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By A. B. Cook, C. J. Walker, G. B. Spencer

Although water will displace oil from a petroleum reservoir to a greater extent than gas will, there are some reservoirs in which gas rather than water should be used for pressure maintenance. This is indicated by the high-percentage oil recovery in the case history reports on the Pickton field1 in East Texas and the Raleigh field2 in Mississippi. In gas cycling, total oil recovery includes vaporized products from the immobile oil in addition to oil produced by displacement. If a large part of the immobile oil is vaporized, total oil recovery may be higher than that obtainable from pressure maintenance by water injection. However, the amount of immobile oil vaporized may range from almost 0 to 100 percent, and no simple and reliable method has been presented in the literature for calculating oil vaporization. Development of such a method was the purpose of this study. Several papers concerning the calculation of oil vaporization have been published,3 6 and each is based on the concept dealing with K values — equilibrium constants for the various components in reservoir oils. (K for a component in a system of vapor and liquid in equilibrium is the mole fraction in the vapor phase divided by the mole fraction in the liquid phase.) This appears to be the most logical approach. Yet, the problem is too great for a perfect solution, even with modem laboratories to analyze oils and high-speed digital computers to perform calculations; the number of components in reservoir oils is too large. Because of their complexity no two reservoir oils are exactly alike. Also, K values change not only with variations in pressure and temperature but also with composition of the reservoir oil. In addition, during gas cycling, the lighter hydrocarbons tend to vaporize first. Thus, the reservoir oil becomes more dense and less volatile as gas cycling continues. Furthermore, the greatest amount of oil vaporization occurs near the injection well. Therefore, a simplified method is required for calculating oil vaporization because a rigorous method is not practical. The present methods of calculating vaporization generally require knowledge of the reservoir oil composition in which the mole fractions of the lighter components through hexanes are given; the remaining oil is described as C, + (heptanes and others of greater molecular weights). Assigning one K value for the C,+ system provides the simplest solution, but this incorrectly assumes that K for C, + does not change as gas cycling continues. This assumption can cause large errors because the K value may become less than a thousandth of the original after a large amount of oil vaporization. Another way to solve the problem is to determine changing K values for C, + according to how much of the C, + has been vaporized. To determine these values a sample of the reservoir oil is injected into a pressure-volume cell, and dry gas is batched in and out of the cell. Appropriate measurements and tests are made to determine K

Jan 1, 1970

By A. A. Toprac

The recurring problem of joint failures in ofjshore structures, coupled with the catastrophic collapse of many of these structures during Hurricane Hilda (1964), hay forced reconsideration of techniques presently used to design sfuctural joints. This paper presents results of studies conducted for this reconsiderat?on. Only right-angled T-joint,s and cross-joints where a brace was welded directly to the undisturbed surface of another tube (the chord) were considered. Tests were performed on seven T-joint and 12 oross-joint specimens of two types which were designed to give a broad but practicd range to the geometrical parameters believed to be of significance to the problem. These paramefers were expressed in dimensionless form. Each specimen of the T-joints was instrumented wirh both electrical resistance strain gauges and deflection dials. After the elastic tests were concluded, each specimen was loaded to failure by applying an axial tensile load to the brace. The cross-joints were tested to failure without measuring elastic strains. Theoretical solutions for the stresses in a cylindrical shell due to a distributed radial load over portions of its surface were numerically evaluated. The experimental results are compared with calculated values obtained using Bijlaard's and Dundrova's theoretical analyses. INTRODUCTION During the last IS years a large number of structures were built for the offshore exploration of oil both in the Gulf of Mexico and dong the Pacific Coast.' In all these offshore platforms, the tubular shape was extensively used since this shape provides outstanding strength in proportion to its weight, compared to other shapes, when all directions (x, y, z) are considered. Past use of tubes was hampered because of connection details. But with the advent of welding, it became no more difficult to connect tubular shapes than to connect rolled shapes. However, some problems have been encountered in actual construction in making welded joints that are adequate and yet economical. In trying to connect tubular members, designers have used a varied number of methods; consequently, some of the joints seem to be very expensive in detail while others appear weak and underdesigned. An inspection of offshore platforms owned by different companies indicates the use of a large number of joint arrangements and configurations. Such a variety of joint types in current service indicates the wide divergence of opinion that exists on how such joints should be designed, stiffened and strengthened. Fig. 1 shows the various types of connections that have been used in practice. This paper reviews the present state of art on tubular joints of the T and cross type, and presents results of experimental and analytical work being conducted at The U. of Texas and elsewhere. It is believed that such information will be of great help to designers for the formulation of proper design procedures for joints. CONNECTION PROBLEM Recently, cracks have been observed in several welded connections in offshore structures. Fortunately, until about 1 1/2 years ago, these failures have been localized and have not resulted in the collapse of structures or loss of life. For example, one platform installed in Louisiana during 1955 in about 60 ft of water had been subjected to four tropical hurricanes. This platform successfully withstood these forces and was later removed because operations at this location had been completed. Many joint failures were observed during the removal.

