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By Wayne A. McCurdy

For the third consecutive year, predicted increases in coal production and consumption failed to materialize. Production of bituminous, sub-bituminous and lignite coal for 1961 was estimated by the U.S. Bureau of Mines at 400 million tons, a drop of 15,- 512,000 tons from the 1960 figure. Anthracite production for the year was 17.8 million tons compared to 18.8 million tons produced in 1960. Consumption figures are expected to show a proportionate decline. Of coal's major markets, only electric utilities showed an increase-and even here the increase of approximately 2% was smaller than had been expected. Major cause of relatively low consumption was a decrease of more than 20% in the use of metallurgical coal for making coke. Reductions of lesser importance were registered in general industrial, retail, and export markets.

Jan 2, 1962

By J. Charles Miller

THE expansion of facilities for rapid transportation of perishables by train, truck and airplane has necessitated consideration of refrigerants of a minimum weight and volume per pound of cooling and has stimulated the use of solid carbon dioxide commercially. The gas probably has not had wide application in the past in air-cooling equipment for mines, theaters or buildings, owing to its thermodynamic properties, as will be deduced from examination of Table 2. However, consumption of the liquid in carbonating beverages remains a dominant factor. In addition to these uses, carbon dioxide is employed to a limited degree as an explo-sive in the liquid form, as a freezing agent in plumbing, in laboratories for low-temperature work, and in the manufacture of golf balls.

Jan 1, 1936

By Norris Johnston, Carrol M. Beeson

For many years the permeability of reservoir sands has been measured by flowing air through a cleaned and dried core sample. This differs from the true reservoir permeability in one important respect: the rock particles in the reservoir are surrounded by interstitial water, not air, and their physical shape and condition of hydration are greatly dependent thereon. Permeability as defined must be measured with a single-phase fluid. Since no means exist for removing the oil and gas from a core sample by simply flowing water through it, the sample must be cleaned and then resatu-rated with water before testing. The present discussion attempts to show that after the cleaning process a considerably different permeability is determined with salt or fresh water than is obtained with air. The postulate is made that the salt-water permeability is probably closer to the true reservoir permeability than is the measurement with air. This is discussed in relation to both physically possible and economically feasible measuremerits. Data On more than 1200 core samples are given to show the nature of the effects observed, and a plea is made for others to consider water permeability measurements as a routine necessity, eventually replacing air permeability in regions where the differences are great. Introduction Permeability is defined1 as a "a measure of the capacity of a porous medium to transmit fluids, when there is no interaction between the solids and the fluid." Darcy's law of liquid flow in porous media states: kA?P QµL/A?L [I] where Q represents milliliters of liquid of viscosity p centipoises passed per second through a porous medium of permeability k darcys and cross-sectional area A sq. cm. under a pressure gradient ?P/L atmospheres per centimeter, the flow being understood to be laminar or viscous, not turbulent. This equation defines the darcy. For the case of radial flow in a uniform sand, such as usually exists in the neighborhood of a well in an oil or gas sand, Darcy's law becomes:2 Here h is the net sand thickness in feet, Pe and Pw are pressures at the drainage radius4 and well radius, and re and rw are these radii, respectively. The productivity index3 is defined as the barrels of liquid produced per day per pound per square inch mean pressure differential between ferences and well bore, and is thus: By further definition, the specific productivity index is: or in terms of practical units, and allowing for shrinkage:

Jan 1, 1945

By F. J. Plecity, J. T. Michalak, W. C. Leslie

W. M. Williams (McGill University)-The authors are to be congratulated on completing this detailed investigation of recrystallization behavior. The present writer has recently completed some research at the University of Toronto on the recrystallization and grain growth behavior of a number of "pure" irons, and he would like to take issue with the authors' contention that recrystallization cannot be followed by means of hardness measurements. Two series of specimens of Ferrovac E, a com- mercially available iron, were annealed to complete recrystallization at 525" and 620" C, measurements being made both of Rockwell hardness and of volume percent recrystallized as a function of annealing time. Good correlation was found between these two quantities and, following the earlier practice of Cook and Richards for copper, hardness measurements were used in an extensive investigation of recrystallization. No anomalous behavior was observed as a result of this practice. Specimens which showed complete softening always showed, (metallographically and by X-rays), completely re-crystallized structures. These observations do not, of course, detract in the least from the results of the work under discus-

