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By F. C. Muttitt

The physical arrangement of the continuous casting facilities at Algoma have been described a number of times in previous papers. For the purposes of this discussion, it is sufficient to state that the casting plant is located at a considerable distance from the basic oxygen shop which supplies it, involving a relatively lengthy ladle transfer movement. (Fig. I) The handling of the ladle by two separate cranes, first to the argon station, and thence to the casting machines, results in an average interval, from start tap to start cast, of 45 minutes. The effects of such extended retention time on temperature control and on refractory performance are well known. Tapping temperatures well above normal are necessary to insure that the ensuing heat losses do not result in an undue incidence of premature tundish freeze-offs. The heat lost, as well as being a function of the retention time, becomes more critical with smaller ladle size; winter temperatures add to the problem with their effect in chilling ladles and increasing radiant losses.

Jan 1, 1972

By Ian M. Thomson, Robert W. Greene

Last August, American Commercial Barge Line Co. (ACBL) began moving coal from mines on the old Camp Breckinridge property in Western Kentucky to TVA's new 2600 MW steam plant at Cumberland City, Tenn. By April of 1973, this movement will reach a level of 7 million tpy. TVA bought the coal rights to this property from the General Services Administration in 1965 for approximately $7 million and is now in possession of reserves containing about 120 million tons of recoverable No. 9 coal, and about the same recoverable amount of No. 11 coal. TVA then contracted through competitive bidding with Peabody Coal Co. to mine the No. 9 seam through two slope shafts. The mines are about 300-ft deep and are separated by the one major fault on this property. The mine portals are approximately 3 ½ mi apart, with the northern portal being over nine miles distant from the Ohio River.

Jan 1, 1971

By W. A. Dunkley, W. W. Odell

The sulfur content of coal is perhaps more important in the manufacture of illuminating gas than in any other coal-using industry. Whether the gas is made by the distillation of coal in retorts or ovens or by steaming incandescent coal or coke in the water-gas process, a portion of the sulfur present in the fuel always passes into the crude gas. Practically all the sulfur that remains in the finished gas is transformed into sulfur dioxide (SO2) when the gas is burned. Sulfur dioxide is a pungent suffocating gas and, if present in the air in any perceptible amount, is deleterious to health and comfort and damaging to house furnishings. SO universally is this recognized that laws regulating the amount of sulfur that may be permitted to remain in the gas are very generally in force. The capacity of a plant to purify gas frequently limits the selection of coal for gas making. This condition may arise from different causes. Some plants were originally designed to handle a certain grade of low-sulfur gas coal, and very little leeway was allowed for growth or for the use of inferior coals. Other plants, when built, had ample capacity to purify gas from relatively higher sulfur coals, but their output has grown so rapidly that their purifying capacity is now limited and only the low-sulfur coals can be handled. There is a great quantity of coal in the United States that would satisfy the requirements of the gas manufacturer, were it not for the high sulfur content. The coals containing less than 1 per cent. sulfur are becoming scarcer year by year and, in time, the gas industry will probably be compelled to use coals that are now considered out of the question. Sulfur Compounds in CRude Gas Sulfur exists in unpurified illuminating gas in a variety of compounds; chief of these are hydrogen sulfide (H2S) and carbon disulfide (CS2). In crude coal gas H2S is usually present to the extent of 0.5 to 2.0 per cent., by volume, equivalent to about 300 to 1200 gr. per 100 cu. ft. of gas. In carbureted water gas, the amount of sulfur compounds depends not only on the sulfur content of the coal or coke used, but also upon cite

