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By H. L. Lovell, L. H. E. Weyher

Cyclones have been used successfully in the mineral industries to solve solid-liquid as well as solid-solid separation problems in the processing of fine particles. Substantial information is available about the operation of cyclones as thickeners, classifiers, and concentrators using a dense medium. However, very little is known about the operation of the cyclone as a fine coal concentrator not using dense medium. This application of the cyclone, namely to wash fine coal in water, requires that classification phenomena be minimized in order to arrive at an effective separation of the high density ash and sulfur-bearing mineral particles from the low density coal particles over a wide particle size range. The authors have investigated the role of feed pressure, orifice diameters, and vortex-finder length in the cyclone washing of fine coal (--1/4 in.) in water. The results of this investigation show that cyclone washing of fine coal in water is an effective unit operation particularly capable of reducing the inorganic pyritic sulfur content. The combination of hydrocyclones with complimentary equipment such as Sieve bends, shaking tables, and flotation units appears to be especially promising and may ultimately yield fine coal processing systems that could approximate the high recovery efficiencies of today's coarse coal cleaning circuits. In the future, fine coal beneficiation can be expected to receive even greater research emphasis as a result of increasing sulfur restrictions on all major coal markets. In a previous paper, work, conducted at the Pennsylvania State University, on the hydrocyclone washing of fine coal was discussed.' The initial evaluation based on that wo-rk demonstrated the feasibility of hydrocyclones as fine-coal cleaning devices, and in that previous paper selected test data were presented that showed in principle how product yield and assay respond to variations of the major cyclone operating variables. The present paper reports in greater detail on the findings and presents a comprehensive evaluation of the data as follows: (1) Hydrocyclone throughput rates were related to feed pressure and other variables by regression equations. These equations are compared with other capacity-vs.-pressure drop expressions taken from the literature on classification cyclones. (2) The flow ratio was found to be the most important variable for the separation of the solids. Control of this ratio through various cyclone operating parameters is discussed. (3) The data on the product yield as well as the ash and sulfur assays from the tests were evaluated by means of correlation and multiple regression analyses. Because size-classification phenomena cannot be suppressed completely in hydrocyclone washers, product yield and assay data are regressed against cyclone operating variables separately for different size classes. These equations then reveal how the interactions of the cyclone operating variables vary in terms of the separation for different size classes. (4) Density partitions from additional tests were analyzed by supplementing product-size analyses with sink-float analyses of the separated product size classes. The evaluation of these data show how classification phenomena affect separation by density. The results demonstrate in particular the feasibility of the hydrocyclone washer for removing pyritic sulfur from fine coal. In addition to these specific findings, the investigation points up the value, in general, of using hydrocyclone washers in combination with unit operations such as screening, table concentration, and flotation. In order to make optimum use of the hydrocyclone washers and work out the most effective combination of unit operations, it is important to have careful flowsheet analyses corresponding to the given feed and product requirements. Analyses of this kind are now possible by means of computer simulation of flowsheets and other operation research tools. INTRODUCTION Before proceeding with the detailed treatment and evaluation of our results, it will be useful to review the fundamental aspects of cyclone separators and also restate the experimental procedures and data handling employed in these studies. Review of Cyclone Fundamentals: AS shown in Fig. 1, the basic components of cyclones commonly used

Jan 1, 1970

By R. Ebeling, M. F. Ashby

The paper is in two parts. The first develops the formulae and method needed to calculate the size, nu)nber, spacing, and volume fraction of hard or inert particles in the interior of a specimen from measurernents made on an extraction replica; throughout, the spread of- particle sizes in a single specimen is taken into account, and the extraction efficiency of the replica is considered. A method for testing whether the particles are randotnly distributed in space is described, and the spacing of randomly distributed particles is discussed. The second Part describes the application of the method to copper containing spherical particles of silica; the description includes an estimate of the errors involved, and a comparison of this with alternative methods. All parameters except uolume fraction can be determined satisfactorily, and the method offers advantages over other electron-,rzicroscopic techniques when dealing with hard particles in a softer matrix, or inert particles in a chem-ically less inert matrix. 1 HE experimental measurement of sizes and numbers of discrete particles of a second phase embedded in a matrix material from opaque, plane sections has been considered by many authors, notably by Fullman.' It is assumed that, when the specimen is sectioned, the particles are also sectioned, so that the diameters of the circles of intersection of particles with the plane of the cross section ("surface diameters") are measured. It is difficult to derive the distribution of true particle diameters ("volume diameters") from measurements of the distribution of "surface diameters" on a plane section. The measurement of size and numbers of small second-phase particles by transmission electron microscopy through thin foils of matrix containing the particles has been described by Cahn and ~uttin~' and by ~illiard.~ Because of overlap and the fact that particles which intersect the foil surface may be sectioned whereas those in the bulk of the foil are not, it is again difficult to measure the true distribution of particle sizes. The use of replicas for this sort of measurement has not been analyzed in detail. A replica made from an opaque cross section, thus replicating the circles of intersection of particles with the plane of section, is analyzed by Fullman's method and suffers from the same difficulties. Under certain circumstances, however, extraction replicas can be used, and offer a special advantage in that they make the determination of the true distribution of particle diameters particularly simple. It is the purpose of this paper to describe this extraction replica method. Consider the example of an alloy consisting of SiOz particles, whose mean diameter is about 1000A, dispersed in a copper matrix. When the alloy is sectioned and mechanically polished, the particles are not sectioned, because they are much harder than the matrix, and so will be either left in the surface or pulled out whole, and because the particle size is smaller than the abrasive size of even the finest abrasive. The particles are chemically inert in solutions which chemically etch or electropolish the matrix, so that chemical treatments do not section the particles either. (Experimental measurements of particle shape in this alloy confirm this—truncated particles are never seen.) Small, hard or inert, particles are therefore not sectioned when the specimen is sectioned and polished. An extraction replica taken from this polished surface shows the true "volume" diameter of each extracted particle; the distribution of diameters seen on the replica is the surface distribution of true "volume" diameters, and the volume distribution of true "volume" diameters is easily derived from it. The extraction replica method is not subject to the difficulties associated with sectioning of particles, and avoids the problem of overlap from which the transmission method suffers. The method is well-suited for studying hard particles in a soft matrix. Examples are provided by internally oxidized alloys, oxide-dispersion strengthened metals like T.D. Nickel, and carbides, nitrides, and strong intermetallic compounds in metals. It should be possible to adapt polishing techniques in alloys containing softer but inert particles to avoid sectioning the particles (say by electropolishing or etching). The method is tested and illustrated in Sections 8 and 9 by applying it to a dispersion of spherical SiO2 particles in a copper matrix. I) SYMBOLS Symbols are defined where they first appear in the text. Volume fractions of particles are denoted by the symbol f, particle diameters by x, center-to-center particle spacings by D, and numbers of particles by N. Mean particle diameters and standard deviations about these means are denoted by x and a. Both arithmetic (subscript A) and geometric (subscript G) means are employed. In this paper we measure the distribution of true diameters of particles which touch or pass through a random-plane section of the specimen. We may want to know the distribution of particle diameters in the

