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By J. W. Hickman, E. A Gulbransen

The physical and chemical structure of the oxide films formed on metals and alloys is of interest in our understanding of their protective properties. According to Pilling and Bedworth,¹ if the specific volume of the oxide is equal to or greater than that of the metal, a compact or continuous structure results; if the volume of the oxide is less, a cellular or porous structure forms. With the cellular type of coating the surface layer of oxide offers no impedance to oxidation; at a given temperature the rate of oxidation is quite constant. On the other hand, the compact type of coating acts as an effective barrier to oxygen and the rate of oxidation will follow a parabolic law. The recent work of Gulbransen2 and of Leontis and Rhines3 on the oxidation of magnesium indicates that it is not necessary for the volume of the oxide to be greater than that of the metal in order that the oxidation may follow a parabolic rate law. One exception to the rule of Pilling and Bedworth¹ is noted by Scheil;4 namely, tungsten. At 500° and 700°C long-time oxidations indicate a linear rate law with time. However, Dunn's6 0xidation measurements from 700°to 1000°C indicate that a parabolic rate law is followed. The oxide is mainly yellow WO a with a thin layer of the blue oxide. Preliminary results on the oxidation of tungsten6 in the temperature range 400° to 500°C indicate that the oxidation does proceed according to a parabolic rate law. Irrespective of the actual rate law that tungsten may obey, it is of interest to compare the results obtained on the oxidation of tungsten in the thin film region with those found when the metal is scaling. A time-temperature study of the oxides formed on both molybdenum and tungsten may indicate whether there exist any peculiarities in the oxide structures of the thin film region compared with those of the scaling region of oxidation. In a recent paper the authors7 presented an investigation of the structures of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper. The results of these studies are presented in graphical form as existence diagrams of the oxides on a time-temperature scale. The existence diagrams of the oxides occurring on some of the metals are simple and show few chemical transitions, but there are many cases in which the physical state of the oxide surface changes as a function of time and temperature, as evidenced by the appearance or disappearance of orientation effects and sharpness of patterns. In general an increase in temperature results in an increase in

Jan 1, 1947

By R. M. Leibrock, C. W. Ziemer, R. P. Vincent

The Stanolind flowmeter, which employs a hot-wire anemometer connected in a Wheat-stone bridge circuit, has proved useful for determining the relative productive ability of individual sand members of gas wells. The operation of this instrument in measuring gas velocities in the well bore above each producing member has provided both a direct and accurate means of analyzing reservoir performance. Results of tests conducted with the well flowmeter in the Hugoton gas field of western Kansas have indicated some rather unusual production characteristics. In two cases it was found that all or the greater part of the total gas produced was coming from one section in wells where four "pay" sections had been perforated individually. These actual measurements contradict in many instances the indications of data obtained from electric logs and from core analysis; the fact that these latter sources often give incorrect results, demonstrates the necessity of a method, such as is provided by the well flowmeter, for accurately determining the amount of gas coming from each producing member. Introduction In any gas well where a number of pay sections have been perforated individually and are producing to a common outlet, the question arises as to the relative amounts of gas being passed through each set of perforations. In the past it has been the policy to depend on core analysis to estimate relative productivities, or, where the sections were not cored, to obtain some idea of production characteristics from electric-log studies. The weaknesses in these methods are readily apparent and indicate the need for more reliable means of measuring gas flow from each zone. The Stano-lind flowmeter* was developed for this purpose. Preliminary tests were made with the instrument in the Katy gas field near Houston; however, the bulk of the routine work with the well flowmeter has been confined to the Hugoton gas field in western Kansas, where results obtained have been encouraging. A description of the instrument, the field technique employed in testing, and a few of the results obtained in the Hugoton area are discussed in this paper. Description or Instrument The well flowmeter is 1¾ in. od and 7 ft long; it is entirely self-contained, can be run through tubing as small as 2 in. id in wells with high pressure (4500 psi) and temperature (210°F) and is lowered on a wire line commonly used for other instruments of the bottom-hole type at falling rates up to 500 ft per minute. It will detect gas flow as low as 10 ft per minute linear velocity, and yet withstand and record velocities of 1000 ft per minute without damage to the detecting element. Killing the well is not required nor desirable for running a production profile when using the instrument, and it is necessary to stop flow for only a short time. The detecting element of the instrument is a hot-wire anemometer connected in a

