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By Leo Horvitz

PETROLEUM and natural gas are composed principally of the saturated hydrocarbons ranging from methane, the lightest, to nonvolatile liquids and solids containing approximately thirty-five carbon atoms. A technique for locating buried accumulations of these hydrocarbons before drilling obviously requires that some of the hydrocarbons leave the deposit and migrate toward the surface of the earth where they may be detected in their original form. Earliest attempts to link near surface hydrocarbons to petroleum at depth were apparently made by Laubmeyer1 in Germany and by Sokolov2 in Russia. These investigators collected samples of soil air from boreholes one to two meters deep and analyzed them for traces of hydrocarbons. They found that soil air over producing areas is richer in these constituents than is soil air over barren areas.

Jan 12, 1954

By W. M. Weigel

The rapid advance, during recent years, in the manufacture of articles that have been in common use for generations and the development of new materials entering into appliances and devices unheard of fifty years ago have created a demand for some of the more common non-metallic minerals. To supply this demand there has quietly developed a branch of the mining industry of which little is known by most mining engineers —the mineral-filler industry. In this paper, and generally in the trade, the term mineral filler is applied to a mineral used in its natural state after mechanical preparation only (such as grinding, milling and washing), without undergoing any chemical change and without exerting any chemical action on the substance with which it is incorporated. The consumption of mineral fillers is confined chiefly to large manufacturing centers in the Eastern and Northern Statcs. Where available, materials originating near the place of consumption are used, as most fillers bring a comparatively low price and, frequently, the freight may equal the cost of the finished filler at the mine. The Southern States have abundant deposits of non-metallic minerals suitable for fillers, which supply the manufacturing industries in adjacent states. Many of these deposits are equal to, or superior, in quality to those mined in the North, but they can not compete with them because of the freight rates. The mineral-filler industry has felt the present depression, but it has suffered less than most mining industries, for as a rule the mills are simple, the overhead expenses are low, and the labor is entirely local and can revert to farm work when the plant closes down. Many other deposits in the southern district will undoubtedly be developed when business revives and freight rates are adjusted. Most of the non-metallic mines are small and the tonnage handled is low in comparison with the tonnage involved in modern large-scale mining of coal, iron, copper, etc. On the other hand, at nearly all non-metallic

Jan 1, 1923

By W. M. Weigel

The rapid advance, during recent years, in the manufacture of articles that have been in common use for generations and the development of new materials entering into appliances and devices unheard of fifty years ago have created a demand for some of the more common non-metallic minerals. To supply this demand there has quietly developed a branch of the mining industry of which little is known by most mining engineers —the mineral-filler industry. In this paper, and generally in the trade, the term mineral filler is applied to a mineral used in its natural state after mechanical preparation only (such as grinding, milling and washing), without undergoing any chemical change and without exerting any chemical action on the substance with which it is incorporated. The consumption of mineral fillers is confined chiefly to large manufacturing centers in the Eastern and Northern Statcs. Where available, materials originating near the place of consumption are used, as most fillers bring a comparatively low price and, frequently, the freight may equal the cost of the finished filler at the mine. The Southern States have abundant deposits of non-metallic minerals suitable for fillers, which supply the manufacturing industries in adjacent states. Many of these deposits are equal to, or superior, in quality to those mined in the North, but they can not compete with them because of the freight rates. The mineral-filler industry has felt the present depression, but it has suffered less than most mining industries, for as a rule the mills are simple, the overhead expenses are low, and the labor is entirely local and can revert to farm work when the plant closes down. Many other deposits in the southern district will undoubtedly be developed when business revives and freight rates are adjusted. Most of the non-metallic mines are small and the tonnage handled is low in comparison with the tonnage involved in modern large-scale mining of coal, iron, copper, etc. On the other hand, at nearly all non-metallic