Jan 1, 1967

By G. E. Perry, J. F. Bruskotter, D. G. Russell, J. H. Goodrich

The depletion performance of gas wells has been investigated by mathematical simulation techniques. The gas well model which was studied consisted of a single well located in the center of a bounded, cylindrical, homogeneous reservoir. Dependency of gas compressibility and viscosity on pressure was considered in studies of well performance at both constant mass flow rate and constant flowing pressure conditions. To carry out the investigation, the nonlinear, second-order, partial differential equation which describes Darcy flow of a nonideal gas through porous media was solved numerically. Some of the previous investigations of gas well performance have been of limited general use, because assumptions were introduced to simplify either the gas properties or the basic differential equation. Other studies have been rigorous in these respects but have presented a very limited set of calculated results. The present study was attempted to present a rigorous theoretical model and sufficient numerical results to permit meaningful conclusions to be drawn. It was found that all terms must be retained in the partial differential equation to make accurate predictions. The neglect of higher-order terms, e.g., terms of the order of the "gradient squared", leads to serious material balance errors at large times and to conservative estimates of gas well performance. The higher the gas flow rate and/or the lower the permeability-thickness product of the formation, the more pronounced are these deviations. For example, in a well draining 640 acres in a 25-md-ft formation (8,120 MMcf gas in place) at a constant rate of 993 Mcf/D, the rigorous solution predicts a bottom-hole pressure decline from 4,000 to 1,000 psia in 8.7 years. If higher-order terms are neglected in the differential equation, this decline in pressure is predicted to occur in 5.3 years. With the results of the numerical solution of the differential equation as a basis, simple, easy-to-use approximations for predicting gas well performance for Darcy flow conditions have been developed. These simple approximations are based on the familiar equations for flow of a single, slightly compressible fluid. The approximate methods possess a high degree of accuracy and enable the prediction of long-term gas well performance to be made quickly and accurately without the use of a digital computer. Both transient and stable flow period approximations were developed. INTRODUCTION In recent years income from the sale of natural gas and associated products has represented an ever-incre as ing fraction of the industry's total revenue from operations. To meet the surge in demand for natural gas, the industry has depended heavily upon established reserves and has actively pursued development of new reserves. The search has progressively led to reservoirs which yesterday were too tight and/or deep to yield the desired return on invested capital. More than ever before, evaluation accuracy is now required to forecast the criteria upon which engineering recommendations and management decisions are based. Considerable effort has been expended by both research and operations personnel on the development and application of methods for analyzing and predicting the performance of gas wells. Fundamentally, the problem is the familiar one of extracting data during the drilling, testing and early production life of a well and applying these data within an accurate simulation model to predict long-term behavior. During the past 30 or more years a voluminous literature dealing specifically with gas field problems has been generated. A recent book' lists a comprehensive bibliography of published material through 1959. Over 1,200 references are cited. Since then 39 additional articles on natural gas technology have been published in Transactions volumes of the Society of Petroleum Engineers of AIME. Most existing theory for predicting gas well performance requires that one or more idealizations (e.g., steady-state flow, ideal gas of constant viscosity, small and constant compressibility and constant-viscosity fluid) be applied. Although existing theory may apply directly or be adapted by various artifices to describe specific gas well and reservoir behavior, no widely applicable method is available, and existing methods appear to be subject to appreciable error unless better limits of applicability are defined. The objectives of this paper are (1) to present numerical solutions to the partial differential equation describing gas flow under conditions of general interest in gas well performance prediction work, (2) to present solutions which possess a high order of accuracy for both transient and stabilized flow periods of a well producing at constant rate or constant pressure, and (3) to develop and present simplified relationships which can be used as high-order approximations to the exact numerical results for fast and accurate predictions of gas well performance at the operating level. Combined, these objectives are designed gen-