By L. E. Lynd

Ilmenite concentrates prepared from beach and dune sands of Florida, India, Australia, and other localities deviate to varying degrees from the theoretical composition of pure ilmenite, and generally contain more TiO2 than the formula FeTi03 would indicate, and some Fe2O3. This variation in composition is due to different amounts of altered ilmenite in the concentrates. (') The alteration has been shown to take place by oxidation and leaching of the iron in ilmenite, to yield residual products consisting of amaphous or very finely crystalline titanium dioxide and ferric oxide. Other studies(2) have stressed that ilmenite may alter first to an amorphous titanium-iron oxide, or to an amorphous mixture of titanium and iron oxides, with later alteration to crystalline titanium dioxide. There has been some speculation as to whether alteration of ilmenite is usually caused by weathering or by hydrothermal pr0cesses.(3,4,5 Three main methods of approach were used to study the mechanism and rate of ilmenite weathering. (1) Etch tests were used to learn the relationship between crystallographic orientation and the rate of chemical attack on ilmenite. (2) Altered ilmenites in New Jersey sands were compared with ilmenite in rocks of the area from which the sands were probably derived. (3) Experiments were carried out to determine at what rate, and by what agents, originally fresh ilmenite could be altered in the laboratory under simulated weathering conditions. ETCH FIGURES ON ILMENITE CRYSTAL PLANES A rather large ilmenite crystal from Sannidal, Norway, about 11/2 x 11/2 x 2 inches, bearing a few natural faces with imperfect surfaces, was prepared for etching by grinding and polishing crystal planes whose Bravais-Miller indices (referred to hexagonal axes) had been determined by X-ray methods to be 00.1, 10.0, and 10.2. Metallographic examination showed that the crystal was homogeneous, and uniform in orientation, except for the presence of twin lamellae which were oriented with their broadest surfaces parallel to the 00.1 planes of the large crystal. Since ilmenite is rather inert to standard etch reagents, strong solutions of hot sulfuric acid and cold hydrofluoric acid were used. Preliminary tests established that better etch figures were obtained using HF than with H2So4 solutions. The etch figures produced on 00.1 and 01.0 planes of ilmenite by etching 3 to 5 minutes in cold concentrated HF solution are shown in Figures 1, 2, and 3. The figures on 00.1 are "etch hillocks", rather than pits, and according to Honess(6), this phenomenon

Jan 1, 1961

By H. S. Price, J. C. Cavendish, R. S. Varga

A numerical formulation of bigh-order accuracy, based on variational methods, is proposed for the solution of multidimensional diffusion-convection-type equations. Accurate solutions are obtained without the difficulties that standard finite difference approximations present. In addition, tests show that accurate solutions of a one-dimensional problem can be obtained in the neighborhood of a sharp front without the need for a large number of calculations for the entire region of interest. Results using these variational methods are compared with several standard finite difference approximations and with a technique based on the method of characteristics. The variational methods are shown to yield higher accuracies in less computer time. Finally, it is indicated how one can use these attractive features of the variational methods for solving miscible displacement problems in two dimensions. INTRODUCTION The problem of finding suitable numerical approximations for equations describing the transport of heat or mass by diffusion and convection simultaneously has been of interest for some time. Equations of this type, which will be called diffusionconvection equations, arise in describing many diverse physical processes. Of particular interest here is the equation describing the process by which one miscible liquid displaces another liquid in a one-dimensional porous medium. The behavior of such a system is described by the following parabolic partial differential equation:

Jan 1, 1969

By Fritz Wald, Richard W. Stormont

lHE general constitution of a number of metal-lead telluride and metal-tin telluride systems has recently been studied in an effort designed to furnish background information for the study of degradation mechanisms on junctions between thermoelectric power generation materials and metals.1"4 This paper reports further results of that effort. It was found that cobalt-lead telluride constitutes a stable pseudobinary section through the ternary Co-Pb-Te system. Materials used in the study were lead and tellurium of semiconductor-grade purity (American Smelting and Refining Corp., 99.999+ pet). Cobalt (Johnson Matthey & Co., 99.999 pet purity) was used in the form of slices cut from rods of 5 mm diam. Twenty- gram charges of the alloys were melted in evacuated quartz ampoules. Thermal analysis, as described previously,2'3 and metallographic and X-ray diffraction methods (Debye-Scherrer photographs) were used as investigative tools. Substantial difficulties were encountered in polishing, as reported previously for the lead telluride-iron system.3 A number of different etches were used, including dilute aqua regia, Murakami solution, an etch containing copper nitrate,3 and HC1-HNO3-acetic acid-water mixtures. None of these etches gave consistent results over the complete range of cobalt concentrations. On the alloys containing bulk cobalt in the form of primary