Jan 1, 1923

By W. J. Rooney, James Fisher, W. O. Hotchkiss

During the summer of 1927, the Department of Terrestrial Magnetism of the Carnegie Institution of Washington joined with the Michigan College of Mining and Technology in conducting a series of earth-resistivity measurements in the Michigan copper country. The geological structure in this section is quite varied and fairly well known. The purpose of the investigation was to discover the correlation between the variations in electrical resistivity of large masses of soil and rock in place and the geological structure below the surface. The work done may be roughly divided into two parts: (1) Measurement and study of the variations in resistivity with depth, or with volume, to establish such general relations as exist between the two; and (2) the determination of the specific resistivity of various formations in order to make available more fundamental data which may aid in the interpretation of the results of the former type of measurement. A report by Mr. Rooney, which gives in detail the measurements made and the results obtained, forms the basis for this article. Measurement and Study of Variations in Resistivity The possibility of applying data from measurements of the physical properties of earth material to the study of the geological structure has long been recognized, and a number of methods for determining the position and character of concealed rock strata by means of seismic, gravitation, magnetic and electrical measurements made on the surface are being used with varying degrees of success. One physical property which varies widely for different materials, and hence affords an opportunity for distinguishing between them, is their electrical resistance. Locations • were selected where the geological structures were well known and where the depths to the water level and bed rock had been determined by drilling. The problem was to determine the value of measurements of resistivity and its variations as indications of the geological structure below the surface.

Jan 1, 1929

By G. M. Wiles

The increasing number of problems of the modem mine manager has led the author to discuss the art of management. He lists the principles concerning selection of personnel, exploitation and development, new equipment, process improvements, new processes, maintenance, operating cost data and public relations. Application of the principles to problems of mine startup, operation and rehabilitation are described. Since D. C. Jackling was famous for his adeptness at organizing and training teams of operating personnel, the subject of mine management is particularly appropriate for a Jackling Lecture. In fact, it is doubly appropriate because in very basic ways Jackling's career changed the nature of the tasks and challenges facing a mine manager. Management of mines, of course, is the art of finding and winning minerals economically from the earth's crust, and it involves the use of all the engineering sciences. But also of prime importance is a skill which is not yet a science - the area of management often referred to as human engineering. Since expenditures on staff and labor may well involve more than 50% of the direct costs of operating a mine, ability at human engineering is just as important as the ability to plan and put into effect the most efficient operating procedures. In addition to his ability to select and train operating personnel, Jackling possessed, to a degree unmatched by many of his contemporaries, broad, analytical powers covering both the economics and operating phases of large scale mineral extraction. His breadth of vision found its greatest expression at the time he analyzed the Utah copper deposit. Fortunately, Messrs. Penrose and Gemmell had enough faith in his analyses to furnish the capital needed to begin operations. The result, as is well known to all of you, was Kennecott's lucrative Utah copper mine — and the beginning of the open pit porphyry copper era. The Utah copper mine, and Jackling's subsequent similar successes in Arizona, New Mexico and Nevada, had one thing in common —all of these large porphyry deposits were worthless until open pit, large daily tonnage schemes were developed for their exploitation. The successful development of such schemes made vast new mineral resources available for economic exploitation. But at the same time, the trend away from smaller high grade operations in favor of the far more complicated operations required to handle large deposits of low grade ore have greatly altered a mine manager's problems. We are all familiar with the saying "mines make managers." There is still some truth in this statement, but far less than there used to be in the days when high grade properties were the rule rather than the exception. When high grade orebodies prevailed, many managers, superficially at least, could not make a mistake because the profits of their mines

