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By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of quartz with oleic acid as collector and barium, calcium, aluminum, iron, and tin as activators were studied using a simple vacuum-flotation technique in glass-stoppered graduates. The detailed study of barium activation led to an interpretation based on ideal Langmuirian chemisorption.

Jan 5, 1950

By H. M. Chance

Jan 1, 1886

By Charles Austin

IN an earlier series of studies on 18-8 stainless steel at 600°, 700°, and 800°C.1 one pretreatment was used throughout; viz., 15 min. in hydrogen at 950°C., followed by an air quench. Several manufacturers of this alloy since have expressed doubt as to the suitability of the temperature employed, recommending instead the more customary Strauss treatment as promising superior results. In this subsequent investigation on the effects of the temperature of pretreatment several interesting points have arisen, which are described in this paper. Previous work on our equipment had shown a marked difference between alloys of "similar chemical composition" that had been manu-factured by different companies. Accordingly, one mill-bar length was selected from which to prepare all specimens. It could then be assumed that any marked differences in creep characteristics would be due to effects resulting from variations in the pretreatment of the alloy. The material was furnished by the Allegheny-Ludlum Steel Co. in the form of 5/16-in, dia. rod, finished by air cooling from a mill anneal at 1950°F. (1066°C.). It was analyzed only for the elements shown: carbon, 0,07 per cent; chromium, 18.73; nickel, 9.46; manganese, 0.40. Three pretreating temperatures were chosen, the specimens being held for 15 min. in hydrogen at either: (1) 1150°C., to conform to the recom-mended Strauss treatment; (2) 950°C., to compare with the results of previous tests; or (3) 750°C., to initiate precipitation of carbides in the material before testing. As the test cross sections were only 1/8 -in. dia., air cooling followed the annealing treatment. These treatments per-mitted two direct comparisons: (1) between the 1150° and 950°C. treat-ments to indicate the effect of grain size when all carbides were probably in solution at the start of the test; and (2) between the 950° and 750°C. treatments to indicate the effect of carbide "nucleation" for similar grain sizes.

Jan 1, 1940

By L. E. Porter

The demand for crude oil on the Pacific Coast during the year 1945. was so acute that the California crude supply had to be augmented by tank-car imports from the Texas and Rocky Mountain fields. Crude imports reached a high of 64,800 bbl. per day during June, with a total of 14,259,000 bbl. imported during the first 11 .months. The U. S. Navy also implemented the crude output from California pools by drilling and completing approximately 300 wells in the Naval Petroleum Reserve No. 1 (Elk Hills), from which an established production of 65,000. bbl. per day was reached in late February and maintained until Aug. 17, 1945, when it was reduced to its preprogram level of 15,000 bbl. per day. Even with the conclusion of the Pacific war on V-J day (Aug. 14), the military petroleum product requirements have permitted little material reduction in output of California crude to prewar rates. During the year, a total of 327-760,000 bbl. of crude was produced, or 19 per cent of the total crude production within the United States during the same period, as compared with 310,996,000 bbl. or 18.4 per cent of the nation's crude production in 1944.

Jan 1, 1946

By AUDLEY H. STOW

I. INTRODUCTION. THE general drift of the discussion as to the relative merits of pressure- and exhaust-fans has resulted, if we may judge from the prevailing practice, largely in favor of the latter. The subject has been hitherto treated, however, with special reference to highly gaseous mines, the effect of the form of ventilation upon dust-explosions having been too little considered. Even in mines containing practically no gas, dust-explosions may occur; and if, as I believe, pressure-fans are to be preferred for their effect upon dust, it may be worth while to reopen the debate, and to challenge the advisability of exhaust-ventilation under certain conditions. There are several forms of colliery-ventilation, which may be described as follows: Plain or simple pressure-ventilation, in which the fan acts as a pressure-fan, and the movement of coal is unobstructed at the surface by doors or equivalent devices in drifts or shafts, the traveling and haulage thus being in the return-current. Plain exhaust-ventilation, in which the fan acts as an exhaust-fan, the movement of coal being likewise unobstructed at the surface, and the traveling and haulage being in the intake. Obstructed pressure-ventilation, in which the movement of coal is obstructed at the surface, in order that the traveling and haulage may be in the intake. Obstructed exhaust-ventilation, in which the movement of coal is obstructed at the surface, in order that the traveling and haulage may be in the return. The apparent advantages in running a fan "pressure" during working-hours, and " exhaust" between shifts, seem to justify the recognition of this combination as a standard form of ven-