Jan 1, 1920

By R. W. Snyder, H. J. Ramey

This paper presents the results of applying the Buckley-Leverett' displacement theory to petroleum reservoirs consisting of a finite number of layers. The layers are assumed to communicate only in the wellbores, and the reservoir may be represented as a linear system. Most previous investigations of this nature were limited by assumptions and by inconsistent calculation techniques. This study improves on previous work by applying the Buckley-Lev-erett displacement theory to a noncommunicating layered system where permeability, porosity, initial saturation, residual saturation and relative permeability vary from layer to layer in a logical and consistent manner. Gravity and capillary-pressure effects are neglected. A modification of the Higgins-Leighton calculation method was used in this study. Waterflood predictions were made with all properties varying, and then with only permeability varying using several inability ratios. These results were compared with the Stiles and Dykstra-Parsons predictions. It is shown that the latter methods generally give poor values for the breakthrough recovery and pessimistic predictions for the performance after breakthrough. Similar results were obtained for a gas-displacement case. lNTRODUCTION Field experience with immiscible displacement usually shows constant producing conditions until breakthrough of the displacing fluid. Then oil production continues at increasing displacing-to-displaced fluid ratios until the economic limit is reached. Three different ideal mechanisms are known that will produce this behavior: (1) relative permeability effects as described by Buckley-Leverett frontal advance theory,' (2) vertical stratification as considered by Stiles,2 Dykstra and Parsons5 and others and (3) different path lengths involved in areal (two-dimensional) flow between wells as described by Dyes et al.4 Without question, a combination of these factors modified by formation heterogeneity and other known and unknown factors actually does control the behavior of real systems. This paper presents results of an investigation of certain factors that should affect performance but which have received little attention to date. In 1944, Law5 demonstrated that porosity and perme- ability are often found to have normal and logarithmic-normal distributions, respectively. throughout cored intervals in natural formations. This led to the concept of the noncommunicating, multilayered reservoir model for immiscible displacement. This model assumes that the reservoir is composed of a number of layers that communicate only at the wellbores. Each layer is individually homogeneous, but may be different from every other layer. Stiles' presented one of the earliest applications of this model to waterflood performance. In addition, Stiles assumed that the initial saturations and relative permeabilities were the same for each layer, porosity was the same. displacement was piston-like, fluids were incompressible and injection into each layer was proportional to that layer's permeability capacity (permeability-thickness product). The last assumption would be true if the mobility ratio for the displacement were unity.21 Dykstra and Parsons" used the same model as Stiles, but rigorously included mobility ratios other than unity for piston-like displacement. Dykstra and Parsons used their general result to produce charts for log-normal permeability distributions between layers. Similarly, Muskat6 Pub1ished analytical solutions for linear and exponential permeability distributions. In 1959, Roberts' described a scheme for calculating water-drive performance for the noncommunicating, layered reservoir model which considered two-phase flow in the displaced region. Roberts used the same model and assumed that the injection rate into a layer was proportional to that layer's permeability capacity, but that flood front locations could be evaluated from the Dykstra-Parsons results. These assumptions are inconsistent, and a material balance cannot be maintained except for a mobility ratio of unity. At the same time, Kufus and Lynch8 coupled Buckley-Leverett displacement theory with the layered model to provide an improvement of the Dykstra-Parsons method that was consistent. In 1960, Higgins and Leighton9 resented a numerical method for calculating waterflood performance also considering two-phase flow in the displaced region. The result was used to investigate variation in absolute permeability and oil viscosity. An excellent, detailed history of using the noncomrnunicating, layered reservoir model was presented by Nielsen.'" The preceding techniques (and many related ones) were similar in that differences in initial saturations, residual saturations and relative permeabilities from layer to layer were neglected. It is well known that the irreducible water saturation is an important function of absolute permeability. Calhoun11 showed that the irreducible water saturation

By Samuel L. Hoyt

THIS paper gives a short account of plastic deformation as observed in single crystals of zinc, zinc having been selected for the experiments described herein because the phenomena are comparatively so simple and can be studied throughout such a wide range. It is hoped that the paper will serve to show the type of information which studies of single crystals afford and will contribute toward the solution of the general problem of metallic behavior. PRODUCTION OF ZINC SINGLE CRYSTALS The method of Czochralski,1 as modified by von Gomperz,2 was used to produce the crystals studied. The equipment is shown in Fig. 1. Molten zinc is held in a crucible at a temperature which is not far above its melting point, as measured by a pyrometer. A lava disk floats on ,the melt, and is provided with a central hole about 1 mm. in diameter. A glass tube, drawn into a capillary at the lower end, is suspended from a string which is wound up by an electric drive at the speed desired. At the start, the glass capillary is let down into the melt and the hoist is started.. The capillary brings up a small quantity of molten metal with it to a point just above the lava disk. At this point, a jet of hydrogen cools it and causes it to crystallize, with the result that a small crystal forms. As the hoisting is continued, more molten metal is drawn up, in turn to be solidified by the jet of hydrogen. This additional metal continues the growth of the crystal already formed, and a long, cylindrical crystal results. The speed of hoisting used was generally between 0.1 and 0.5 mm. per sec., and the crystals were from 4 to 6 in. long and about 1 mm. in diameter. By varying the conditions, crystals of quite different orientations were obtained and were used in the study of the phenomena to be described.

Jan 1, 1927

IN THE early period of steelmaking, ingot structure and segregation presented no difficult problems. Crucible melting required very small ingots which, if properly deoxidized, gave little segregation, and a small inserted hot top prevented pipe. As larger ingots were poured [ ] from Bessemer and open-hearth furnaces, segregation, piping, and gas evolution became increasingly important. The first studies of solidification were made by Gathmann (l) and the Brearley's (2) who used stearine to show the effects of shrinkage and mold shape. Figure 78 shows a series of stearine ingots at various stages of solidification. These studies indicated that the liquid solidifies at a nearly uniform rate, starting at the walls and bottom of the mold and progressing inward, and demonstrated the formation of secondary pipe in big-end-down molds. Stearine illustrates the mechanics of solidification, and exaggerates pipe because of its great

Jan 1, 1944

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By W. C. Winegard, J. E. Gruzleski