Jan 1, 1948

By H. H. Uhlig

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

Jan 1, 1940

By David White

THE search for potash salts in the great "Red Beds? region of the Southwest, conducted for several years by the U. S. Geological Survey, the work being carried on for a part of the time in coöperation with the Bureau of Economic Geology and Technology of the University of Texas, has resulted in the discovery, within shafting depth, of potash salts, apparently of workable thickness and commercial quality, and prob-ably of great extent. Definite information is lacking as to the exact thickness of the potash beds, the size and boundaries of the areas underlain by workable strata, and the locations of the deposits richest and most favorably situated for exploitation. Briefly to review the salient features, of the general situation: We have in the great Red Beds region of the southwestern United States, embracing portions of central Kansas, western Oklahoma, eastern New Mexico, and northern and western Texas, .a series of sandstones. shales, anhydrite beds, clays and limestones, which; through an interval of 1000 ft., more or less, carry beds of salt, estimated by Darton1 to contain over 30,000 billions of tons of rock salt. It is the greatest known salt field of the world. At some points the intercalated beds of rock salt, one of which is reported by the driller to exceed 300 ft. in thickness, aggregate, accord-ing to the drillers' records, over 1000 ft. The sedi-mentary strata are similar in composition to those carrying the potash deposits of western Europe, and they were laid down at the same time and under condi-tions which, in many respects at least, were similar The stratigraphy and character of the beds are des-cribed by Darton2 and a, part of the area and the reported aggregate thicknesses of salt are shown, with some revision after Darton, in the accompanying map Fig. 1. The assumption that in the great areas of shallow evaporation basins spread over -the vast base-level region of saline deposition in the Southwest during Permo-Triassic time, potash salts were in some places, and at different stages, thrown down in crystalline deposits associated with the beds of rock salt, anhydrite, and gypsum, is, geologically speaking, more than reason-able. They are to be expected, and the conviction that they are probably present has long been held both in the Texas Bureau of Economic Geology and Tech-nology, under Dr. J. A. Udden, and in the- U. S. Geological Survey. Accordingly, for many years, efforts to determine whether potash deposits are present in this region have been made, though under very great difficulties, such as insufficient funds for boring, hack of drilling on private initiative in the more promising regions, hack of interest at first on the part of the drillers and companies, and, hater, inadequacy both of the methods of boring and of the sampling, to reveal in definite terms the thickness-of any saline stratum of given composition.

Jan 4, 1922

By J. H. Scaff, H. C. Theuerer

Germanium may be reversibly converted from n to p type by heat treatment. Data for the conversion and the associated changes in resistreatment.tivity are given and the results are interpreted in terms of changes in the donor-acceptor balance. MEANS for controlling the electrical properties of germanium in a predictable manner are of interest because of the increasing utilization of this element as the semiconducting material in electrical devices. Since both the mechanism and the magnitude of the electrical conductivity depend upon the kind and quantity of impurities present, the conductivity usually is adjusted by first carefully purifying the germanium, and then, by standard alloying procedures, adding the elements desired. The elements usually added are from the third or fifth periodic groups depending upon whether p- or n-type germanium is desired. However, in the development of germanium rectifiers during the war, it was found that it was possible also to modify reversibly the conductivity of germanium and even to produce conversion from n to p type by heat treatment.1,5 Since then a detailed study of this effect has been made. The data are presented in this paper and an explanation is offered for the effects observed. Preparation and Experimental Procedure The method used in preparing the germanium ingots for this investigation has been previously described.' The method consists essentially of (1) reduction of GeO2* and (2) preparation of a 50-g ingot from the reduced material. Graphite containers are used in both steps. In the first step the GeO2 is reduced in hydrogen at 650 °C to form a sponge germanium which, to assure complete reduction and to obtain massive materials, is fused subsequently in the reduction furnace by gradually raising the temperature to 1000°C. The button of germanium thus obtained corresponds to a yield of 99.8 pct. The final ingot is prepared by fusion of the germanium button in a helium atmosphere. A cylindrical crucible in a vertical silica tube furnace is employed and the crucible is heated by an external induction coil. The ingot is solidified from the bottom upward by raising the induction coil at a constant rate with power to the coil kept at a fixed value. In such ingots, segregation is normal and most of the impurities are concentrated in the last region of the ingot to freeze. It follows then that the major portion of the ingot is purer than it would have been if freezing had occurred in a random fashion. Moreover the orderly advance of the freezing surface during solidification establishes in the ingot a succession of surfaces of constant composition, if it is assumed that the liquid is homogeneous and that diffusion in the solid is negligible. Therefore, some information on the distribution of impurities in the ingot may be acquired by determining the shape of the solid-liquid interface at different stages of solidification. This is of importance because the concentration of impurities will be seen to affect the response of germanium to heat treatment. Such information is difficult to acquire by direct means, for the impurities responsible for the electrical properties of germanium prepared in this way are present

Jan 1, 1952

By J. H. Lightfoot, Stuart E. Buckley

DEEP drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.1 The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen4,5,6 and by others,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems.9-17 It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 lb. per sq. in. Thus, at pressures of 2500 lb. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 600°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduction. The combined effects of pressure and temperature on condensation and vaporization of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpretation of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate systems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21.22 it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has