Jan 1, 1967

By Eugene S. Meieran

The effects of methods of crystal growing, wafer sawing, polishing, routine handling, diffusion, and epitaxial growth on the defects in GaAs are reviewed and studied using reflection and transmission X-ray topographic techniques. In general, it was found that boat-grown crystals exhibited fewer defects than Czochralski crystals, although all crystals showed large numbers of precipitates visible when examined in the electron microscope. Mechanical surface treatments such as sawing and mechanical polishing introduce damage to a depth of about 5 µ, most of which can be removed by suitable chemical or chem-mechanical polishing. In addition, defects can be introduced through routine handling of wafers, for example with metallic tweezers. These defects can be quite severe, and have been observed 20 µ below the wafer surface. Defects can also be introduced through diffusion and epitaxial growth. These defects, which include precipitates, growth pyramids, stacking faults, dislocations, and so forth, can be detrimental to device fabrication. It is shown that wafers or films which appear defect-free optically can contain defects visible in the X-ray topographs. WHILE the use of GaAs in the semiconductor industry has increased very rapidly in the last few years, due mainly to the recent development of many important GaAs devices,1,2 the major limit to the production of commercial quantities of many GaAs devices remains a severe lack of suitable materials technology. This lack is apparent in two critical areas. First, production quantities of high-quality GaAs crystals, reproducibly doped and precipitate-free, simply are not available commercially, although some reasonable quality material is available on a limited first-come, first-serve basis. Second, in comparison to silicon technology, little is known about the effects of processing variables on the defects either present in as-grown GaAs or introduced through processing and handling of wafers. These areas are now receiving some attention from semiconductor device manufacturers, who are studying defects in GaAs in order to better understand how either to prevent their occurrence or to cope with their existence. Most investigations of the defects in GaAs have been made by optical microscopy3-5 or transmission electron microscopy techniques.'-' Recently, however, the imaging techniques of X-ray topography, electron mi-croprobe analysis, and scanning electron microscopy are being applied to the study of GaAs.9-14 In the case of X-ray topography, a one-to-one image is obtained that must be photographically enlarged. In compensa- tion, the defects within entire wafers may be imaged by simple scanning (Lang technique15) if the wafer is reasonably perfect, or by using the scan oscillation technique developed by Schwuttke16 if the wafer is warped or distorted. The purpose of this paper is to both review and extend the general application of X-ray topographic techniques to GaAs. Emphasis will be placed on the effects of growth and process variables on the quality and perfection of both bulk and epitaxial GaAs. Reference to optical or electron microscopy results will be made when useful. Since the effects on defects of a wide variety of processing variables such as crystal growing, sawing, polishing, diffusion, and epitaxial growth will be somewhat superficially reviewed, a fairly extensive bibliography of the most important recent results in these areas is included. However, for completeness, important defects will be illustrated here, although such defects have been previously shown by others. While this paper is concerned with defects rather than with the physics of X-ray scattering, the mechanisms of contrast formation in the topographs will of necessity be briefly mentioned. EXPERIMENTAL GaAs crystals, both boat-grown18 and Czochralski-grown,'8 containing a variety of dopants of various concentrations, were purchased from outside vendors. Wafers were sliced from the crystals using a Hamco ID saw and were mechanically polished using 1 µ diamond paste. Chem-mechanical polishing was done in bromine-methanol as described by Sullivan and Kolb.18 Chemical polishing was done using a modified sulfuric-peroxide solution, 11 parts H2SO4, 1 part 30 pct H2O2, 1 part DI water.5 Zinc diffusion was carried out in a closed tube, using a 10 pct Zn-In source at 825°C for 1 hr. Oxide masking techniques were used to select the area to be diffused. Epitaxial wafers were either purchased or prepared here. All epitaxial runs prepared here were carried out using a Ga-GaAs-AsC13 source in a closed tube at a substrate temperature of 750°C. Wafers were chem-mechanically polished and gas-etched prior to deposition. The X-ray topographs were taken on a Krystallos Lang camera, operating in the transmission scanning geometry (Lang technique15) or in the reflection scanning geometry (modified Berg-Barrett technique20,21). MoKa, radiation was used for all transmission topographs using a Jarrell-Ash 100-µ spot focus. CuKal radiation was used for all reflection topographs using a General Electric CA-7 1-mm spot focus X- ray tube. Topographs were printed from an intermediate contrast inversion film, so the contrast shown in all figures here is the same as that of the original 50-µ-thick emulsion L4 Iiford nuclear plate used to record the topograph.

