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By A. W. Bethune, L. M. Pidgeon

The equilibrium vapor pressure of zinc has been determined over the systems: ZnS(s) + Fe(s) = FeS(s) + Zn (vapor) and ZnS(s) + 2Cu(s) = Cu2S(s) + Zn (vapor) by reacting the components in an evacuated tube containing a thin copper fiber, and allowing equilibrium to be established with respect to the brass formed and the zinc in the vapor phase. The composition of the brass formed was determined and equilibrium vapor pressure values obtained from existing data. Between 850' and 1000°C, values for the first reaction ranged from 8 to 58 mm Hg; for the second reaction from 1.8 to 22 mm Hg. THE direct reduction of metallic sulphides may be indicated by an equation of the form MS + X = XS + M [1] where X is some suitable reducing agent. In the case where M is a metal of relatively high volatility, the use of vacuum will displace the equilibrium to the right at comparatively low temperatures in the face of the usually unfavorable thermochemistry. For this technique to be feasible, MS, X, and XS, must of course be nonvolatile compared to M. In this regard, zinc becomes an obvious metal both from the point of view of its volatility and the fact that most commercial ore deposits of this metal occur as the sulphide, and its direct reduction would avoid the expensive roasting process necessary prior to present day reduction methods. Two reducing agents are of interest, namely copper and iron, with the former having the added attraction of being relatively easily regenerated by oxidation in the copper converter. The possibility of these reactions has been considered before. Imbert1 patented a process whereby zinc sulphide was reduced by either copper or iron. The process as described took place at atmospheric pressure and, at the high temperatures required, the system was molten, resulting in the formation of a matte with the consequent reduction in the activities of the reactants. Peterson2 did further experimental work on these reactions and, although promising results were obtained on a small scale, attempts to increase the size of the furnace led to excessive "blue powder" formation. The early workers failed to realize the large reduction in temperature afforded by the use of vacuum and its desirable results. More recently, the direct reduction of zinc sulphide by iron has been the subject of a thermody-namic investigation by Kelley,3 and Gross and War-rington' have studied the kinetics of the reaction in the temperature range 900" to 1000°C, their experiments being conducted using vacuum and indicating that the reaction would proceed practically to completion in 1 to 3 hr, depending on the temperature. A qualitative examination of the system ZnS-Cu carried out at this University indicated that 98 pct of the theoretical zinc in the charge could be recovered in 1 hr at 1000°C when operating under reduced pressure. The purpose of this research program was to study the equilibrium of the two reactions. During the investigation, reference to the experimental work of Schenk5 was found but, due to lack of detail in the report, it was felt that it would be desirable to continue the equilibrium measurements. Selection of Method The measurement of vapor pressure of metals presents obvious problems resulting from the high temperatures which must be employed. In the present case, the production of the "reaction pressure" introduces a further difficulty since a chemical reaction must proceed before any metal vapor pressure is produced, resulting in depletion of the re-

Jan 1, 1954

PRESIDENT. CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS. CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT. BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER. GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS. ROSSITER W. RAYMOND NEW YORK, N. Y.

Jan 5, 1913

By Thomas E. Ban, Charles D. Thompson, Charles A. Czako

Continuous sintering-a metallurgical process for more than 50 years-has broadened from its origin in nonferrous metallurgy to present-day applications in ferrous, chemical, and nonmetallic fields. During the past year, self-fluxing sinter production has been a subject of active interest to iron metallurgists in North America. Accomplishments however, have come predominantly from Europe and proper interpretation of these reports requires an understanding of European raw materials and European economics. The technology, of course, can be applied universally.

Jan 10, 1959

INTRODUCTION TO PROBABILITY THEORY The mathematical theory of probability provides the foundation for the interpretations and inferences that can be made from statistical techniques. Probability theory is a broad field of study in itself, and can only be touched on here in order to provide the necessary back- ground for a more complete understanding of statistical analysis. Probability is concerned with the outcome of random events. It had its beginnings in the theory of games of chance which were of great interest to European mathematicians during the last half of the 17th century. The outcome of a random process or experiment is defined as an event. The collection of all mathematical points associated with each event is called the sample space for an experiment. Consider a random experiment having a finite number, n, of possible outcomes, some of which have a characteristic A. What is the probability that A will result from a single