Jan 1, 1941

By P. R. Sperry, P. A. Beck, Hsun Hu

As described by means of quantitative pole figures, the inside texture of highly rolled aluminum and copper strips may be approximately described by four equivalent ideal orientations near (123) [121]. If rolled in reversed passes, the surface texture of copper is also near (123) [121], that of aluminum is (100) [011]. The inside texture of highly rolled brass is (110) [112]. The surface texture is the same, if rolled in reversed passes. The surface texture of all three metals is related to the inside texture, but asymmetrical, if rolled without reversal between passes. MANY previous investigations dealing with the subject of the present work were reviewed by Wassermann.1 Barrett,2 Brick,3 and Richards.' The recent introduction of quantitative methods for pole figure determination by Decker, Asp, and Harker,5 Schulz5 and others made it possible to reinvestigate some of the finer points which the earlier more qualitative photographic methods left undecided. The rolling textures of silver and of 70-30 cartridge brass have been quite consistently characterized by the ideal orientation of (110) parallel to the plane of rolling and [112] parallel to the rolling direction. On the other hand, it has been recognized by several investigators that certain other face-centered cubic metals, such as copper and aluminum, developed rolling textures rather different from that of brass. These textures have been variously described by the following ideal orientations, singly or in combinations with each other: (110 [112]: (112) [111]; (135) [335]; (135) [211], etc. The discrepancies usually have been attributed to the lack of sharpness in the textures and to the attendant difficulty of associating "ideal orientations" with pole figures showing great scatter of orientations. It seemed desirable to investigate by the new quantitative methods to what extent the apparent lack of sharpness may have been brought about by the qualitative methods used previously, rather than by the textures themselves, and to decide, if possible. between the various ideal orientations which have been proposed. Another problem, not satisfactorily settled by earlier investigations. concerns surface textures in rolled metals. For instance, in rolled aluminum the surface texture in some cases appeared to be similar to the texture inside the sheet, whereas in other cases it was reported to be entirely different.' The conditions under which such differences may have arisen, and the possibility of the occurrence of different surface textures in other face-centered cubic metals do not appear to have been examined in detail. The present work was undertaken to investigate the above questions. Some of the results obtained have been described- riefly. Experimental Procedure Specimen Preparation: In the present investigation 2s aluminum, electrolytic tough-pitch copper, and commercial 70-30 brass were used. These materials were available in the form of cold-drawn rods. 1 in. diam for tough-pitch copper and commercial 70-30 brass and 11/2 in. diam for 2s aluminum. The cold-drawn bars were alternately annealed and rolled 30 pct lengthwise in several cycles until a penultimate thickness of 0.500 in. was reached. The intermediate and the penultimate anneals were carried out for 30 min at 380°C with 2s aluminum, and for 30 min at 550°C with 70-30 brass. For tough-pitch copper, the intermediate anneals were 30 min

Jan 1, 1953

By R. G. Clay, C. F. Seaman

THE mines of The Tennessee Copper Co. are in the Ducktown Basin, in southeastern Tennessee. The ore is a heavy sulphide consisting principally of chalcopyrite, pyrite and pyrrhotite and in places running as high as 95 per cent sulphur and iron. Operating mines are the Burra Burra and Eureka. Development of the Boyd ore body was started in 1940. Late in 1939 the decision was made to change from fuse and cap to all electric blasting and at the same time electric cap lamps were installed to replace carbide. These changes were made to improve the safety and working conditions in the mines. Both the Bureau of Mines and explosives manufacturers recommended electric blasting as a safety measure. Until that time, electric blasting had been used only for shaft sinking and in places where it was absolutely essential for safety. Very few men had had experience in this type of blasting, as the places where it was required were those that also required direct supervision. It was necessary for the mining staff to work out methods, procedure, and equipment to be used. In this they were ably assisted by representatives of the explosives manufacturers. Many mistakes were made and it is the purpose of this paper to describe the original plan and installation, show the major difficulties encountered, the remedies applied, and present the practices now being followed. Comparison of costs of the two methods will also be discussed. About six months were required to make the change and eliminate fuse and cap blasting entirely. The first electric blasting stations were installed in November 1939 and the last fuse was taken underground in May 1940. A very unusual condition forced the use of fuse for a short time in one heading after May, but that will be discussed later. ORIGINAL EQUIPMENT AND INSTALLATION A power line is generally recommended as a source of current where permanent blasting stations are used. The plan worked out for electric blasting was to tap 220-volt alternating-current lines when they were available and use 250-volt direct current from the trolley wire at all other places. A blasting machine would be available at each shaft for places where there were no regular blasting stations and could be used if a regular station should fail. The equipment decided on was No. 16 duplex reinforced lamp cord for lines to within about 50 ft. of the working place and No. 20 lead wire from that point to the shots. An open double-pole, double-throw switch with slate base was put in the circuit, so connected that the down position would close the line to the shots and the up position would connect it to the line from the power contactor. This switch was located in the circuit as close to the blast as was safe (should the shots explode when it was placed in the shooting

Jan 1, 1942

By R. L. Perrine

This paper shows how stability theory can be used to optimize solvent recovery of oil. Application of the theory leads to definition of the limiting conditions required for stable displacement to occur. One of these conditions is that the size of a solvent "slug" must at least equal a prescribed minimum. The criteria to be satisfied are miscibil-ity and stability. Stability implies that no viscous fingering will occur and that mixing will be caused only by a dispersion process. Miscibility implies that complete recovery will be obtained from the swept regions. Thus, for any specified set of reservoir conditions, an optimum use of solvent is defined. INTRODUCTION The early outlook for solvent flooding as a means to increase oil recovery was very favorable. Some laboratory results indicated that a "slug" containing perhaps 2 to 3 per cent of a hydrocarbon pore volume could be successful. However, other data suggested as much as 30 per cent would be required. The difference is of considerable economic importance. A theoretical explanation for these divergent results has been advanced by the author.1,2 Stability theory defines conditions for two distinct flow regimes. In stable displacement, solvent and oil become mixed by a dispersion process, and the solvent requirement is small. On the other hand, unstable displacement can degenerate into viscous fingering. The practical result is a considerable increase in the extent of mixing and, thus, in the solvent required. The present paper shows how to use stability theory to optimize solvent recovery of oil. Oil is usually considered to be displaced by a small amount, or a slug, of solvent. Gas in turn follows solvent. Any fingering will permit contact of nearly solvent-free gas and oil, leading to immiscibility and reduced recovery. Thus, our optimum is defined by two restrictions — stable flow and miscibility. Although an immiscible solvent process could prove more profitable than any miscible process, such processes lie outside the selected definition of an optimum. The usefulness of computations based on the present work will depend on the validity of the general theory. Because the important idealizations required tend to minimize the predicted solvent requirement, the results should state correctly the limiting conditions required. Therefore, theoretical calculations should have practical value. This paper first reviews several principles that result from stability theory. The following section describes use of these ideas in relatively simple systems which symmetry makes appear one-dimensional. Of particular importance is the step-by-step design of 3 stable minimum-solvent slug. The use of stability theory in cases of multi-dimensional displacement is discussed and, finally, suggestions are given for simplified practical application of the theoretical results. PRINCIPLES OF STABILITY THEORY The use of perturbation methods to derive stability conditions has been shown by the author.l The discussion is presented in terms of the fractional concentration of solvent in the single hydrocarbon phase. Quite generally, any disturbance can be represented as a Fourier series, of which only the least stable term need be considered. Denoting this term at time t = 0 by cn,