Feb 1, 1909

The Institute conducts jointly with the American Society of Civil Engineers, American Society of Mechanical Engineers and American Institute of Electrical Engineers, certain activities as listed below, and is joint owner with them of certain properties situated at 29 West 39th Street in New York City United Engineering Trustees, Inc. When Mr Carnegie made his gift, "for the erection of a suitable union home" for the engineering societies, United Engineering Trustees, Inc (then United Engineering Society) was chartered un¬der Chapter 703, Laws of the State of New York, 1904, for "the advancement of the engineering arts and sciences in all their branches, and to maintain a free public engineering library " The Corporation was further empowered to acquire real and personal property and to use, maintain and occupy it, with the provision that any building erected by the Corporation shall be used perpet¬ually as a meeting place and headquar¬ters for the Founder Societies Thus the Carnegie gift realized the ideal of bring¬ing the engineering societies together under one roof, and the Corporation through its members nominated in equal numbers by the four Founder Societies had the necessary authority to act for the Founder Societies in their joint in¬terests in owning and operating for them not only Engineering Societies Building, but in the course of time, Engineering Societies Library, and The Engineering

Jan 1, 1952

By K. Mukherjee

A quasi-thermodynamic calculation is presented for estirt~ating vacancy Parameters in fcc metals. For fcc metals the equilibrium vacancy concentration at the melting point can be approximated by a constant mole fraction. The Gibbs free energy of formation of the vacancies can then be expressed as a simple function of the absolute melting temperature alone. From this description the formation energy Ef, the vibrational entropy Sv, and the formation volume of a vacancy can be calculated in terms of known thermodynamic parameters. The calculated values are in good agree-rnent with available experimental results. IT appears that many of the physical parameters associated with lattice defects can be empirically related to thermodynamic melting parameters.'-7 Besides the implicit correlations between melting phenomenon and point defects, the melting temperature itself at atmospheric pressure can be used as a reference temperature for the purpose of comparison of vacancy concentrations in a given crystal class. The concentration at the melting point then corresponds to the maximum vacancy super saturation in the crystalline state at a fixed pressure. For pure fcc metals such as Au, Cu, Al, Ag, Pb, and Pt the mole fraction of vacancies at the melting point8 is of the order of 10*"3 to 10"1. The equation expressing the equilibrium vacancy concentration at the melting point contains three parameters: the formation energy, the vibrational entropy, and the absolute melting temperature, see Eq. [2]. Since these three parameters cover a wide range of values8 in the above-mentioned metals, it can be assumed that in other fcc metals, for which no reliable data are available, the mole fraction of vacancies at the melting point most likely lies in the range 10~3 to lO"4. This is then the basis of the calculations described in this article. Within this range the mixing entropy can be linearized and the vibrational entropy, the formation energy, and the vacancy formation volume can be calculated in terms of known thermodynamic constants. 1} LINEARIZATION OF MIXING ENTROPY The Helmholtz free energy of a crystal containing n vacancies at the melting point can be writteng as where Ef, T,, k, and S, are the formation energy of a vacancy, the absolute melting temperature, Boltz-mann's constant, and the vacancy formation entropy, respectively. After applying Stirling's approximation in Eq. [l] and minimizing with respect to n where (n/N), is the equilibrium vacancy concentration in mole fraction at the melting temperature at 1 atm pressure. If instead of setting (6~/6n) = 0 immediately after Stirling's approximation in Eq. [I], the configurational partition function is simplified, then some useful and significant results can be obtained by utilizing the experimental inforrnation After applying Stirling's approximation and rearranging is plotted as a function of (n/N) in Fig. 1. The points, not all of which are shown, are fitted by a straight line substituting from Eq. [5] into Eq. [I] and minimizing with respect to n combining Eqs. [6] and [2] It must be emphasized that Eq. [7] is only a crude approximation based on an oversimplified model of