Jan 1, 1969

By M. G., Corson

1. In addition to the alloys of copper with iron previously found by Hanson and Ford to show an increase in the concentration of the alpha range with increase in temperature the following binary and ternary systems have been found by the author to exhibit: the same feature: (a) Copper-chromium. (b) Copper-cobalt. (c) Copper-silicon. (d) Copper-nickel-silicon and its pseudo-binary section Cu-Ni2Si (formula of compound definitely established). (e) Copper-cobalt-silicon and its pseudo-binary section Cu-Co2Si (formula of compound established with some probability but not as definitely as for Ni2Si). (f) Copper-chromium-silicon; formation of a compound definitely established (compare Figs. 1 and 2). The formula of this compound may be either Cr2Si or Cr3Si. (g) Copper-iron-silicon; presence of a phase containing both iron and silicon established in an indirect way only. No definite microconstituents observed. 2. RANGES OF SOLID SOLUBILITY (percentage at various tempera¬tures). (a) For copper-chromium: 0.8 at 1000° C.; 0.5 at 900° C.; 0.25 at 800° C.; 0.05 to 0.1 at 500° C. (b) For copper-cobalt: 3.4 at 1000'C.; 2.4 at 900'C.; 1.7 at 800'C.; 0.9 at 600°C.; 0.35 at room temperature. (c) For copper-silicon (Fig. 3) : 6.8 ± 0.1. per cent. at 800° C.; 3 per cent. at 400° C. and probably below 2 per cent. at room temperature if sufficiently long annealed. (d) For copper-cobalt silicide: 3.3 at 1000° C.; 2.4 at 900° C.; 1.6 at 800° C.; 0.7 at 600° C.; 0.3 at 300° C. (e) For copper-nickel silicide (Fig. 4): 8.2 at 1000° C.; 5.5 at 900° C.; 3.6 at 800° C.; 1.6 at 600° C.; 0.7 at 300° C.

Jan 1, 1927

By F. A. Forward, A. H. Ross, J. Halpern

Application of the carbonate leaching process to carno-tite ores has often been limited by the difficulty of obtaining simultaneous high recoveries of uranium and vanadium. The chemical aspects of this problem are discussed and the effect of prior roasting procedures on this discovery is described. IN treating carnotite ores by carbonate leaching it is often necessary to subject the ore to a prior roast. Among the advantages that may result from roasting are: 1) improvement in settling and filtering characteristics of the ore; 2) destruction of carbonaceous impurities that would otherwise contaminate the leach solution and consume carbonate reagent; and 3) substantial increase in extraction of vanadium, which is usually low when the un-roasted ore is leached. Recovery of vanadium may be an important factor in processing carnotite ores, and the fact that vanadium is usually recovered in good yield by acid leaching has often been an economic advantage over results obtained with carbonate leaching. It has been found that response of an ore to carbonate leaching, following roasting, depends primarily on its composition and on the conditions of the prior roast treatment, particularly with regard to the roasting temperature, the atmosphere maintained above the charge during roasting and cooling, and the presence of certain reagents. These factors, especially the last, virtually determine the extractions of uranium and vanadium attainable by carbonate leaching, as well as the reagent consumption on leaching, whereas adjustment of the leaching conditions has only a limited influence. These variables were examined systematically to elucidate roasting and carbonate leaching of carnotite ores and to establish a treatment yielding high recoveries of both uranium and vanadium. Tests were conducted on samples of four different Colorado Plateau ores, described in Table I. Roasting Procedure: The roasting tests were conducted in an electrically heated furnace in which the temperature was controlled to ±15°C. The ore (usually a 500-g charge) was ground to —100 mesh, mixed with the desired reagent, and spread in a silica tray to a bed depth of about 1/2 in. During the roast the charge was rabbled at intervals of 15 min. To provide free access of air the furnace was usually ventilated; however, in a few experiments a controlled atmosphere such as carbon dioxide or hydrogen was maintained above the charge. Leaching Procedure: The pulp, generally comprising 500 g of ore and a 2000-cc solution containing 80 g per liter of Na2CO8 and 20 g per liter of NaHCO3, was agitated in an autoclave at 120°C, under 30 psi 02. Samples were withdrawn periodically, and the solution and ore residue were analyzed. Under the conditions employed, maximum attainable extractions were generally achieved in 4

Jan 1, 1959

By AIME AIME

Award of a Gold Medal : to the Institute. The Jury of Awards of the Jamestown Ter-Centennial Exposition has conferred a gold medal, the highest distinction within its power,. on the American Institute of Mining Engineers for the excellence of its publications during the past decade. ; A half-tone photographic reproduction of both sides of the medal is given in the accompanying illustration.