By J. B. Newkirk, D. L. Martin, A. H. Geisler, R. Smoluchowski

A FUNDAMENTAL investigation of the mecha-nism of the ordering reaction and of the accompanying changes in properties has been undertaken, since an extensive study of this process could well contribute to the knowledge of phase transitions in alloys. Cobalt-platinum alloys were chosen for the study since they exhibit interesting and unusual permanent magnet properties.1,2. In addition, the ordering reaction in cobalt-platinum alloys is a convenient one to study experimentally because of the high maximum ordering temperature, the large difference in the X-ray scattering power of cobalt and platinum atoms, and the relative ease with which the alloys can be plastically worked into wire and strip. In the early stages of this study, it became apparent that the published phase diagrams&apos;, &apos; of the cobalt-platinum system contained questionable features, in the region of 40 to 60 atomic pct Co, which were considered in another publication by the authors.4 That portion of the research reported elsewhere on the equilibrium states of cobalt-platinum alloys does not confirm the presence of a previously reported, high temperature disordered tetragonal phase and a low temperature body-centered cubic phase. On the other hand, the structure of the ordered phase is face-centered tetragonal with an atomic distribution analogous to that of CuAu.4 This lattice forms from the disordered face-centered cubic phase in such an orientation that the <100> directions are parallel to the <100> direc-tions of the disordered phase. At compositions other than the ideal 50 atomic pct the ordered phase can exist in equilibrium at high temperatures with the disordered phase. A Widmanstatten pattern of plate-like particles of the ordered phase parallel to (110) planes of the disordered matrix is observed when an initially disordered alloy is held at these temperatures. The temperature range of the two-phase region has been determined for three alloys by X-ray diffraction analyses, microscopic examination, and electrical resistivity measurements, and these results are incorporated with some of those of Gebhardt and Köster in the revised phase diagram of fig. 1. The purpose of the investigation reported here was to examine the mechanism of ordering in co-balt-platinum alloys by X-ray diffraction and metal-

Jan 1, 1951

By J. N. Butler, R. J. Morris

A series of organic collectors has been developed which successfully float synthetic secondary uranium minerals, such as autunite, carnotite, and torbernite. Recoveries up to 97 pct have been obtained. With cleaning of rougher concentrates, ratios of concentration as high as 15:1 are possible on head assays of 0.10 to 0.50 pct U 3 O 8. Additions of certain base metal salts aid in recovery and materially increase the rate of flotation and selectivity of the collectors for the synthetic minerals. Flotation tests on natural uranium minerals have not yet equaled results obtained on the synthetics, although these collectors do give better results than conventional collectors for nonsulfide minerals. RAPID increase in mining and milling uranium ores during the past seven years and the discovery of large tonnages of uranium-bearing material too low in grade to stand the cost of leaching have developed considerable interest in possible methods for beneficiating these marginal ores. Such ores are generally classed as those containing less than 0.10 pct U3O8. Development of a beneficiation method that would give both high recovery and high ratio of concentration would also make possible the beneficiation of higher grade ores and would provide higher grades of feed to existing leaching plants. Although considerable research and testing on physical or physico-chemical beneficiation of domestic uranium ores has been done in the past, to the best knowledge of the authors only a single application of physical beneficiation is now in operation on a commercial scale. Flotation has been attempted on the basis of mineral association rather than by direct concentration of the contained uranium minerals. Flotation studies conducted on this project on certain ores gave recoveries of 60 to 70 pct of the uranium by the use of conventional flotation agents such as oleic acid, but ratios of concentration were in the order of 1.5:1 to 2.5:1. Subsequent cleaning to upgrade the concentrates rapidly increased losses in the cleaner tailings, which were not later refloated in the rougher flotation. Selection of Collector: In selecting desirable organic collectors for these oxide systems, a thorough study was made of the relationship between structural characteristics and collector activity by an examination of the behavior of a number of different functional arrangements present in a variety of organic molecules, (see Fig. 1). It is generally accepted that a collector must have a relatively long-chain hydrocarbon radical and a chemically reactive elec-trophilic center. Such a requirement could be met by a large number of compounds, but steric effects at the uranium mineral surface, solubility, compat-ability with aqueous systems, air avidity, bond strength at the mineral surface, interfacial concentration of the collector, and diffusion rate of the formed complex from the air-water interface eliminated many as unsuitable for this purpose. Preliminary investigations were completed of possible collector designs consisting of aliphatic and aromatic hydrocarbon radicals attached to stable combinations of nitrogen, oxygen, sulfur, and halogen electrophilic centers, Fig. 1.Tests were made to determine melting point spans, solubility of mineral-collector combinations in various solvents, reactions with soluble uranium salts, contact angles, and floatability by semi-quantitative beaker methods.&apos; Contact angle determinations were not too useful because of the fine particle sizes of available mineral samples. From the foregoing study it appeared that nitrogen-sulfur electrophilic centers coupled with straight-chain saturated alkyl hydrocarbon radicals would hold the most promise for floating secondary uranium minerals. As the dithiocarbamate compounds can be made to combine these attributes they were selected for further study. The dithiocarbamates form a parallel structure to the xanthates, with the fortuitous exchange of