The stages in the development of cells in the Sn-Cd eutectic have been studied by unidirectionally solidifying specimens under known conditions of growth rate, temperature gradient, and impurity concentration. By means of a quenching technique, the shape of the solid-liquid interface during solidification could be observed. Cells are shown to develop from defects or depressions which exist on the solid-liquid interface of even a pure eutectic. Th,e container wall, grain boundaries , and fault lines in the micro structure play an important role in cell development. A two-phase eutectic dendrite found at high impurity concentrations is described. L HE cellular or colony structure formed during eutectic solidification caused much confusion among early workers in their attempts to classify eutectic structure, and a major advance in our understanding of eutectic solidification was made when the colony structure was identified with a cellular interface caused by the presence of impurity elements.1'2 To date, however, no detailed investigation of the stages in cell development in eutectics has appeared, and little work has been done on the cell morphology. The present paper presents the results of such an investigation. EXPERIMENTAL The Sn-Cd eutectic was used in this investigation with lead as the impurity element to promote cell formation. Materials of 99.999 pct purity were zone-refined to an approximate purity of 99.9999 pct. Alloys as close as possible to the eutectic composition, 67.75 wt pct Sn, were prepared using zone-refined tin and cadmium. The alloys were then zone-melted to the exact eutectic composition, as described by Yue and Clark,3 using a total of twenty to twenty-five passes on each eutectic bar. Only those portions of the bars which contained no primary phases were used in subsequent experiments. Master ternary alloys were prepared by melting together the required amounts of lead and the Sn-Cd eutectic in a sealed Pyrex tube under argon, and these alloys were then diluted with pure Sn-Cd eutectic as required. Unidirectional solidification was conducted vertically upward using the two-element resistance furnace shown schematically in Fig. 1. With this apparatus, it was possible to obtain a range of growth rates and temperature gradients so that the cell structure could be studied under different growth conditions. Growth rates in the range of 0.4 to 9.1 cm per hr and temperature gradients from 2.25° to 1475°C per cm were used. To ensure steady-state solidification, power to the furnace was stabilized, and the entire apparatus was enclosed in a large box in which the temperature was controlled to within ± 0.2°C. The apparatus was arranged so that the specimen could be quenched in situ during solidification by pouring a large quantity of water down the central vycor tube. Excellent delineation of the solid-liquid interface at the time of the quench was obtained because of the structural changes accompanying the rapid solidification of the remaining liquid. The quenching rate was always extremely rapid as no evidence of a transition in the lamellar spacing at the interface was ever observed. The alloys to be solidified were contained in degassed, high-purity graphite tubes, 1 cm OD and 0.6 cm ID. The specimens were about 18 cm in length. After the alloy had been cast into the tubes, three 0.8-mm holes were drilled in the tube to the center of the specimen. One hole was placed 1 cm from the bottom of the ingot, and the other holes were placed at 8 and 9 cm, respectively, from the base of the ingot. Thirty-four-gage chromel-alumel thermocouples were sealed in the holes. The lower thermocouple was used to position the solid-liquid interface at the start of each experiment,

Jan 1, 1969

By L. L. Melton, W. T. Malone

Fluid mechanics research conducted with non-Newtonian fluid systems now permits prediction of the behavior of these fluid systems in both laminar and turbulent modes of flow through circular pipes. Present work concerns non-Newtonian fluid systems currently used in the hydraulic fracturing process. During fracturing treatments, an unsteady-state condition may frequently be encountered arising from. the reaction rate of a chemical additive. This condition must be evaluated in order to predict the actual behavior of a particular fluid during field application. Design and operation of the apparatus used to determine fluid-flow behavior permit obtaining data under such non-equilibrium conditions. This paper shows methods used to obtain rheology measurements, develop hydraulic relationships and evaluate chemical reactions producing unsteady-state conditions. Engineering application of this research is illustrated by employing measured rheological values and developed hydraulic retationships to produce frictional pressure loss (psi/100 ft) us flow rate (bbl/min) charts of common tubing and casing sizes for an example fracturing fluid. How these charts and chemical reaction rate information are then combined to predict actual turbulent hydraulic behavior during unsteady-state field conditions is also discussed INTRODUCTION Many fluids used in hydraulic fracturing contain chemical additives which impart non-Newtonian fluid properties that may drastically alter their hydraulic behavior. Equally drastic alteration in wellhead pressure, injection rate and hydraulic horsepower requirement may result from these fluid properties. Prior research conducted to relate non-Newtonian fluid properties with hydraulic behavior has not as yet produced a universal relationship, particularly for the turbulent flow region. which of the many Possible non-Newtonian fluid properties is responsible has not been conclusively established. A systematic description, suggested by Metzner, of the many possible non-Newtonian fluid properties exhibited by real-fluid behavior, and a current discussion of theoretical and applied aspects of non-Newtonian fluid technoloy can be found in Handbook of Fluid Dynamics. f Little or no research has previously been attempted with fluids exhibiting time - dependent properties. Addition of chemicals during a fracturing treatment is often accomplished by continuously mixing and displacing the fluid. This produces a time-dependent effect or unsteady-state condition while the fluid is progressing through surface and wellbore conductors. This condition is due to solution or chemical reaction of the additive. Considerable departure from conventional methods of obtaining and interpreting data was found necessary to consider these conditions. Therefore methods were developed to obtain hydraulic behavior information under these complex, unsteady-state conditions. Relationships presented in this paper to predict hydraulic behavior of non-Newtonian fluids in circular pipes were obtained by constructing and operating a small pipeline apparatus in the manner of a pilot-plant study. These relationships are suggested as scaleup equations and are not proposed as fundamental rheological parameters. While perhaps deficient from a fundamental research viewpoint, a pilot-plant study does permit the determination and convenient evaluation of variables pertinent to a process. A pilot-plant study can result in a valid engineering application procedure even when fundamental relationships are still undefined. An excellent series of articles by Bowen has appeared in the chemical engineering literature.2-8 These give a thorough review of proposed hydraulic relationships and their limitations for non-Newtonian fluid behavior in circular pipes. A graphical method is presented to scale up data for a fluid exhibiting an anomalous hydrau1ic behavior in the turbulent flow region. Considerable assistance has been obtained from these articles to interpret the anomalous behavior noted during this investigation. These articles also provided assurance that a pilot plant is a practical approach to evaluate the hydraulic behavior of non-Newtonian fracturing fluids. _____________

