried, and cemented into brass grips with an epoxy resin. In addition to the torsion specimens, several tensile specimens with their basal planes at 45 deg to the stress axis were also prepared with similar dimensions except that the gage sections were increased to 4 in. in length. The torsion specimens were tested in the apparatus

Jan 1, 1970

By N. E. Brown, F. L. Versnyder

THE apparent dependency of the electrical characteristics of hexagonal crystalline selenium on microstructure has aroused much interest in microscopical studies of selenium. Microscopic observations on the crystallization of selenium have been made by Escoffery and Halperin,' P. H. Keck,' and other investigators. It is the purpose of this paper to discuss the microstructural changes observed on polished cross-sections of single layers of selenium after various heat treatments. Observations were also made on crystallization of the free-surface layer of these deposits. In general, all of the transformations studied were either transformations of the vitreous selenium to hexagonal selenium or micro-structural transformation of the hexagonal selenium itself. Procedure The selenium used in this work was obtained from the American Smelting and Refining Co. and was approximately 99.96 pct pure. An intentional impurity of 1 part per 2,000 of bromine was added to the material prior to evaporation. A thickness of approximately 0.002 in. of this selenium was vapor deposited on an aluminum base plate. The maximum plate temperature during the vacuum vapor deposition was 140°C. Mounting of the cross-sectional specimens for metallographic study could not be done in plastic mounting media, as is customary, since temperatures in excess of 50°C would cause unwanted transformations. Consequently, a simple clamp-type device was used to mount the specimens for preparation. All grinding operations were then done carefully by hand in order that the specimen not become heated during this operation. Wet polishing was done on the conventional metallographic polishing laps, using successively finer grinding powders. An extremely careful polish is necessary, since observation and micrography of the specimens are done in the unetched condition under polarized light. The two observations of crystallization made on the free surface of vitreous selenium deposits (Figs. 4 and 5) were made on surfaces which were perpendicular to the cross-sections studied. These free-surface layers were examined directly, i.e., no pre- vious metallographic preparation, as obtained from the vacuum vapor deposition. Microscopic Observations A study was made of polished cross-sections of the vitreous selenium as-deposited. It was noted that in all cases there was columnar crystallization adjacent to the base plate, which appeared to occur during the vacuum deposition process. This observation has also been made by Keck? It also was observed that vagrant spherulitic crystallization occurred in the vitreous selenium. The term "vagrant" is used, since these spherulitic grains appear to crystallize at random throughout the vitreous selenium during the vacuum deposition process. Columnar crystallization at the A1-Se interface and a typical spherulite observed in a polished cross-section of "as-deposited" vitreous selenium may be seen in Fig. 1. Cross-sectional samples of vitreous selenium studied after heat treating individual samples for 20 min in 10" steps from 80" to 220°C revealed that crystallization—in this case, columnar crystal growth —proceeds from the aluminum base plate to the surface of the specimen (Fig. 2). Crystallization was microscopically observed to be complete after the 130°C heat treatment. Visual examination of the free surface of the specimen after the 130 °C heat treatment revealed the readily recognizable grey appearance of the completely crystallized selenium, in corroboration of the microstructural observations. No microstructural transformations then appeared to take place between 130" and 190°C. At 190°C the beginning of recrystallization appeared and proceeded until the columnar grain structure had been completely transformed to equiaxed grains between 210" and 220°C (Fig. 3). Naturally, the grain size of the recrystallized grains at the lower temperatures (190" to 210°C) was smaller than is illustrated in Fig. 3. In addition, polished cross-sections of deposits heat treated at 140°C for 10 min to cause complete crystallization and, subsequently, heat treated in 10" steps from 80" to 220°C for 20 min were studied. As expected, no microstructural transformations took place until the beginning of recrystallization was observed at 190°C. A comparison with the previously studied specimens revealed that recrystallization proceeded almost identically in the two experiments although in the first case the deposits were vitreous prior to the series of heat treatments and in the second case they had been crystallized by a previous heat treatment. By heat treating for longer times (180 min) at lower temperatures, the