Jan 1, 1962

By A. R. Troiano, E. A. Steigerwald, F. W. Schaller

The initiation of localized cracking in hydrogenated high strength steel was dependent on the developmeni of a critical hydrogen conceniration and relatively insensitive to the magnitude of the applied stress. The stress was believed to influence the deluyed failure process by providing the means for grouping the hydrogen. On the basis of an assumed distribution law the observed changes in the lower critical stress as a function of notch acuity, yield strength, and temperature were predictable over a significant range of these variables. THE phenomenological characteristics of delayed failure in high-strength steel have been comprehensively investigated and the behavior has been attributed to the strong embrittling action of hydrogen.1-3 Delayed failure or, as it is also termed, static fatigue, is the most sensitive means of detecting hydrogen embrittlement since it allows the maximum time for hydrogen diffusion during a test.3 The nature of delayed failure cail be aptly described by four parameters which are schematically depicted in Fig. 1. The upper critical stress corresponds to the rupture stress in a conventional notch tensile test. The lower critical stress or static fatigue limit is the stress below which no delayed failure will occur. The incubation period is the time required for the formation of the first crack and the fourth parameter is the failure time. An increase in hydrogen content, notch acuity, or strength level of the material increases the susceptibility for delayed failure by decreasing the lower critical stress, the incubation period, and the time to failure.lY3 A decrease in test temperature prolongs the incubation period in accordance with the lower diffusion rate of hydrogen, and also de-

Jan 1, 1961

By E. R. Gilbert, D. E. Munson

Creep of copper under 75 to 1.50 kg per sq cm stresses at temperatures near the melting point was found to he a complex reaction controlled by three mechanisms acting in parallel. In order of appearance with decreasing temperature, the auerage activation energies, Qc , are 168, 79, and 24 kcal per mole. Stress dependence of the minimum creep rate was found to he an exponential for the two high-Qc processes and a power law for the low-Qc, process. Transition of control occurs from one mechanism to another. The relative transition temperature depends upon the applied stress, and the range oiler which the transition occurs depends upon the difference in the activation energies of the mechanisms. The creep behavior at high temperature is explained by the climb of dislocations through thermally or mechanically formed jogs, CREEP in pure fcc metals at temperatures in excess of one half the absolute melting point is normally controlled by dislocation c1imb.1,2 A climb model which seems applicable, according to an extensive analysis of data,3 was derived by Weert-man.4 This model assumes jog-saturated dislocations and predicts an activation energy, Qc, nearly equal to that for self-diffusion, USd. Although the requirement of jog saturation is restrictive, agreement between theory and experiment seems adequate. Many other theoretical treatments, including an early model by Mott,5 include detailed consideration of jog formation as an initial requirement for climb. These models predict activation energies for creep which differ from those of self-diffusion. Seeger6,7 postulates an observed activation energy related to the stacking-fault energy. Thus, Usd <Qc<5Usd + Uj where Uj is the jog-formation energy. Seeger incorporated qualitatively the influence of the relative numbers of thermal and athermal jogs. Expanding this concept, Shoeck8 explicitly states a function based on formation mode and relative numbers of vacancies: e r ci exp {-uf/k T} exp {-Um/k T} [ 1 ] where Uf and Um are energies of vacancy formation and migration, respectively. The concentration of jogs, Cj, depends upon the manner of jog production. For intersection jogs, Cj is not sensitive E. R. GILBERT, Junior Member AIME, formerly with De- to temperature; for thermal jogs, Cj is proportional to exp {—Uj /k T}. Schoeck regards each mode as a distinct mechanism; therefore, the mechanisms may act together.299 The diversity predicted by theory, surprisingly, has not been substantiated by experimental results. A significant investigation must include the extremes in stacking-fault energy. Extensive creep studies of aluminum10 and nickel,11,12 high stacking-fault energy metals, have been made. Comparable studies on a low stacking-fault energy metal, such as copper, have not. It is the purpose of this paper to report the results of an investigation of the creep of copper under conditions which favor thermal jogs. EXPERIMENTAL Cylindrical compression creep specimens (0.240 in. in diameter by 0.400 in. long) were machined from cold-drawn rods of electrolytic tough-pitch copper containing 0.0007 Mg, 0.002 Fe, 0.001 Ni, 0.0005 Ag, Cd < 0.005, and Pb < 0.005 wt pct impurities. Undetected spectrographically was a nominal 0.04 wt pct 0, which occurs as a Cu2O constituent distributed discontinuously at grain boundaries. Vacuum annealing at 900°C for 15 min produced a stable 0.03-mm average grain diameter. Testing was carried out using apparatus similar to that described by sherby,13 modified by enclosing platens and a push rod in a vacuum cylinder. Normally this arrangement resulted in pressures less than 10 Only a slight surface tarnish, less than 0.0005 in. in thickness, occurred during the test. The applied stress, corrected for atmospheric pressure, was maintained within 2 pct of the desired true stress by the addition of lead shot at fixed strain increments. Creep strain was measured with dial gages as a relative displacement of the upper and lower platens; accuracy of measurement was 0.0001 in. Two creep-test methods were used, the differential or cyclic temperature14 and the isothermal, to obtain creep data at stress levels of 150, 100, and 75 kg per sq cm over the temperature range of 620° to 1032°C. Minimum creep rates were used from both test methods; this was considered proper because comparable temperature tests or cycling to the same temperature gave the same creep rate, within experimental error. The cold vacuum test chamber, with the unstressed specimen in place, was heated to temperature by placing a preheated furnace over the chamber. Temperature equilibrium was attained within 30 min. For the cyclic tests, the stress was removed during the 5 to 10 min necessary to effect the temperature change and re-