Jan 1, 1969

By Nicholas J. Grant, Joseph T. Blucher

High-purity aluminum and an Al-10 pet Zn alloy zvere tested in axial fatigue from 80" to 900oF, at struzn vales of 5 and 150 pct per min, at a strain amplitude of 1 pcl. Cycles to failure were recorded as well as the load per cycle during the entive test. Several grain sizes were examined in each material. Examination was made of modes of deformation, initiation and growlh of' cracks, and vecovery mechanisms such as srbgrain formation and boundary migration. Strain rate effects on cycles to failure are first observed ahoi'e 50O0F, the highev vate vesulting in longer lije. Crack initiclion at room temperature may be truns-or iutercrystalline but fructures are transcrystalline. Abore 600'F, crack iniliation and growth ave largely inlercvystalline. Boundary wzigratiotz to 45-deg positions is observed above 70Oo F, and fractrrves are a combination of grain bol~ndary voids and cvacks. It is only in recent years that studies of deformation and fracture which prevail in fatigue at elevated temperatures have attracted significant attention.' Of such studies considerably less attention was given to high strain-low strain rate fatigue. Moreover, the majority of high-temperature fatigue studies were performed at conventional machine speeds (1000 to 10,000 cpm). As it is well-demonstrated in uniaxial creep-rupture series, at high strain rates, even at high temperatures, metals undergo work hardening with little or no attendant recovery or recrystallization thus the nature of deformation and fracture which is observed is similar to that encountered at lower temperatures.'-" Thus, for example, fatigue testing of a stainless steel at 750°F does not involve high-temperature deformation processes,2 and might more correctly be termed "fatigue testing at an elevated temperature". It was the purpose of this work to study deformation and fracture in fatigue as a function of low strain rates and temperature, selecting conditions which would result in grain boundary sliding, migration, fold and subgrain formation, and intercrystalline cracking in high-purity aluminum and a high-purity A1- 10 pct Zn alloy. Grain size was an additional variable. Extensive studies of the deformation and fracture behavior of these aluminum materials in simple creep had been done in the authors' laboratory, and were to serve as a basis of comparison for the observed effects in fatigue:'-'' the range of the creep test temperatures was 80° to 1150oF. MATERIALS AND EXPERIMENTAL PROCEDURE The compositions of the 99.99 pct pure A1 and the A1-10 pct Zn alloy are shown in Table I. Button-head specimens, with a liberal fillet, of 0.20 in. diam and of gage length 0.40 in. were machined from wrought bar stock. The ratio of 2:l gage length to diameter was selected after preliminary tests showed that a shorter length gave a shorter life, probably due to end effects, and after evidence of buckling in longer gage length specimens. After machining, the specimens were chemically polished to remove the worked outer layer, and were subsequently heat-treated to stabilize the selected grain sizes. Both the high-purity aluminum and the A1-10 pct Zn alloy were heat-treated to produce grain diameters of approximately 0.5 and 2 mm in each case. These grain sizes are referred to in the text as fine and coarse grain, respectively. One lot of the high-purity aluminum was heat-treated to produce a still coarser grain size in which the cross section was occupied by 2 to 3 grains. This structure is referred to as very coarsegrained. After heat treatment, the specimens were again electropolished. To avoid complications of both stress and strain gradients in the cross section of the specimen, a hydraulic, axial fatigue machine was designed and built. A button-head specimen, 1/2 in. diam at the head, was firmly gripped in a split-type holder free of any play in the grips. The test temperatures varied from 80" to 900°F. The strain amplitude in all of the reported tests was 1 pct for a total strain amplitude of 2 pct. The strain range was set by precision micrometers and measured by a precision dial gage. Constant strain rates of 5 and 150 pct per min were selected so that high-temperature type deformation and fracture would occur in the higher-temperature tests5,6 The strains and strain rates must be regarded as nominal values because they are based on the original specimen dimensions, which changed significantly as a result of necking and crack propagation, as can be observed from Fig. 8. For the elevated-temperature tests, a thermocouple was inserted into a well in the head of the specimen; the selected temperatures could be maintained with less than ± 5oF fluctuation during the entire test. To avoid changes in grain size before the test, specimens were heated to the test temperature in less than 15 min; similarly, they were cooled to room temperature after fracture with an air blast to avoid or minimize recovery or recrystallization. During the fatigue tests, load vs strain curves were recorded by a strain gage load cell for each fatigue cycle. In addition, the maximum values of load amplitude were recorded for the entire test.

Jan 1, 1968

By J. T. Crawford

ALTHOUGH nearly 10 pct of the total tonnage of coal produced annually within the United States is handled by bulk freighters on the Great Lakes, very little of the detail connected with it has been published other than occasional newspaper stories and publication of tonnage statistics. Of the total tonnage floated on the Lakes each year some 10,000,000 is stored and distributed from the port of Duluth Superior, at the western end of Lake Superior commonly known as the Head of the Lakes. This port has the largest single area concentration of coal docks in the world. Since this area contains the largest ore docks, the largest movable material handling bridge, the largest and highest grain elevator and the largest coal briquetting plant in the world, it is entirely fitting and proper that here also should be located the largest coal dock and what we believe to be the worlds largest clam shell. Of the sixteen coal docks operated by ten companies, five are owned and operated by the North Western-Hanna Fuel Co. which has two docks on the Superior, Wis. water-front and three docks in Duluth, Minn. It is with these five docks that we are primarily concerned. GENERAL HISTORY In the summer of 1871 a small sailing vessel entered the harbor of Duluth Superior with the first commercial coal cargo. All the coal brought up that first year did not amount to more than 3000 tons. During the year 1877 the first dock equipped for handling coal was built in Duluth. Coal receipts increased to 52,785 tons in 1879 the first year for which an official record was kept. Since then the volume of water-borne coal to the Head of the Lakes steadily increased to a maximum of 12,688,321 tons in the year 1923. This tonnage was nearly equalled in the year 1927 and the next highest tonnage recent year was in 1946 when 10,105,703 tons were unloaded. The average annual bring-up over a ten year period 1938 to 1947 was 8,605,231 tons. Approximately 30 pct of the coal unloaded at the Head of the Lakes is handled over the docks of the North Western-Hanna Fuel Co. Competition of other fuels coupled with expansion of coal fields in the mid-west have held coal receipts for Duluth-Superior at a relatively constant figure during the last eight years although the total tonnage of coal floated on the Great Lakes has more than doubled in the past 25 years. From the shovel and wheelbarrow method of unloading early cargoes to the horsepowered windlass derrick with a wooden tub was but a short step. The first movable coal handling, steam operated,