Jan 1, 1980

By John A. Church

IT is a well-known fact that under similar conditions a ton of pig iron can be made from any ore with less fuel when charcoal is used than when coke or anthracite is employed for heating. The cause of this superiority is entirely undiscovered, and no explanation has yet been offered which has won even temporary acceptance. Such as they are the hypotheses heretofore presented are of two general kinds, and they come from those two divisions of the working force which are so often antagonistic in all professions, the scientific and the practical men. The theory of the scientific men is drawn from the chemical reactions which are known to go on in the furnace, and it is well expressed in a recent paper by Prof. Akerman, of the Stockholm (Sweden) School of Mines. It makes the superiority of charcoal as a fuel in the blast furnace to depend upon its quick and thorough reduction of carbonic acid. This property belongs to charcoal in virtue of its porous structure. Its cells have a diameter of only one twenty-four hundredth of an inch, and one grain of charcoal has been computed to have a surface of two and four-tenths square feet. According to the theory in question, carbonic acid is formed by the first impact of the air upon the fuel; but in charcoal furnaces the acid is immediately reduced to oxide by taking the necessary amount of carbon into combination, and the gas reaches its highest reducing power even in the near vicinity of the tuyeres. Coke, being harder, does not produce so strong a reducing gas in that part of. the furnace. Carbonic acid is formed as in the case of charcoal, and remains longer before its reduction to oxide is completed. Anthracite is the

Jan 1, 1879

THE education of adolescents to perform the duties and assume the responsibilities of maturity has been a characteristic of human society since the dawn of history. In the beginning the members of the immediate family performed this function, and in modern life they still have an important part in it. Possibly religion was the first field in which education began to be functional; young people were sent for instruction to a teacher who had a broader and deeper knowledge of the subject than was possessed by the family. It does not seem necessary for our purpose to attempt to determine how, when, or where instruction in the practical arts first began to become functional, and the brief outline which follows must suffice. The discovery and utilization of mineral substances to improve and maintain the conditions of human living is a practical art, which must have had an almost accidental origin and have been developed by empirical experiments. We do not know, nor would it be useful to try to fancy, how men first learned that they could make use of mineral substances to their benefit, but however that knowledge was initially gained it was certainly trans- mitted through instruction in the family. At fist such activities must have been merely a minor part of the making of a living, bit in time those who excelled found it better to devote them-

Jan 1, 1941

By C. J. Leith

A study of the effect of rock composition, rock structure and degree of weathering on the stability of cut slopes is being sponsored jointly by the U.S. Bureau of Public Roads and the North Carolina Highway Commission. In 58 mountain and piedmont counties of North Carolina the percentage of failed cut slopes is greatest in micaceous metasediments, gneisses, and schists, and in saprolite and soil derived from these rock types. Soil slope failures outnumber rock slope failures by two to one. Joints and similar planes of separation exert a strong influence on size and shape of the sliding mass. They may or may not act as failure surfaces, depending on their orientation with respect to the active forces. Climatological data, though indicative of weathering conditions, do not correlate well with slope failure frequency. Because of the presence of joints and similar planes of weakness in soil and rock materials, conventional methods for analyzing slope stabilities are not directly applicable. Empirically derived modifications of these methods are being investigated. A study of the stability of highway cut slopes, sponsored by the U. S. Bureau of Public Roads and the North Carolina State Highway Commission, began in 1962 at North Carolina State of the University of North Carolina at Raleigh. As part of this study all slides, rockfalls and other types of cut slope failures on Federal and State highways in the 58 mountain and piedmont counties in North Carolina were located and described, and the data catalogued in a punched card file system. A major objective of the project is to relate slope failures to properties and physical conditions of the geological units in which the slopes were constructed, and to correlate soil type and/or geological unit with type and frequency of slope failure. The complexities of the problem of slope stability and the limitations which these complexities impose on methods for analyzing slopes have been recognized for many years. A great variety of factors and processes may lead to slides, often making it almost impossible to analyze theoretically the conditions required for stability of slopes. One of the principal factors determining maximum safe slopes is the shear strength of the material in which the slopes are cut, but unfortunately there are very few data available concerning shear strengths of residual soils. Vargasl tested clay derived from gneiss and granite in southern Brazil; the properties of decomposed granite occurring near Hong Kong were determined by Lumb.2 These data are being used, when applicable, to supplement the test data obtained in the present study by Yorke.3 The locations of the North Carolina slope failures, more than 400 in number, are shown on Fig. 1. This map, adapted from the Geological Map of North Carolina,4 suggests the possibility of a relationship between frequency of slide occurrence and rock type. However, the evaluation of this possibility requires consideration not only of the type of rock, but also of its large and small scale structural features, its susceptibility to and degree of weathering, and the composition and structure of the weathering products. Soil slope failures in thoroughly weathered soil material and saprolite outnumber rock slope failures two to one. INFLUENCE OF ROCK TYPE The agricultural soil type involved in each soil slope failure was identified and each failure was catalogued in terms of the parent material from which the soil was derived. These data indicate that most of the slope failures, whether in the rock or in the derived soil, are associated with metamorphic rocks (see Fig. 2a). The data may be skewed somewhat because of the relative sizes of the total areas underlain by the various rock types, but Leith and Gupton5 have demonstrated that the preponderance of failures in metamorphic rocks is of much greater magnitude than could be accounted for by the areal factor alone. The dominance of metamorphic rocks is emphasized when soil slope failures are considered in terms of the specific rock types from which the soils were derived (see Fig. 2b). In particular, mica schists and mica gneisses account for more slides