Jan 1, 1965

By Auguste J. Rosh

The use of titaniferous ores in the blast-furnace has been the subject of much controversy for many years. Divers objections have been raised against them, and, for one cause or another, the verdict

Jan 1, 1893

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös&apos; law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By Leonard Obert

The structural stability of any mine or under- ground opening in rock is dependent on the stress field, that is, the state of stress in rock before mining, the stress distribution in the rock created by the opening, and the in situ strength of the rock. In the past mine design problems have been considered by assuming that the stress field is due only to the weight of the overlying rock, the stress around the opening can be calculated from elastic theory using laboratory-determined elastic constants, and the in situ strength of the rock can be determined from laboratory tests on small specimens. Solutions to hypothetical problems using this procedure are given in a report by Obert, Duvall, and Merrill.&apos; Because of the uncertainties of these assumptions, this method can give only a rough approximation to the solution of actual structural problems. Obviously, this approach to determining the stability of underground openings would be greatly improved if the rock stress could be measured in situ, and it is undoubtedly for this reason that in recent years many investigators have spent considerable effort on the development of procedures for measuring rock stress. In this report a method is described for determining in situ the absolute stress in rock. The method requires the measurement of the deformation of a borehole before and after the rock is stress-relieved. The magnitude and direction of the applied stresses are calculated from the borehole deformation and modulus of elasticity of the rock. Also, the results of absolute stress determination made in the walls and pillars of underground openings in five rock types are presented. From these results a number of conclusions are drawn regarding the accuracy and limitations of this method and the problem of stress measurements in general.