Jan 7, 1908

By H. T. Shore, J. M. Schultz

A number of experimental rnethods—X-ray powder diffractometry, Laue photography, X-ray small-angle scattering, and transmission electron microscopy and dijfraction—have been utilized to examine the morphology associated with precipitation from the terminal, g, solid solution of a Zn-1 pct Cu alloy. A significant age hardening was observed in a 1 pct Cu alloy. X-ray and electron diffraction results showed that the structural inhomogeneities associated with the hardening were isotructural with the matrix. The average size and shape of the inhomogeneities were deduced from the electron microscopy and X-ray small-angle scattering. The preprecipitates are hexagonal platelets some 300? in diam. and some twelve unit cells thick. The orientation of the platelets was deduced from Laue photographs and electron diffraction. The platelet plane is (0001). When a large amount of pre-precipitation is present in a localized volume the new lattice is often disoriented by a rotation about (0001) of of the matrix. WhILE dilute Zn-Cu alloys have been commercially important for some 50 years, relatively very little is known metallographically about this material. The "Zilloys", zinc with about 1 wt pct Cu and sometimes a small addition of magnesium, are used to produce rolled zinc which is harder and stronger than that produced by other rollable zinc alloys.' According to the phase diagrams of the zinc-rich side of the Cu-Zn system, such dilute Zn-Cu alloys should age-harden;2-5 the solubility of copper in zinc, g-phase, at 424°C is 2.68 pct, while at 0°C it is only to 0.3 pct. However, the published literature on the aging of this system appears to be limited to a documentation of the contraction of 1, 2, and 3 pct Cu alloys aging at 95°c,6 and an attempt to measure changes in lattice parameters during aging.' In the latter work, no lattice parameter changes were detected, although a broadening of the highest-angle lines was detected and considerable diffuse scattering was observed. Micro-structural investigations have been limited to the latest stage of aging, wherein Widmanstatten precipitates are formed.3,47 These alloys are of interest for still another reason. The two most zinc-rich phases in the Cu-Zn system, 77 and E, are both hcp. Moreover, the change in a, between 17 and t for a 1 wt pct Cu alloy is onlv 3.64 -,~ct: the change in Co is 12.0 ict. It would be anticipated that precipitation in such a material might occur through metastable phases or G.P. zones with epitaxy along mutual 0001 planes. The goals of the present work are aimed at partially filling the void of knowledge concerning the early stages of precipitation from the g phase. In particular, we have attempted to document the magnitude of the age hardening of this system and to determine the size, shape, and orientation within the matrix of the elements of precipitation in an early stage of condensation. EXPERIMENTAL A) Specimen Preparation. Specimens were prepared In two somewhat different ways, one method being used for X-ray Laue and diffractometer measurements, optical microscopy, and Rockwell hardness measurements and the other used for electron microscopy and X-ray small-angle scattering. In the first case zinc and copper in the proper proportions to yield a 1 wt pct Cu alloy were melted together in a closed graphite crucible. Castings so made were free of apparent segregation or oxidation. The castings were then solution-annealed at 400°C for several days and then quenched in water to room temperature. Filings of portions of the specimens were made for use as X-ray powder diffractometry specimens. The electron microscope material was made as follows. Castings were made under vacuum with copper powder placed inside a hollow zinc cylinder to insure good contact of the materials. These 1 wt pct Cu pieces were then rolled to 0.1 mm with an intermediate anneal in vacuo. The rolled sheets so formed were then annealed for about 6 hr at 225°C. Finally the specimens were electropolished slowly until thin enough for transmission electron microscopy. The polishing is discussed in greater detail in the Results section. B) Measurements. X-ray measurements of three types were performed. A G.E. XRD-5 diffractometer was used to examine powders of the alloy for identification of second-phase material. A Kratky small-angle camera, also operating from a G.E. tube, was used to investigate the sizes of small precipitate particles. In both cases, nickel-filtered copper radiation was utilized. Finally, individual grains of the large-grained castings were examined in the back-reflection Laue geometry. Electron microscope studies were carried out with a J.E.O.L. Model 6A instrument. RESULTS A) Hardness Measurements. Hardness measurements performed at room temperature on the large-grained polycrystalline specimens showed a hardening which was essentially complete in 3 hr. Fig. 1 shows a typical plot of hardness vs aging time. The relative magnitude of the ultimate hardening varied from run to run between 150 and 200 pct of the value for the material immediately after quenching from the solution anneal. Most probably the variations reflect small changes in the time taken to remove the specimen from the vacuum furnace after the solution anneal.