Jan 1, 1967

By K. H. Coats

This paper presents the development and solution of a mathematical model for aquifer water movement about bottom-water-drive reservoirs. Pressure gradients in the vertical direction due to router flow are taken into account. A vertical permeability equal to a fraction of the horizontal permeability is also included in the model. The solution is given in the form of a dimensionless pressure-drop quantity tabulated as a function of dimensionless time. This quantity can be used in given equations to compute reservoir pressure from a known water-influx rate, to predict water-influx rate (or cumulative amount) from a reservoir-pressure schedule or to predict gas reservoir pressure and pore-volume performance from a given gas-in-place schedule. The model is applied in example problems to gas-storage reservoirs, and the difference between reservoir performances predicted by the thick sand model of this paper and the horizontal, radial-flow model is shown to be appreciable. INTRODUCTION The calculation of aquifer water movement into or out of oil and gas reservoirs situated on aquifers is important in pressure maintenance studies, material-balance and well-flooding calculations. In gas storage operations, a knowledge of the water movemenr is especially important in predicting pressure and pore-volume behavior. Throughout this paper the term "pore volume" denotes volume occupied by the reservoir fluid, while the term "flow model" refers to the idealized or mathematical representation of water flow in the reservoir-aquifer system. The prediction of water movement requires selection of a flow model for the reservoir-aquifer system. A physically reasonable flow model treated in detail to date is the radial-flow model considered by van Everdingen and Hurst.1 In many cases the reservoir is situated on top of the aquifer with a continuous horizontal interface between reservoir fluid and aquifer water and with a significant depth of aquifer underlying the reservoir. In these cases, bottom-water drive will occur, and a three-dimensional model accounting for the pressure gradient and water flow in the vertical direction should be employed. This paper treats such a model in detail — from the description of the model through formulation of the governing partial differential equation to solution of the equation and preparation of tables giving dimensionless pressure drop as a function of dimensionless time. The model rigorously accounts for the practical case of a vertical permeability equal to some fraction of the horizontal permeability. The pressure-drop values can be used in given equations to predict reservoir pressure from a known water-influx rate or to predict water-influx rate (or cumulative amount) when the reservoir pressure is known. The inclusion of gravity in this analysis is actually trivial since gravity has virtually no efFect on the flow of a homogeneous, slightly compressible fluid in a fixed-boundary system subject to the boundary conditions imposed in this study. Thus, if the acceleration of gravity is set equal to zero in the following equations, the final result is unchanged. The pressure distribution is altered by inclusion of gravity in the analysis, but only by the time-constant hydrostatic head. The equations developed are applied in an example case study to predict the pressure and pore-volume behavior of a gas storage reservoir. The prediction of reservoir performance based on the bottom-water-drive model is shown to differ significantly from that based on van Everdingen and Hurst's horizontal-flow model. DESCRIPTION OF FLOW MODEL The edge-water-drive flow model treated by van Everdingen and Hurst1 is shown in Fig. la. The aquifer thickness b is small in relation to reservoir radius rb. water invades or recedes from the field at the latter's edges, and only horizontal radial flow is considered as shown in Fig. 1b. The bottom-water-drive reservoir-aquifer system treated herein is sketched in Fig. 2a and 2b. Here the aquifer

By J. A. Richardson

J. A. RICHARDSON[t]-Mr. Stuckey's account of the geology of the kaolins of North Carolina suggests that they exhibit some features similar to those of the Malay Peninsula. About one half of British Malaya (some 26,000 square miles) is occupied at the surface by igneous rocks, of which granite and its associated derivatives constitute fully 90 pct. The average granite is a biotic variety. It is predominantly potassic but carries, in addition, notable amounts of soda and lime so that albite and albiteoligoclase are generally common constituents of the rock. The minor derivatives from granite "magma" likewise include potassic and sodi-potassic members. Decomposition of the granitic rocks has led to the formation of kaolin in many localities, but, in general, the deposits are rather small and, at present, none is exploited commercially. True primary or residual kaolins (as defined by Stuckey; p. 48 Vol. 173, p. 2 TP 2219) have been developed from feldspar veins, pegmatites and from other granitic differentiates which cut through the larger masses of granite; they are usually small and narrow. Kaolin has been derived from aplite, quartz porphyry, quartz micro-porphyry, felsites and microgranites belonging to a complex known as the Chegar Perah-Pulai intrusion in northwest Pahang and southwest Kelantan. The bulk of the component rocks has been more or less strongly sheared. Kaolin-like end products have been formed from both sheared and nonsheared varieties. Kaolin has been formed also by the complete breakdown of trondjemite flanking the northwestern and western margins of the complex Bukit Ranjut syenite intrusion in northwest Pahang. These trondjemites range in composition from essentially quartz-free albiteplagioclasites to quartz-free microcline rocks; they are, in effect, the syenitic homologues of white sodic and potassic granite-aplites. The granites in Malaya have generally undergone more or less severe surficial weathering leading to the production of a spongy and rather cellular or a soft "mealy" material (sandy clay) down to depths of about 100 ft; in places the granite is strongly decomposed down to 150 ft. There has occurred, therefore, widespread partial kaolinization, but, in general, no extensive deposits of good quality kaolin seem to have been formed by these processes of decay. Frequently, the katamorphic processes of desilicification have advanced beyond the production of kaolin towards the formation of lateritic end products. The more important Malayan kaoiins seem to be confined to the western alluvial plains, particularly in areas either where granite crops out at surface, or where it forms the bedrock of the alluvium. There are numerous excellent examples around Gopeng and elsewhere in the Kinta Valley of Perak. Such kaolins belong to Stuckey's groups of secondary deposits, and, like them, these also may be bedded. Field observations have established the existence of what for want of a better name is referred to by the Malayan Geological Survey as "granite wash." It is believed that granite, undergoing extensive deeply penetrative and probably rather rapid destruction under humid tropical weathering (temperature around 90°F; rainfall about 100 in. per annum; high humidity) "flowed," was moved by "creep" and, in addition, probably slumped in large waterlogged masses of sandy clay from topographic salients onto the adjacent flats. Either during this period of transmigration or later when the sludged granite detritus, after having more or less come to rest, was attacked by flowing water, differential sorting and erosion took place with the result that the resorted debris was moved and later deposited as bedded alluvium. In this way, banded "granite wash" was produced comprising alternating bands of clayey sand (resorted granite sludge) and white

