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By Lawrence Addicks

THrough the courtesy of Dr. James Douglas I am permitted to give a summary of some of the results obtained in leaching slimes tailings in a series of experiments conducted under my direction at Douglas, Ariz., during the past year. While the test run for which the data are given deals with a particular case, much of the work is general in its application and may therefore be of interest. This work was done upon the ores of the Burro Mountain Copper CO. A description of the geology of the district will be found in the paper by R. E. Somers published in this volume, p. 604. The mineral is pyrite and chalcocite very finely disseminated throughout the gangue and a characteristic of all the ores is the large amount of alumina present. A representative analysis of the particular ore under consideration would be about as follows: Cu, per cent..................... 2.35 S, per cent...................... 3.0 Ag, ounces per ton.............. 0.05 CaO, per cent.................. 0.5 Au............................ None K2O, per cent.................... 4.0 Fe, per cent..................... 1.50 SiO², per cent.................... 70.0 Alz²O³, per cent....................13.OO The leaching of the ore direct was early dismissed from consideration for the following reasons: 1. The ore would have to be quite finely crushed to liberate the mineral for leaching; concentrating after crushing would cost but a few cents a ton; and a higher total reeovery would result from leaching tailings rather than ore. 2. Rough concentration would yield a suitable material for roasting to make sulphur dioxide or sulphuric acid in connection with the leaching scheme. 3. Such a program put the question of cost vs. recovery on a basis where flotation and discarding of tailings were directly comparable. Concentrating experiments already available indicated that the tail-

Jan 1, 1916

By Seymour G. Epstein

Using a modified capillary-reservoir technique, electromigration of dilute solutions of silver in liquid bismuth has been measured with relatively good precision. The effects of experiment duration, temperature. current density, and silver concentration have been investigated. Chemical diffusion coefficients of silver in liquid bismuth were also measured at temperatures ranging from 300°to 600°C. The effective valence of silver in bismuth was calculated as a function of temperature from a comparison of electric mobilities and diffusion coefficients. In an alloy containing 1 wt pct Ag, the electric mobility of silver increased from 1.65 x X sq cm per v-sec at 300°C to 2.38 x 10-4at 600°C; the diffusion coefficient in-creased from 3.0 to 17.5 x 10-5 sq cm per sec over the same temperature range. Calculated values of effective valence decreased from 0.28 at 300°C to 0.10 at 600°c. ALTHOUGH there has been considerable progress in the theoretical treatment of electron-transport properties in liquid metals, the mechanisms of mass-transport phenomena in liquid metals are still not clearly understood. This is especially true for the case of electro migration, alternatively termed elec-trotransport or electrodiffusion, which is mass transport induced by an applied electric field. A thorough knowledge of the mechanisms governing electromigration will considerably aid in understanding the electronic state of an impurity atom in a liquid metal. Electromigration has been long observed and studied in liquid metals and alloys. However, no satisfactory theory to explain the observed effects has been developed. The disparity in the present theoretical treatments, summarized by Verhoeven,1 has been attributed to the difficulty in describing the momentum transfer between electrons and ions and to the lack of precise measurements in liquid metals, especially at elevated temperatures. Prior to the last decade most of the electromigration studies were qualitative, in that only the direction of migration of alloy constituents was determined with any degree of reliability. These results have been summarized by schwarz,2 who was able to measure the electric mobility of several elements in mercury. More recently electromigration in liquid metals has been measured by a variety of techniques, with a varying degree of success. Mangelsdorf3,4 made precise measurements on dilute amalgams at room temperature, using a technique relating changes in composition to changes in alloy resistivity, but was unable to make measurements at elevated temperatures. Using a modification of this technique, Verhoeven and Hucke5 measured electromigration and resistivities in liquid Bi-Sn alloys. However, the resistivity technique is not sensitive to small composition changes and is impractical for very dilute alloys. Verhoeven and Hucke6 also measured electromigration of several solutes in liquid bismuth by adapting the capillary-reservoir method for determining diffusion coefficients in liquids. The reported precision of these measurements was poor, however, primarily due to the large uncertainties in the chemical analyses to determine concentration changes. Belashchenko7 has summarized the recent Russian investigations of electromigration, many of which, however, are of questionable accuracy. The present study was initiated to develop an experimental technique which would be both versatile and sufficiently sensitive to yield precise measurements of electromigration of solutes in dilute metal alloys at elevated temperatures. Using this technique, a comprehensive study of silver in liquid bismuth was made to determine the effects of experimental variables on the apparent electric mobilities. Chemical diffusion coefficients of silver in liquid bismuth were also measured over the same temperature range for comparison with the electromigration data. EXPERIMENTAL TECHNIQUE Electromigration Measurements. Electromigration of silver in liquid bismuth was measured by the capillary-reservoir technique, similar to that used by Verhoeven and Hucke,6 but modified to yield more