Jan 1, 1965

By N. S. Bornstein, M. A. DeCrescente

ThE nickel and cobalt base superalloys employed in gas turbine engines under some conditions' oxidize at an accelerated rate when exposed at elevated temperatures to atmospheres containing minor quantities of sea salt. It is generally agreed by investigators in the field that the major steps comprising this phenomena of accelerated oxidation, also called hot corrosion or more commonly, sulfidation, are a) a slag composed primarily of Na2S04 is formed on turbine components, b) the protective oxide scale is rendered ineffectual, c) the slag reacts with. the substrate to form metal sulfides, and d) the substrate is rapidly oxidized. Sodium sulfate, a minor constituent of sea salt, is formed within the gas turbine engine from the reactions between NaC1, the major constituent of sea salt, and the oxides of sulfur.' Depending upon concentration, engine compression ratio, and temperature, the Na2S04 will be present in the gaseous or condensed state. It has been determined that in order for sulfi-dation to occur the Na2S04 must be present in the condensed state.' Although a number of sulfidation mechanisms have been postulated, there is no consistent explanation of oxide scale breakdown and subsequent catastrophic oxidation. Some investigators believe that after oxide scale breakdown, the Na2SO4 reacts with the substrate to form lower-valent sulfur compounds. The accelerated rate of oxidation is due to oxidation of a nickel-sulfide phase." Other investigators believe that sulfur from the fused salt reacts with chromium in the alloy to form chromium-rich sulfides; thereby depleting the alloy of an element which imparts oxidation resistance.3,4 This publication will demonstrate that the accelerated rate of oxidation associated with sul-fidation is due to interactions between Na20, a con-stituent of NazSO.,, ancl the substrate. The aim of this study was to separate and determine the effect of compounds of sulfur and sodium on the oxidation kinetics of various nickel-base superalloys, in order to elucidate the sulfidation mechanism. The work reported herein is sponsored in part by the Naval Ship and Development Center-Investigation of EXPERIMENTAL PROCEDURE The nickel base alloys B-1900, U-700, and Waspaloy were chosen for this study. The nominal compositions are presented in Table I. The specimens, approximately 1 in. by 1 in. by 0.060 in. received in the "as cast" condition were polished with 600 grit emery, washed, and rinsed with acetone immediately prior to oxidation experiments. Sulfida-tion attack was duplicated in the laboratory by apply-ing a saturated aqueous solution of Na2S04 onto the al loy substrate and subsequently exposing the specimens in oxygen at elevated temperature. The method of Na2S04 application is described elsewhere in detail.6 In another set of experiments the affected substrate microstructure associated with sulfidation was reproduced free of the normal oxide scale, by reacting and diffusing elemental sulfur into the alloy. The experimental procedure is also described elsewhere in detail. All oxidation studies were performed using an Ainsworth thermobalance type RV-AU-1, which is readable to 0.01 mg and is reproducible to ±0.03 mg. The specimens, introduced into a heated furnace, were exposed in the temperature range 800" to 1000°C

Jan 1, 1970

By Harold S. Davis

SURROUNDING the nuclear core of an atomic energy plant there are usually one or more thick walls of concrete, as required to protect instruments and personnel from the harmful effects of nuclear radiations. Sometimes these massive walls are of ordinary concrete weighing about 150 pcf. To reduce wall thicknesses, concrete weighing 200 to 350 pcf may be used. Such high densities are obtained by using natural aggregate processed from heavy ore, or by using steel slugs or iron shot in concrete. Mix data for a number of high-density concretes are summarized in Table I.1 High density at low cost is of prime importance in shields designed to absorb gamma rays. On the other hand, biological shields located near the reactor core must attenuate neutrons as well as gamma rays. In general, a biological shield should contain: 1) heavy elements to slow down high energy neutrons and to absorb gamma rays, 2) either light elements or hydrogenous materials to moderate neutrons of intermediate energy, and 3) materials to absorb neutrons once they have been slowed down to thermal energies. Some shield materials, iron and water for example, are effective in one or more of the above ways. On the other hand, some otherwise excellent shield materials have certain undesirable radiation properties that limit the ways or number of places they can be used. For example, when iron absorbs neutrons it emits secondary gamma rays of high energy. On the other hand, boron absorbs neutrons avidly without producing high energy gamma rays. In spite of its high cost, boron is sometimes used in concrete to minimize production of secondary gamma rays. In some shielding applications it is necessary to avoid materials that become radioactive when subjected to neutron bombardment, continuing to give off high energy gamma rays for long periods after being removed from a neutron field.