Jan 1, 1969

By J. T. Lapsley, I. I. Cornet, A. E. Flanigan, R. Hultgren, J. E. Dorn

WITH the greatly expanding use of magnesium during the war, it appeared necessary to the War Metallurgy Committee that procedures of heat treating common magnesium casting alloys be investigated systematically. Accordingly, the National Defense Research Committee of the Office of Scientific Research and Development placed a research contract with the University of California, supervised by the War Metallurgy Committee. Research on the solution heat treatment and aging of magnesium alloy AZ92, (formerly ASTM No. 17; also known as Dowmetal C or AM260) which was done under "Restricted" Project NRC-21, in 1942-1943, and reported, in detail in a final report to the OSRD on September 3, 1943, is the basis of this paper, which has been released for publication by the OSRD. American experience with magnesium alloys prior to World War II was limited, although some of these alloys had been in commercial use since 1909. Requirements of the aircraft industry for light alloys made it imperative to understand and utilize the advantageous strength-weight properties of magnesium castings. Magnesium casting alloys are commonly solution heat treated to increase their ultimate tensile strength and ductility; this treatment may be followed by an age hardening at elevated temperatures, which raises the tensile yield strength but diminishes the ductility. In the present investigation, AZ92 was studied to determine the effects on properties of various solution heat treatment and aging schedules. The principles of heat treatment of magnesium alloys are the same as for other non-ferrous alloys. The alloy studied, AZ92, has a nominal composition of 9 pct aluminum, 2 pct zinc, and minor constituents. Fig I shows, by the projection of isothermal sections on the concentration plane, the solubility surface1 of the ternary magnesium-rich solid solutions as determined by X ray analysis. From this figure it may be seen that above approximately 375°C (707°F), AZ92 alloy is a single phase alloy at equilibrium; below this temperature the equilibrium condition is a. two phase alloy. The beta constituent which precipitates from the solid solution exerts a hardening effect. Because the zinc concentration is only 2 pct, and because of its solubility relations, AZ92 resembles a binary alloy of magnesium with aluminum. The solubility curve1 of Fig 2 shows how rapidly the solubility of the beta phase decreases with decreasing temperatures. Unlike many aluminum alloys, magnesium alloys do not age harden at room temperatures; precipitation hardening of AZ92 alloy is performed at about 177°C (350°F). At this temperature about 3 pct aluminum

Jan 1, 1947

By L. Ekstrom, J. P. Dismukes

The homogeneity and microstrcture of zone-leveled Ge-Si alloys haw been investigated by sellera1 physical techniques and by metallography as a function of growth rate in the range 3 x 10 1x10 cm-sec', and as a system of alloy composition throughout the system. The temperature gradient at the solid-liquid interface was about 50 deg-cm-' Cellular or dendritic structures char-acteristic of constitutional supercooling were ob-served except at very slow growth rates, which ranged from about 2 x 10 cm -sec for Ge 1 sio alloy to about 2 X 10'5 cm-sec'1 for Ge .sSio.s alloy. Using a simple model similiar to that employed for dilute solid the dependence upon compo-sition over the entire system of the critical growth rate for the onset of constiutional supercooling was calculated, and was .found to he in good agreement with the experimental results. THE recent discovery of the low thermal conductivity of Ge-Si alloys' at high temperatures has revealed that these alloys have high efficiencies for thermoelectric-power generation.', Therefore, a reliable method was needed for the preparation of homogeneous samples required for definitive measurements throughout this alloy system. Due to the low diffusion rates in the solid alloys, the segregated samples obtained by quenching a melt are not readily homogenized by annealing.475 However. isothermal solidification from a melt of constant composition can produce uniform material. Of the available semiconductor crystal-growth procedures, the zone-leveling technique6 applied to a complete solid-solution alloy system by Wang and Alexander' and by others provides a simple method of doing this. In the present work, the homogeneity and microstructure of zone-leveled alloys have been correlated with growth conditions, and the conditions for preparing homogeneous Ge-Si alloys have been established. This has provided insight into the solidification process of alloy semiconductors. EXPERIMENTAL PROCEDURE Sample Preparation. The Ge-Si alloy phase diagram4 shown in Fig. l(a) consists of a complete series of solid solutions. The zone-leveling technique used to prepare most of the samples consists of moving a zone of liquidus composition (C1) through charge material of the corresponding solidus composition (C,), as is illustrated in Figs. l(b) and l(c). To prepare the charge materials, high-purity germanium and silicon were pulverized in a steel hammer mill, cleaned magnetically, and melted together to make uniform chill castings. The zone leveling was carried out in a resistance-heated furnace similar to that of Mitrenin et al.' shown in Fig. 2. However, a few specimens of high silicon content were prepared by the Czochralski technique. The growth rate ranged from 3.5 x X6 to 1.2 X 10~3 cm-sec-'. Temperature gradients in the solid and in the melt were determined by recording the temperature as the molten zone passed over a Pt-Pt 13 pct Rh thermocouple contained in a small