Jan 1, 1957

By R. W. Kraft, F. D. George, F. D. Lemkey

From a conszderation of the geometrically possible ways in which an array of lines or linear features in three-dimensional space can depart from a statistically random arrangement, a system was developed to describe and measure different types of anisotrypic arrangements of lines in opaque solids. The technique was applied to a specimen of unidirectionally solidified Al-Cwll, eutectic which contained microstructural imperfections termed lamellar faults. Experimental data obtained from photomicrographs of different facets of a grain of this alloy were then analyzed using this system. It was deduced that the defects, which are essentially linear in natuve, were predominantly parallel to one another but not parallel to the nominal growth direction probably because of some lateral heat flow during solidification. InGOTS of lamellar eutectic alloys which have been unidirectionally solidified under growth conditions which prevent colony formation consist of large elongated grains in which the lamellae are approximately parallel to one another. Deviations from a parallel lamellar structure within a grain are caused by extra lamellae which form occasionally during the solidification process. Three-dimensional analyses of such specimens have revealed that one extra platelet produces two defects, termed 1amellar faults, which can and do grow more or less independently of one another.&apos; The faults are analogous in many ways to edge dislocations in crystals. If a lamella of one phase is considered to be basically two-dimensional, e.g., a surface, then a fault can be defined as the locus of points which delineates an edge (or half the periphery) of one extra lamella as it grows and forms bridges and saddles in an otherwise parallel arrangement oi lamellae, Fig. 1. Were it not for the fact that bridges and saddles occur in the structure, the extra platelet could be defined as the unit defect and the concept of linear faults of positive and negative character around the periphery of the extra platelet would be unnecessary. If an extra platelet is merely inserted (actually it is grown in) between other parallel platelets, the fault line around the periphery of the extra platelet would circumscribe one and only one platelet, namely the extra one, and the faults would lie in a plane parallel to the lamellae. But when an extra platelet merges with adjacent ones and each side grows independently of the other, it is no longer topologically possible to delineate "the extra plate." A fault circuit which either closes on itself or passes out of the specimen still occurs although it no longer will be coplanar with the lamellae. In fact, it is usually not even Planar even if the lamellae are. Under these conditions a concept that a specimen contains N extra platelets of a given size per unit volume would be very artificial and consequently meaningless. Therefore, because of the topological complexity of the alloys, it was deemed necessary to define one-dimensional

Jan 1, 1962

By E. H. Citron

CLEANING fine coal in jigs is not new in Europe, where the feldspar jig is being used almost exclusively for this purpose. A feldspar jig operates with an artificial bed made up generally of feldspar or other hard rock material. Dimensions and specific gravity of this material must be of suitable values for good bedding qualities. For good efficiency, the size should range between 1x2 in. and 2x2x½ in. thick. The disadvantage of an artificial bed is that it is not mobile and must be replaced every so often with new material to obtain good cleavage characteristics. A semi-mobile bed has been developed to retain only a part of the feldspar on the sieve screen— the other part is drawn off with the refuse material, from which it is reclaimed and returned to the jig feed. Recirculating this feldspar rock offers definite advantages. However, in time it will lose its original shape because of wear, and new bed material must be added to the jig feed. The latest feldspar jigs arc generally air-pulsated, Baum-type jigs, although more than 70 pct of the feldspar jigs operating in Continental Europe are still of the piston type. These jigs are very popular in Europe, but they do require a great deal of time and attention. New Theory to Eliminate Artificial Bedding: At the preparation plants of Pittsburg & Midway Coal Mining Co. it has always been the contention that a small piston-type jig could be developed to clean fine 1/4x0-in. coal down to 28 to 60 mesh efficiently by obtaining and admitting bedding material from the present plant refuse circuit to the jig feed. This eliminates use of artificial bedding materials. The jig should incorporate these essential adjustable features as follows: Adjustable Sieve Screen A screen that can be raised and lowered to increase or decrease washing compartment depth. The sieve screen also can be set on an incline level, or decline. Adjustable Plunger Eccentric Length of stroke can be adjusted to increase or decrease pulsion and suction. Variable Plunger Speed Variable speed reducer for decreasing and increasing the number of strokes per minute. Water Distribution Adjustable baffle plate separating the plunger and sieve compartment so the water can be distributed uniformly over the entire sieve screen area. Refuse Ejector Special unique rubber-type refuse ejector gate operated by air and electrically controlled (as a conventional jig). Automatic Control Conventional float that measures the specific gravity of the coal-water refuse medium in the jig is of the submerged type. The float is mounted on a vertical stem held in position by two parallel arms. A movable weight regulates the effective specific gravity of the float. The float stem can be raised and lowered, having a graduated scale to indicate the depth of bed for the setting of the float. Hutch Drawoff Hutch material is drawn from the cell compartment to the elevator compartment by gravity. The first one-cell experimental jig incorporating all these features was built in January 1955 by Ore