Jan 8, 1962

By J. Brett, S. Friedman

A study of the diffusion of nickel into both fibrous and recrystallized 0.065-in.-diam silica-alumina doped tungsten wire at 1200°C has been conducted. The diffusion profiles were determined by chemical dissolulion of successive circumferential layers and spectro-photometric determination of nickel in the etchant. It was shown that the diffusion of nickel into tungsten is markedly structure-sensitive. No significant amount of nickel could be introduced at 1200°C into tungsten which had first been recrystallized at temperatures of 2300°C, leading to an upper limit estimate for the bulk diffusivity of nickel in tungsten of 10-11 sq cm per sec at 1200°C. However, nickel did diffuse into initially fibrous wires, caused re crystallization, and was alsays present at the advancing recrystallization front. The accumulation of nickel in an initially fibrous region ceases when the recrystallization front arrives. The characteristics of the resulting diffusion profiles are explained in terms of the relation between diffusion processes and micro structural changes. WHILE it is well-known that the presence of nickel and certain other metals causes low-temperature recrystallization of the cold-worked fibrous structure of doped tungsten,&apos;&apos;&apos; the character of the phenomenon is not well understood. Recently it was shown that the recrystallization reaction can be induced at low temperatures by the presence of solid nickel on the surface of doped wire, but not by exposure to nickel vapors.3 Once recrystallization was initiated, a continued source of nickel was required for propagation of the recrystallization front. The phenomenon appeared to be a complicated solid-state reaction since, in addition to the change in structure of the tungsten from fibrous to equiaxed grains, diffusion of nickel from the surface into the recrystallized and fibrous structures was occurring with possible chemical reaction between nickel and tungsten at the surface and interaction of nickel with the dopants which ordinarily stabilize the fibrous structure within the wire. The objective of the present work was to study the diffusion of nickel into fibrous and recrystallized tungsten structures in order to clarify the relationship of the diffusion process to nickel-induced recrystallization. Studies of interdiffusion in the Ni-W system4"7 have been principally concerned with the mobility of tungsten in nickel. Information on diffusion of nickel in tungsten is meager, and there seem to be no studies of the mobility of nickel in tungsten which elucidate the structural aspects of the phenomenon. The present experiments were designed to determine the diffusivity of nickel at 1200°C in fibrous tungsten, in large-grained tungsten prerecrystallized at high tem- perature, and in tungsten recrystallized at 1200°C due to the presence of nickel. Although the concentration profiles were determined in these experiments, unexpected changes in boundary conditions or complex diffusion paths complicated the analysis of these profiles so that the interpretation could not be readily expressed in terms of simple diffusivities. EXPERIMENTAL PROCEDURE The experiments were conducted on Sylvania 0.065-in.-diam silica-alumina doped commercial tungsten wire, hereafter designated as ordinary doped wire. A special lot of 0.065-in.-diam silica-alumina doped low-nickel wire was also used. Impurity analyses of the wire are given in Table I. The experimental design is shown in Fig. 1. All heat treatments were conducted in vacuum. Two groups of ordinary doped wire were prepared for diffusion with nickel. One group in the as-received (fibrous) condition was elec-tropolished, nickel-plated, and annealed at 1200°C for 20 and 40 hr, or was exposed to nickel vapor at 1200°C for 20 and 40 hr. The second group was recrystallized to an equiaxed grain structure at 2300°C for 3 hr, electropolished, nickel-plated, or exposed to nickel vapor for anneals at 1200°C for 20 and 40 hr.

Jan 1, 1969

By D. A. Stevenson, R. A. Burmeister

Single-phase silver antimony telluride has been prepared by zone-melting techniques using initial compositions of A new phase appears upon prolonged annealing of this material, but the reaction does not appear to be a simple eutectoid decomposition. A complete analysis of the phase equilibria is complicated by the slow kinetics involved. The Hall coefficient, magneto -resistance, electrical resistivity, and Seebeck coefficient are all sensitive to the presence of second phases. The low Hall mobilities measured for single-phase material indicate that the usual band theory is inadequate to explain the observed transport properties in the system. Density anomalies of up to 2.5 pet between measured and theoretical density were observed but are not conclusive evidence for a defect structure. COMPOSITIONS in the Ag-Sb-Te system have been studied previously by several investigators.1"18 The interest in this system arises from potential thermoelectric applications of alloys on the Ag2Te-Sb2Tes vertical section. Although the composition corresponding to the formula AgSbTe, has received most attention, it has been found to consist of more than one phase.7&apos;8 A thorough understanding of the properties of this heterogeneous material has been impeded by both lack of knowledge of the properties of the homogeneous phases comprising it and the problem of analysis of transport properties in an inhomogeneous system. The present work describes the preparation of the homogeneous ternary phase and the corresponding electrical properties of both homogeneous and heterogeneous material. MATERIAL PREPARATION Most specimens for this investigation were prepared by encapsulating the elements in evacuated quartz tubes after which they were melted and homogenized in the liquid state. The ambient temperature was then dropped to 500°C and the resulting ingot zone melted. The growth rate, width of zone, stoichiometry, and number of passes have an effect on the resultant microstructure. Grains several centimeters in length were easily produced by this method. Other solidification techniques were also used, including uniform slow cooling of the entire specimen and rapid freezing. The microstructures of specimens produced by these techniques frequently differed appreciably from similar compositions prepared by zoning. A variety of nonequilibrium microstructures characterized by long needlelike particles resulted from the rapid-freeze method. PHASE EQUILIBRIA The lack of information on phase equilibria is a major difficulty associated with a comprehensive study of the Ag-Sb-Te system. Considerable confusion has resulted from the use of the formula AgSbTe, to identify the cubic ternary intermediate phase even though it has been established that material of this stoichiometry normally contains AgzTe as a second phase.798 In this paper, silver antimony telluride will denote the cubic ternary intermediate phase comprising the major portion of AgSbTe,. The term "single phase" will denote material which consists of only the cubic phase (as evidenced by metallographic examination and X-ray diffraction) and the term heterogeneous will describe multiphase material containing AgzTe, SbzTe3, or other phases in addition to the cubic phase. The single-phase material may actually contain a variety of inhomogeneities—gradual changes in composition on a macroscopic scale, localized fluctuations in composition, clusters or other products of early stages of the precipitation process, and a variety of point and line defects—all of which will not be detected by the present techniques for determining homogeneity. Single-phase material has been prepared from compositions close to 59 mole pct SbzTe3 21 (this notation refers to the location on the Ag,Te-Sb2TeS vertical section). Zone widths of =2 cm and growth rates 51.2 cm per hr were used. The single-phase region at elevated temperatures extends off the vertical section to a composition which can be expressed approximately as Ag,,SbzgTes,.9 The latter two compositions as well as AgSbTe, are represented in the conventional Gibbs triangle in Fig. 1. It is not presently possible to ascribe exact values to the limits of the single-phase region on a given isotherm or vertical section due to the extremely