Jan 5, 1957

By John G. Simmons

A tutorial account of the tunnel effect between metal electrodes separated by a thin insulating film is presented. Energy diagrams of metal-insulator -metal sandwiches are briefly discussed, and the isothermal and thermal J-V characteristics for symmetric and asymmetric tunnel junctions are derived from a generalized expression. Experimental data from tunnel junctions are presented, and it is shown how, correlation between theory and experiment permits a determination of some of the oxide properties. Finally, the barrier heights in AT-Al2O3-A1 junctions determined by various inr3estigators are discussed. The object of this paper is to give a tutorial account of the electric-tunnel effect between metal electrodes separated by a thin insulating film and to illustrate its utility in the study of metal-oxide interfaces. This paper will emphasize the theoretical aspects of the electric-tunnel effect: however, a brief account of the more recent experimental work will be presented. A more comprehensive experimental study of the tunnel effect will be presented in the following paper by Drs. Pollack and Morris, see p. 497. We will open with a discussion of the energy diagrams for metal-insulator-metal junctions and what we mean by the electric-tunnel effect. Following this is an account of the theoretical studies of Sommerfeld and Bethe, and Holm, and the recently reported calculations on symmetric and asymmetric junctions using the generalized formula. The theoretical presentation is concluded with calculations on the temperature dependence of the tunnel J-V characteristic. In the experimental section, it is shown how barrier heights and thicknesses are determined by comparing the experimental data with the theory. Finally, the results of various investigators on the determination of the barrier heights in Al-Al2O,-A1 systems are discussed. I) POTENTIAL BARRIERS BETWEEN CLOSELY SPACED ELECTRODES Since it is necessary to supply energy to a metal in order to observe electron emission from its surface, it is evident that the potential energy of an electron within a metal is lower than that of an electron at rest outside the metal. It follows, then, that the electron must undergo a change in potential as it crosses the metal-vacuum interface. In the Sommerfeld1 free-electron theory of metals it is assumed that the free electrons, the electrons responsible for the electrical characteristics of metals, move in a constant potential environment in the metal, and are contained within the metal by a potential barrier at the metal-vacuum interface. It will be evident that the idea of a constant potential environment is a very idealized model, since the potential energy of an electron is influenced by all of the atoms and the other electrons within the metal; however, its use is justified by the many excellent results it gives.2 Fig. l (a) is the energy diagram of the model envisaged by Sommerfeld; the metal is represented by a potential-energy well of depth V,; the vacuum level represents the energy of an electron at rest outside the metal. At 0°K the electrons, which exist in pairs in discrete energy levels, fill up the well to an energy ?, the Fermi level. The distance, Vo - ?, from the Fermi level to the vacuum level is known as the work function of the metal, and represents the minimum energy required to free electrons from the interior of the metal at 0°K.

Jan 1, 1965

By W. H. Smith

IN connection with some recent work on the effect of impurities on the ductility of chromium, it appeared desirable to know the solid solubility of carbon in chromium. A literature survey indicated that this information was not available. Although considerable work has been done on the Cr-C phase diagram,&apos;.&apos; previous investigators have been more concerned with the structure and phase boundaries of the carbide phases than with the terminal solid solution. The phase diagram shown in Fig. 1 is taken from the work of Bloom and Grant&apos; and represents the most recent determination. As indicated by the dashed line, the a solid-solubility limit was not determined. Experimental Procedure Alloys of chromium were prepared from hydrogen-treated and vacuum-degassed electrolytic chromium plus spectrographic grade carbon. The oxygen and nitrogen content of the alloys was <0.002 pct. After melting, analysis of the alloys showed them to contain 0.02, 0.08, 0.15, and 0.55 pct C. Pieces of the alloys were heated in a protective atmosphere to various temperatures and then quenched after holding for a time sufficient to insure equilibrium. Microscopic examination of the as-quenched alloys for the presence of a second phase was used as a measure of the solubility limit. The heats were made in a multiple hearth arc-furnace using a zirconium-gettered static argon atmosphere. A zirconium melt was made before each Cr-C heat. Triple melting was used to insure ingot homogeneity as shown by microscopic examination. The alloys were prepared by adding portions of a 4.5 pct C-Cr master alloy to high purity chromium. The carbon contents listed previously were those obtained by analysis. The nitrogen and oxygen contents after arc melting were both <0.002 pct. Sections 1/8X1/4X1/2 in. were cut from the 100-g ingots and a hole drilled in one end in order to suspend the sample from a molybdenum wire. After the surface was carefully cleaned, a sample of each melt was hung in a mullite tube heated externally by a platinum resistance furnace connected to a vacuum system. The lower portion of the mullite tube was sealed to Pyrex and closed off several inches below the furnace. This was filled with sili-cone oil kept cold by circulating cold water around the outside of the Pyrex. Quenching into the oil bath was achieved by melting a fuse wire supporting the sample. It required about 4 sec for the sample to cool from 1400" to 600°C. This severity of quench was considered satisfactory to freeze-in the high temperature equilibrium. For tests made at temperatures of 900" to 1200°C, heating was done in vacuum; for tests above 1200°C, an argon atmosphere was used. The holding time employed ranged from 12 hr at 900°C to 6 hr at 1400°C. Experiments were performed at temperatures of 900°, 1000°, 1100°, 1200°, 1300°, and 1400°C. Microscopic examination for evidence of a second phase was done at X1500. Experimental Result The microstructures of a 0.08 pct C-Cr alloy as-cast and after quenching from 1300°C are shown in Figs. 2 and 3. A 0.15 pct C-Cr alloy quenched from 1300°C is shown in Fig. 4. The data obtained from the quenching experiments is shown graphically in Fig. 5. If the Van&apos;t Hoff equation is obeyed, a plot on a logarithmic scale of the mol fraction of solute vs the reciprocal of the absolute temperature should give a straight line. For dilute solutions the weight percentage can be substituted for the mol fraction without introducing any appreciable error. The Van&apos;t Hoff equation can then be written as where H is the heat of solution in calories per mol. The slope of the straight line on the log pct C vs 1/T plot gives the value of AH. Assuming that the Van&apos;t Hoff equation is obeyed, which is probably justified for the dilute solution of carbon in chromium, the heavy straight line shown on Fig. 5 represents the best fit of the data. This line was obtained as follows. On Fig. 5 the results of the microscopic examination of all alloys following quenching were plotted and designated as to whether one or two phases were seen. Below 1100°C all alloys showed a second phase on quenching. The heavy vertical lines shown in Fig. 5 therefore represent the possible range of the ter-