Jan 1, 1967

By H. Siebert, G. Raitt

With the advent of the Interstate Highway Pro- gram, many problems have been encountered in the application of highway design standards to topography, particularly rock cut design. A rigid application of slope ratios with little respect to rock type, dip, foliation, structure and height of cut face is a problem. Generally a slope ratio of ½ : 1 or 63º for shallow cuts and 1/3: 1 or 71º in deeper cuts are used in Connecticut. The deepest cut face constructed recently was greater than 185 ft. With cuts of this size, rock fall and stability become a problem, and a way to reduce the problem is to construct a stable face initially. A search of the literature indicates that adequate information on the construction of stable rock slopes is not available. A major highway contract was awarded in 1962 to Savin Brothers, Inc., in which line drilling on 6-in. centers was required in many portions of the contract where the cut was greater than 60 ft and one or more benches were to be constructed. From the start of the project many variations were attempted regarding slope hole spacing and distribution of explosives in the holes. Rock ranged from a competent granitic gneiss to an incompetent soft graphitic schist. Generally, the roadway alignment was roughly normal to the strike of the foliation having a dip of ± 60º. An important factor affecting construction of rock slopes was the existence of intersecting joints and faults. The spacing used in less competent rock was about one ft on center. Loading of holes was purposely varied. As competency of the rock increased, hole spacing was also increased. Thus, on a different project in similar rock, spacing was kept at 4 ft.

Jan 4, 1966

By J. L. Rodda, M. L. Fuller

In connection with an investigation in this laboratory on the high-zinc side of the copper-zinc system, it was observed that well developed segregate structures of the Widmansttten type were formed when a secondary phase precipitated from the solid solution of copper in zinc. This paper presents an analysis of the crystallographic relationship between the segregate and the solid solution matrix. The data to be presented are an interesting addition to the literature on segregate structures in that the plane of segregation is one of the less densely populated planes. In agreement with the generalization of C. H. Mathewson and D. W. Smith' the plane of segregation in the matrix contains the direction of closest atomic packing of the lattice. Furthermore, the matrix and the segregate are both hexagonal close-packed, which has not been reported hitherto in the 1iternture.l The increasing commercial importance of zinc alloys containing copper makes this fundamental study of value to the metallography of zinc alloys. Zinoeich Copper-zinc Alloys Copper enters into solid solution with zinc to at least 1.8 per cent at 400" C., according to W. M. Peirce.3 The solubility is less at lower temperatures. Thus a solid solution of copper in zinc, saturated at an elevated temperature, will precipitate the excess copper in a separate phase at a lower temperature, conditions of concentration, time, and temperature being suitable. The nature of these two phases has been established by the X-ray method of crystal analysis. Westgren and Phmgmén4 and also Owen and Preston5 have shown that the solid solution eta (7) is of the substitu-tional type with copper atoms replacing zinc atoms on the hexagonal

Jan 1, 1933

By G. C. Bernard, L. W. Bernard, L. W. Holm, W. L. Jacobs

The effect of loam on the permeability of porous media to water was studied as a {unction of foaming agent concentration, specific permeability, pressure gradient, length of a porous medium and its oil saturation. At a given fluid saturation in a porous medium, the permeability to water was found to be the same whether loam was present or not. Foam decreases the permeability to water by developing a higher trapped gas saturation than that obtained by water flooding without loam present, increasing the concentration of foaming agent increased the trapped gas saturation and thereby decreased the permeability to water. The presence of oil reduced the capability of most foaming agents to decrease the permeability of a porous medium to water. A few surfactants were found to be effective loaming agents even in the presence of oil. These results are similar to those reported in a previous paper on the effect of loam on the permeability of porous media to gas. The effect of loam was found to persist in long porous media at moderately high reservoir temperatures and during the passage of many pore volumes of surfactant-free water. INTRODUCTION This paper describes part of a study on a novel approach in the use of surfactants for oil recovery; the use of foam rather than water to displace oil. Previously it was found that foam can displace oil which normally is not displaced by water.4 The foam is formed by successively injecting a suitable surfactant solution and gas into a porous medium. Foam appears to have at least two uses in the field: (1) it shows promise as a superior oil recovery agent, and (2) it shows promise as a selective permeability reducing agent. Foam may be very useful in water floods, or in other oil recovery processes, where highly permeable streaks or unfavorable mobility ratios are a problem. A previous paper reported the effect of foam on the permeability of porous media to gas.1 In the present study the effect of foam on the permeability of porous media to water is reported. The specific objectives of the study were to determine: (1) the effect of foam on the permeability to water in porous media of various specific permeabilities, (2) the effect of foam on the permeability to water in the presence of oil, (3) the effect of foam and crude oil on the trapped gas saturation, (4) the effect of foam on permeability to water at trapped gas saturation, (5) the effect of pressure gradient on the permeability to water under foaming conditions, (6) the persistence of foam during the passage of surfactant-free water through the porous medium, and (7) the effect of various foaming agents, length of the porous medium and temperature on the permeability reduction caused by foam. EXPERIMENTAL PROCEDURES EQUIPMENT AND MATERIALS The experimental apparatus consisted of consolidated and unco n soli dated porous media, wet test meters and constant delivery pumps. The porous media consisted of consolidated sandstone cores (6 to 36 in. long), and unconsolidated sand packs (3 to 30 ft long). The consolidated cores had permeabilities of 32 and 1,000 md and porosities of about 20 per cent. The sand packs had permeabilities of 3,500 to 211,000 md and porosities of about 40 per cent. (Throughout this report a term such as 100 md sand" is used. This term means that the porous medium had a dry, nitrogen permeability of 100 md.) Fluids used in the experiments were distilled water, 1 per cent NaCl solution, aqueous solutions of foaming agents, nitrogen gas, air and crude oil.