Jan 1, 1947

By T. S. Lundy, J. Askill

J. Askill and T. S. Lundy (Oak Ridge National Laboratory)—Moore has proposed a simple correlation between the activation energy for solute diffusion in fee metals and the atomic volume of the diffusing species using both tracer and chemical-diffusion data. The first point we wish to make is that it is wrong to attempt such correlations without separating the two types of data. Activation energies obtained using tracer techniques cannot, in general, be directly compared with those obtained from chemical-diffusion experiments. A knowledge of the variations of chemical potentials with composition is necessary and chemical-diffusion data must be corrected for such variations, even for dilute alloys, before a comparison is possible. Secondly, for nickel, iron, aluminum, and lead, Moore neglected a number of recently published works, e.g., Al26 and Mn54 in aluminum,46 cr51 in nickel,47 and Fe55 in iron.48 These and others should have been used. If one considers only the tracer diffusion data, there is left no simple correlation of the type proposed by Moore. For example, in the case of solute diffusion in aluminum the only reliable tracer data listed by Moore are for zinc and aluminum. The nickel, cobalt, and iron data of Agarwala49 are representative of near-surface diffusion-not bulk diffusion. In conclusion we suggest that for tracer diffusion data in these fee metals there is no justification for proposing any simple correlation of activation energy with atomic volume using the limited data that are presently available. R. H. Moore (author's reply)—The writer has proposed a simple correlation which is useful in estimating the internal consistency of diffusion data. The accuracy of the correlation is, of course, a function of the number of data available. Lundy and Askill take issue with the writer's decision to include data for the systems: nickel, iron, aluminum, and lead, taking the view that the data are insufficient to establish the correlation. The writer agrees that the data are insufficient and has cau- tioned the reader that the correlation is tentative in these instances. Inclusion of these systems is justified by the interesting trends the correlation reveals. For example, the distinction between interstitial and substitutional diffusion may be clearly established, Figs. 4 and 6, and the behavior of transition elements and nontransition elements is indicated to parallel the behavior illustrated by the silver and copper systems. Lundy and Askill have singled out the aluminum system for special criticism. The writer chose to discuss the data for diffusion of iron, nickel, and cobalt in aluminum in the terms used by the original authors9 and has included the comments of Balluffi.l0 The writer did not intend the reader to conclude that data for these elements should correlate with data for the nontransition elements as Lundy and Askill have evidently assumed. Iron, nickel, and cobalt form intermetallic compounds with aluminum, so the activity coefficients of these elements may be expected to deviate markedly from unity. This may account for the low frequency factors observed by Hirano.9 The nontransition elements, on the other hand, yield relatively simple phase diagrams with no evidence for intermetallic compound formation as in the case of iron, nickel, and cobalt. In dilute solution, Henry's law should be closely obeyed, the activity coefficients should not deviate markedly from unity, and the effect on the activation energy should not be large. The accuracy of the correlation applied to these systems will improve as the data is extended. It does not seem unreasonable to conclude that its extension should be encouraged.