Jan 1, 1965

By R. J. Wasilewski

Axial expansion has been determined by X-ray diffraction up to 600° to 760°C in a titanium and four high-oxygen alloys. Expansion data cannot be fitted to the usual quadratic expression and anomalies observed are believed indicative of the changes in the bonding configuration of the valence electrons. Furthermore, there is significant disagreement between data obtained on poly crystalline and single crystal powder specimens. The major disagreement occurs within the temperature range (-470°C) where both mechanical and electrical properties also show markedly anomalous behavior. X. HIS work forms part of an investigation of physical properties of pure titanium and its osolid solutiono alloys with oxygen and nitrogen. In view of the anomalies observed in both the electrical resistivity' and the susceptibility behavior it was decided accurately to determine the thermal expansion behavior of the pure and alloyed a titanium. PREVIOUS WORK The axial expansion coefficients reported for pure titanium are listed below. As can be seen, there is a marked discrepancy between the axial expansion and the experimentally determined coefficients on poly crystal line material. Thus, if we take the most recently reported axial expansivities3,4 we obtain perature interval of 25o to 700°C. The experimental value reported for polycrystalline metal is, however, of the order of 9.7 x 10o6 per OC. EXPERIMENTAL I) Pure Titanium. High purity titanium powder of -325 mesh was used throughout most of this work. The only significant impurities present were the interstitials, oxygen and nitrogen, which analyzed respectively 650 and 80 ppm. The purity of the ma-

Jan 1, 1962

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971

By S. S. Marsden, S. A. Khan

Externally generated foam was injected continuously into short porous media. Both flow rate and pressure drop were measured. Liquid saturation was determined by electrical conductivity. Foam yuality I, expressed as the ratio of gas volume to total volume, was varied from 0.70 to 0.96. As measured with a modified fann VG Meter, apparent viscosity of this foam µa decreases with increasing shear rate but usually falls within the range of 50 to 500 cp. At a given shear rate, µa increases almost linearly with I-. When measured with a Bendix Ultraviscoson, kinematic pa is independent of V but absolute pa increases with T from about 3 to 8 cp. The effective permeability -apparent viscosity ratio ke/µa decreases almost linearly with V for porous media of high permeability, but the rate of decrease becomes less for tighter ones. The relative permeability-apparent viscosity ratio kr/µa us V data does not fall on a single line. The kr/µa ratio increases with liquid saturation in the porous medium and with surfactant concentration. Estimates of pa for foam in porous media vary from 30 to 100 cp. INTRODUCTION Although research on the development of a foam-drive, oil recovery process has been going on for almost a decade, most of the significant publications have appeared within the last several years. This illustrates well the rate at which interest in this process is accelerating. Bond and Holbrook 1 were the first to describe the use of foam to improve oil recovery in their patent of 1958. They proposed that an aqueous foaming agent slug be injected into the formation and that this be followed by gas to produce a foam in situ. Fried 2 studied the injection of foam into porous media which had already been subjected to conventional gas or water drives and found that gas could be used to drive a foam bank which would, in turn, displace additional oil in the form of an oil bank. He attributed the increased oil recovery to the high effective viscosity of foam flowing in porous media. His microscopic observations showed the importance of foam generation and regeneration within the porous medium. By injecting both air and aqueous surfactant solution, Bernard3 generated foams within the porous medium in which oil displacement was being studied. In a separate empirical test, he also measured the dynamic foaming characteristics of the same surfactants in water and/or oil. With some exceptions and for the seyen surfactants studied, there seems to be a qualitative relationship between the efficiency of liquid rlisplacrment and the dynamic foaming testtsed. This relationship was not consistent enough to eliminate the necessity of actual foam flood tests in porous media for surfactant selection. In a study basic to gas storage in aquifers, Bennett4 described the displacement of brine by foam in consolidated porous media. Among other things, he stated that the ability of a surfactant solution to foam is more important than the stability of its foam. The presence of a foam bank between the displacing air and the displaced brine improved both breakthrough and ultimate recovery. In a continuation of this work Kolb5 attributed the great reduction in surfactant solution production rate as displacement by air progressed to a decrease in relative permeability to gas. These several effects reported by both Bennett and Kolb can all be attributed to the high apparent viscosity of foam which was obviously flowing in the porous media. Bernard and Holm6 observed that gas permeability in the presence of foam was much less than in the absence of foam when both were measured at the same gas saturations. This reduction in permeability was proportionately greater for more permeable sands and sandstones than for the less permeable. Viscosities of the surfactant solution and air were used for their calculations rather than apparent foam viscosities. The foam stability increased with decreasing permeability, which was probably due to the natural regenerative properties of porous media, and the permeability reduction increased