Jan 1, 1966

By Nicholas J. Grant, H. C. Chang

Microscopic observations during creep tests were made on AI-20 pet Zn, 80 pet Ni-20 pet Cr, and 25 and 3S aluminum specimens. All these materials failed in an inter-crystalline manner under certain stress and temperature conditions. Particular atten-tion was given to the initiation and propagation of intercrystalline cracks in coarsegrained AI-20 pct Zn specimens. The geometry of the grains and grain boundaries in these specimens was known before the tests. On the basis of the observations and a knowledge of the interaction between grains and grain boundaries, a mechanism of intercrystalline fracture and propagation of the fracture has been proposed. METAL, and alloy fracture occurs essentially in two ways: transcrystalline and intemrystalline. In the past most of the work done in this field was centered on the determination of stress criteria for fracture. The specimens used for these studies were tested under varying conditions of stress state, temperature, and strain rate. Unfortunately, very little attention was given to the initiation and propagation of the fracture, whereas the nature of fracture was examined closely only after failure. Several extensive reviews of these studies have been published by Orowan, Smith, Barrett, and Petch.1, 4 It is well known that a material which exhibits a ductile and transcrystalline fracture can be made to exhibit a brittle and intercrystalline fracture by modifying its composition and by heat treatment. This modification may or may not result in microscopically observable precipitation in the grain boundaries." In the creep of any one alloy the transition of transcrystalline to intercrystalline fracture is a function of stress, strain rate, and temperature." The tendency for intercrystalline fracture to occur increases as the strain rate decreases and the testing temperature increases. Extensive work on high purity aluminum (99.995 pet) under creep conditions showed the importance of the interaction between grains and grain boundaries, and the different responses of grain and grain boundaries to the variables: stress, strain rate, and temperature.7, 8 It was also shown that grain boundary deformation necessarily has to be accommodated in the grains by various deformation means as. for example, fold formation. The type of fracture resulting from the creep of high purity aluminum was invariably found to be transcrystalline. On the other hand, 2S and 3s aluminum were, under certain conditions, found to fracture in an intercrystalline manner." One reason given for this was that the grains could accommodate to a lesser extent the deformation of the grain boundaries.19 It was decided to examine this line of reasoning in greater detail and to investigate the particular interactions between grains and grain boundaries that result in the incidence and progression of inter-ct,ystalline fracture. It is also the purpose of this paper to show where and how intercrystalline cracks start and how they propagate to result in fracture. Several alloys—Al-20 pct Zn, 80 pet Ni-20 pet Cr, 2S and 3s aluminum-— were used for this study, but attention was paid mainly to the behavior of an A1-20 pet Zn alloy, since its general creep behavior has been established." From the results of this study a mechanism of intercrystalline fracture is proposed. Experimental Procedure The experimental procedure was similar to that used in previous work and has been detailed elsewhere.' Two parallel flat surfaces were milled from an originally round specimen, giving a gage portion which was 1x0.09X0.17 in. Some round specimens, 1/4 in. round by 1 in., were also tested. The A1-20 pet Zn specimens. which were annealed at 1030°F for 24 hr, showed two to four grains across the width of the test bar, and most of the grains occupied the whole thickness of the specimenu. Before some of the specimens were subjected to creep, the grain arrangement was mapped out in a development drawing, Fig. 1. The initiation and

Jan 1, 1957

By S. Katz, M. E. Nicholson, J. J. Kelly, D. R. Curran

A series of wedges of 1020 steel (2 1/2 by 6 by 8 in.) were explosively loaded, as shown in Fig. 1. A slab of explosive on the surface of the steel wedge was initiated simultaneously along one edge, producing an essentially two-dimensional oblique shock in the metal. Pressure and density in the metal were measured as a function of distance from the explosive-metal interface by a method described elsewhere.' While for pressures below 130 .kbars the technique produces accurate results, for greater pressures the presence of two shock waves in the metalzy3 makes interpretation of the data uncertain. However, the location of the transition in pressure at 130 kbars can be readily identified from the data. The assumption of a single shock in the region above 130 kbars overestimates the pressure computed on a multiple-shock model. After firing, the wedges were sectioned, lapped, and etched with 2 pct Nital. A photograph of an etched specimen is shown in Fig. 2. The specimens were examined metallographically. The dark region, at the top of the specimen, was heavily banded, Fig. 3, while the lighter area was comparatively free from banding, Fig. 4, the boundary between the two regions being quite abrupt. The very light regions at an angle of about 45 deg to the explosive-metal interface show virtually no banding. The origin of these light regions, which are not Luder's bands, is not yet explained. The thickness of the heavily banded area was measured and compared with the pressure at the boundary between the heavily and lightly banded regions. The results of these measurements and calculations are given in Table I. For all shots, the pressure at the boundary is approximately the same