Jan 1, 1965

John Duer Irving, who left his post as Professor of Economic Geology at the Sheffield Scientific School, New Haven, Conn., to join the Eleventh Regiment of Engineers shortly after the declaration of war, died in France, July 26, 1918, from an attack of pneumonia. Through the initiative of Mr. Benjamin B. Lawrence, a memorial service to Captain Irving was held at St. Paul's Chapel, Columbia University, on Sunday afternoon, August 4, which was' attended by members of Captain Irving's family, and about four hundred of his friends from Columbia, Yale, the American Institute of Mining Engineers and the Association of the 11th Regiment of Engineers. Professor James F. Kemp delivered the memorial address, and has prepared for the Institute the following account of Captain Irving's life, Professor Kemp and Captain Irving having been associated on the most intimate terms for a number of years. , The war has brought home to friends and kin in the western shores of thc Atlantic many losses whose suddenness has the shock of a blow. Many more will follow, but none can leave a sharper sense of regret than the news that the keen and productive mind; the inspiring teacher; the successful and considerate editor, the fine, true man and friend had all passed away when John Duer Irving made the final great gift to the service of his country, in the cause of decency and right. In the closing days of July, the cable brought the tidings that toward midnight on the twentieth of the month pneumonia had proved too great a tax upon one already worn by excessive labors. John Duer Irving was born in Madison, Wis., August 18, 1874. His father, Roland Duer Irving, was at the time professor of geology, mineralogy and metallurgy in the State University of Wisconsin.' Roland . Irving, the father, had entered Columbia College in 1863, but trouble with his eyes compelled him to suspend his studies in the classical course in his sophomore year, and to replace study with some months of life and travel in England. Ultimately his eyes became stronger, and he entered the School of Mincs, completing the course for the degree of Engineer of Mines in 1869, with the third class graduated. The class of eleven contained other future geologists. It numbered on its roll Henry Newton and Walter P. Jenney of the early survey of the Black Hills, where John, future son of Roland, was in the course of years to make his doctor's dissertation, and with its publication his really serious entrance into the profession. Roland Irving was a favorite student of Professor J. S. Newberry, affectionately known to all of his students as "Uncle John," and after some experience in mining and smelting in Pennsylvania and New Jersey, joined the Ohio Survey under Dr. Newberry. The work in Ohio was largely performed during the vacations of the University of Wisconsin, to whose chair Roland Irving was called in 1870. Later, his residence in Wisconsin led to two events of prime importance in the history of American geology. He began the study of the Gogebic iron range and caught the clue to the origin and stratigraphy of the iron ores of all the Lake Superior ranges; and he later undertook the mapping and description of the copper-bearing rocks of the Lake Superior basin. The formative years of the son, John, were passed in a home where the father.

Jan 1, 1920

By A. Hansson, G. E. Tardiff

WHILE it is generally known that cold-worked low-and medium-carbon steels exhibit substantial increases in tensile rupture ductility with increased deformation velocity172 (up to the von Karman limit), the observations for annealed or normalized steel do not permit simple generalization. Various investigators, for example, have reported both small increases1,3 and small decreases4,5' in rupture ductility with increased rates of deformation of normalized low-carbon steel. The purpose of the present note is to report on the dependence observed for strain-aged steel since preliminary work here indicates that strain aging results in the development of a consistent type of behavior that is understandable in the light of current knowledge of the lower yield dynamics for steels which deform inhomogeneously.6 This realization throws additional light on the influences responsible for the behavior of normalized steel. The results presented here were obtained for a 0.21 pct C, 0.012 pct N sheet (0.012 in. thick) steel which was received in a temper-rolled condition (approximately 3 pct reduction in thickness after process annealing); the as-received material had a spherodized structure with a ferritic grain size of ASTM 8. The material was selected for testing after 6 months room temperature aging, at which time the static lower yield and ultimate tensile strength measured 79 and 82 kpsi, respectively. ASTM 2-in. reduced section, 1/2-in.-wide specimens were used in smooth bar tests and 3/4-in.-wide specimens containing two 60-deg opposed edge notches (root radii = 0.002 in.) were used in notched bar tests. To facilitate strain measurement, the smooth bars were blued with ink and marked at 0.1-in. intervals along the gage length; the notched

Jan 1, 1968

By R. P. Fischer

The Colorado Plateau region has been the principal domestic source of uranium, vanadium, and radium. The value of these commodities produced from the region through 1964 slightly exceeds $2 billion. Most of the deposits occur in streamlaid lenses of sandstone in the Chinle and Morrison Formations. The ore minerals below the zone of oxidation are low-valent oxides and silicates of uranium and vanadium; all of these, except the quite stable vanadium silicates, oxidize readily to a variety of high-valent uranium and vanadium minerals. The ore minerals partly replace fossil wood but mainly impregnate sandstone, typically forming tabular ore bodies that are nearly concordant to the bedding of the host rock. The deposits range in size from those containing only a few tons of ore to those containing more than 1 million tons. Stratigraphic, lithologic, and sedimentary structural factors obviously influenced the localization of these deposits, but igneous activity, hydrothermal mineralization, and tectonic structures show no similarly consistent influence on localization. The deposits are epigenetic, but the source of the ore metals, the nature of the ore-bearing solutions, and the time of ore emplacement are uncertain. A few uranium deposits in the region are dominantly discordant to bedding and occur in collapsed breccia pipes or along linear fractures. Their origins are also uncertain.