Jan 1, 1962

An Appreciation of Dr. Douglas by Dr. ALBERT R. LEDOUX The Bulletins of the American Institute of Mining Engineers and the program of the International Engineering Congress, held last September at San Francisco, called attention to an important feature in the pro¬ceedings of the Congress; viz., the public presentation to Dr. James Douglas of the John Fritz Medal, for notable achievements in mining, metallurgy, education. and industrial welfare. Dr. Douglas' health, unfortunately, did not permit of his taking the journey to California. While he had been willing that the bestowal of the medal should be a public ceremony, his natural modesty made him shrink somewhat from what he considered something of an ordeal, and he begged those who were to take part in it to use restraint in anything which they might have to say as to his work and attainments. It was, therefore, with some considerable satisfaction on his side that he learned that the medal would be given him without a public, ceremony in New York, or elsewhere. . On Dec. 5, 1915, the writer of this had the pleasure of handing him the medal, certificate, and official letters of transmittal, at his home at Spuyten Duyvil, where lie was surrounded by his children and grandchildren, with one or two of his most intimate friends. He begged the writer to return his thanks to the Committee of Award; and again to express the feeling that nothing in his career merited so great an honor. On this point all of the members of the Institute will share the writer's feeling that Dr. Douglas is too modest. James Douglas was born at Quebec, Canada, in November, 1837. His father Was a distinguished physician and surgeon, employing his skill in the field of philanthropy: He established the first retreat for the insane in the Dominion, to which lie. devoted himself up to the time of his departure from Canada, when it was taken over by the Government. The son spent 2 years in study at the University of Edinburgh, which lie entered in 1855. Returning to Canada, he graduated from Queens University, at Kingston, Ontario, with the degree of Bachelor of Arts, having also studied medicine, and later theology. After his graduation he traveled extensively with his father in Europe and in the Orient, visiting Egypt several time's. They returned with important archaelogical collections, which Dr. Douglas subsequently donated to the Metropolitan Museum of Art in this city. He then returned to Edinburgh, where he continued his course in medicine, surgery being perhaps his chief interest at that time. He was subsequently licensed to preach and his contemporaries bore testimony to his broad philanthropy and to the sympathy which dominated his every act. His taste was distinctly literary; he had carried off a prize at Edinburgh in English literature.

Jan 1, 1916

By L. P. Davidson

THE new electrolytic zinc plant of the American Zinc Company of Illinois commenced operation in April 1941. The simple flowsheet using the standard current density and the economic reasons that dictated it are given herewith. The Evans-Wallower Zinc Co. built an electrolytic zinc plant at Monsanto, Ill., in 1929 and operated it for about two years. The plant stood idle from 1932 and was purchased by the American Zinc Co. in 1940. Because of the condition of the equipment, excepting the motor generator set, a complete rebuilding was necessary. The Fairmont City plant of the American Zinc Co. could treat the leach residues, the purification cake and the skimmings from the melting furnace in its various plants. This possibility permitted a simple flowsheet with good economic results. The flowsheet is shown in Fig. I. The calcined concentrates are leached in mechanically agitated tanks with spent electrolyte and such ferric iron solution as necessary. When the acid has been neutralized and the iron coagulated, the fluid is discharged to settling tanks. The underflow from these thickeners is filtered on a Moore filter; the filter cake leaves the plant for retreatment and the filtrate joins the thickener overflow. Zinc dust is added to this solution until the copper and cadmium are precipitated. The pulp is filtered through Shriver presses, which deliver the purified solution to storage tanks, and the copper-cadmium-zinc cake is shipped for retreatment and recovery of these three metals. The purified solution is electrolyzed; the regenerated acid is returned for use in the leaching plant and the cathode zinc, after stripping, goes to the melting furnace, from which it is cast in slabs. The skimmings from the melting furnace are shipped to the Fairmont City plant for reduction to metal in the retort furnaces. The choice of this simple flowsheet was made possible only because of the facilities of the Fairmont City plant. The long leaching period, with high acid content and high temperature which characterize the high-density process, gives a higher zinc extraction but also dissolves more impurities, which must be removed. The same is true to a lesser degree of the multi-step leaching of the western low-density plants. By the sacrifice of some initial extraction, solutions can be obtained that are relatively easy to purify and give good ampere efficiency. This loss in initial extraction is made up in the retreatment of the residues in the Waelz plant. The impurities that accompany the zinc thus extracted are inconsequential when the Waelz product is treated in a distillation plant. It was recognized that this flowsheet would require a somewhat greater amount of sulphuric acid-either as acid or as sulphate sulphur in the calcine-because of poorer washing. The sulphuric acid plant at Fairmont City could deliver 60° Bé. acid to compensate for the sulphate loss and the cost would be less than the cost of more intensive washing.