Jan 1, 1967

By G. Krauss, W. Pitsch

The fine structure of the bcc martensite formed in an Fe-33 wt pct ATi single crystal of arrstenite is sho~on by transmission electron microscoPy to consist of combinations of transformation twins, stacking faults, deformation twins, and regular arrays of parallel screw dislocations. These structures constitute evidence for the multiple lattice-invariant deformations which operating during the formation of martensite could produce the real habit-plane scatter measured by a two-surface analysis of the plates formed in the single crystal of this investigation and reported in the literature for other Fe-Ni rnartensites. CRYSTALLOGRAPHIC theories1,2 of martensitic transformation show that the habit plane of martensite in a parent lattice is dependent in part upon an inhomogeneous distortion or lattice-invariant deformation which takes place on a fine scale within a martensite plate during its formation. Several recent theoretical papers3,4 have addressed themselves to an analysis of a wide variety of conceivable lat-tice-invarient deformations and the habit planes which they produce, while experimental investigation have been concerned with either the measurement of habit planes or the description and identification of the martensitic fine structure which reflects the nature of the lattice-invariant deformation operating during transformation. In Fe-Ni alloys with subzero Ms temperatures, the group of alloys with which this paper concerns itself, habit planes have often been found to scatter an amount greater than might be expected from possible experimental errors,5-7 and fine twinning has been identified as a major constituent of the fine structure of martensite.8-11 It has been suggested3,4 that more than one type of invariant shear occurs during martensitic transformation. This possibility has been experimentally supported12,13 by the observation of both dislocation configurations and twinning in a single martensite plate. The purpose of this paper is to report additional evidence for multiple lattice-invariant deformations in martensite and so to account for the real scatter in the habit planes of the martensite plates formed in Fe-Ni alloys. EXPERIMENTAL PROCEDURE The Fe-Ni single crystal was produced by pulling a high-purity iron and nickel charge through a single-crystal vacuum furnace in an alumina crucible. The crystal was double-melted to promote homogeneity and to increase its size by further additions on the second pass. In its final form the crystal was 4 cm in diam and 5 cm long. The nickel and carbon contents were analyzed at 32.9 and 0.006 wt pct, respectively. The austenite of this alloy first transformed to martensite by bursts at about -120°C, and, to preserve as much of the austenite as possible, all transformation was performed just below -120°C. Some observations were made on transformed samples which had been heated for 2 min at 340°C. It is assumed that the features of the martensite of these samples, Figs. 1 and 4, are the same as those of the as-quenched martensite. Orientation of the crystal by X-ray diffraction established 10.735 0.609 0.3161? as the axis of the crystal, an orientation that was checked within 2 deg by neutron diffraction. Further checks by electron diffraction of samples cut normal to the axis confirmed this orientation within the larger limits of error inherent in electron diffraction of thin foils. The X-ray orientation was the one used for the two-surface analysis of the martensite habit planes. A two-surface analysis was performed on the quadrant of the single crystal which had been oriented by both X-ray and neutron-diffraction techniques. Photomicrographs at X50 were made on two surfaces along an edge 2 cm long. Fiducial marks and the fact that many of the plates were almost completely surrounded by retained austenite made good matching of individual plates on two surfaces possible. The habit-plane trace on a surface was taken as the best line parallel to the long axis of a plate. A measure of the accuracy afforded by this criterion was provided by a family of very large plates which appeared at intervals along the entire 2 cm length of the edge. The plates all had habit-plane traces within 2 deg of one another. Many of the plates did not show midribs and, therefore, the use of midribs7 to represent habit-plane traces was not feasible in this investigation. The over-all experimental accuracy is estimated to be better than ±2 deg. Samples for transmission examination in a Siemens Elmiskop I at 100 kv were prepared by cutting 2-mm-thick discs from the single crystal, removing about 0.5 mm by chemical polishing,14 trans-

Jan 1, 1965

By Harry L. McNeill

The Selective Media Process was developed by the author in a laboratory provided by The Steams-Roger Manufacturing Co. It is the outcome of an investigation into the possibilities of coarse beneficiation by sink and float without using the conventional heavy media. Commercial work to date has been limited to the treatment of minus 3/8-in. iron ore at the Hill Trumbull washing plant of the Cleveland Clifis Iron Co., at Calumet, Minnesota. Two cut away prints of the machine are shown (Figs. I and 2). A rotary conical impeller is mounted within a stationary cone (Fig. 2). This impeller is adjustable vertically by a 12-ton screw jack. The speed of the impeller can be varied from 14 to 32 r.p.m. by the Reeves variable-speed motor pulley mounted on the 7½-hp. motor drive. Attached to the bottom of the stationary cone is the automatic control valve for sink product, actuated by a ¼-hp. gear motor. The sink product is dewatered in a conventional drag driven by a 7½-hp. motor and discharged onto an inclined conveyor containing from 6 to 10 per cent moisture. Two plants are operated at the Hill Trumbull property. All the ore is first treated in a typical washing plant (Fig. 3). when treating "wash ore" a finished concentrate can be produced by the log washers and Akins classifiers, as the separation involves only fine silica (minus 48-mesh) and free iron. However, when "jig ore" is led to the washing plant the coarse