Jan 1, 1968

By L. Seigle, R. Resnick

An inert-marker movement experiment indicates that the ratio of the intrinsic diffusion coefficients DC:DTa = 80:l in TaC at 2500°C. Measurements of the diffmion coefficient of carbon in nonstoichiometric TaC at temperatures from 1700° to 2700°C reveal that Dc increases with decreasing carbon content, but much less than expected from the probable change in vacancy concentration with carbon content. A diffusion process involving two simultaneously operating mechanisms is postulated, and shown to be theoretically feasible. The average value of the carbon diffusion coefficient is given by DC = 0.18 exp[(-85,000 ± 3000)/RT] sq cm per sec over the composition range 46 to 49.5 at. pct C. BECAUSE of their high melting points and hardness, the carbides of the IV, V, and VI group transition metals, along with those of uranium, have attracted considerable interest for applications at high temperatures. In these applications the reactivity of the materials is important, and, since rates of diffusion within the compounds influence reactivity, a knowledge of diffusion kinetics and mechanisms is desirable. While many investigations of the mechanical and electrical properties of these compounds have been made, only two fundamental investigations of diffusion in the carbides are known. Chubb, Getz, and Townleyl measured the diffusivity of carbon and uranium in UC, and Gel'd and Liubimov2 measured the diffusivity of carbon and niobium in NbC. This paper describes an investigation of the diffusion of carbon in tantalum monocarbide and, in particular, the influence of carbon deficiency on this process. Tantalum carbide melts at approximately 3800°C, which makes it one of the highest melting materials known. The compound exists over a rather wide range of carbon Content.3-7 At the peritectic temperature, 3240°C, the phase extends from about 36 to 50 at. pct C. Although the compound can exist with a substantial carbon deficiency, the high carbon phase boundary remains near the stoichiometric composition over the entire temperature range; i.e., no carbon excess is observed. The structure of TaC is the NaCl type wherein carbon atoms normally occupy the octahedral sites in a somewhat expanded fcc lattice of tantalum. Decrease of the lattice parameter with decreasing carbon suggests that the removal of carbon introduces octahedral vacancies into the lattice. I) EXPERIMENTAL DETAILS AND RESULTS Inert-Marker Experiments. In a compound such as TaC the interstitial element would be expected to diffuse more rapidly than the metal. This was confirmed by an inert-marker experiment, following Srnigelskas and irkeendall.8 Ideally, the markers should be placed at the interface between a slab of low-carbon TaC and graphite, and their movement during subsequent inter-diffusion measured. Unfortunately, no solid could be found which is unreactive in contact with carbon at the high temperatures employed in these experiments. In order to circumvent this problem, a specimen was designed in which the markers consisted of several small canals running just below the surface of a tantalum slab. This specimen was prepared by machining grooves on the surface of the tantalum slab and then diffusion-bonding a thin plate of tantalum to the slab over the grooves. The surface of the plate was then ground down until the distance between the canals and surface was as small as possible (about 0.01 cm). Thus, the canals would lie entirely within the TaC phase after a short period of diffusion. The diffusion anneal consisted of immersing the metal sample in high-purity graphite powder and heating for approximately 10 hr at 2500°C under vacuum. At this temperature, the vapor pressure is sufficiently high and the transfer of carbon from graphite sufficiently rapid to allow the surface of the diffusion sample to attain the stoichiometric carbon concentration very quickly. Conclusions regarding the relative diffusion rates of carbon and tantalum in the compound layers (TaC and Ta2C) can be drawn from the location of the canals after the diffusion anneals. If the growth of the layers is governed mainly by the diffusion of carbon, as expected, the canals should remain close to the sample surface. If the diffusion of tantalum contributes appreciably to formation of the compound layers, the distance from the markers (canals) to the surface should increase. Fig. 1 shows, diagrammatically, the appearance of the specimens after diffusion, and Table I presents the depth below the surface at which the

Jan 1, 1967

By Roland Kammel

For electrolytic recovery of silver from dilute aqueous solutions improved mass transfer is necessary to achieve favourable current efficiencies and high space-time yields. The many cell designs proposed for this application can be divided into two different groups: cells from which the silver must be redissolved and cells from which the deposit can be reclaimed as a metal. Introduction Electrolytic silver recovery methods have proven advantageous under technical and economic aspects for the treatment of rinse water, still rinses and spent silver solutions in the electroplating and surface finishing industry, of exhausted fixing baths from photographic processing, bleed electrolytes from silver refining processes and leach liquors. Examples of the compositions of typical dilute silver solutions are listed in Table I.