Jan 1, 1964

By J. E. Hilliard

Various methods are given for estimating the number per unit volume and average size of convex particles from measurements on a projection through a slice of the structure. The determination of the size distribution is considered specifically for spherical particles. The results are applicable to any type of transmission microscopy and also to the correction of measurements made by reflected light on semitransparent materials. WITH the advent of electron transmission microscopy, the metallurgist is confronted with the problem of relating a projected image to the three-dimensional properties of the structure. This paper deals with the estimation of the number per unit volume and size of particles dispersed in a matrix. The case of convex particles will first be treated (the results will be applicable as approximations to particles of more general shape) and then spherical particles will be considered specifically. The latter represent a special case frequently encountered in practice and one which is also amenable to a calculation of the effect of overlap on the observed particle-size distribution. Although the present treatment was prompted by the needs of the electron microscopist, the results are applicable to transmission studies with any type of radiation. In addition, they can be used in the analysis of semitransparent materials by reflected light, the depth of light penetration corresponding to the thickness of the slice or section used in the transmission studies. 1) CONVEX PARTICLES 1.1) General Expression for N,. We will suppose that a "center" (such as the center of mass) is assigned to each particle. The convention used for defining the center is immaterial providing it does not depend on the orientation or location of the particle. Consider a slice through the structure having a pair of parallel faces a distance t apart. It will be assumed that the slice is randomly located with respect to its perpendicular distance from some fixed point, but it is not necessary to assume that its orientation is random. Our problem is to deduce the relationship between the number of par- ticle images seen on an orthogonal projection through the slice with the number, Nv, of particles per unit volume in the original structure.* *Symbols are listed in the Table. The expected number of particles with centers lying within the slice is Nvt per unit area. In addition, there will be elements in the slice contributed by particles whose centers lie without. The number of such elements will be the same as the number of intersections occurring on a two-dimensional plane through the structure; namely N~K, where K is the mean distance, Fig. 1, between tangent planes to a particle averaged over all particles, i.e., Where Ni is the number of particles of class i having the same shape and size, and pi (4, 8) is the probability that an i particle will have a given orientation with respect to the slice. If the particles are randomly oriented, then K is independent of the orientation of the slice and equal to the mean cali-per diameter. The total number of particle elements in the slice is therefore Nv(t + K) per unit area, but fewer will be seen as separate images on the projection plane because of overlap. If MA is the number of elements "lost" by overlap, the number of images per unit area will be NA = Nv(t + K) -MA 121 MA is a function of the slice thickness and must vanish at t = 0. As t increases, NA at first increases, reaches a maximum, and thereafter decreases as the overlap term MA becomes predomi-

Jan 1, 1962

By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757&apos; and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick &apos;needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,&apos; are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed&apos; by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke&apos;s law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967