Jan 1, 1947

By Harry L. McNeill

The Selective Media Process was developed by the author in a laboratory provided by The Steams-Roger Manufacturing Co. It is the outcome of an investigation into the possibilities of coarse beneficiation by sink and float without using the conventional heavy media. Commercial work to date has been limited to the treatment of minus 3/8-in. iron ore at the Hill Trumbull washing plant of the Cleveland Clifis Iron Co., at Calumet, Minnesota. Two cut away prints of the machine are shown (Figs. I and 2). A rotary conical impeller is mounted within a stationary cone (Fig. 2). This impeller is adjustable vertically by a 12-ton screw jack. The speed of the impeller can be varied from 14 to 32 r.p.m. by the Reeves variable-speed motor pulley mounted on the 7½-hp. motor drive. Attached to the bottom of the stationary cone is the automatic control valve for sink product, actuated by a ¼-hp. gear motor. The sink product is dewatered in a conventional drag driven by a 7½-hp. motor and discharged onto an inclined conveyor containing from 6 to 10 per cent moisture. Two plants are operated at the Hill Trumbull property. All the ore is first treated in a typical washing plant (Fig. 3). when treating "wash ore" a finished concentrate can be produced by the log washers and Akins classifiers, as the separation involves only fine silica (minus 48-mesh) and free iron. However, when "jig ore" is led to the washing plant the coarse

Jan 1, 1947

By J. L. Moriarty, Irving Johnson, H. M. Feder

The crystallization of ternary alloys has been studied as a coprecipitation phenomenon by measuring the substitutional carrying of trace metals with CeCd11 precipitating from liquid cadmium. The Doerner-Hoskins logarithmic distribution law has been found to apply in all cases; the coprecipitation coefficients obtained were: 1.48 (La), 1.06 (Th), 0.63 (Pr), 0.24 (Gd), 0.17 (Sm), 0.13 (U), 0.10 (Er), 0.09 (Sr). Li, Na, K, Ba, Y, Sc, and Zr were not measurably carried. It has been observed that coprecipitation was most extensive for those tracers which form with cadmium an intermetallic compmdnd isostructural with CeCd11 or closely related thereto. For these tracers an inverse relation between Solubility in cadmium and coprecipitation coefficient was noted. THE partition of impurities between the liquid and solid phases of a metal or a congruently melting intermetallic compound has been extensively studied by the methods of zone melting.' However, when the composition of a liquid alloy and of the solid phase crystallizing from it differ grossly, partition of an impurity cannot be investigated in this manner. Partition of the impurity under equilibrium conditions may be studied by investigation of the appropriate phase diagram and partition under nonequi-librium conditions may be studied by observation of coring in the solidified alloys.2 The nonequilibrium case is of special interest in metallurgical practice because many complex alloys are cooled too rapidly to permit the uniform diffusion of impurities throughout the crystallizing phase(s). With this in mind, the present study was undertaken to obtain quantitative data on the phenomenon of coprecipitation via substitutional solid solution in certain metallic systems. It will be noticed that rather than adopting metallurgical ter- minology we have chosen to refer to the partition of impurities during alloy crystallization as coprecipitation.3 In the terminology of coprecipitation the impurity is referred to as the tracer and the precipitating phase as the carrier. From aqueous solution, coprecipitation may occur as a result of adsorption on the surface of the carrier, by occlusion of the liquid within the crystals, or by solid solution of the tracer in the carrier. By slow cooling of liquid metallic solutions it is relatively easy to form large, regular crystals of the carrier; the effects of adsorption and occlusion may be minimized and the influence of substitutional solid-solution formation may be made to predominate. Previous studies of the crystallization of some intermetallic compounds4 and of copper, silver, and gold5 have shown that the coprecipitation or partition behavior of trace metals is entirely analogous to that observed in aqueous systems when ionic substitution occurs, e.g., coprecipitation of Ra++ with BaSo4. The precipitation of CeCd11 from liquid cadmium was chosen for study. This choice was influenced by the following consideration. If the relative atomic sizes of the tracer atom and the atom for which it substitutes determine the tendency to coprecipi-tate, then a lattice having a substitutional site of well-defined size would be desirable. In CeCd116 (structure type cubic BaHg117) the cerium atom is completely surrounded by a cage of twelve nearly equidistant cadmium atoms. Thus, atoms much larger or much smaller than cerium should be poorly accommodated in this cage. The choice of a lanthanide central atom allowed the testing of the size hypothesis with a number of lanthanide tracers which differed in size but not in valence or electro-negativity. EXPERIMENTAL The general technique of this investigation was to prepare a slightly undersaturated solution of carrier in liquid cadmium to which a tracer was added. The concentration of tracer was always so low that saturation over the entire temperature range investigated was never exceeded. The solution was cooled in a stepwise fashion. After each step a por-