Jan 1, 1984

By F. A. Schaufelberger

Early work on chemical precipitation of metals from metal salt solutions is reviewed. The chemistry and thermodynamics of precipitating copper, nickel, cobalt, and cadmium metals by reaction with hydrogen are discussed. Mechanisms of metal precipitation, nu-cleation, growth, and agglomeration are reviewed, as well as some solubility phenomena of cleation,gases and solids at elevated temperatures. Experimental data presented deal mainly with the reaction of copper sulfate solution with Hz. METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on p. 701. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.2 The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited" to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SCV which may lead to contamination with sulfur, or CO," which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents: which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere." It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution cohposition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farbenm claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic. antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373"C), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred. probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By Alec M. Crowell, J. W. Sanders

While the production of crude oil and condensate in South Arkansas increased only 1.7 per cent over the 1940 figure, complete utilization of gas produced with the oil and condensate, and heretofore wasted, was beginning to be evidenced. There were 26,229,264 bbl. of oil and condensate produced in South Arkansas during 1941, as against 25,790,380 bbl. for the year 1940. (Fig. I.) Since 1936, deep producing sands have been discovered in 18 fields and during that period only 40 per cent of the total state production has come from Upper Cretaceous formations while 60 per cent came from the Lower Cretaceous and Jurassic formations. The gas produced with crude oil and condensate from the latter formation contains large quantities of hydrogen sulphide, the maximum being 6900 grains per 100 cu. ft. in the Patton pool of Lafayette County. Gas Utilization During the latter part of 1940 and the early part of 1941, pilot plants were placed in operation to determine whether the hydrogen sulphide and deleterious material in South Arkansas gases could be removed economically. The Federal Government desired to build a large aluminum plant in the Ouachita Valley and was seeking cheap fuel for the generation of electricity. The fact that the gases were produced with appreciable quantities of crude oil and condensate made it available at a very low price, since the state's conservation law prohibits the flaring of any gas. As a result of these experiments the first large-scale unit for the processing of gases containing hydrogen sulphide was placed in operation on Sept. I, 1941. The plant is in the Magnolia oil field, Columbia County. It processes residue gas from the Shell Oil Company's gasoline plant in that field and also raw gas from the Village field, 6 miles east of the Magnolia field. The gas entering the desulphuri-zation unit is laden with approximately 1400 grains of hydrogen sulphide per 100 cu. ft. and is stripped to a content of 4 grains per 100 cu. ft. The capacity of the plant is 15 million cu. ft. of gas treated daily under a pressure of 160 lb. per sq. in. The cost of treatment, exclusive of depreciation, is appreciably less than I per 1000 cubic feet. Two other plants of much greater capacity have been announced and priorities have been granted, which should bring the total amount of gas treated to 150 million cu. ft. daily. The gas to be treated will have a maximum hydrogen sulphide content of 4500 grains per 100 cu. ft. and will be processed under a pressure of 600 lb. per sq. in. These developments are something entirely new in field practice for the industry. The fact that this heretofore wasted gas is available at very low cost has led to the location of some eight war industries within the state, in addition to the alu-minum plant. Recovery OF Sulphur The Susearch Corporation and the Southern Acid and Sulphur Co. placed in operation during 1941 pilot plants to de-

Jan 1, 1942

By Alec M. Crowell, J. W. Sanders

While the production of crude oil and condensate in South Arkansas increased only 1.7 per cent over the 1940 figure, complete utilization of gas produced with the oil and condensate, and heretofore wasted, was beginning to be evidenced. There were 26,229,264 bbl. of oil and condensate produced in South Arkansas during 1941, as against 25,790,380 bbl. for the year 1940. (Fig. I.) Since 1936, deep producing sands have been discovered in 18 fields and during that period only 40 per cent of the total state production has come from Upper Cretaceous formations while 60 per cent came from the Lower Cretaceous and Jurassic formations. The gas produced with crude oil and condensate from the latter formation contains large quantities of hydrogen sulphide, the maximum being 6900 grains per 100 cu. ft. in the Patton pool of Lafayette County. Gas Utilization During the latter part of 1940 and the early part of 1941, pilot plants were placed in operation to determine whether the hydrogen sulphide and deleterious material in South Arkansas gases could be removed economically. The Federal Government desired to build a large aluminum plant in the Ouachita Valley and was seeking cheap fuel for the generation of electricity. The fact that the gases were produced with appreciable quantities of crude oil and condensate made it available at a very low price, since the state's conservation law prohibits the flaring of any gas. As a result of these experiments the first large-scale unit for the processing of gases containing hydrogen sulphide was placed in operation on Sept. I, 1941. The plant is in the Magnolia oil field, Columbia County. It processes residue gas from the Shell Oil Company's gasoline plant in that field and also raw gas from the Village field, 6 miles east of the Magnolia field. The gas entering the desulphuri-zation unit is laden with approximately 1400 grains of hydrogen sulphide per 100 cu. ft. and is stripped to a content of 4 grains per 100 cu. ft. The capacity of the plant is 15 million cu. ft. of gas treated daily under a pressure of 160 lb. per sq. in. The cost of treatment, exclusive of depreciation, is appreciably less than I per 1000 cubic feet. Two other plants of much greater capacity have been announced and priorities have been granted, which should bring the total amount of gas treated to 150 million cu. ft. daily. The gas to be treated will have a maximum hydrogen sulphide content of 4500 grains per 100 cu. ft. and will be processed under a pressure of 600 lb. per sq. in. These developments are something entirely new in field practice for the industry. The fact that this heretofore wasted gas is available at very low cost has led to the location of some eight war industries within the state, in addition to the alu-minum plant. Recovery OF Sulphur The Susearch Corporation and the Southern Acid and Sulphur Co. placed in operation during 1941 pilot plants to de-