Jan 1, 1965

By Cyril Stanley Smith

Somewhat over ten years ago the author described studies1'2 on the constitution of the copper-silicon system. The copper-rich portion of this diagram is shown in Fig. 1. The experimental points freely dotted about the diagram seemed to justify an otherwise unconvincing diagram and for several years the curious reverse bend in the alpha-phase boundary was accepted as substantially correct, even by later investigators3 of the system who introduced changes in the high-silicon phases. The binary diagram has been used as a base for several ternary systems5-9 without any suggested changes. Voce10 suspected the existence of another phase from his study of the cast alloys in the copper-manganese-silicon system, but evidently hesitated to extrapolate this to the binary diagram, particularly in view of the too ingenious explanation that was advanced1' to account for the pools of constituent clearly visible in castings; namely, that they were secondary alpha of twinned orientation deposited from beta. Von Schwarz,12 in 1932, called attention to the fact that this micro-constituent in copper-silicon alloy castings was anisotropic under polarized light and asserted that a new phase, not cubic, should be placed in the diagram .adjacent to alpha. Sautner,l3 on the basis of investigations with the polarizing microscope and with X-rays, introduced this phase into the diagram at about 6 per cent Si. The relevant part of his diagram is shown in Fig. 2. Sautner called the new phase beta, renaming the old beta phase zeta. To avoid confusion, in redrawing Fig. 2 the phases have been renamed in accordance with the terminology adopted in the present paper, in which the new phase is called kappa and the other phases retain the designation given them by Arrhenius and Westgren.4 The thermodynamic impossibility of Sautner's diagram and the paucity of experimental data left the exact location of the new phase field most uncertain, although his work proved beyond doubt that an additional noncubic phase exists. Because of the industrial importance

Jan 1, 1940

By Cyril Stanley Smith

Somewhat over ten years ago the author described studies1'2 on the constitution of the copper-silicon system. The copper-rich portion of this diagram is shown in Fig. 1. The experimental points freely dotted about the diagram seemed to justify an otherwise unconvincing diagram and for several years the curious reverse bend in the alpha-phase boundary was accepted as substantially correct, even by later investigators3 of the system who introduced changes in the high-silicon phases. The binary diagram has been used as a base for several ternary systems5-9 without any suggested changes. Voce10 suspected the existence of another phase from his study of the cast alloys in the copper-manganese-silicon system, but evidently hesitated to extrapolate this to the binary diagram, particularly in view of the too ingenious explanation that was advanced1' to account for the pools of constituent clearly visible in castings; namely, that they were secondary alpha of twinned orientation deposited from beta. Von Schwarz,12 in 1932, called attention to the fact that this micro-constituent in copper-silicon alloy castings was anisotropic under polarized light and asserted that a new phase, not cubic, should be placed in the diagram .adjacent to alpha. Sautner,l3 on the basis of investigations with the polarizing microscope and with X-rays, introduced this phase into the diagram at about 6 per cent Si. The relevant part of his diagram is shown in Fig. 2. Sautner called the new phase beta, renaming the old beta phase zeta. To avoid confusion, in redrawing Fig. 2 the phases have been renamed in accordance with the terminology adopted in the present paper, in which the new phase is called kappa and the other phases retain the designation given them by Arrhenius and Westgren.4 The thermodynamic impossibility of Sautner's diagram and the paucity of experimental data left the exact location of the new phase field most uncertain, although his work proved beyond doubt that an additional noncubic phase exists. Because of the industrial importance

Jan 1, 1940

By Malcolm C. Bridges, Ian A. Goddard

INTRODUCTION Mount Isa mine is a major producer of both copper and lead-zinc- silver ores. During the 1975/76 year, 4.3 million tonnes of copper ore were extracted at an average grade of 3.4%, and 2.4 million tonnes of lead-zinc-silver ore at average grades of 7.0%, 6.7% and 173 grams per tonnes respectively. Systematic lead-zinc mining has continued for just over 45 years and copper mining for just over 30 years. Virtually all mining is underground. The composite and somewhat schematic longitudinal section of Figure 1 shows the overall distribution of ore at the Mount Isa mine. The mine can be roughly divided into two parts about a central shaft complex: to the north there is predominantly lead-zinc ore and to the south there is copper ore. Underground operations are serviced by three shafts in the central shaft complex (P61, R62 andU62) and another to the south in the copper mining area (X41). Mining is spread over a total strike length of 2.9 km and extends to a depth of 960 m. Currently, lead-zinc ore is being extracted between 15 and 11 levels and is hauled to the central ore-hoisting shaft on 13 and 15 levels. Copper ore is being extracted between19 and 13 levels and is hauled to the central shafts on 19 level. The principal lead-zinc mining methods used now, as they have been over the last ten years, are sublevel open stoping and cut-and- fill stoping, with about equal tonnages of ore from each (Figure 2). Since about 1970, there have been several interesting developments in lead-zinc mining methods and procedures, principally: • the development of an effective method for the recovery of pillars between open stopes and • the evolution of safer and more productive cut-and- fill methods. During this period also, the focus of mining has moved 120 m deeper