Jan 1, 1960

By K. Thirumalai

Although the term "spalling" has long been known, Norton l first referred to its usage for the fracture or disintegration of materials subjected to rapid temperature changes. Spalling of ceramic materials at high temperatures has received attention in the past.2-4 Removal of the char formed during ablation in reentry of space vehicles has been referred to as mechanical spalling.5 The first experiments to evaluate the process of rock fragmentation by thermal spalling were conducted by Stoces6 using a series of gasoline burners on the quartz veins of the Zinnwald deep mines in Germany. After the development of rocket-jet burners, the principles of thermal spalling combined with high fluid momentum found wide practical application in rocks. The well-known jet piercing process for drilling blastholes in taconite and for jet channeling in the quarrying of granite are among the more notable of these application.7 For the purposes of this study, thermal spalling or spallation of rocks is defined as progressive failure caused by thermal stresses induced by a sudden application of heat from a high temperature heat source. Gray observes that the size of the spall is dependent on the pattern of induced thermal stresses before failure. The spallability or the relative susceptibility of rocks to failure by thermal spalling is a complex but potentially useful parameter for qualitative comparisons. Fundamental differences exist in the degree of spallability among different types of rocks. Accurate prediction of spallability of any particular rock has so far not been possible. Measurement of the state of stress and temperature in the rock during the rapid thermal spalling process poses difficult problems that must be solved. Identifying the parameters that influence the thermal spalling proc-

Jan 1, 1970

By Eugene A. Stephenson

Critical analyses of the work expended in producing oil by the utilization of gas energy have appeared in the publications of Shaw,' Pierce and LewisI2 and Herold,3 authors who have ably discussed the factors which must be taken into consideration in comparing energy consumed per barrel in various wells which are flowed by means of gas-lift. However, two distinct phases of oil production are concerned with the ratio of gas energy consumed to oil produced. One of these phases is the gas-lift, which utilizes the differential gas pressures for the purpose of flowing oil, whether these pressures be natural reservoir pressures or be induced by artificial compression of gas or air. The other phase has to do with prorating oil production in pools which are operated either as units, or are subject to such restrictions as those imposed at Oklahoma City by the Corporation Commission, or by similar controlling groups in other fields. An abundance of literature is available relative to the problems of flowing wells by gas-lift, but the first suggestion that the energy of the gas within the oil and gas pool might serve as a basis for proration, appeared in the timely article by Mc Williams.4 Much of the dissatisfaction with proration in certain fields arises because some operators feel that besides the hazard to the wells which accompanies the test, the method of allocating production on the basis of the " potential" gage is inequitable and gives some operators a distinct advantage over others.5 The most severe penalty may be exacted from the most progressive operators or those who attempt to produce their oil with a minimum quantity of reservoir gas. If no difficulties ever developed in drilling, shutting off water, or in well completion, it might

Jan 1, 1931

By Charles W. Bauer

Most of the aluminum produced in the United States today is derived from foreign bauxite deposits. Earth Sciences, Inc. initiated a program to evaluate domestic non bauxite sources for alumina in the 1960's. In the initial evaluation of alunite, domestic resources were not sufficient to support development. An exploration program led to the discovery of large deposits of alunite in Utah and several other western states. Identification of alunite is difficult as both its physical and chemical characteristics are similar to the minerals with which it is associated. Most of the significant alunite deposits in the western United States are replacement type deposits. These deposits have formed as a result of hydrothermal alteration of volcanic, sub-volcanic, and igneous rocks. Typical alunite deposits contain between 30 and 50% alunite and 50 and 70% quartz, with minor amounts of other minerals. Four mineralogical zones are common in these systems. They include a siliceous zone, a quartz-alunite zone, a kaolinite zone, and a chlorite-montmorillonite zone. Total US reserves of alunite were estimated at 20 Mt fat 30% alunite) by the US Bureau of Mines in 1941. More recent work by the US Geological Survey estimates reserves of 252 Mt and potential resources at 1.4 Gt. Reserves and resources estimated for 23 properties on which field work has been done by ESI are considerably higher. Most of these properties have reserves and potential resources of several hundred million metric tons. The combined demonstrated reserves of these properties are estimated to be about 650 Mt. Inferred reserves are estimated at 2.5 Gt and potential resources at 8 Gt. It appears that the US has sufficient reserves and resources for alunite to be considered as a potential nonbauxite source of alumina.

Jan 1, 1982

By A. S. Eve

This paper gives a brief summary of theory on radiation waves and describes experiments by the United States Bureau of Mines and by the Canadian Geological Survey at the Mammoth Cave, Kentucky. Dr. D. A. Keys, Dr. F. W. Lee and the writer did the experimental work, and Dr. L. V. King some of the theoretical work. In prospecting for orebodies underground it is a usual practice to employ a loop of wire carrying an alternating current that induces an electromotive force in good conductors beneath the earth. The conduc-tars are usually of such low resistance and impedance that currents of considerable magnitude may result in these orebodies or conductors, and these currents in turn induce an electromotive force in a detecting coil placed near the surface of the ground. By using amplifiers it is possible so to enhance the effect of this electromotive force in the detecting coil that the currents in the underground conductors are detected in spite of the powerful effects coming directly to the coil from the primary loop. In such cases distance or depth has primary importance, for the effects have to pass down to the orebody and the secondary effects induced therein have again to pass back through the ground to the observer's detection coil on the surface. However, there is another factor to consider—absorption of the electromagnetic disturbances by the intervening soils and rocks. This absorption will vary with their composition. Thus the main factors that determine the possibility of detecting ore underground are: 1. Its depth beneath the surface, 2. The magnitude of the conducting orebody, 3. The excellence of the conductivity of the orebody as compared with that of the surrounding strata, 4. The frequency of the alternating current,