Jan 1, 1942

By E. I. Larsen

Powder metallurgy has been described as being "as old as the pyramids and yet as new as the latest bomber." While this may be true literally, it has been only in the last Io or 1 5 years that widespread use has been made of this method of fabricating various articles One of the first items fabricated by powder metallurgical methods on a commercial scale was electrical contacts, which were fabricated from metal powders as early as 1920. The reason why these contacts have been made for so many years by powder metallurgy is because the compositions of most of these materials arc such that they could not be made by the conventional methods of melting, casting, rolling, drawing, etc. Classes of Contacts In general, electrical contacts fabricated from metal powders fall into two classes, both from the point of view of the method of fabrication and the components that make up the chemical composition. One class is composed of silver or copper and a refractory metal such as tungsten, molybdenum, or compounds thereof such as carbides. The second class contains a predominant amount of silver and a semi-refractory material such as cadmium oxide, nickel, cobalt, or graphite. Electrical contacts of the first class have been developed primarily as facing materials for heavy-duty circuit-interrupting devices. This class of material unites the high melting point, high boiling point, great resistance to electrical erosion, and the refractory characteristics of molybdenum, tungsten, or their carbides with the high thermal and electrical conductivities and low contact resistance properties of silver or copper. The second class of material is used for lighter duty or specialized applications such as heavy-duty, direct-current aircraft relays. Varieties Electrical contacts fabricated from metal powders are made in a wide variety of compositions, shapes, and sizes. In general, the sizes of electrical contacts fabricated from powders vary from contacts weighing approximately 0.001 oz. up to those weighing 3 to 4 Ib., the contacting face being as small as 0.001 sq. in. up to approximately 6 sq. in. in area. The shapes consist of: sound or rectangular buttons, some of which have radii or bevels on the contacting faces; rings, cups, rectangular bars, the contact face of which may have a radius across the width and/or at one end; and form-pressed pieces of a wide variety such as angles, both acute and obtuse, irregular shapes comprising a radius blended into a flat, which in turn may have steps. The size or shape of the contact is dictated principally by the mechanical design of the manufacturer, who in turn may have problems to be met such as: (I) size, weight, or space limitations; (2) electrical conditions such as blowout coils arc chutes, baffies, gas passages.

Jan 1, 1945

By S. Yukawa, M. J. Sinnott

A high resolution autoradiographic study of the diffusion of a nickel isotope (NP3) into copper in the temperature range of 650° to 925°C, with particular emphasis on grain boundary diffusion, has been made. The extent of grain boundary diffusion is a function of the grain boundary angle and the diffusion temperature. The ratios of the grain boundary diffusion coefficient to the lattice diffusion coefficient ranges from 104 to 105. The activation energy for grain boundary diffusion decreases with increasing grain boundary angle. STUDIES and reviews&apos;-8 of metallic diffusion have indicated that grain boundary diffusion is a common phenomenon but quantitative studies of the many variables involved are not numerous. The present work was concerned with determining the influence of the crystallographic orientation of the grain boundaries and the temperature on the extent of boundary diffusion of nickel into copper. The study involved essentially three steps: 1—the production of grain boundaries of known crystallographic orientation, 2—the determination of the extent of diffusion into the boundaries, and 3—the analysis of the resulting data in terms of the usual diffusion concepts. The grain boundaries investigated approximated the simple tilt variety having l° of freedom. They were produced by controlling the solidification from a melt of Cuprovac (a high purity vacuum-melted copper obtained from Vacuum Metals Corp.) of a pair of seed crystals so that the bicrystals of copper produced had a common <100> axis. By rotating one seed crystal relative to the other, a simple tilt boundary was produced. The angle of rotation between the two crystals is the grain boundary angle 8, or what is sometimes termed the misfit angle. In all, some 16 boundaries ranging from 2" to 72" in 5" to 10" steps were investigated. The crystallographic orientations were measured with the use of both X-ray and optical goniometric techniques. The <100> axes in the crystals were found to be parallel within 2" to 3" with the exception of one crystal (8 = 12") in which the axes were 6" from being parallel. All bicrystals showed evidences of sub-grain structures. Laue analyses showed that these subgrains differed in orientation up to a maximum of 2". Because of these variations, and some curvature in the boundaries, the grain boundary angles listed are actually average values and deviate from the 1 o of freedom boundaries. The stripping film technique of high resolution autoradiography was used to detect the diffusion of the nickel isotope into the grain boundaries of the bicrystals of copper. Kodak experimental permeable stripping film with an emulsion layer 5 u thick