Jan 1, 1964

By B. Ramaswami, U. F. Kocks, B. Chalmers

The latent hardening of silver and an Ag-Au alloy was investigated by lateral compression, overshoot in tension and cormpression, and the stability of multiple-slib orientations. The latent hardening of a secondary slip systenz depends on its relation to the primary slip system. For most secondary slip systems the latent hardening is larger for Ag-10 at. pct Au than for pure silver. The maximum increase in. flow stress on a secondary slip system over that of the primary slip system was 40 pct. The work hardening during the lateral-compression test on the latent system after prestress on the primary system is iuterbreted in terms of the preferential distribution of barriers to dislocation movement with respect to the active slip system in work-lzardened fcc crystals. The work-hardening in fcc crystals is mainly due to the dislocation interactions and the barriers to dislocation movement formed as a result of reactions between dislocations of different slip systems. The operation of sources on the latent system depends on the flow stress of those systems; hence, the increase in flow stress of a latent system due to glide on an active system, which is called latent hardening, is an important element in understanding the phenomenon of work hardening. The problem of latent hardening has attracted the attention of many investigators in the past. For example, a theoretical study of the elastic latent hardening of the latent systems due to glide on an operative system has been made by Haasen' and ~troh. These calculations, however, neglect the stress required for the intersection of forest dislocations by the glide dislocations, a factor which would be important for producing macroscopic strains on the secondary slip systems. The importance of this factor will become evident from the results presented here. Attempts have also been made to determine the latent hardening of different slip systems by experimental means by the methods summarized in Table I.3-9 The experimental methods used have been subject to certain limitations. For instance, in the method used by Hauser,9 frictional constraints between the specimen and the compression platen were not eliminated by proper lubrication (see Hos- ford10). Secondly, with the exception of Kocks,6 Hauser,9 and Rohm and Kochendorfer,11 latent-hardening studies have been made on only one of the slip systems, i.e., on either the conjugate or the coplanar slip system; hence, extensive results are not available on the latent hardening of different slip systems in the same materials, with the exception of aluminum.6 It was therefore decided to study the latent hardening of the conjugate, critical and half-related slip systems in silver. Similar experiments were done in Ag-10 at. pct Au to study the effect of solute (gold) on the latent hardening of silver. Lastly, indirect evidence can be obtained by a study of the orientation stability of crystals of multiple-slip orientations in tension and compression. This method has been used by Kocks6 to supplement his studies of latent hardening in aluminum. Similar studies were made at room temperature in single crystals of silver. EXPERIMENTAL PROCEDURE The single crystals of the desired orientations were grown and the tensile test specimens were prepared as described in Ref. 12. The compression tests were made on 1/4-in.-cube specimens. The specimens were cut from single crystals, in the Servomet spark-erosion machine.13 The two cut surfaces were planed using the lowest available planing rate in the machine to minimize the deformation layer. A brass strip was used as the planing tool. This method of preparation ensured plane parallel faces for the compression tests. The deformed material was removed by prolonged etching in a weak etching solution. A weak etching solution was used to prevent pitting of the surfaces and to ensure uniform etching. About 25 to 50 µ of material were removed from all faces by the etching treatment. The specimens were then annealed for 24 hr at 940°C in oxygen-free helium and cooled in the furnace to room temperature over a period of 7 hr. After annealing, the orientation of the specimens was determined by Laue back-reflection technique to make sure that no recrystallization had occurred on annealing. The compression-test technique and setup are described in Ref. 14. The Laue back-reflection technique was used to study the overshoot in tension, the overshoot in compression, and the stability of the axial orientation in tension and compression. The tests were interrupted after every few percent strain to determine the axial orientation. In investigating the overshoot in compression, the operative system was determined by studying the asterism of the Laue spots.

Jan 1, 1965

By J. M. McDowell

A study has been made to deter~r~irre how the behavior of a water drivee reservoir changes as a function of the permeability of the formation and as a function of the size of the aquifer. The effect of pressure maintenance programs on the rote of nat11rn1 water influx is also studied, (IS well as the influence on the influx of the position of water injection we1ls with reference to the oil-water contact. The results are determined by the use of an electrical reservoir analyzer and are plotted as families of curves of pressure, natural water influx, and water injection vs time or cumulalive production. Two size aquifers are studided. One is limited with a 36-inile radius, and the, other approximates an infinite reservoir. The field remains the same in all respects for the completed. study except that the permeability is changed to agree with that assumed for the aquifer. 1 N TR ODUCTI ON this study was undertaken in -dcr to determine how the pres- sure decline and water influx of a water drive field would change as a function of the rate of fluid withdrawals, as a function of the permeability of the formation, and as a function of the size of the aquifer. The effect of pressure maintenance programs on the rate of natural water influx was also studied as was the position of water injection wells with reference to the oil-water contact. The information has been determined by the use of an electrical reservoir analyzer1, sometimes referred to as a Carter type analyzer. This instrument is an analog type computer which can be set up to represent a water-drive oil field. It can reproduce the past performance of the field in terms of analogous electrical quantities when the proper circuit analog of resistors and condensers has been determined, also, it can determine the future behavior for any method of production which may be selected, or permit the comparison among several different methods. Although most applications of the reservoir analyzer"" have been to thc study of specific field performance, it is intended to use the analyzer here to help understand how various reservoir characteristics effect the final performance of the field and to sec under what conditions water injection will be of benefit and to what extent. Within the oil industry the performance of water-drive reservoirs was first described analytically by LV. Hurst' and M. Muskat2 for certain types of boundary conditions. The solutions of the equations developed involved products of exponential functions and Bessel functions. Later publications by Hurst4 and van Ever-clingen" and the hooks of Muskat6 gave further information on reservoirs with other boundary conditions. They also presented rather extensive curves and tables to help evaluate the analytical expressions involved. A rccent series of publications by Chatas. bascd on the work of Hurst and van Everdingen, gives quite complete charts and tables of data to evaluate the pressure decline or water influx in infinite or limited radial reservoirs. and in linear reservoirs. The curves in all of these publications are given in dimensionless form