Jan 1, 1948

By C. E. Ells, A. Sawatzky

The effect of neutron irradiation on tensile properties of the Zr-2.5 wt pet Nb-0.5 wt pet Cu alloy has been evaluated for integrated neutron fluxes up to 3 x 1020 n per sq cm (E > 1 Mev). Specimen temperature during irradiation was normally 300°C. The material was studied both in annealed and in quenched and aged conditions. When the alloy (fab-ricatedfrom sponge zirconium) is quenched from a temperature =40°C below the a + ß/ß transformation and aged 6 hr at 535oC, neutron irradiation up to the maximum studied has little effect 071 reduction in area, although there is a drop in uniform elongation and the yield strength is increased by = 25 pct. Conversely, irradiation of the alloy in an annealed condition can result in much greater changes in properties, with yield-strength increases of up to 200 pet. The dose dependence of irradiation hardening obeys the saturation equntion proposed by Makin and Minter to explain hardening in copper and nickel: Act = C[1 - exp(-Døt)/1/2 A rnodel is proposed to explain the effect of niobium content and metallurgical condition on irradiatiotz behavior. THE Zr-Nb alloys form a class of material susceptible to marked strengthening by quench and age heat treatment. With niobium concentrations as low as 2.5 wt pet, strengths can be developed which are double those of annealed zircaloy-2.1 Since the neutron-capture cross section of the Zr-2.5 wt pet Nb alloy is nearly identical to that of Zircaloy-2, significant gains in power-reactor neutron economy could be obtained by replacing stressed in-reactor components of Zircaloy-2 with the heat-treated Zr-Nb alloy. When the solution heat-treatment temperature is in the high (a + ß) phase, then the tensile properties of the quenched (and aged at 500°C) material have been shown to be relatively insensitive to neutron irradiation.1-3 Addition of small quantities of copper to the binary Zr-2.5 wt pet Nb alloy gives a useful reduction to the corrosion rate in air and carbon di- oxide,&apos; and a ternary alloy of composition Zr-2.5 wt pet Nb-0.5 wt pet Cu was chosen for one component in the Douglas Point Reactor. This application utilizes both the corrosion resistance to a moist air-carbon dioxide environment and the strength developed by a quench and age heat treatment. By suitable choice of solution heat treatment and aging temperatures, tensile properties of the ternary alloy can be made nearly identical to those considered as optimum for the binary alloy. One effect of the copper addition, however, is to give marked changes in the aging kinetics of the alloy.&apos; For this reason, it appeared that neutron irradiation might promote overaging in the ternary alloy, particularly at the elevated service temperature (=300°C). This paper describes the effect of neutron irradiation on the tensile behavior of the Zr-2.5 wt pet Nb-0.5 wt pet Cu alloy in several metallurgical conditions pertinent to its use as a reactor material. The metallurgical conditions included those for which aging occurs in the unirradiated material, and fully annealed conditions for which a higher degree of thermal stability could be expected. 1) EXPERIMENTAL Two batches of alloy were used, both made from sponge zirconium. The fabricator&apos;s analysis of principle constituents showed no significant difference between the two batches, Table I. The rod material was rolled to 1.5 in. diam, and then swaged to final sizes of 0.5 to 0.375 in. diam at nominal temperatures of 785" and 625°C for the AM and AS batches, respectively. Subsequent hydrogen analyses at CRNL confirmed that the hydrogen concentration of the as-received rod was indeed <20 ppm. However, it was found that the (a + ß)/ß transus for the AM material was approximately 25°C lower than that of the AS material, indicating rather more difference in oxygen concentration than given in Table I. Except for a small difference in yield-point behavior, the tensile prop-

Jan 1, 1965

By R. W. Fountain, M. Korchynsky

The precipitation phenomena occurring in cobalt-tantalum alloys have been investigated in the temperature range frm 500" to 1050°C by correlating the results of metallographic, X-ray, micro-and macrohardness, and electrical resistivity studies. The property andmacrohardness,changes were found to depend on 1) general precipitation, and 2) lamellar precipitation. Two new intermetallic phases have been identified: 1) a Co3Ta, a metastable ordered face-centered-cubic compound, and 2) a stable ß Co3Ta phase of hexagonal structure. In addition, the previously reported Co2Ta phase was found to exist in two allotropic modifications: the hexagonal MgZn,-type and the cubic MgCu2-type Laves phases. SINCE a large variety of structures can result as a consequence of the decomposition of a solid solution, predictions on the nature of property changes are difficult, if not impossible, to make. For any rational attempt to correlate properties and structures of a precipitation-hardenable alloy, a detailed understanding of the kinetics of decomposition and morphology of phase separation, as well as knowledge of phase relationships, appears to be prerequisite. Information of this type has been accumulated in the past for many alloy systems, both of theoretical and pastforpractical importance.1,2 Although the presence of intermetallic compounds has been reported in cobalt-base alloys,3 the amount of published information on precipitation-hardenable cobalt-base systems is very limited. A survey of the binary phase diagrams of cobalt indicates that cobalt-tantalum alloys might be of interest as typical of other cobalt-base systems in which Laves phases of the A,B type can be precipitated from solid solution. The present work has been undertaken, therefore, to study the kinetics and morphology of the precipitation reaction in this system and to establish a base for a correlation between the structural aspects and properties in this class of alloys. PREVIOUS WORK The only available phase diagram of the cobalt-tantalum system is based on the work of Koster and Mulfinger. According to these authors, the maximum solubility of tantalum in cobalt is about 13 pct (at 1275°C) and. less than 7 pct at room temperature. Tantalum additions lower the temperature of allotropic transformation of cobalt (about 420°C), and at 7 pct Ta, the high-temperature face-centered-cubic modification (ß cobalt) is retained at room temperature. The precipitating phase was originally designated as Co5Ta2 compound (55.2 pct Ta, about 1550°C melting point), but subsequent investigations by wallbaum5" identified this constituent as the A,B-type Laves phase. Wallbaum&apos;s data indicate that there are two modifications of this intermetallic compound: one richer in cobalt (Co2.2 Tao.8)of the hexagonal MgNi, type; and another of a higher tantalum content (Co2Ta) of the cubic MgCu, type. On the other hand, Elliott7 found that the cobalt-rich alloy (CO2.10,Tao.~l) was predominantly the cubic MgCu, type at 800°C and a mixture of both the MgCu2 and the hexagonal MgZn,-type Laves phases at 1000°C. At 1200°C, Elliott found only the MgZn, type while at 1400°C, he observed only the MgCu2 type. At the stoichiometric composition, Co2Ta, Elliott reported only the cubic MgCu2-type Laves phase in the temperature range of 600oto 1600°C. The precipitation of the cobalt-tantalum intermetallic compound is accompanied by a marked increase in hardness. According to Koster&apos;s4 data, the Brinell hardness of an 8 pct Ta-Co alloy increases from 230 to 340 upon short-time aging at 800°C. EXPERIMENTAL PROCEDURE The binary cobalt-tantalum alloys investigated contained 5, 10, and 15 pct Ta. The range of tantalum additions was thus slightly broader than the reported minimum and maximum solid solubility limits of tantalum in cobalt (7 and 13 pct, respectively)4 The alloys were vacuum-induction melted in a magnesia crucible using cobalt rondelles and technically pure tantalum sheet as raw materials. Deoxidation of the melt was accomplished with carbon, and the chemical analysis of the alloys is given in Table I. The effect of isothermal aging treatments on the progress of precipitation was studied on samples cut from cast ingots. These samples were solution treated for 2 hr at 1250°C and water-quenched. Aging was conducted in the temperature range from 500" to 1050°C for periods between 15 min and 1000 hr and followed by water-quenching. To prevent contamination from the atmosphere, all samples were sealed in evacuated Vycor or quartz tubes for heat-treatments. For solution treatment, argon at 0.2 atmospheric pressure was introduced prior to sealing of the capsule to prevent collapse at high temperature, and titanium sponge was placed at one end of the capsule to act as a getter. MACROHARDNESS The effect of aging on Vickers hardness (Dph) of