Jan 1, 1932

By S. F. Ramseyer, E. A. Steigerwald

INFILTRATED structures represent composite materials which are capable of combining high-temperature strength with adequate low-temperature toughness and thermal shock resistance. Although copper- and silver-infiltrated tungsten structures are actually being used in rocket nozzle hardware, adequate understanding of the fracture mechanics of these composite systems is not available. Specifically the relative importance of the strength, ductility, and modulus of the infiltrant in determining composite properties is not known to the extent that optimum composites can be selected. The major portion of experimental effort in the area of composite strength has been devoted to fiber-reinforced systems1 or to systems where a discontinuous phase is imbedded in a relatively ductile matrix.2'3 In the case of high-temperature systems, which are composed of a relatively brittle matrix, such as tungsten or an oxide, a continuous phase exists for the propagation of a crack. The method by which the presence of a conjugate ductile continuous phase influences the gross properties of the composite represents an area which requires further investigation. This technical note presents results which evaluate the effect of infiltrant strength on the strength of the tungsten-base composite. A tungsten matrix and copper-base infiltrant were selected for the initial studies because of the ease of fabrication. Tungsten structures with nominally 20 and 30 pct porosity were evaluated. The porosity was controlled by varying the initial powder size and a ratio of open-to-total porosity greater than 95 pct was obtained by selective sintering cycles. The processing sequence involved hydrostatic pressing followed by a 72-hr presinter in hydrogen at 2000° F and a final sinter at 4000°F for 4 hr in vacuum. The 20 pct porous structure was obtained

Jan 1, 1965

By Courtenay de Kalb

The Exposed Treasure gold-mine has, for the past four years, been one of the largest producing mines of Southern California, its annual output havirig con~tituted I per cent. of the total gold and silver production of the entire State. At the present moment the property is idle, owing to the large quantity of water encountered on the lower levels, which will require the installation of a powerful pumping-plant before operations call be recommenced. Moreover, a prompt change in the character of the ore has occurred at water-level, which makes imperative an extensive campaign of development in the region of the un-oxidized ores before a plant adapted to their treatment call be definitely decided upon. The character of the changes encountered in these deeper ores makes the geology of this deposit a matter of importance, riot only for the immediate district, but for the desert region of Southern California in general, where many mines exist having in the oxidized belt conditions that, in many respects, resemble those in the Exposed Treasure mine. The deposit is situated in an apparently isolated butte about 2.5 miles south from the town of Mojave, on the Mojave desert. The butte, though apparently isolated, is in Fact geologicallg part of an extinct volcano, known as Soledad butte, which rises out of the plain 1.5 miles SW. of' the mine, to an altitude of 4,650 ft. above sea-level. Other buttes also rise from the desert plain toward the south and east, and again to the westward, all being closely related geologically to Soledad butte,—the whole constituting a single system as to origin and time. Since the end of the period of active volcanism in this region, there has been extensive denudation, the ancient plateau having been dissected during an epoch of apparently exces-

Jan 1, 1908

By J. J. Gilvarry

Recently, Gilvarry1,2 has given a rigorous derivation of the proper distribution function for fragment size in single fracture, based on a closely defined physical model and deduced strictly by the laws of probability. The physical point of departure is Griffith's theory of brittle strength, identifying sub-microscopic flaws as the cause of the low strength of a solid in comparison with values implied by cohesive energies. Gilvarry and Bergstrom,4-7 and Gilvarry8 have compared the predictions of the theory with experiment, and have found excellent agreement, in general. The purpose of this communication is to sketch the extension of the theory to the case of comminution, and to indicate the applications to some examples in nature. The present treatment represents an amplification of a brief discussion appearing elsewhere. 9 Although the basic ideas of the Griffith theory are perfectly general for rupture of brittle solids, it was originally formulated with very brittle materials such as glass in mind. Moreover, Griffith's original experimental work was carried out on glass specimens. Recently, however, the theory has been extended by race" to apply directly to rocks. This extension makes the theory immediately applicable to the materials generally of interest from the standpoint of comminution. GENERAL CASE To obtain the distribution function for fragment size in single fracture, three assumptions are made, that: 1) Fracture proceeds by activation of preex-istent Griffith flaws in the volume, faces, and edges of a fragment; 2) the distributions of flaws of these three types are independent of each other; and 3) activated flaws of a particular type are distributed at random, individually and collectively, in the sense of Fry.11 The last assumption implies that each distribution is separately of Poisson type.