Jan 1, 1958

By Paul D. Conatore

INTRODUCTION There are important reasons for a discussion of tungsten resources, reserves, and production in the Circum-Pacific area. First, the world&apos;s chief tungsten deposits, as well as most of the world&apos;s tungsten reserves and production, occur in this region. It is well known that the world&apos;s largest tungsten reserves are located in southeastern China and that for many years, the largest individual mine in the world was there. Although China still has the world&apos;s greatest tungsten production, the very high-grade scheelite mine of Canada Tungsten Mining Corporation in the Northwest Territories is the largest producer of tungsten today. There is certainly a great quantity of tungsten in Asia, but the strategic importance of this fact is now offset by the wide distribution of mines and production facilities throughout the world, especially in other parts of the Circum-Pacific area such as Australia, Canada, and the United States. In addition, much of the Circum-Pacific area is comprised of Mesozoic-Cenozoic orogenic belts. These global tectonic units are regarded as very favorable for additional tungsten deposits, particularly scheelite-bearing tactites, and consequently, prospecting and exploration will most likely be concentrated in the Circum-Pacific area. Second, tungsten must be regarded as one of the, most important metals of modern industry because of its very special properties. It has the highest melting point, the highest tensile strength at elevated temperatures, and the smallest compressibility of any metal. The metal also possesses a very high density, excellent corrosion resistance, good thermal and electrical conductivity, and a low coefficient of expansion. As a result, tungsten has found increasing importance in a wide range of industries. From the filament in an electric lamp, to cutting tools and drilling bits, to the exotic radiation shields that protect supersonic aircraft and spacecraft, tungsten plays an indispensable role in our daily lives. The primary objective of this paper is to present an overview of important facets of known and suspected tungsten in the Circum-Pacific area. Resources, reserves, current production, planned capacity expansions, and new operations, as well as an assessment of the probability for development of deposits in the Circum-Pacific area, are discussed. RESOURCES The average crustal abundance of tungsten has been estimated at 0.0015 kilograms per tonne. A comparison of the abundance of various metals in crustal rocks to that of tungsten is presented in Table 1, which shows that tungsten abundance is similar to that of its commonly associated metals, tin and molybdenum. Table 1. AVERAGE CRUSTAL ABUNDANCE OF VARIOUS METALS (Grams per Tonne) [ ] With careful thought, it can be realized that tungsten ore deposits result from the concentration of the metal, through normal geologic processes, to levels substantially greater than its average crustal abundance. The minimum technologically and economically workable tungsten concentration, or cutoff grade, is a function of (1) deposit tonnage, (2) mining and milling methods, (3) production tonnage, (4) capital and operating costs, (5) tungsten market conditions, and (6) value of associated recoverable metals. The tungsten cutoff grade that is currently exploitable at a profit varies from 0.09% W03 to 1.55% W03, reflecting concentration factors from 470 to 8200, as shown in Table 2. Table 2. CURRENT TUNGSTEN CUTOFF GRADES [ ]

Jan 1, 1982

MINING and Metallurgy closed the year 1928 showing a small profit, the receipts, exclusive of the charge against members, dues for subscriptions, having been $43,067.81, and expenditures $40,925.58. In accord with the policy of the Board the budget is made each year with the purpose of balancing the accounts rather than the maximum of profit from the undertaking since it is the service the journal performs for members that justifies its existence. This service is being constantly increased. Within the year a number of changes have been made in the dress of the magazine, a new cover adopted, color more frequently used, and illustrations more generally employed. These changes seem to have been appreciated both by readers and advertisers. More space has been devoted to papers read before local sections and to the news of their activities. It is believed that this has helped materially in sustaining and increasing the interest in such meetings. The general, regional, and division meetings have also been fully reported and news of Board meetings, of the work of the various committees, of the employment service and other activities of the Institute has been spread before its members month by month. The 570 pages of reading matter printed in the course of the year constitute not only a record of what the Institute was doing but of what the most representative sections possible of the members of the mining and metallurgical professions were thinking. With 9000 members scattered around the world, occupying key positions in the industry, the Institute affords through its own journal an unsurpassed medium for broad contact and enables the readers with the minimum of expenditure of time and at no extra money expense to keep a general contact with the whole range of subjects touched by miners and metallurgists. In these days of intense specialization but rapid change such contact is particularly valuable. The more formal papers presented to the Institute are published in the Transactions, Technical Publications and the special volumes. Mining and Metallurgy carries abstracts of all papers published ,by the Institute and prints in full the shorter, less detailed papers and those which reflect work in progress rather than finished. Such papers have a news value which is supplemented by editorial comment, discussion by members and others, and the actual news of the organization itself. Without therefore attempting to fill the place of a general news sheet, it has a timeliness that gives it an immediate value much appreciated by the readers. In accord with the general policy of the Board every effort will be made constantly to improve the quality of the magazine to the full extent that its revenue will permit. Your Committee feels that, through the intelligent cooperation of the official staff in the office, Mining and Metallurgy has been improved in