Jan 1, 1977

By William F. List, Marvin A. Schuster

Monolithic electrooptical mosaics of 2500 photo-transistor elements with internal row and surface column interconnections have been fabricated by epitaxial-planar diffsion techniques. Unique access to any elemed of the mosaic is provided through one of the fifty X and one of the fifty Y external leads. The sensor mosaic can be used for imaging applications and has a 1:1 aspect ratio, a resolution of 100 lines per in., a dynamic range in excess of lo3, a sensitivity of 0.5 per pw, element response within a 2:l range over 75 pct of the mosaic, and a minimum detectable signal of the order of 10-' w. Design considerations which ilnpose particclar fabrication yequirements are disctussed along with some of the problems peculiar to the epitaxial and planar-dijfision techniqes by which this device is fabricated. The solid-state silicon monolith has an imaging area of 0.5 by 0.5 in. and an element center -to- center spacing of 0.010 in. J monolithic solid-state electrooptical device has been developed as the photon-sensing mosaic for use in an image-converter system.' This system is the solid-state equivalent of the vidicon and can image radiation in the visible and near-infrared regions of the spectrum. The electrooptical image converter has the desirable size, weight, reliability, and low-power characteristics inherent in solid-state devices. It is read out by direct-wire means rather than by beam-scan techniques. The packaged unit is shown in Fig. 1. A selection of material for the sensor was based on considerations of both reliable fabrication techniques and material spectral response. Silicon was selected both for its response from the lower end of :he visible to the long-wavelength cut-off above 11,000A and for its well-developed epitaxial planar-diffused technology. The electrical image is composed of M x N discrete information bits with each bit emanating from one of the individual phototransistor sensors. The interconnected mosaic concept was introduced to provide a structure which is both manageable in its number of leads and compatible with conventional viewing systems which accept XY data. Interconnections along the Y direction are provided by internally diffused strips, while interconnections along the X direction are formed by vacuum-deposited metal surface bars. Unique access to any individual element of the M x N mosaic is available through one of the M and one of the N external leads. PHOTOTRANSISTOR DESIGN A phototransistor structure2 was selected for the discrete photon detectors of which the mosaic is com- posed. Basically, the mode of phototransistor operation is such that incident quanta are absorbed in the base area of the element where they generate electron-hole pairs. If the electrons are liberated within a diffusion length of the depletion region around the collector junction, they will diffuse to this depletion region and be swept across the junction where they account for a small component of the photocurrent. Similarly, the holes which are created within a diffusion length of the emitter junction will diffuse to this region where they forward bias the emitter and so induce injection of minority carriers into the base. This accounts for the substantial transistor photocurrent. This mechanism of operation implies several design and fabrication goals for the individual sensor elements: high electrooptical conversion efficiency, sufficient carrier lifetime in the base regions, and a maximum volume in which photons can be absorbed within a diffusion length from the depletion layer about the junction. Moderately high transistor gain is desirable to permit readout at low light levels; however, very high gain has a deleterious effect on mosaic dynamic range. The mosaic must also be characterized by good uniformity of element response as well as by good isolation between elements. The above set of conditions imply that junction depths must be optimized with respect to photon ab-

Jan 1, 1967

By C. Crussard, R. Tamhankar

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers accord-ing to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Gerhurd Derge Carnegie Institute of Technology Schenley Park Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Staff Coordinator, James J. Burke THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chiprnan, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. W. Thornton, Chairman; Dennis Carney, John Chip-man, J. C. Fulton, J. H. Hollomon, H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: T. B. King, Chairman; S. J. Dickenson, R. P. Hermsdorf, R. Schuhmann, Jr., and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman, F. Lincoln Vogel, Jr., Vice-chairman, W. A. Backofen, R. W. Balluffi, J. H. Bechtold, M. B. Bever, R. S. Busk, C. G. Goetzel, Paul Gordon, C. D. Graham, .Jr., Robert F. Hehemonn, R. I. Jaffee, F. E. Jaumot, Jr., Irving R. Kramer, A. J. Lena, Harold Margolin, C. J. McHorgue, Russell A. Meussner, J. B. Newkirk, H. W. Paxton, G. E. Pellissier, I. S. Servi, Alan U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B. King, F. C. Langenberg, W. 0. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription $20 per year for non-AIME members in United States and North, South, and Central America; $25, foreign; $5 for AIME members. Single copies, $4.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed in its publications . . . Copyright 1958 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AIME New York ... Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts... Second class postage paid at New Yark, N. Y., and Ann Arbor, Mich. Volume 212, Number 6.

Jan 1, 1959

By Walter W. Bradley

AT ONE TIME OR ANOTHER and in greater or less amounts, gold has been mined in at least 40 of California's 58 counties. It may not be inappropriate, by way of introduction, to give a brief historical statement relative to her production of the yellow metal. The presence of gold in the gravels of San Gabriel, San Francisquito, and other streams near Los Angeles, was known and they were worked in a small way by the Indians, at least as early as. 1841' and possibly 1820. -On March 2, 1844, Don Manuel Castanares, deputy for California to the Congress of Mexico, reported' to his government that placers near Los Angeles had yielded up to December, 1.843, a total of 2000 oz. of gold dust, most of which had been sent (via Mexico) to tile United States Mint at Philadelphia.