Jan 1, 1964

By B. D. Cullity, J. T. Norton, M. Telkes

THIS investigation of antimony-selenium alloys was undertaken in an attempt to find a suitable material for use in power-generating thermocouples. The chief requirements for such a material are high thermoelectric power, low electrical resistivity and low thermal conductivity. Measurements of the first two properties mentioned are usually sufficient to determine whether or not a material is suitable for use in a thermoelectric generator. As a first approximation the requirements are: 1. Thermoelectric power greater than 200 microvolts per °C. 2. Electrical resistivity less than 0.002 ohm-cm. 3. Thermal conductivity less than 0.015 watt per cm per "C. These quantities are averages for the Operating temperature range. Previous Work Experimental investigations of equilibrium in the antimony - selenium system have been summarized by Han-sen². These investigations extended from 1906 to 1921. In Hansen's judgment, the most accurate phase diagram is that determined by Parravano, in 1913 and this is reproduced in the upper part of fig. 1. The most notable parts of this diagram are the liquid miscilibility gap, extending from about 12 to 36 wt pct selenium, and the intermediate phase Sb2Se3 containing 49.3 wt pct selenium. The crystal structure of Sb2Se3 has not been determined. Pelabon3,4 made measurements of the electrical resistivity of a few antimony-selenium alloys but his investigation was not very complete. He found that the resistivity increased with the selenium content and became very large as the composition of Sb2Se3 was approached. For alloys containing less than 50 at. pct (39.3 wt pet) selenium, he found that the resistivity increased regularly with temperature. For alloys containing larger amounts of selenium, he found various results: in some cases, the resistivity decreased with increas-

Jan 1, 1951

By Matti J. Saarivirta

The relative machinabilities of the precipitation-hardenable Cu-0.9 pct Cr, Cu-0.25 pct Zr, and Cu-0.9 pct Cr-0.25 pct Zr alloys are improved from 18 to 80 pct by 0.75 to 1.25 pct Pb. The Lead also improves the tensile strength, hardness, ad resistance to softening of the Cu-Cr and Cu-Cr-Zr alloys. When the alloy containing 0.7 to 2.2 pct Cr, 0.10 to 0.25 pct Zr, 0.75 to 1.25 pct Pb, and balance copper is solution-annealed at 1000°C (1830°F) and then aged at 525°C (Y75°F), tensile strength of 65,000 psi, 16 pct elongation, 62Rb hardness, and 84 to 87pct IACS electrical conductivity are obtained. The copper base Cu-Cr, Cu-Zr, and Cu-Cr-Zr alloys have high electrical and thermal conductivities, high strength and resistance to softening at elevated temperatures, but their machinability is poor, i.e., close to that of the pure copper. In the manufacture of various components such as welding electrodes or electrical and thermal conductors it is ofter desirable that the alloy have good machinability for high production rates and long tool life. Thus, alloys that combine these properties may be used not only for existing applications, but for new ones where good machinability is a requirement. This investigation was undertaken to improve machinability without impairing other desirable characteristics of the Cu-Cr, Cu-Zr, and Cu-Cr-Zr alloys. These commercial alloys contain about 0.4 to 1.2 pct Cr, 0.10 to 0.25 pct Zr, and balance copper. Lead was selected as an element that should improve the machinability and possibly other characteristics of the alloy. WORK PROCEDURE This investigation began with a study of the effect of lead on the hardness, tensile strength, electrical conductivity, and machinability of the binary alloy containing 0.10 to 1.30 pct Cr and balance copper. This was followed by an investigation of the effect of lead on the Cu-0.1 to 0.4 pct Zr and Cu-Cr-Zr alloys. The alloys were made from initially oxygen-free copper and for comparison some castings were made from phosphorus-deoxidized Lake Copper. Commercially pure chromium, zirconium, and lead were used for alloying. In melting the chromium was added to molten copper at 1400°C (2550°F), the heat held for 15 min at temperature, and the temperature then lowered to 1350°C (2460°F) when the other elements were added. The alloys were held for 15 min at this temperature and cast into a cast-iron mold. One-kilogram, 3-in.-diam castings were made. An argon cover was maintained during melting and casting to prevent oxidation. The chemical compositions of the alloys are shown in Table I. The micro structure and properties of the alloys were studied in the cast and wrought conditions prior to and after various solution-annealing and heat-treating cycles. The relative machinability was determined as a function of the lead content and compared with the free-machining Cu-lpct Pb alloy. To determine the machinability, 13/16-in.-diam cast specimens were cut by a machine hack saw using a constant cutting speed of 50 fpm, a fixed feed force, and a new blade for each alloy specimen. Molybdenum highspeed steel saw blades, 0.032 in. thick with 14 teeth per in., were used in all tests. No cutting fluid was used. Five tests were made on each specimen and the average elapsed time per test was taken as a measure of the relative machinability for that alloy. The variation of cutting time for each alloy was less than 110 pct.