Jan 1, 1929

By John W. Vanderwilt

THE unpredictable behavior of ground movement and subsidence has complicated the problems that attend the extraction of large quantities of ore. Special studies, particularly relating to coal mining, have yielded such a voluminous literature and so many involved controversial theories that a partial review would be difficult. Limited space makes any kind of a review impractical. The features to be considered cover only a relatively small part of the broad problems of ground movement and subsidence, but it is believed that this small part is critical. The practical aspects are important, since they bear directly on safety of mine workings, on recovery of ore and on dilution of ore in block caving and related systems for extracting large quantities of rock. The ground movement to be described occurs outside the vertical boundaries of a caved block in the area that is commonly referred to as being in the "zone of draw." "Draw" is a term that originated in the subsidence problems related to coal mining, and it is defined by a line drawn from the margin of the area caved underground to the most distant fracture at surface on the same side of the caved area as shown in Fig. I.1 " A line thus drawn is called the cave line, and its angle with respect to the horizontal is the cave angle or angle of draw. It is understood that the line is taken normal to the limit of mining, and in a vertical plane. The prevailing theories as to draw and angle of draw assume that appreciable movement occurred along the cave line, which has been described as a fracture resulting from the shearing action brought about by the weight of the overlying load. Fig. 2 shows diagrammatically the mechanics of ground movement adjacent to an area of subsidence according to the prevailing theory of draw (A, from Royce2) and, for comparison, ground movement observed in the Climax mine (B). The text in Peele&apos;s Handbook2 referring to Fig. 2 does not state the meaning of the "original position of top of workable ore" in the rectangular space above "ore in place," and the arrows are not explained. However, this presentation is most concerned with the zones outside the rectangle. According to the prevailing theory, as shown at the extreme left under A, Fig. 2, the vertical tension cracks at surface change at a shallow depth to shear fractures forming the cave line, and it is assumed that appreciable movement takes place along the cave line toward and into the subsiding caved block. The mechanics of ground movement observed in the Climax mine, as shown under B, Fig. 2, does not accord with the prevailing theory, particularly as regards the cave angle and draw. The vertical

Jan 1, 1946

By John J. Secretary Egan

The present list of problems relating to the physical chemistry of steelmaking has been prepared by the Committee on the Physical Chemistry of Steelmaking, from answers to a questionnaire submitted to a number of metallurgists engaged in both industrial and educational work throughout the United States. The purpose of the project is to make available to research laboratories a list of problems, all reduced to their simplest terms, the solution of which would aid in creating a better understanding of the steelmaking process. It is not intended to restrict the problems to practical steelmaking. The list also includes the study of the properties, and their correlation, as well as the physical and chemical reactions, of all substances that occur or that may be in any way associated with steelmaking operations, such as metallic substances, refractories, nonmetallic inclusions, and the constituents of slags. Many of the problems can be carried out in university or other research laboratories. Others may be most successfully attacked by cooperation of the research men with the operating personnel. It is the Committee&apos;s earnest wish that this cooperation be fostered. It is requested that investigators who are working on any of the problems listed and who anticipate future publication of their results, notify the Secretary of the Committee that such investigation is in progress. Suggested additions to the present list are also requested. The Committee is undertaking to act as a clearing house for information regarding the topics in this field that are being actually studied. Interested persons are invited to correspond with the Secretary. I. Data involved in the state of equilibrium for the various systems (laboratory work, almost entirely). A. Specific heats, heats of formation, entropies and free energies of various PURE ELEMENTS OR COMPOUNDS; ALSO CERTAIN TYPICAL SLAGS AND REFRACTORIES I. Determination of specific heats and entropies of oxides, sulphides, nitrides, etc, over a wide temperature range. 2. Determination of free energies of oxides, sulphides, nitrides, etc., over a wide temperature range. 3. Determination of the heats of formation of the oxides, sulphides, nitrides, etc. 4. Determination of the thermodynamic properties of the more important mineral-ogical constituents of the basic open-hearth slags such as calcium silicates, calcium phosphates, calcium ferrites, manganese silicates, FeO and Fe2O3. 5. Determination of the specific heats of open-hearth slags, including liquid silicates, if possible.