By Arthur Notman

SacRamento Hill is a mass of granite porphyry intruded along a fault between Paleozoic sediments and pre-Cambrian schists in the Bisbee district, Cochise County, Arizona. The intrusion invaded both walls of the fault to a large extent, and the accompanying extensive mineralization of the Paleozoic limestones is the locus of the great high-grade copper orebodies of the Bisbee mines. Prior to 1909, although the presence of ore in the masa of the hill itself had long been suspected, systematic exploration had not been attempted. A few shallow pits on the surface here and there had disclosed some chal-cocite with associated carbonates as stringers in a mass of strongly brccciated, silicified, and iron-stained porphyry. The workings in the surrounding limestones had penetrated the porphyry in a dozen or SO places for some distance from the contact but had disclosed no ore. However, the rock had been largely altered to quartz and sericite and very thoroughly impregnated with pyrite and traces of the copper sulphides. A close geological study of the conditions, both surface and underground, strengthened these suspicions, and plans for prospecting the hill were made in 1909. Reference to the accompanying illustrations, Figs. 1 and 2, will give an idea of the general appearance of the surface. The mineralization is more intense in two main zones, one at the west end and the other at the east end of the hill. The outcrop of the hill is elliptical and approximately 3,000 ft. long by 1,400 ft. wide. The Sacramento shaft, which is the main hoisting shaft of the mine and situated at the east end of the hill, as shown by the accompanying map (Fig. 3), offered a convenient base for prospecting that end of the hill, while the workings from the Holbrook shaft offered a similar opportunity at the west end. The choice of level for the first work was determined by analogy with the most favorable depth for enrichment below surface obscrved in the other disseminated deposits of the Southwest.

Jan 1, 1916

By K. E. Brown, J. P. Brill, T. C. Doerr

A wide range of intermittent gas-lift tests way conducted in a 1,500-ft experimental well through 11/4- and 11/2-in, nominal size tubing. The well was equipped with two gas-lift valves, four Maihak electronic pressure transmitters and surface facilities to measure casing and tubing pressures, temperature, liquid production and the rate and volume of gas injected. For each tubing size, tests were conducted varying the slug length, gas volume injected and liquid viscosity and surface tension. From these tests, an empirical "fallback" or liquid loss correlation has been developed. No general fallback correlation could be obtained, and the correlation is presented in the form of one curve for each slug length of a given liquid and lubing size. A conceptual model has been developed which combines the fallback correlation with equarions which govern liquid slug pow. A mathematical simulation of the model in the form of a digital computer program is used to calculate total recovery, gas volume used and clearance time for a given test. Tubing pressures at the gas-lift valve and at the gm-slug interface are calculated as a function of time. Tubing pressures at the surface during slug clearance ore also calculated. The results compare favorably with the test data and verify the conceptual model. The extent to which the model can be used for other tubing sizes, depths, liquids and gas-lift valves can only be determined with additional experimental data. Data are also necessary so that a fallback curve can be constructed for the particular test conditions studied. INTRODUCTION The flow of liquid slugs in vertical conduits has long been an established production method in the petroleum industry. Under the name "intermittent gas lift", many advances have been made in engineering design. However, the unsteady-state nature of liquid slug flow has discouraged attempts to describe the problem analytically. The result has been that intermittent gas lift is dominated by rules-of-thumb engineering practices developed over many years. The advent of slim-hole completions has increased the demand for a more rigorous solution to the intermittent problem. Small-diameter conduits offer more frictional per intermittent cycle. Small-diameter conduits are defined to be 1%-in. nominal size tubing or smaller. When oil is produced from the reservoir in which it is found, and transported to surface tanks by intermittent gas lift, three separate flow stages are encountered: flow of the fluids to the wellbore through a porous medium, vertical flow of a liquid slug from the point of gas injection to the surface, and horizontal flow of the liquid slug through the surface flowlines from the wellhead to the surface tanks. The three stages are depicted schematically in Fig. 1. The present study deals with liquid slug flow in both the vertical and horizontal conduits, ending when the bottom of the liquid slug reaches the surface. Due to the large number of variables involved, the analytical study of intermittent gas lift is extremely complex. The possibility of flow regimes other than slug type, the nature of the force fields acting on the system, the interfacial instabilities involved, the varying operational principles of existing gas-lift valves and the complete unsteady-state nature of the physical phenomena occurring in an intermittent gas-lift cycle relate some of the difficulties encountered.