Jan 1, 1969

By Walter Crafts, D. C. Hilty

The liquidus diagram for the iron field of the Fe-S-O system has been derived experimentally. The solubility of oxygen in molten Fe-S alloys has been measured at several temperatures and found first to decrease slightly and then increase rapidly with increasing sulphur content. IT is well-known that the types, distribution, and amount of inclusions in any given steel are closely allied with the oxygen and sulphur contents of the metal, so that the term "deoxidation" as conventionally applied in steelmaking refers not only to the control of oxygen and oxide inclusions but to collateral modification of sulphide inclusions as well. Inclusions commonly occur in steel as mixtures of oxides and sulphides, sometimes closely associated and sometimes apparently completely divorced. Their effects on the properties of the metal may vary widely depending on their types and distribution as well as on their quantity. The mechanism by which inclusions form, however, and the means for controlling it are exceedingly complex and not well understood. Nevertheless, as described by Benedicts and Lofquist' and by Wentrup' all oxide and sulphide inclusions, excluding mechanically entrained matter, must result from specific modifications of the basic equilibria of the Fe-S-O system. In an investigation of the mechanism of deoxidation and inclusion formation being carried out at the Union Carbide and Carbon Research Laboratories, it became evident that quantitative data for the fundamental Fe-S-O system were essential to a better understanding of the problem. Consequently, the liquidus surface of the portion of the Fe-S-O diagram of interest in steelmaking has been determined, and the solubility of oxygen in liquid iron containing sulphur has been measured. Fe-S-O Diagram The portion of the Fe-S-O diagram of specific interest in steelmaking is the Fe-FeS-FeO corner. Of the contiguous binary diagrams for this partial system, only those for Fe-FeO and Fe-FeS are known with reasonable certainty.3 Several attempts to derive the FeO-FeS diagram have been made, chief among them being the work of Giani as reported by Oberhoffer,4 and, more recently, that of Vogel and Fulling." Although both Giani and Vogel and Fulling published diagrams for the FeO-FeS system, their observations indicated that the oxide component approximated Fe3O4 rather than FeO, so that there is doubt whether the system is truly binary. Benedicts and Lofquist and also Wentrup published qualitative sketches of the ternary diagram based on the assumption that it was of the type described by Marsh for a ternary system in which two of the contiguous binary systems are simple eutectic systems and the third exhibits a solubility gap in the liquid. Apparently, however, the only previous effort to establish the diagram experimentally was that of Vogel and Fülling whose results are reproduced in Fig. 1. Although defining approximately the limits of the miscibility gap and the location of the ternary eutectic, point E in Fig. I, Vogel and Fülling's diagram must be considered only semiquantitative. It was derived from a limited number of observations mainly along two quasi-binary sections, and the directions of the tie-lines and the location of the critical point, K in Fig. 1, were estimated by computation. Experimental Procedure The experimental technique employed for the present investigation involved melting mixtures of ferrous sulphide and ferric oxide in contact with iron. Since it was considered that in this part of the system the vapor pressures of sulphur and SO, are so low that they would not affect the results significantly, the melting was carried out in a current of argon to sweep out products of any initial re-

Jan 1, 1953

By J. M. Smith, G. P. Willhite, J. S. Dranoff

Heat transfer rates were measured in sandstones with flow of gases perpendicular to the direction of energy transfer. Effective thermal conductivities ker ranged from 0.7 to 1.7 Btu/(br)(ft)(°F). The contribution of the solid phase appeared to be the most important in these consolidated materials, although the thermal conductivity of the gas had some effect. The velocity of the gas through the pores of the sandstones had no influence upon ker up to values of 168 lb/(br) (sq ft) in agreement with data obtained for unconsolidated beds of glass beads. The present results indicated that gas mixing, and hence heat transfer by convection in the pores, is less for perpendicular transfer of energy than when fluid flow and energy transfer are in the same direction. HEAT TRANSFER PERPENDICULAR TO FLUID FLOW IN POROUS ROCKS Heat transfer in porous media with pore sizes in the micron range depends upon the fluid in the pores and the geometry of the solid phase. The best characterized system is a bed of solid spherical particles. Heat transfer in this system has been studied extensive1y (Ref. 8 summarizes the literature up to 1959) when the pores contain stagnant fluid. When the fluid is in motion the directions of flow and energy transfer have an effect on the heat transfer rates, as demonstrated by comparing the work of Willhite, et al l3 for perpendicular flow and that of Kunii and Smith9 for parallel flow of energy and fluid. For perpendicular flow, no increase in effective thermal conductivity ke was noted up to mass velocities G of 77 lb/(hr) (sq ft). In contrast, for parallel flow ke, increased with G in the same range of flow rates. These higher values of ke in the direction of flow also have been observed3,4,10 in beds of larger particles, 0.1- to 0.5-in. diameter. For beds of consolidated materials, such as porous rocks, data are not available for these compar- isons, although Adivarahan1 reported results for the parallel case. Hence the primary objective of this work was to measure ke values for perpendicular flow of fluid and energy in porous rocks. Of interest also was the variation in effective conductivity with fluid velocity. APPARATUS AND PROCEDURE In the experimental method, a constant heat flux was applied to the inner surface of an annular section of the porous rock. By cooling the outer wall, a temperature gradient through the annular sample was established and measured with thermocouples placed within the sample at various radial positions, and at three elevations (A,B.C). The location of the 2-in. O.D., 3.75-in. long sample in the apparatus is shown in Fig. 1. Fluid entered the bottom (1) of the 3-in. I.D. (approximate) steel shell, flowed upwards through the sample and out at the top (3). pressure taps (2,4) were used to check the permeability of the sample. The energy flowed radially from the centrally-located electric heater through the sample and was absorbed in the water-cooled jacket. The samples studied were naturally occurring sandstones from different locations with the properties given in Table 1. These materials are identical with those used by Adivarahan 1 for the parallel flow of energy and fluid. Prior to use they were refluxed with toluene to remove hydrocarbons and leached with distilled water to remove soluble salts. Each sample was visually examined and discarded if large nonhomogeneities, such as cracks or stone particles, were noted. Eight copper-constantan thermocouples were inserted in holes drilled radially into the sample with