Jan 1, 1959

By Charles C. Templeton

Any explanation of the nature of multiphase fluid flow through porous media must ultimately involve a knowledge of the mechanism of such flow through the individual pores of the medium. To provide quantitative information of the latter type, a study was made of gas-liquid and liquid-liquid displacements in single uniform Pyrex capillaries with diameters as small as 4 microns. Quantitative observation of air-liquid displacements with zero contact. angle indicates the adequacy of a model based on Poiseuille&apos;s Law and the independence of capillary pressure and interfacial velocity. Consequently, this work discounts previous claims that flow is abnormally retarded in very small capillaries. For the displacement of a very viscous oil by water in a capillary initially filled with water, flow is faster than predicted by the above model. This behavior is probably due to the existence of a thin annular film of water between the oil column and the capi1lary wall as postulated by Yuster. INTRODUCTION The need for experimental observation of the microscopic nature of multiphase fluid flow, to further the understanding of the results of macroscopic flow investigations, has been previously recognized. Chatenever and Calhoun1 in connection with the API Project 47B have extensively studied the flow of fluids through layers of glass or lucite spheres between glass or lucite plates. Lowman2 prepared an interesting film concerning flow in a single capillary, using an apparatus which made a moving interface appear stationary in the field of a microscope. The purpose of the present investigation was to deter- mine what contribution might be made to this field by comprehensive quantitative observation of gas-liquid and liquid-liquid displacements in single capillaries of uniform, very small diameter. The techniques used are similar to those of Lowman but incorporate improvements necessary for quantitative work. Quantitative observations must begin with fluids of simple chemical composition to provide a basis for analyzing the more complex behavior that may be expected with natural reservoir fluids. However, some qualitative observations on systems involving crude oils are presented. Experiments of this sort involve the observation of the velocity of the interface separating two fluids, and have been performed in horizontal or vertical capillaries by several investigators.3,4,5,6,7,8 The most general treatment of their mechanics, by Brittin,9 involves forces due to capillarity, viscous resistance, gravity, an "end-drag" effect, and the rate of change of momentum of the capillary contents. Since the range of pore diameters of interest in petroleum reservoirs is about 0.1 to 100 microns, it was desired to perform these experiments in the smallest capillaries possible, to ascertain whether capillary diameter had any effect on the existing theory based on data from larger capillaries.* It was also important to be able more systematically to vary the direction and rate of displacement than was done by previous investigators. Finally, to concentrate attention on viscous and capillary forces by eliminating gravity as a parameter, this study involves only horizontal capillaries. The work of Eley and Pepper&apos; with a "large" (0.766-mm diameter) horizontal capillary is the previous investigation which is most similar to the present method of quantitative observation. Here capillaries with diameters as small as 4 microns will be studied.

Jan 1, 1955

By John R. Gould

A mathematical treatment of multiple-pass floating-zone refining of semiconductors, including the evaporation of solutes from the melt at reduced pressure, is presented. Vapor pressures and evaporation rate constants for phosphorus, arsenic, and antimony in germanium have been determined from floating-zone experiments conducted at 10 mm Hg. Rate sensi-tivity of arsenic in germanium has been examined over the range of 1 to 10 in. per hr growth rate. The equilibrium value of the segregation coefficient of arsenic in germanium, as determined by an extrapolation of these data, was found to be 0.09. PFANN has treated the segregation of nonvolatile solutes in the zone-melting process, Bradshaw and Mlavsky2 considered the evaporation of solutes in a vacuum during the growth of crystals by pulling from the melt, and van den Boomgaard3 has shown that it is possible to bring a volatile impurity element homogeneously into an ingot by means of zone-melting under a constant pressure of that element. This paper is concerned with the volatilization of solutes during zone - melting in a vacuum. The mathematical analysis by Lord4 of multiple-pass zone melting is extended to include evaporation of solutes. A method is presented in which evaluations of vapor pressures, evaporation rate constants, and distribution coefficients may be derived from the variation of solute concentration in the floating-zone refining of germanium at 105 mm Hg. EXPERIMENTAL Ingots of zone refined germanium, approximately 1/4 in. in diam and 10 to 12 in. in length, were subjected to several floating-zone passes at 105 mm Hg in order to provide intrinsic material for these studies. These ingots were then seeded in a [Ill] direction and solid-doped to a constant impurity concentration of approximately 1015 atoms per cmS in a forming gas ambient (10 pct H - 90 pct A) at 1/2 atm gage. The resulting crystals were subjected to repeated floating-zone passes at 105 mm Hg and a concentration profile along the length made after termination of each pass. Concentrations were determined from four-point probe resistivity measurements, and proper precautions were taken to prevent contamination during handling. A constant zone length, crystal cross section, and growth rate were maintained during zoning. A stationary coil and moving crystal system were employed for floating-zone growth with neither the section of crystal above nor below the melt rotated.