By Kurt Stock

The war caused a demand for enormous quantities of high-grade zinc, which were not available and could not be produced from pure ores in sufficient amounts and in the time required. Redistillation of virgin spelter on a large scale was practiced to supply this demand; this paper gives a full description of the process used by the Oklahoma smelters of the Bartlesville Zinc Co. As the redistillation of zinc has become of historical interest only, having been superseded by the electrolytic process, it was deemed advisable to give expression to this phase of the metallurgy of zinc that, in the past, had never gone beyond laboratory experimentation. THE grades of spelter demanded by the consuming industries were not definitely established until the American Society for Testing Materials undertook to fix specifications, based on the varying percentages of the common impurities (lead, iron, and cadmium) as follows: TOTAL, NOT LEAD, IRON, CADMIUM, OVER. PER PER CENT. PER CENT. PER CENT. CENT. A. High grade 0.07 0.03 0.05 0.10 B. Intermediate 0.20 0.03 0.50 0.50 C. Brass special 0.75 0.04 0.75 1.20 D. Prime western 1.50 0.08 The question which grade was the best for certain purposes and why was left unanswered. The conservatism of the zinc-smelting industry and the unwillingness of the spelter-consuming industries to engage in research work prevented the full benefits being obtained that such standardization promised. The custom smelters, producing spelter in pigs or plates, found it impossible to adhere closely to the established limits on account of the variety of ores treated; and the smelters with long-established and known brands, or those manufacturing their metal into marketable products, like sheet zinc, did not have to abide by the newly established grades based on chemical percentages.

Jan 7, 1924

By D. Geoffry Minnes, Ray Blair, Stanley J. LeFond

Nepheline syenite is a silica deficient crystal-line rock consisting of albite and microcline feldspars and nepheline, together with varying but small amounts of mafic silicates and other accessory minerals. Nepheline-bearing rocks are widely distributed around the world but only in Canada, Norway, the Union of Soviet Socialist Republics, and the United States are deposits worked commercially, Because of its low melting point and fluxing ability, nepheline syenite was investigated in the early 1900s by many students of glass and ceramics. Although the nepheline syenite deposits in Methuen Township, Ont., Canada, were discovered as early as 1897 it wasn&apos;t until 1935 that the first mill was erected to produce nepheline syenite products. In Canada, nepheline syenite deposits are worked by Indusmin Ltd. and International Minerals and Chemical Corp. (Canada) Ltd. who have combined production capacity in excess of 1800 stpd. Between 1935 and 1972 seven million tons valued at $78 million were produced from the Methuen Township deposits. In Norway, the Norsk Nefelin Div. of Elkem Spigerverket has produced nepheline syenite from a deposit on Stjernöy Island in western Finland since early 1960. Production has increased from 8 kt in 1961 to over 200 kt in 1980. Nepheline syenite has been under investigation in the Union of Soviet Socialist Republics (USSR) since at least 1928. In 1951 the first commercial alumina works was brought on stream at Volkhov, near Leningrad, utilizing nepheline concentrates from the Kola peninsula as mill feed. Since then two others have been completed and more are planned. Large quantities of portland cement, sodium carbonate, and potassium carbonate are produced in conjunction with the alumina. A material called nepheline syenite, but actually a pulaskite, is produced in Pulaski County, Arkansas, by the McGeorge Construction Co. for construction aggregates and by the 3M Co. for roofing granules. The Dome Fill Co. purchases the fines and uses them in the preparation of enclosed construction fill. Production is over 2,000,000 stpy. Chap. 16 on "Feldspar, Nepheline Syenite, and Aplite" in the 3rd ed. of Industrial Minerals and Rocks (Castle and Gillson, 1960) and Nepheline Syenite Deposits of Southern Ontario (Hewitt, 1960) contain excellent accounts of earlier commercial development of nepheline syenite as a glass and ceramic material. As in the 4th ed., this chapter deals mostly with the period since 1960 and with matters not previously reported in detail. An English monograph on Nepheline-Syenite and Phonolite (Allen et al., 1968) is a complete survey, at the time, of nepheline syenite which, with its very complete list of references, is an excellent source book. End Uses Nepheline syenite from the Canadian and Norwegian producers finds use primarily in the manufacture of glass and ceramics. One producer also makes several grades of nephellne syenite that are useful as extender pigments and fillers in paint, plastics, and rubber. In the Soviet Union nepheline is used in increasing quantities in the manufacture of alumina, alkali carbonates, and portland cement and to a lesser degree it is used in the manufacture of colored container glass.