Jan 1, 1932

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult's law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman' equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,' Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell's value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1' has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970

By William I. Busenbark, Elmer C. Newman

At Bingham Canyon, the world's largest open-pit copper mine, annual grease consumption is in the neighborhood of 109 000 kg (240,000 lb), all of which was 544 (120-16) purchased, warehoused, and distributed in 54-kg (120-1b) and 180-kg (400-1b) drums. While perhaps a menial and mundane chore, grease distribution shows on the ledger as a significant expense item. To improve labor and cost performance, Kennecott maintenance engineers undertook a study to find the most direct method for moving multi purpose grease (MPG) from the refinery to the point of final consumption. What they found was a direct vendor system for hulk grease so simple and flexible that long-established drum distribution is being phased out in favor of the newer method throughout 75% of the operation.

Jan 9, 1977

By Edna A. Dancy, Gerhard J. Derge

The specific conductance of FeOx,-CaO melts in contact with iron was found to decrease from 200 ohm-1 cm-1 for FeO, to 40 ohm-1 cm-1 for a melt containing 26.3 pct CaO at 1400°C. The temperature coefficient was positive at all compositions, but became smaller at high CaO contents. Current efficiencies for electrolysis increased from 2.5 pct in FeOx to 17.3 pct at the high CaO composition, indicating a change from predominantly electronic conduction to conduction with a substantial ionic contribution. It was shown that Ca++ ions as well as Fe++ ions carry the ionic current. A subsidiary investigation on the apparent effect of atmospheres of argon, helium, and nitrogen on the electrical conductivity showed that this could be correlated with surface temperature losses, which varied with the thermal conductivities of the gases and resulted in precipitation of metal by the reaction 3 Fe++ = 2 Fe+++ + Fe. The work described in this paper is offered as a contribution to the general fund of knowledge concerning metallurgical slags. Measurement of electrical conductivity and electrolysis are comparatively trouble -free methods for investigating molten materials, but, although these methods had been used for complex slags, it was not until the work of Bockris et al.1 that the approach of examining simple binary slag systems was employed, and CaO-SiO2, MnO-SiO2, and Al2O3-Si9 were studied. Two groups have performed work of particular relevance to the present investigation. Inouye, Tomlinson, and chipman2 studied the conductivity of wustite as a function of temperature and of the addition of 5 mol pct of a number of oxides, including CaO. They concluded that molten FeOx in equilibrium with iron is a semiconductor. Simnad, Derge, and ceorge3 demonstrated the ionic nature of liquid iron silicate slags and also concluded that, although the conductivity of FeOx in equilibrium with iron is predominantly electronic in nature, there is a small ionic contribution. The work reported here on FeOx,-CaO slags consists of three main parts, namely, the determination of the specific conductance over a wide composition range, an investigation into the nature of the conductivity through current-efficiency measurements over the same composition range, and an attempt to identify the current-carrying ions, as well as a subsidiary investigation on the apparent effect of the nature of the inert atmosphere on the conductivity. EXPERIMENTAL Materials. The slags, varying in composition from FeOx to 27 pct CaO, were prepared by heating reagent- grade Fe2O3 in an ingot iron crucible with a suitable amount of CaCO3 and, in some cases, powdered iron, in air. This prefused material was then used for the runs. At the end of each run the cell was removed from the furnace and quenched by immersing the bottom half in water. After crushing, the slags were analyzed for calcium and total iron by the usual wet methods. The oxygen content was obtained by difference. Specific Conductance: Apparatus and Method. Fig. shows the experimental setup, with the conductivity cell and leads of ingot iron. The standard four-probe method for measuring high conductivities was used. In this, the potential drop across the unknown resistance is compared with the potential drop across a known resistance connected in series, i .e., same current through both resistances. Thus there are both current and potential leads to the center electrode and to the crucible, which acts as th other electrode. Both ac and dc circuits were available for the measurements; they have been described in earlier work performed in this laboratory.4,5 The geometry of the cell was such that the center electrode was equidistant from the bottom and sides of the crucible. This ensured that the current path was the same irrespective of the magnitude of the conductivity of the material in the cell. Cell constant were measured with KC1 or NaCl solutions, which have considerably lower conductivities (0.0013 to 0.25 ohm-' cm) than the slags, and this precaution in design made sure that the determined cell constants applied to the cells with contents of any conductivity. The cell-constant determinations were made with the ac measuring circuit to prevent polarization. The four-probe method eliminates lead resistance but not the resistance of those parts of the center

Jan 1, 1967