Jan 1, 1956

The Du Pont Magazine for August and September gives the following interesting information regarding recent progress in the use&apos; of explosives. Blasting -Clay.-"The place where I tried blasting down clay for a brick yard had been worked for some years by old-time pick and shovel method. There was a large shallow pit, irregular in shape, with a perpendicular face at one end. I put down a line of holes 3 ft. deep and 6 ft. back from this face, loading each hole with one and one-half car-tridges of Red Cross Extra 40 per cent. dynamite. The charges were connected up to a blasting machine circuit and fired electrically. "Two of these shots kept the brick yard men very busy for two days taking out the loose clay. "I am convinced that if any brick yard man will try this method he will always have a blasting machine and dynamite on hand thereafter, because it cuts labor cost almost in two to get down the clay in. this way." In some clay pits the practice is to blast a large amount of clay in the fall, allowing it to freeze and thaw through the winter. Such clay is much easier to puddle in the spring than freshly dug or blasted clay. When the clay contains stones, the blasting loosens them and makes their separation-easy. Well-Drill Holes in Quarrying.-The well drill or cable drill method of working a quarry face is now in quite common use. The use of large drills is constantly increasing among quarrymen. In fact the growing tendency is for large machinery of all kinds such as mammoth crushers, steam shovels, etc. Volume is what is wanted nowadays. The advantages of the big drill over the piston driven drill are numerous. By carrying the holes the full depth of the face the stone is loaded and treated on one working floor. It eliminates the cost of bench cleaning. Loading operations are less frequent, thus lessening the danger. Stone can be shot down in greater volume and in better shape, making it economical to use a steam shovel. No bench cleaning makes it safer for the men. It is cheaper and can be used in outlying and temporary operations where the cost of installing a power plant would be out of the question. It permits a greater spacing of bore holes and eliminates the necessity of "squibbing" or springing. In this method usually holes from 4 in. to 6 in. in diameter are drilled the full depth of the face from 15 ft. to 2,0 ft. apart, and as far back and the whole face shot down at one time. The cost of well drilling may vary all the way from 20 cents to 75 cents: per foot, and in extremely hard rocks up to $1.50 per foot.

Jan 10, 1916

By B. N. Whittaker, C. J. Bonsall

The paper gives an account of the factors influencing the stability of coal mining tunnels and goes on to examine various bases of support and lining design of such tunnels in relation to geological and mining conditions. The different types of coal mining tunnels are compared and comments made regarding the factors influencing their choice and basic design features. Foremost amongst design considerations is the design method and special thought has been given to the validity of different formulae as related particularly to UK Carboniferous geological conditions. Emphasis is placed on the role of the stress field in relation to tunnel stability. Shape of mining tunnel has been investigated and conclusions drawn regarding the merits of different commonly excavated geometries from a stability point of view. Detailed design aspects pertaining to determination of tunnel lining strength and resulting stability are critically examined and current design methods are compared. Data from UK mining tunnels are included as the basis for comparison of these design methods.