Jan 1, 1960

By David E. Hyatt

The chemical attributes of cyanides have long been exploited in ore pro- cessing schemes for the recovery of copper, molybdenum, gold, silver, and other metal values. Blast furnacing operations are significant unintentional producers of cyanides which find their way into process waters. Many of the more than 20,000 electroplating facilities in the United States utilize cyanide plating baths and generate cyanide containing wastes. As social, political, and economic pressures for water quality attainment, maintenance, and preservation grow, the requirements for the development of treatment technology to control cyanide levels in wastewater become increasingly apparent. Just as the chemistry of the cyanide ion 1s an integral part of its industrial applicability, so must this chemistry be a fundamental part of any decomposition or removal technology used to control its level in effluent or recycled waters. The complexity of this chemistry is substantial and it cannot be considered in a superficial or cursory manner if control system design is to be both efficient and reliable.

Jan 1, 1975

By Henry M. Otte, Ralph P. I. Adler

The changes of line position and integral line breadth in the X-ray diffraction pattern of a polycvys-talline Cu-30Zn tensile test piece, incrementally loaded (and unloaded) up to fracture, have been an-alyzed in detail. The stacking-fault probahility, cv, increased linearly with increasing strain, E, wheveas the effective domain size, De(hkl), decreased with decreasing E-1 Over the greater part of the stress-strain curve the rate of work hardening was essentially constant (about 86 kg per sq mwz), and could be correlated with the slope of stage II of the single-crystal stress-strain curve. Consequently the theories of work hal-dening (particularly those parts relating to stage 11) as developed by Mott and Hivsch and others could be applied to the observations made on the polycrystalline brass. A relationship of the form Aa = Aao - MhklEhkl between the change, Aa, in the extrapolated lattice pararneter and the rvns strain, Ehkl, was derived and found to fit the results acceptably well. From this and other relationships developed in the papev it was estimated that the equilibrium stacking-fault energy of Cu-30Zn was between 8.4 and 12.5 ergs per sq cm, in fuirly close agreement with the (corvected) value obtained by Howie and Swann (1961)43 using transmission electron microscopy. The theory of work hardening in the jorm developed and recently presented by Hirsch (1964)3 successfully described all the pvesent observations. In order to test certain aspects of the theories of work hardening, as developed by Mott,1 Hirsch,2,3 Seeger et el,4-7 and others (for review see Nabarro, Basinski, and Holt8), several recent investigations have been concerned with relating the dislocation density, p, with the shear stress, 7 (and strain, y), applied to the specimen. The results of these investigations have shown that the square root of the dislocation density appears to be linearly related to the applied shear (or flow) stress for fcc as well as bcc metals and alloys. Furthermore, the relationship appeared to apply not only to the deformation of poly-crystalline specimens, but also to stages I and I1 of the deformation of single crystals. An expression of the form has thus come into wide use. Here b is the Burgers vector for a total dislocation, G is the shear modulus, and 70 and q are constants. A review9 of available values of q shows it to have values (at room temperature) in general between 0.3 and 0.6. Forms of Eq. [1] can be deduced from, or predicted by, the current theories, and the various constants adjusted so that they are compatible with the experimentally found value of q . No unique relationship has yet been found between the dislocation density and the applied shear strain. There are several serious objections to the use of Eq. 11]. In the first place, it relates the shear stress to the density of the dislocations without regard to their arrangement, type, or distribution; the significance of the relation may therefore be justly questioned.5 In the second place, the values of the experimental quantities usually substituted into Eq. [11 are those of the applied shear stress and the total dislocation density measured after unloaditzg. The dislocation density value that should in fact be used is that for the mobile dislocations present in the specimen when under the applied load.* Finally, in cases where the values used for p, the dislocation density, are those obtained by electron microscopy, p is subject to considerable error,&apos; both systematic and random. The corrections to be applied are still controversial. Dislocation densities can also be measured by etch-pit and other techniques,&apos;&apos; each having their specific limitations. An objective of the present investigation has been to obtain information about the dislocation configyration and distribution by analyzing the changes in the position and shape of X-ray diffraction profiles as a function of deformation. The X-ray techniques employed, also open to criticism, have certain advantages, however. Thus, although the X-rays diffract only from the surface layers to an effective depth of about 20 p, the measurements can be made while the specimen is under load. The value of the dislocation density obtained by the X-ray method is also subject to errors, which are different from those of the electron microscope. Though a considerably larger volume of material is sampled by the X-rays, thereby reducing some of the statistical errors inherent in the electron microscope data, the information obtained is less detailed and is dependent on the method of analysis used to obtain a value for the dislocation density. Nevertheless, important observations can be made because the aforementioned advantages outweigh some of the limitations. In the present paper the X-ray method is briefly described and applied to a brass specimens deformed in tension. The results are then discussed in terms of some of the current concepts of work hardening. 1) EXPERIMENTAL PROCEDURE Details have already been extensively published elsewhere11-14 and therefore will only be dealt with briefly here. 1.1) Materials and Specimen Preparation. Commer-