Jan 1, 1962

By E. A. Gulbransen, J. W. Hickman

The physical and chemical structure of the oxide films formed on metals and alloys is of interest in our understanding of their protective properties. According to Pilling and Bedworth,¹ if the specific volume of the oxide is equal to or greater than that of the metal, a compact or continuous structure results; if the volume of the oxide is less, a cellular or porous structure forms. With the cellular type of coating the surface layer of oxide offers no impedance to oxidation; at a given temperature the rate of oxidation is quite constant. On the other hand, the compact type of coating acts as an effective barrier to oxygen and the rate of oxidation will follow a parabolic law. The recent work of Gulbransen2 and of Leontis and Rhines3 on the oxidation of magnesium indicates that it is not necessary for the volume of the oxide to be greater than that of the metal in order that the oxidation may follow a parabolic rate law. One exception to the rule of Pilling and Bedworth¹ is noted by Scheil;4 namely, tungsten. At 500° and 700°C long-time oxidations indicate a linear rate law with time. However, Dunn&apos;s6 0xidation measurements from 700°to 1000°C indicate that a parabolic rate law is followed. The oxide is mainly yellow WO a with a thin layer of the blue oxide. Preliminary results on the oxidation of tungsten6 in the temperature range 400° to 500°C indicate that the oxidation does proceed according to a parabolic rate law. Irrespective of the actual rate law that tungsten may obey, it is of interest to compare the results obtained on the oxidation of tungsten in the thin film region with those found when the metal is scaling. A time-temperature study of the oxides formed on both molybdenum and tungsten may indicate whether there exist any peculiarities in the oxide structures of the thin film region compared with those of the scaling region of oxidation. In a recent paper the authors7 presented an investigation of the structures of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper. The results of these studies are presented in graphical form as existence diagrams of the oxides on a time-temperature scale. The existence diagrams of the oxides occurring on some of the metals are simple and show few chemical transitions, but there are many cases in which the physical state of the oxide surface changes as a function of time and temperature, as evidenced by the appearance or disappearance of orientation effects and sharpness of patterns. In general an increase in temperature results in an increase in

Jan 1, 1947

By Rush Greenslade

The oil and gas lease is the basic contract of the oil and gas industry; it is the foundation stone upon which the producing industry, particularly, is based. As the industry is precarious and highly speculative, the foundation contract should be of the utmost integrity and certainty. But right there an anomaly exists; the oil and gas lease is the most obscure, most uncertain, doubtful contract in the realm of law today. That is a condition that must be considered when taking oil and gas leases, and when buying, selling, and holding them. It may fairly be asked why should this industry rest upon so insecure a foundation. Why should not the oil industry rest upon the contract that is the basis of all industry, the warranty deed? There are many contributing reasons, but the principal one is business expediency. The Anglo-Saxon idea of ownership of land is that every land owner owns from the center of the earth to the sky—all that is above and all that is below—consequently the oil and gas are owned by the person who owns the surface. That idea is not exactly true with reference to oil and gas, for many states have adopted the doctrine that oil and gas are like wild animals; they are fugacious and migratory and belong to the man that traps them. But, except for that doctrine, we believe that oil and gas are owned by the owner of the surface, wherein we differ from the Latin-American countries where the mineral rights are owned by the government. The United States was settled largely by homesteading. The owners of land were, in the main, farmers, who did not have the means or the faith to drill for oil or gas. The operators or speculators did not want to buy the land on the mere possibility of finding oil; hence a compromise resulted by which the land owner gave the speculator or the operator what he called an oil and gas lease, or a right to go upon his land and drill for oil and gas. What is supposed to be the first oil lease placed on record reads as follows: Agreed this 4th day of July, a.d. 1853, with J. D. Angier of Cherrytree township in the county of Venango Pennsylvania that he shall repair up and keep in order the old oil springs on land in said Cherrytree township, or dig and make new springs, and the expense to be deducted out of the proceeds of the oil, and the balance, if any, to be

Jan 1, 1924

By J. L. Bray

Lead has often been suggested as a protective coating for iron and steel. Such a protective coating should possess: (1) good adhesion, (2) durability, (3) ease of application, (4) freedom from pinholes, (5) good appearance and (6) low cost, but, unfortunately, lead coatings so far produced do not have all of these characteristics. Because of the necessity of carrying out the coating process cheaply, and because lead solutions have poor plating characteristics, most of the efforts have been directed toward the hot-dipping process rather than electroplating. The hot-dipping processes using lead have not been successful chiefly because of the lack of adherence between iron and lead. In any coating process involving iron a bond can be obtained only by the formation of an intermetallic compound, the formation of a solid solution, or mechanical means. Lead forms with iron two immiscible liquid solutions, and in the solid state no intermetallic compounds or solutions. It is necessary, therefore, to employ some other element or elements as a binding agent. Tin may be used as in terneplate, or copper in the form of a thin film of electrolytically deposited metal to which the lead will adhere. Because of its physical and chemical properties, lead as a coakkg medium would undoubtedly be limited in its use to sheet and wire and then only when the article is not subject to abrasion or wear. A very large tonnage of these products is being used under such conditions and a successful lead-coating process should be a valuable contribution to the science. Two other difficulties stand in the way of successful lead coating—that of poor appearance of the weathered surface and the tendency of the lead to form pinholes during solidification. Since lead is commonly accepted as cathodic to iron, these exposed areas are ones of accelerated corrosion. Use of Zinc.—The method under consideration involves zinc as a binding agent on both the steel sheet and in the molten bath. This