Jan 1, 1941

By John J. Secretary Egan

The present list of problems relating to the physical chemistry of steelmaking has been prepared by the Committee on the Physical Chemistry of Steelmaking, from answers to a questionnaire submitted to a number of metallurgists engaged in both industrial and educational work throughout the United States. The purpose of the project is to make available to research laboratories a list of problems, all reduced to their simplest terms, the solution of which would aid in creating a better understanding of the steelmaking process. It is not intended to restrict the problems to practical steelmaking. The list also includes the study of the properties, and their correlation, as well as the physical and chemical reactions, of all substances that occur or that may be in any way associated with steelmaking operations, such as metallic substances, refractories, nonmetallic inclusions, and the constituents of slags. Many of the problems can be carried out in university or other research laboratories. Others may be most successfully attacked by cooperation of the research men with the operating personnel. It is the Committee&apos;s earnest wish that this cooperation be fostered. It is requested that investigators who are working on any of the problems listed and who anticipate future publication of their results, notify the Secretary of the Committee that such investigation is in progress. Suggested additions to the present list are also requested. The Committee is undertaking to act as a clearing house for information regarding the topics in this field that are being actually studied. Interested persons are invited to correspond with the Secretary. I. Data involved in the state of equilibrium for the various systems (laboratory work, almost entirely). A. Specific heats, heats of formation, entropies and free energies of various PURE ELEMENTS OR COMPOUNDS; ALSO CERTAIN TYPICAL SLAGS AND REFRACTORIES I. Determination of specific heats and entropies of oxides, sulphides, nitrides, etc, over a wide temperature range. 2. Determination of free energies of oxides, sulphides, nitrides, etc., over a wide temperature range. 3. Determination of the heats of formation of the oxides, sulphides, nitrides, etc. 4. Determination of the thermodynamic properties of the more important mineral-ogical constituents of the basic open-hearth slags such as calcium silicates, calcium phosphates, calcium ferrites, manganese silicates, FeO and Fe2O3. 5. Determination of the specific heats of open-hearth slags, including liquid silicates, if possible.

Jan 1, 1941

By Carl Henrich

The Ducktown copper-mines are located in the southeast corner of Tennessee. The name Ducktown was originally given to a district occupying the southeast corner of Polk county, which in turn occupies the southeast corner of the State. Fig. 1 is a map of the vicinity of Ducktown, taken from the topographical surveys of the United States Geological Survey. The Ducktown district is bounded on the east by Cherokee county, North Carolina (the boundary-line between the two States running here a little east of north along the western slope of Pack mountain), and on the west by the eastern foot-hills of Little Frog mountain. On the north, Stansbury mountain, really a chain of low mountains or hills, forms the dividing-line between Ducktown and Turtletown districts. On the south, the Ducktown district extends beyond the Ocoee river to the Georgia State line.. This line, in going west, gradually recedes southwards from that river into the foot-hills of Big Frog mountain, the highest mountain of the neighborhood, which rises about 4300 feet above sea-level, while the surface of the Ocoee river, where it leaves the Ducktown district, is less than 1500 feet above sea-level. It will be seen from this description, and from a study of the map, that the Ducktown district occupies the northern part of a kind of basin, bounded on the east by Pack mountain and on the west by Little and Big Frog mountains. Between these mountains the Ocoee river, draining the basin, cuts its way to the Hiwassee and the Tennessee rivers in a narrow gorge, through the crystalline slates and schists, which from their excellent exposure in this Ocoee gorge have received the local

Jan 1, 1896

By Louis V. Bender

AfteR investigating the work of coal-dust fired reverberatories of the Canadian Copper Co., at Copper Cliff, Ontario, the management of the Washoe Reduction Works decided to experiment with and ascertain the advantages of using coal dust as a fuel in their reverberatories. Consequently, during the month of June, 1914, reverberatory furnace No. 8 was changed in order to use powdered coal as a fuel. The results obtained by this method of firing are gratifying and show a decided saving in cost of smelting as compared to grate firing with lump coal. The furnace, as remodeled, is 124 ft. long by 21 ft. wide, and varies in height from 8 ft. 6 in. at the back end to 5 ft. 7 in. at the skimming end. The general construction of the furnace is similar to that of the other furnaces at this plant. There are no side doors to this furnace, as it was thought that with the present arrangement for feeding no "fettling" or "claying" would be required. The interior of the furnace can be inspected through the burner port holes, after shutting off the burners and giving a few seconds&apos; time for the gases inside the furnace to clear away. The charging is done on either side of the furnace from longitudinal hoppers, extending a distance of 74 ft. from the back end of the furnace. Leading from the hoppers into the furnace are 6-in. pipes, spaced 191/4 in. apart, through which the charge is intermittently dropped. The charge is kept well above the slag line at all times; in this way the side walls are protected and no fettling is needed on this portion of the furnace. The remainder of the furnace requires fettling. After operating for three months, we found that the bricks were eaten into along each side wall from the skimming door back to the point where the charge had been dropped. The depth of this cutting away was 8 in. close to the front end and gradually tapered to zero at a distance of 50 ft., and was greatest on the side of the furnace having the larger flue connection. Hoppers will be put in for the entire length of furnace, from which fettling material will be dropped, to prevent this cutting. After the run of three months, the roof was in excellent condition. At the back of the furnace the bricks were not cut into at all; at 30 ft.

Jan 1, 1915