Jan 1, 1956

By E. O. Wagner, V. F. Parry, W. S. Landers

Development work has shown that the yield of primary tar from coal is proportional to the heat in the volatile matter of the coal and that the yield of tar from noncoking coals may vary from 10 to 45 gal per ton on the ash-free and moisture-free basis. Pilot plant operations have proved that 100 to 135 pct of the bench-scale carbonization-assay yield of tar can be obtained. FOLLOWING investigations by the Denver Bureau of Mines on drying fine coal in the entrained state,'. ' Texas Power & Light Co. employed the fluidized technique to upgrade Texas lignite for use in power plants. Because of the rapidly rising cost of natural gas in Texas the company agreed to cooperate with the Bureau of Mines in studying further the upgrading of lignite by low-temperature carbonization, since potential value of the tar would help offset the cost of fuel. Considerable interest was aroused, therefore, when Aluminum Co. of America decided to use dried lignite in its 240,000-kw power plant at Rockdale, Texas, operated by Texas Power & Light. Carbonization of coal before burning in a power plant is not new. Plants in Germany have been operated for many years on carbonized brown coal and lignite briquets produced in large integrated plants. Large-scale experiments in carbonizing pulverized coal with hot flue gases were made 30 years ago at Milwaukee," and many inventors have proposed other processes. In the U. S., technical and economic problems have prevented successful operation of large plants on carbonized coal. but new techniques of handling solids in fluidized beds may overcome these difficulties, particularly if the higher volatile noncoking coals are used. Any bituminous material will decompose when heated to about 900°F to yield primary tar, gas, and char. The quantity of tar obtained from various coals depends on their rank and volatile content and to some extent on rate and method of heating. The liquid products derived from thermal decomposition of peat, brown coal. lignites, oil shale, and noncoking bituminous coals can be easily liberated by rapidly heating these materials in a fluidized bed at about 500°C (932°F). Since it takes only a few minutes to heat small particles of fuel to carbonizing temperature in a fluidized bed, processing plants can be built to handle up to 50 tph at relatively low cost. The pioneering development work being conducted at Rockdale, Texas, by Alcoa and Texas Power & Light will solve many engineering problems of such operations. The Bureau of Mines at Denver has studied the carbonizing properties of several hundred coals by small scale assay at 500°C, deriving a simple correlation between the potential yield of tar and the proximate analysis. This correlation, shown in Fig. 1, compares the heat in the volatile matter of the coal with the potential yield of primary tar. The yield of primary tar varies from 12 to 50 gal per ton of pure coal." About the same amount of heat is needed to * MAF equals moisture-and-ash-free basis. distil any dry coal at 500°C, and the time required to carbonize a given particle size is about the same for any coal. It is therefore obvious that coals rich in volatile matter will show the greatest profits when processed. Texas lignites are rich in volatile matter, which contributes some 5700 Btu per lb of MAF coal, and the potential primary tar and oil yield from this lignite averages 12 pct by weight or 27 gal per ton from the pure lignite. Texas lignites are considerably richer in potential tar than lignites of North Dakota and Montana. During 1950 the Bureau of Mines conducted many experiments on carbonizing fine dry coal in the entrained state, publishing a report4 n major features of pilot and commercial-size units required to carry out the process. Additional experimental work has been done at Denver and the pilot plant has been improved, particularly the facilities for studying removal of fine dusts from tar vapors and gases at high temperatures by electrostatic precipitation. A number of materials have been carbonized, including sawdust, peat, brown coal, Brazilian oil shale, lignites, and the lower rank bituminous coals having noncoking properties. Straight coking coals cannot

Jan 1, 1957

By N. J. Grant, A. W. Mullendore

Three aluminum alloys of 0.94, 1.92, and 5.10 pct Mg, prepared from very high purity metals, were tested at 500°, 700°, and 900°F in creep rupture. The degree of strengthening through solid-solu-tion alloying and the effects on the deformation characteristics and fracture were examined. The ductility of the alloys as a function of stress and temperature was closely followed. STUDIES of the creep process in pure metals in recent years have done much to expand the understanding of the fundamental deformation and recovery processes that contribute to overall creep behavior. In order that this knowledge may be applied to commercial alloys, it is necessary to know the principles governing the effect of alloying on the mechanisms of creep. A limited amount of work has been performed in this field, but few investigators have attempted to follow the changes in particular creep mechanisms with alloying. Recently, studies of the effects of solid-solution alloying on the plastic properties of aluminum have been conducted by Dorn, Pietrokowsky, and Tietz,1 Sherby, Anderson, and Dorn,2 and Sherby and Dorn.3 This paper presents the results of an investigation of the effect of solid-solution alloying of high purity aluminum with magnesium on the creep-rupture properties, and correlates these observations with changes in the creep mechanisms. This work is thus an extension of the creep-rupture observations of Servi and Grant4,5 and the deformation studies of Chang and Grant.6,7 Experimental Procedure Three alloys of aluminum containing approximately 1, 2, and 5 pct Mg were tested. These alloying additions are all within the solid-solubility limit at the testing temperatures.' The analysis of the materials is presented in Table I. The tests fall into two categories: l—creep-rup-ture tests at 500°, 700°, and 900°F, and 2—structure study tests performed primarily at 700°F. Speci-mens of 0.160 in. diameter with milled flats for metallographic observations" ' were utilized for the structure studies. All specimens were annealed in one step to give the desired grain size for the tests. Table II presents the annealing data and final grain sizes. The specimens were polished electrolytically before testing with Jacquet solution (2/3 acetic anhydride, 1/3 perchloric acid) at 25" to 30°C, and 15 to 20 v. Creep-rupture testing was performed under constant load with the apparatus previously described." Results and Discussion Creep-Rupture Properties: The log-log plots of creep-rupture data are presented in Figs. 1 and 2. For these very pure single-phase alloys, the minimum creep rate and the rupture life both exhibit straight-line dependence on stress in this method of plotting as they have for commercial alloys0,10 and for pure aluminum." Curve breaks, based on the use of straight-line segments, at 500°F have been found by metallographic study to correspond to a transition from low to high temperature behavior and so represent zones of equicohesion. Specimens on the high creep-rate side of the break showed normal granular deformation processes whereas those on the low creep-rate side showed rapidly increasing grain-boundary sliding and migration with extensive evidence of intercrystalline cracking at 500°F. Two micrographs of the 0.94 pct Mg alloy, Fig. 3, show the increased participation of the grain boundary in the deformation process at 500°F with decreasing stress. In Fig. 3a is shown the structure of a specimen which exhibits little deformation along the grain boundaries and failed transgranularly; in Fig. 3b is shown the increased deformation along the grain boundaries at a lower stress for a specimen which showed appreciable intercrystalline cracking. The severity of intercrystalline cracking increased with increasing magnesium content at 500°F. Intercrystalline cracking disappeared in most of the specimens at 700°F and persisted only in the 5 pct Mg alloy at high creep rates. At 900°F all of the specimens deformed with extensive grain-boundary participation, including extensive grain-boundary migration. None of the alloys at 900°F showed intercrystalline cracking.

Jan 1, 1955