Jan 1, 1968

By M. J. Richards, A. Szirmae, G. R. Speich

The formation of austenite from ferrite, ferrite plus retastable carbide, spheroidite, and pearlite has been studied in a series of irons, Fe-C alloys, and plain-carbon steels using fast heating techniques. In the absence of carbide, austenite nucleates at ferrite/ferrite grain boundaries; nucleation is followed by the rapid growth characteristic of a massive transfornation. The trarnsformation occurs at 950°C at heating rates of 106º C per sec and cannot be suppressed. Metastable carbide dissolves before austenite forms and does not influence the transformation kinetics. For spheroidite structures, austenite nucleates preferentially at the jinction between carbides and ferrite grain boundaries. Growth from these centers proceeds until the carbide is completely enveloped; subsequent growth occurs by carbon diffusion through the austenite envelope. For pearlite structures, austenite nucleates preferentially at pearlite colony intersections. Carbide la)?zellae dissolve at the advancing austenite interface but complete solution of carbide does not occur; the residtial carbide is eventually dissolvled or spheroid-ized depending on the carbon cuntent. The magnitude and temperature dependence of the austenite growth rate into Fe-C pearlite when incomplete carbide dissolution is assumed are satisfactorily explained by an approximate colume diffusion model. The impurities present in plain-carbon steel reduce the growth rate of austenite in comparison to that jound in an Fe-C alloy. The formation of austenite has been studied in much less detail than the decomposition of austenite. This is primarily a result of the importance of harden-ability in determining the mechanical properties of steel. Recently, more interest in the kinetics of austenite formation has resulted from the discovery by Grange1 that rapid heating techniques strengthen steel by refining the austenite grain size. Although the strengthening effect is not large, it is accompanied by no loss in ductility. In addition, interest continues in rapid heat treatment of low-carbon steel sheet for tin plate applications.2,3 Among the few systematic studies of austenite formation are the early work of Roberts and Mehl4 on formation of austenite from pearlite and recent work of Molinder5 and of Judd and paxton6 on formation of austenite from spheroidite. Also, Boedtker and Duwez7 and Haworth and paar8 have recently studied the formation of austenite from ferrite in relatively pure iron, Kidin et al.9,10 have studied the formation of austenite in 8 pct Cr steels, and Paxton has recently discussed various aspects of austenite formation in steels." The present work was undertaken to determine the kinetics of austenite formation for a variety of starting structures including ferrite, ferrite plus metastable carbide, ferrite plus spheroidal cementite, and ferrite plus pearlitic cementite. Emphasis was placed on determining the active sites for austenite nucleation, determining the temperature and time range of austenite formation, and in the case of pearlite a careful study of the growth rate of austenite was made in the absence and presence of impurities. By using a variety of heating techniques including laser-pulse heating, it has been possible to study austenite formation in an isothermal fashion over a wide range of temperatures. EXPERIMENTAL PROCEDURE The alloys studied in the present work are a zone-refined iron with 4 pprn C, an Fe-C alloy with 130 pprn C, 2 Fe-C alloys with 0.77 and 0.96 wt pct C, and a plain carbon steel with 0.96 wt pct C. The zone-refined iron and Fe-C alloys contained 60 pprn and 200 pprn total substitutional impurities, respectively. The plain carbon steel contained 2400 pprn Si, 2000 pprn Mn, and 900 pprn Cr. Various heat treatments were given to these alloys to produce different starting structures of equiaxed ferrite, ferrite plus metastable carbide, fine pearlite, and spheroidite. These heat treatments are given in Table I. A wide range of heating rates were employed in this work because many of the reactions occur so quickly at temperatures in the austenite range that they are completed during the initial heating cycle unless very fast heating rates are used. Essentially the same heating techniques employed by Speich et a1.12 and Speich and Fisher13 were used in this work. For time intervals of 2 sec to 20 hr, simple hand immersion of 0.010-in. thick specimens in a Pb-Bi bath was employed. These specimens were quenched in a 10 pct NaC1, 2 pct NaOH aqueous bath. For time intervals of 100 m-sec to 2 sec, an automatic dunking and quenching device was employed with 0.002-in. thick specimens. Again, liquid Pb-Bi baths were used for a heating medium but now helium gas quenching was employed. For time intervals of 2 to 100 m-sec a laser heating device was employed with 0.002-in. thick specimens; a helium plus fine water-droplet spray was now used for quenching. Additional information on heating times shorter than 2 m-sec was obtained by study of the zones around the centrally heated laser spot. Here diffusion of heat from the centrally heated zone raises the temperature of the specimen locally to all temperatures between ambient and the peak temperature, but for times of the order of microseconds. All the heat-treated specimens were examined by