By E. J. Koval

Practical miscible displacement processes will be characterized by lingering of the solvent into the oil. The lingering process is brought on by viscosity differences, and can be accentuated by channeling and longitudinal dispersion. The effects of these factors on the efficiency of unstable completely miscible displacements are combined in what is called the K-factor method. This method, analogous to the Buckley-Leverett method, predicts recovery and solvent cut as a function of pore volumes of solvent injected. Experimental data are included and show excellent agreement with theory for a wide variety of sandstone cores and viscosity ratios. INTRODUCTION Theoretical considerations,1 laboratory experiments,2 and pilot tests3 lead to the conclusion that miscible displacements in the field will be unstable In an unstable miscible displacement, the solvent fingers through the oil. This fingering leads to early breakthrough of the solvent and an extended period during which both oil and solvent are produced. For such a system, there appear to be four principal factors which bring about or accentuate the effects of instability: longitudinal dispersion (including geometrical effects), channeling, viscosity differences and gravity differences. Other factors, such as diffusion and flooding rate, can also influence the effects of instability, but at the flooding rates considered in this report, circa 15 ft/D, they are unimportant. Longitudinal dispersion can be thought of as a spreading of the solvent front caused by the presence of microscopic inhomogeneities. Channeling of the solvent occurs when a porous medium has macroscopic inhomogeneities; i.e., gross permeability variations. Viscosity differences lead to fingering of the less viscous solvent. This difference in viscosity accelerates the growth of fingers along paths previously developed because of permeability variations. Gravity differences lead to overriding by the usually less dense solvent. Al- though gravity effects are generally small at a flooding rate of 15 ft/D, they would, nevertheless, unnecessarily complicate the interpretation of flooding experiments. For this reason, all the experiments reported herein were done with matched density fluids. Fingering and the resultant poor areal sweep were recognized early as the dominant influences on the efficiency and the economics of miscible displacement processes. Much research effort has been spent on ways to minimize fingering and increase areal sweep such as the use of graded viscosity slugs4 or water slugs. Some researchers attempted to work out ways to prevent fingering completely; i.e., to achieve a stable displacement through gravity or latitudinal dispersion stabilization. l Others did not attempt to control fingering but obtained an economic process by merely recycling the solvent and sweeping pattern by pattern.6 During this period, all aspects of fingering came under close scrutiny. Some researchers reported on how fingering looks2 and how it is affected by viscosity ratio,7 geometry,7 and slug size.2,* Peaceman and Rachfordg suggested a mathematical approach to the prediction of unstable miscible displacements in relatively homogeneous sand packs, but their work cannot be extended conveniently to heterogeneous systems. Hence for a heterogeneous system, no method is presently available for predicting solvent cut and recovery as functions of pore volumes of solvent injected. The purpose of this investigation was to attempt to fill in the gap in our knowledge concerning the prediction of performance of unstable miscible dis placements. Necessarily, the system selected for study was a relatively simple one. The restrictions placed on the system were: (1) The system was linear; (2) The solvent was miscible in all proportions with the oil in place; (3) The solvent was continuously injected into the porous medium; (4) Gravitational effects were eliminated by matching densities and (5) All the flood rates were high and constant at 15 ft/D to avoid any small rate effect and to minimize any diffusion effects. To simplify and to indicate that both longitudinal dispersion and channeling arise from permeability variations, the effects which they cause or influence have been termed heterogeneity effects. The use of

By Darwin Soler

This chapter will outline the operating procedures at Freeport Kaolin Co.5 kaolin mining operations in Georgia, with emphasis on explaining new techniques recently introduced to reclaim mined-out areas for reforestation. Kaolin is found in the central Georgia area (See Fig. 1) in lenticular, sedimentary deposits of high purity. The beds are Cretaceous in age and vary from 4 to 60 ft in thickness, under a cover of sedimentary overburden ranging from 5 to 150 ft. The kaolin beds contain the mineral kaolinite (a hydrous aluminum silicate) and have a particle-size distribution ranging from about 20µ to the submicron level and averaging about 60% below 2µ. The only contaminants in the deposits are coarse mica, quartz particles, and minor amounts of iron and titanium oxides. These kaolin deposits vary widely in quality from deposit to deposit and also vary within individual deposits. Some of the controlling quality specifications which are determined during exploration are viscosity in water suspension, optical brightness index as measured by reflectance, amenability to bleaching, and particle-size distribution. For this reason, only a small portion of the total kaolin reserves in the Georgia belt are suitable for wet processing for the present markets being served. Kaolin clays are selectively mined by different mechanical methods and are beneficiated by both wet and dry processing to produce a number of products used as fillers and coatings in the paper industry; fillers or additives in the paint, plastic, and rubber industries; and as basic raw materials for the ceramic industry. The State of Georgia is the largest kaolin producer in the United States, with 3,206,454 tons produced in 1966, according to U.S. Bureau of Mines statistics. Freeport Kaolin Co’s processing plant is located in Gordon, Ga., about 20 miles east of Macon, Ga.

Jan 1, 1969