Jan 1, 1942

By R. Schuhmann Jr., P. J. Ensio

As a first step in a study of the physical chemistry of copper-smelting slags, experimental measurements were made of the oxygen pressure of simple iron-silicate slags in equilibrium with solid iron. The experiments consisted in bubbling CO2-CO mixtures through the slags in iron crucibles and in finding the equilibrium ratios of CO2 to CO. From the data, activities and partial molal heats of solution FeO and SiO2 in the slags were calculated. THE ternary system FeO-Fe,O,-SiO, is the simplest system which can represent adequately the important chemical properties of the slags formed in matte smelting and converting. Accordingly, the experimental study of slags in this system was started as the first step in a general research program on the thermodynamics of copper smelting. A recent paper by one of the authors' outlines this general research program and shows in some detail how information on thermodynamic properties of iron-silicate slags, especially information on oxygen activities, is essential to a full understanding of the chemistry of copper smelting. The FeO-Fe,O,-SiO, system also is the basis of slags produced in other processes, such as acid steelmak-ing processes, and is important in relation to the behavior of silicious refractories. In addition, data on the physicochemical properties of iron-silicate slags should contribute to a general understanding of the nature of slags, since at present such data for all kinds of slags are relatively meager. The principal quantitative information already available on iron-silicate slags consists in Bowen and Schairer's constitution diagram for slags in equilibrium with metallic iron,' Darken and Gurry's complete and precise thermodynamic study of the Fe-0 system,",' and Darken's study of the phase equilibria in the Fe-Si-o system. From the results of this previous work, it was clear that a complete thermodynamic study of ternary iron-silicate melts was a major undertaking which would have to be broken down into parts, including the working out of the ternary equilibrium diagram as well as extensive activity measurements on slags. The experimental measurement of oxygen activity, using CO-CO, and other gas mixtures as yardsticks of oxygen activity, was the basis of Darken and Gurry's study of the Fe-0 system. From the experimental measurements of oxygen activities over a large range of temperatures and compositions, they were able to calculate the activities of other species such as Fe, FeO, Fe,O,, etc., and also the other important thermodynamic properties in the Fe-0 system. At the start of the present investigation, it appeared that the same approach would be fruitful for the study of iron-silicate melts. Also, the experimental measurement of oxygen activities seemed particularly attractive because oxygen activity itself is a quantitative measure of oxidizing or reducing power, which is an important variable in copper-smelting slags. The slag compositions in equilibrium with yFe appeared most suitable for the first investigation of this kind, for the following reasons: 1—Good constitution data2 were available. 2—An iron crucible could be used, thus affording a simple solution to the refractory problem without introducing contarnination. 3—With Fe activity fixed, at unity with respect to a standard state of solid Fe, measurements of 0 activity could be followed by simple calculations of activities of FeO and other Fe-0 complexes and of SiO,. 4—This starting point afforded several possibilities for cross-checking with previous work,

Jan 1, 1952

By H. R. Stahl

FIVE mills are operated in Southeast Missouri by the St. Joseph Lead Co.; these have a total rated capacity of 24,300 tons per day divided as follows: Federal, 12,000 tons; Leadwood, 4800 tons; Desloge, 3600 tons; Bonne Terre, 2400 tons; and Mine La Motte, 1500 tons. These concentrators are similar in a general way, differing mainly in size and type of equipment and in minor variations in flow sheet. No attempt is made rigidly to standardize procedure in the various mills in spite of a general similarity in the ores. Each mill may be regarded as a separate laboratory in which new ideas and changes may be tried. A generalized description of the process is given, noting important differences in procedure at the various plants. The concentration process may be divided into five main stages: dry crushing, wet grinding, desliming and classification, tabling, and flotation.

Jan 1, 1947