Jan 1, 1970

By W. L. Martin, J. N. Dew, H. B. Steves, M. L. Powers

This paper presents and discusses the results obtained during a pilot test in the Loco field in southern Okla homa. The test was conducted in a 2%-acre pattern that was part of a 20-acre conventional waterflood pilot area. The conventional flood was well past its economic limit when the hot waterflood was initiated to obtain technical information and operating experience. Temperature data from nine observation wells showed that about 75 percent of the pattern was affected by heat, and that heat losses were severe in the pilot pattern. About 60 percent of the injected heat was lost to overburden and underburden zones during hot-water injection. Wellbore heat losses were held at tolerable levels at the shallow depth of the test by providing a low-pressure air annulus between the injection tubing and well casing. Hot water provided water injectivity increases of 200 to 400 percent. The hot water channeled across the lower portion of the oil sand in three directions through zones of relatively high water saturation. There was no conclusive evidence that natural fractures or pressure partings aflected the flow of fluids in the pilot pattern; however response undoubtedly was aflected by localized pressure gradients and by injection-production rate ratios. The results showed that hot waterflooding increased oil recovery in a reservoir containing 600 cp oil. The total tertiary oil production from the pilot pattern area was 3,896 bbl or about 156 bbl/acre-ft swept by heat. The corre.sponding WOR was about 34:I. Description of the Hot Waterflood Process To hot waterflood an oil reservoir, water is injected that has been heated to a temperature substantially higher than the original reservoir temperature, but lower than the vaporization temperature of water at the prevailing pressures. In the reservoir the hot water flows continuously into cooler sand and rapidly loses heat to the sand until it has been cooled to the original reservoir temperature. Thus, a heated zone and a region or "bank" of cooled water begins to accumulate immediately after hot water injection is started. This bank of cooled water continues to grow ahead of the heated zone, which also grows, but at a slower rate. This occurs because heat transfer is almost instantaneous, and the ratio of heat capacities of water to rock is such that two or three unit PV of hot water must be injected to heat a given unit bulk volume of the reservoir. The primary displacement mechanism is the same for both hot and conventional cold waterfloods; i.e., "piston" displacement occurs at the original reservoir temperature. The incremental benefits of hot waterflooding usually occur long after the breakthrough of cold water at producing wells, and the increased oil recovery necessarily is accomplished with high WOR&apos;s (water-oil ratios). Heat decreases the viscosity and density of oil and water. These effects result in more rapid and increased recovery of secondary or tertiary oil. If the cost of the required heat is low enough, the ultimate oil recovery of a hot waterflood should be increased substantially over what would be expected at the economic limit of a conventional cold waterflood. The economic benefits of any hot-fluid injection project depend primarily upon the cost of the heat required to produce more oil at an increased rate. This cost depends in part upon the amount of heat lost to surrounding formations. Heat loss depends upon reservoir thickness, water injection rate and temperature, the depth of the formation, well spacing, and the characteristics of the reservoir rock and surrounding formations. In general, percentage heat losses decrease as injection rate and reservoir thickness increase. Although it is an old idea, hot-water injection has not received widespread field application in the oil industry as a drive process. Much of the original field work with hot water was done in Pennsylvania fields where water permeabilities and injection rates are low. In these cases, hot-water injection was used primarily as a means of increasing in-jectivities — not as a recovery process. Ramey&apos; recently has published an excellent review of the development of hot fluid injection processes. Recent publications"&apos; and our own experiences now indicate that hot water or steam injection also can effectively increase the oil recovery from reservoirs containing viscous crudes. However, the economics of these methods as displacement processes have not been established. Several theoretical predictive techniques have been published (for a review see Ramey&apos;), but simplifying assumptions make

Jan 1, 1969

By Dodge, C. E.

ONE of the first mining areas to be developed in Arizona was that in the district centering about Clifton and Morenci. Traces of metals were first noticed by Henry Clifton on an expedition in 1864. Definite copper outcroppings were also reported in the following year by General J. H. Carleton when he led his troops into the district on an Indian raid. Actual mining operations were started in the early seventies. and the first smelter was finished in 1873. Two adequately financed companies acquired most of the property, and both commenced production about 1882. These were the Arizona Copper Co.. owned by a group of Scotch investors, and the Detroit Copper Mining Co., afterwards purchased by the firm of Phelps, Dodge & Co. Later the Shannon Copper Co. acquired and operated a number of claims in the northern part of the district. These three companies all operated underground, mines independently for many years.

Jan 1, 1942

By John M. Kelly

This report covers the development, exploratory drilling, and production of oil and gas in New Mexico during 1945. The statistical information was gathered from state regulatory agencies and other sources believed to be reliable; it is presented here in combined form for general information only, and the author assumes no responsibility for its accuracy or completeness.

Jan 1, 1946

By A. Filyk

The current plant practice at Molycorp, Inc., Questa Division, a molybdenum producer in northern New Mexico, is described. An outline of crushing, grinding, flotation, drying, and tailings disposal is included, with emphasis on metallurgy.

Jan 1, 1976

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Jan 1, 1938

Jan 1, 1934

By L. G. Evans, C. Rampacek, G. A. Freeman

A large aggregate tonnage of oxidized and mixed oxide-sulfide copper ore of the southwestern U.S. is not amenable to conventional flotation concentration or sulfuric acid leach treatment. Most of the ores contain chrysocolla as the principal oxide copper mineral, for which no successful commercial flotation method has yet been developed. Acid leaching some ores is not feasible since they contain substantial quantities of calcite and other acid-consuming constituents. Other ores decrepitate during leaching or contain excessive slime and clay minerals which cause plugging of the ore beds.

Jan 10, 1961

Jan 1, 1900

By S. S. Clarke

THE opening of sheet-ground mines in which the ore beds are only from 7 to 9 ft. thick led the Commerce Mining and Royalty Co. to con-sider mechanical loading, in order to avoid the high cost of hand shovel-ing in such mines. Scraper loaders were chosen because the capital investment would be comparatively low; because they are small enough to be used in low working faces, and because they can be mounted on a mobile carrier.

Jan 1, 1939