Jan 1, 1956

By H. Y. Yancey, B. M. Bird

During the past four years the experimental work in coal washing carried on by the U. S. Bureau of Mines and the University of Washington has been devoted mainly to the development of special methods for the tabling of fine sizes of coals that are difficult to wash. One important outgrowth of this investigation has been the application of hindered-settling classification to coal tabling. Although used for many years in ore dressing, the term "classification" as used here may be new to many readers. It may be defined as the separation obtained when a bed of particles is held in a uniform state of suspension in an upward current of water, either continuous or pulsating, just sufficiently strong to keep the bed in a mobile condition. A common example of this type of separation is a jig in which there is no suction stroke. When the hindered-settling classifier is used with the coal-washing table, the fine-size raw coal, instead of being fed direct to tables, as is the prevailing practice, is first fed to the classifier and grouped, according to the rate of settling against the upward current of water, into perhaps six separate products. After dewatering, each of these except the sixth, a refuse product, is elevated to a seperate feed bin arid washed on a separate table. This paper gives a brief discussion of the basis for the use of hindered-settling classification of a table feed; a description of the experimental work; a comparison of the results obtained with and without classification; and a discussion of the application of the classifier in commercial coal washing. Basis for Use oF Hindered-settling Classification of Table Feed Although theoretical reasoning might be used to justify treating a table feed by hindered-settling classification,l the simplest method of demonstrating the need of such a step before tabling is to show the

Jan 1, 1930

By D. E. Coates, G. R. Purdy, S. V. Subramanian

The morphological stability of the planar solid-liquid interface in dilute ternary alloys, undergoing steady-state unidirectional solidification, is analyzed in terms of both the constitutional supercooling principle and the perturbation methods recently developed by Mullins and Sekerka. First, various steady-state solutions for the two solute distributions ahead of a planar interface are examined. The nature of the solutions depends on the size and concentration dependence of the off-diagonal diffusion coefficients. W~thin the framework of the constitutional supercooling principle, a cumulative contribution to instability frorn the two solutes is found to exist in the absence of diffusional interaction. It is shown that the latter can produce a further enhancement of instability or can have a stabilizing influence, depending on the form of the liquidus surface and on the sign of the solute-solute interaction. A perturbation analysis, which ignores diffusional interaction, verifies the cumulative influence of lhe solute fields and demonstrates that the Mullins-Sekerka stability criterion for binary systems (with capillarity accounted for) can be readily extended for application to ternary systems. SOME time ago, Tiller et al.' calculated the solute concentration distribution ahead of the planar solid-liquid interface of binary alloys undergoing steady-state unidirectional solidification. An earlier qualitative proposal that the transition from planar to nonplanar growth morphologies is associated solely with the onset of constitutional supercooling in the liquid layer ahead of the moving interface2 was used in conjunction with this calculation to put the now well-known constitutional supercooling (C-S) stability criterion into quantitative terms. Mullins and Sekerka,3 in a recent and very elegant analysis, established a more complete criterion (hereafter referred to as the M-S criterion). Interfacial stability was investigated by determining the time derivative of the amplitude of a sinusoidal perturbation of infinitesimal amplitude which had been introduced into the originally planar shape of the moving interface. Of particular importance is the fact that capillarity was included in the boundary conditions of their calculation. The purpose of the present paper is to extend all of this earlier work on dilute binary systems for application to dilute ternary alloy solidification. The analysis is divided into three sections. In the first the two solute distributions ahead of a moving planar interface are considered. Mathematical solutions are de- termined for situations in which: a) diffusional interaction is negligible, 6) diffusional interaction must be considered but circumstances permit use of constant diffusion coefficients, and c) the concentration dependence of off-diagonal diffusion coefficients can be described by first-order dilute solution approximations. In the next section, a stability criterion analogous to the C-S criterion is developed and the influence of diffusional interaction on interface stability is analyzed. Finally, the perturbation formalism of Mullins and Sekerka, with capillarity included in the boundary conditions, is extended for analysis of ternary systems in which diffusional interaction is negligible. The study of interface stability in binary systems usually commences with the assumption that the equilibrium distribution coefficient and the slope of the liquidus line are constant at values corresponding to infinite dilution. Similar assumptions have not been introduced into the present treatment; that is, we do not assume planar solidus and liquidus surfaces joined by tie lines which yield constant distribution coefficients. The latter involves the assumption of no ther-modynamic interaction between solute species in both the solid and liquid. We consider a ternary phase diagram for which the solidus and liquidus surfaces are, in general, nonplanar and of course pass through the corresponding binary solidus and liquidus lines. These lines are not assumed to have constant slope. In the dilute regions we are concerned with, the following assumptions are made: i) The solidus and liquidus surfaces are of a form such that both the solidus and liquidus temperatures are monotonically varying functions of each solute concentration. ii) The tie lines are such that the equilibrium distribution coefficient of a given solute is greater than unity for every point on the solidus (or liquidus) surface or it is less than unity for every point. STEADY-STATE SOLUTE DISTRIBUTIONS IN THE LIQUID As will be demonstrated in the next section, a knowledge of the steady-state solute profiles is not a necessary prerequisite for the formulation of a ternary C-S stability criterion. However, in that details, such as the complete description of the equilibrium liquidus temperature profile, require an evaluation of the solute distributions, the overall treatment is enhanced if these distributions are determined. Consider a ternary system (solvent plus solutes 1 and 2) for which a planar solid-liquid interface is in unidirectional motion at constant velocity V. At this stage it is unnecessary to limit ourselves to dilute solutions. For a stationary frame of reference the generalized forms of Fick's equations are:

Jan 1, 1969

By B. C. Craft

The principal events in the oil and gas operations for Louisiana during 1933 have been the rapid development of the Converse field in Sabine Parish, the discovery of three new salt domes, one in North Louisiana and two in South Louisiana, increased development in the Iowa field on the Calcasieu-Jefferson Davis Parish line, and extensive geophysical operations over a wide territory. Other miscellaneous events worthy of mention are the continued leasing of prospective oil lands over a wide area, extension of production at the East Hackberry field, Cameron Parish, discovery of deep sands at Caillou Island, Terrebonne Parish, and the completion of several important wildcats. Despite proration, oil production showed a substantial increase during 1933. The total output for this area was 25,599,802 bbl. as compared with 22,507,387 bbl. during 1932. North Louisiana There were 111 oil wells and 47 gas wells completed in North Louisiana during 1933 as compared with 109 oil wells and 33 gas wells during 1932. North Louisiana oil production decreased approximately 692,625 bbl. in 1933 from its 1932 figure. The normal decline in the old fields was partly offset by increased production at the Zwolle and Converse fields in Sabine Parish. Acid treatment of wells in the Zwolle, Converse and Monroe fields was highly successful. The method of application has been described by H. K. Shearer, Geologist, Pelican Natural Gas Co., as fo1lows:l With tubing in the hole and standing valve removed, the casing is filled with oil to the surface. The limestone solvent is pumped in through the tubing, at the same time bleeding off enough oil from the casinghead to equal the volume contained in the tubing plus the volume of open hole to be treated. The amount of solvent used in most of the wells treated was 1000 gal., which is enough to dissolve about 11 cu. ft. of chalk or limestone. After the computed amount of oil is bled off, the casinghead is closed and the remainder of the solvent is pumped in at whatever pressure is necessary to force it into the oil-producing horizon. The solvent is followed up with enough oil to

Jan 1, 1934

By W. T. Thom

Interest naturally attaches to fissuring and subsidence of the earth's surface, whatever the cause may be, and the induced movement and fissuring of the impervious strata overlying an oil sand is of even greater practical importance because of its bearing upon the recoverability of the portion of the oil not already extracted or extractable by ordinary production methods. It is probably true that significant ground movement induced by oil production occurs only in oil fields in relatively young formations, where the oil comes from incoherent or only slightly cemented sands and oil-soaked clays, but inasmuch as a great proportion of our "gusher" wells produce from "running" sands and yield a large part of the total oil output, it seems worth while to make an effort to inspire the collection and recording of data indicating the nature and magnitude of oil-field subsidence, both surface and subsurface. Goose Creek Field The single known instance in which the nature and magnitude of the surface subsidence incident to petroleum withdrawal has been accurately ascertained is that in the Goose Creek oil field of Texas, described by Pratt and Johnson.' There subsidence caused the submergence of a considerable area within the oil field, and, because the title to the naturally submerged lands of Texas rests in the State, it became necessary to determine whether the submergence was due to natural or artificial causes. A detailed study revealed that the sunken area conformed very closely to the limits of the productive oil field and that the cumulative depression over an eight-year period ranged from zero at the margin to 3.25 ft. at the center. This depression was accompanied by the development of local marginal surface fractures along which the subsiding ares

Jan 1, 1927