Jan 1, 1983

By J. A. Brierley, Roshan B. Bhappu, D. H. Reynolds, P. H. Johnson

Although the economic importance of recovering copper by leaching of mine work dumps from open-pit operations has been realized for some time, serious attempts to understand and to improve such operations through scientifi research has been made only in recent years. This progress report covers the results of chemical, physical, and biological studies pertaining to the dump-leaching process and discusses salient features and parameters that may be helpful in improving such operations. The dump leaching of low-grade copper ores, as an integral part of the open-pit mining operations in the Southwest, has been practiced for the last 50 years and is increasing in importance as one of the major sources of copper. The recent acceleration in dump leaching can be attributed to: (1) the greater tonnages of low-grade ores mined and dumped at newer mines as well as resulting from increased stripping ratios at the older mines, (2) the relatively small investment required for dump leaching facilities per pound of copper recovered contrasted with expansion of milling facilities to recover equal amounts of the metal by raising tonnage throughout, (3) low labor requirements needed for leaching, and (4) the simple and continuous nature of the process needing little close supervision of trained operators. In the past, the mining companies have not worried about efficiency in dump leaching but have been satisfied with whatever metal recoveries could be made without much effort. However, because of the huge amounts of metal accumulating in the low-grade waste dumps, compared to the relatively small amount recovered annually, an operator today cannot leave dump leaching to chance. What appears to be a simple, empirical process is actually a very complex one involving a large number of critical factors that encompass Several Scientific disciplines, such as physics, chemistry, geology, biology, and hydrology. It is imperative that

Jan 1, 1970

By AIME AIME

UNDER the auspices of the Institute&apos;s Committee on Industrial Preparedness, a symposium was arranged for the Annual Meeting on the subject "Ores, Metals, and the War," with many well-known Government men and industrialists participating. Wilfred Sykes, president of the Inland Steel Co., of Chicago, presided, with C. K. Leith and Clyde Williams as vice-chairmen, Mr. Williams presiding over the latter part of the meeting. On the Auditorium stage in the Engineering Societies Building was a formidable corps of "experts," with an audience of several hundred to hear what they had to say and to ask questions.

Jan 1, 1942

By George J. Clark

One of the major problems of operation in the anthracite industry is the disposal and handling of refuse—not because of its complexity but because of the quantity and type of material involved. It is the purpose of this paper to describe the kinds of refuse, methods of disposal, quantities of material to be handled and equipment used, together with present day application at specific operations in the Northern, Eastern Middle, Western Middle and Southern anthracite fields. For the purpose of this paper, refuse is considered to be any material that has no present or foreseeable future value and that must be handled and disposed of in the process of mining and preparing anthracite for market. Included in this classification are tunnel rock, mine rock, cleaner plant refuse, breaker refuse, old timber, ashes and silt. Disposal Methods Old timber is disposed of either by burning or by depositing on the refuse bank. Burning is preferred because timber on the refuse bank is a potential fire hazard. Ashes are deposited on a separate bank, mixed with other refuse, or flushed into old mine workings. In many places, the latter practice has caused considerable difficulty in preparation of coal mined from these areas. In depositing ashes on the surface, it is wise to refrain from mixing them with material containing coal as such contamination may prevent reclamation of the coal in future years. Tunnel work, mine rock, cleaner plant and breaker refuse compose the bulk of the material to be disposed of and handled, and are referred to collectively as "refuse" in this paper. Waste material in or adjacent to the coal beds may be removed at the working face wherever possible. This can be done in flat or lightly pitching beds, and in the Northern field represents a sizable percentage of this type of refuse handled. In the other three coal fields, this method of disposal cannot often be used. Refuse not removed at the working face is taken to the surface and generally is deposited on banks; occasionally it is crushed and flushed into old mine workings. Breaker refuse often is used for constructing berms for silt-retention basins. Disposal Problems The problem of handling refuse is different for each operation, owing to topographical conditions, quantity of material to be handled, anticipated requirements and types of equipment in use elsewhere at the operation. Preparation plants with limited refuse-disposal areas, excessive grades to reach the required elevation and long hauls to disposal areas not readily accessible require the selection of equipment to best meet the conditions. The quantity of refuse to be handled from a given amount of raw material varies considerably throughout the four fields. In mine coal, this varies from a low

Jan 1, 1949