Jan 1, 1983

By Benjamin Petkof

The mineral mica, which has been known to man since ancient times, has played an impor¬tant role in the development of our modern industry. In the latter part of the 19th century sheet mica began finding use as a dielectric insulating material in the newly developing electrical industry. Later, when modern elec¬tronics began to develop, it became a vital insulating and dielectric material for use in electronic equipment. Both the electrical and electronic industries were greatly dependent on some form of natural mica. The manufacture of electric motors of varying sizes, electronic tubes, and other electronic items was dependent on an adequate supply of sheet mica. During World War II this material was so vital to national defense that special efforts were made to mine it in the United States as well as to obtain it from overseas mica-producing areas. However, advancing technology has successfully begun the progressive development of man-made mica-based and non-mica-based materials that can replace mica for many uses. In addition, developing technology has dictated changes that have made sheet mica unnecessary for some uses. As the demand for sheet mica declined, the demand for scrap and flake mica has continued to increase. In fact, today the domestic production and use of scrap and flake mica far outshadows the necessity for good¬quality sheet mica in this country. Historically the United States has always been dependent on foreign sources of material for good-quality sheet mica and imports practically its entire requirement. In the case of scrap and flake mica, the United States is the dominant world producer and consumer. End Uses Sheet mica (Chowdhury, 1941; Rajgarhia, 1951; Skow, 1962) is available in many com¬mercial forms, but these forms can be broadly classified into manufactured and unmanufac¬tured mica. Manufactured mica consists of mica that has been shaped, punched, or other¬wise processed into some form, suitable for a particular end use. Unmanufactured mica con¬sists of partially hand-trimmed or processed material that has not been prepared for any particular end use. Unmanufactured mica is broken into two commercial classes consisting of sheet mica and scrap and flake mica. These classes of mica differ greatly in their ultimate end uses and marketed forms. Sheet muscovite mica can be classified by color, degree of prep¬aration of the crude material, thickness, size, visual appearance, and electrical quality. In addition, phlogopite mica is also classified by its thermal stability. Scrap and flake mica consist of mine, trimming shop, and factory scrap that occurs as remnants from mining, processing, and manufacturing operations, and small particle size mica that is available from the beneficiation of pegmatites, clays, schists, or other mica-rich host rock. The end uses for sheet mica vary so greatly from those of scrap and flake mica that it is necessary to discuss them separately. Sheet Mica Sheet mica consists of relatively flat sheets of material which have been mined as naturally occurring books or runs of mica. These sheets are hand-trimmed to remove any imperfections and are punched or stamped into specified shapes for industrial use. Sheet mica can be further processed and is described or specified as block, film, or splittings based on thickness. Block mica is not less than 0.007 in. thick with a minimum usable cross-sectional area of 1 sq in. Film mica is split from the better quali¬ties of block mica to specified thickness groups ranging from 0.0012 to 0.004 in. Splittings are sheets of mica with a maximum thickness of 0.0012 in. and a minimum usable area of 0.75 in. Other small sized, lower quality block mica

Jan 1, 1975

By Anal J. Mehta, Theodore D. Tiemann

Growing demand for steel and increasing dependence upon foreign ore makes the need for developing the technology for treatment of low-grade iron ores greater than ever before• Representative of these added interests were the studies carried on at the University of Wisconsin• These studies included among others: anionic and cationic flotation, magnetic separation, roasting followed by magnetic separation, electrostatic separation, a hydrogen reduction process,6,7 and caustic digestion• The idea of removing silica by caustic extraction is not new•-1; The principle of concentrating siliceous iron ores by this method is based on the fact that silica is soluble in sodium hydroxide solution while iron oxides are essentially insoluble• For this process to be economically feasible, it is believed that some method of recovering silica from solution as a marketable by-product, with recycling of spent liquor is necessary. Precipitation of silica with carbon dioxide will allow subsequent causticizing of the spent liquor with lime• Caustic thus produced can be recycled for digestion• A flowsheet of the envisioned process is given in [Fig• 1] The purpose of this paper is to describe results obtained from the investigation of carbon dioxide precipitation of silica from sodium silicate solutions, which could be later applied to the caustic extraction process to treat low grade siliceous iron ores, particularly taconites.15 Theoretical Considerations The soluble silicates of sodium include sodium orthosilicate (2Na2O•SiO2), sodium metasilicate (Na20•SiO2), sodium disilicate (Na1O•2SiO2), and more highly siliceous products approaching Na2O•4SiO2• These materials have been described in detail by Vail•16 Stones has reported that the extraction of silica is not significantly affected by the amount of silica in solution until the Si02/Na20 ratio exceeds that of orthosilicate (Ratio = 1/2)• However, as the Si02/Na2O ratio exceeds that of metasilicate (Ratio = 1), silica extraction is significantly impaired• The present experimental work was confined to orthosilicate and metasilicate solutions, as to be successful the envisioned commercial process for the extraction of silica from siliceous iron ores would operate in this region. The mechanism of extraction of silica from aqueous sodium silicate solutions is complex in nature. For the carbon dioxide process-18 of core and mold making in which silica is also precipitated from sodium silicate solutions by gassing with carbon dioxide, the reaction of aqueous silicates with gaseous carbon dioxide has been represented by the equations: [ ] However, these equations are very much oversimplified• It has been shown that the reaction between aqueous sodium silicates and carbon dioxide gas is ionic in nature 18 Considering this fact and the mechanism for digestion of silica in aqueous sodium hydroxide, the overall conversion of aqueous sodium silicates to solid silica may be represented in ionic form by the following equations: [ ] Silicon in the silicate ion is shown here with a coordination number of 6• This may be in doubt, but it is known that ion (SiF°)-2 exists; it seems logical that the Si (OH) e 2 ion should be equally capable of existence•