Jan 1, 1937

By R. L. Robinson, P. DeFrank, R. F. Hatfield

Production equal to or greater than open-hole completions is possible through perforated completions if the flow paths throughout the perforations are free of obstructions.&apos; Previous investigations have indicated that, in some cases, maximum productivity is not obtained due to plugging of the perforations with debris from the wellbore fluid and/or debris from the perforating process. Control of wellbore fluid and proper well completion techniques are very important in the elimination of perforation plugging.&apos; Selection of properly designed perforating equipment also is quite important for maximum well productivity. Studies made with the use of the perforation flow laboratory, in which perforating tests are run under simulated well conditions, have shown that perforation plugging occasionally occurs. Plugs in perforations result from various causes. One of the contributors to plugging that can be controlled by the perforating device is the slug or carrot resulting from jet perforating. This condition has undergone extensive study, and previous developments have resulted in a decrease in carrot size—but not in complete elimination. It was felt that, if a method of completely eliminating the carrot could be found (with charge performance equal or better than previously obtained), a significant contribution would have been made. Such a charge has been developed and is reviewed in this paper. THEORETICAL CONSIDERATIONS OF CARROT ELIMINATION There are several popular theories of how a shaped charge jet is formed."," One of these is the hydrodynamic theory, wherein the liner is treated as a fluid under the impact of the explosive forces. Another is the spalling theory, where the interaction of shock waves in the liner causes small particles to be torn from the inner surface of the liner and projected at high velocity toward a common focal line to form the jet. It is not unreasonable to assume that both of these theories may be partially correct. For purposes of our discussion, it is simpler to use the second theory. Generally speaking, when a plate of metal is attacked by an explosive shock pulse, the pulse is transmitted through the metal at high velocity, as shown in Fig. 1(A). Pressures at the shock front may be 6 X 10&apos; psi or higher. This shock wave (a compression wave) upon striking a free surface, Fig. 1(B), is partially reflected back as a tension wave. The interaction of the tension wave with the decaying compression wave causes a stress concentration in the metal; when this stress becomes great enough, a failure occurs and a small particle flies off and is projected away from the metal surface, as shown in Fig. 1(C). A new free surface is then presented to the shocks; the process repeats itself until there is no longer enough energy to cause failure, leaving a portion of the metal relativcly untouched. See Fig. 1(D). To apply this theory to a perforating shaped charge, consider the flat plate to be folded into a somewhat conical shape, with a column of explosive placed in intimate contact with the cone (Fig. 2). An explosive initiator detonates the charge, creating a shock wave

By S. Isserow

RECENTLY, a description of the wartime work in this laboratory on the U-Si phase diagram was published. This diagram was available earlier in the open literature; as were Zachariasen&apos;s crystal structure identifications for the compounds in the system. The uranium end of the phase diagram is shown in Fig. 1. The most recent work on this system has emphasized the peritectoid E phase, of particular interest for a number of reasons. The early work provided evidence of this phase&apos;s resistance to corrosion in water and of its slight ductility. Further information on these properties has been obtained here. Work elsewhere4 has provided evidence of stability under irradiation. This body-centered-tetragonal phase is relatively isotropic compared to the more usually applied a or ? uranium phases. Unlike the other compounds in this system, it contains no Si-Si covalent bonds.3 In addition, consideration on the basis of Pauling&apos;s concepts leads to the conclusion that in the E phase, uranium has a higher valence than in any of the other phases. Definition of the composition of the ? phase has been of prime concern in the study of this alloy. Evidence is presented below that its silicon content is slightly higher than that of stoichiometric U8Si, the composition frequently assigned this phase on the basis of Zachariasen&apos;s identification. This work on the composition required careful attention to the method of dissolving the alloy for analysis, since apparently low silicon contents could be found under certain conditions, see Appendix. Preparation: Melting, Casting, and Heat Treatment—Almost all the samples were from castings with a diameter of 13/4 or 2 in. and about 1 ft long, weighing 10 to 15 lb. The U-Si charge was melted by heating to about 1650°C in an induction heated vacuum furnace. Beryllia crucibles were used at first, but were replaced by zirconia-washed graphite as the technique of keeping the carbon content low enough (about 500 ppm) was mastered. The alloy was bottom-poured at about 1650°C into graphite molds. A few small buttons, weighing no more than 50 g, were prepared in a small arc melting unit.&apos; Since cast material has a preponderance of uranium and U8Si2, heat treatment is necessary to ob-tain the ? phase by the solid-solid peritectoid reaetion. Once obtained, the ? phase is stable to room temperature, obviating the need for speeial attention to the method of cooling after epsilonization, see Fig. 1. It was found desirable to epsilonize at 800°C for a week. For some purposes, in which residual uranium and/or U8Si2 are tolerable, shorter periods may be adequate. The temperature of 800°C is not critical, since essentially the same results were obtained from 785° to 825°C. Further departure from this epsilonization range is inadvisable.

Jan 1, 1958