Jan 1, 1977

By N. Mungan

Laboratory water floods were performed in oil-wet and waterwet alundum and Torpedo cores, displacing a refined oil with n-hexylamine or Triton X-100 solution. Also, some floods were performed in which a sucrose solution was displaced with n-butyl alcohol. The Purpose ot the tests was to see if the oil recotlery could be increased and to examine what role the inter-facial tension reduction and wettability change play in the recovery mechanism. it was found that the chromatographic transport of amine was influenced by core wettability. In oil-wet cores, the rate of advance of the amine band could be predicted from equilibrium chromato-graphy, while in water-wet cores the amine band moved faster than predicted, indicating a non-equilibrium process. By reducing the interfacial tension to 1.1 dyne/ cm, oil recovery was increased. More oil was recovered from Dri-filmed cores than from water-wet cores. Reversing the wettability of the porous media from oil-wet condition also resulted in some additional oil recovery. Neutral wettability floods did not increase oil recovery. INTRODUCTION Interfacial forces in petroleum reservoirs are responsible for retention of large quantities of residual oil. Increasing exploration costs have created an incentive to attempt recovery of this residual oil by new and novel processes. One novel process involves changing the interfacial forces by introducing a chemical into the reservoir during water flooding. Recently, several investigators have carried out laboratory displacement tests using amines. lt3.4 The amines adsorbed onto initially water-wet core surfaces, changing them to oil wet. Additional oil was recovered when the cores were flooded in a manner reversing the. wettability from oil-wet conditions. In all these studies, the wettability reversal was considered responsible for increased oil recoveries although it was noted that amines also reduced oil-water interfacial tension. In the present study, displacement experiments were performed in water-wet and Dri-filmed cores. The purpose was to separate the effects of lowering the interfacial tension from changing the wettability. LABORATORY STUDY All experimental data given in this paper have been obtained at a temperature of 70F + 1 and prevailing atmospheric pressure. FLUIDS AND MATERIALS The oil used in these experiments* was washed with H2S04 and passed through two 100-200 mesh silica-gel beds to remove unsaturates and surface active impurities. Normal hexylamine** of practical purity was used, and the alundum cores*** were composed of nearly pure A1203. Fused quartz (SiOi) and Lucalox (A12 )t plates were used in the contact angle measurements. DISPLACEMENT TESTS Displacement tests were performed in alundum and Torpedo cores. Before displacement runs, cores were acidized with 0.1 normal HCI, flushed with distilled water and fired at 1,200F to make them water wet. This procedure also reduced water sensitivity of the Torpedo cores. Oil-wet cores were prepared from water-wet cores by flowing several pore volumes of 1 per cent by weight Dri-film SC-87 solution in heptane through the cores, flushing the cores with nitrogen, evacuating, and finally heating the cores at 300F for 4 or 5 hours. Between floods, cores were cleaned by conventional procedures and treated again as above.

Jan 1, 1965

By C. H. Frick

BEFORE presenting the main topic, as indicated by the title, this paper will give some of the high-spot history of the anthracite industry. INTRODUCTION The earliest recorded use of anthracite was in the year 1762, when a company of Connecticut pioneers discovered anthracite near the present city of Wilkes-Barre, Pennsylvania. In the early days of the industry, the coal was used only in large pieces, the smaller pieces being discarded to waste piles. As the output of the industry increased during the nineteenth century, uses were developed for somewhat smaller sizes down to and including pea coal. Early in the twentieth century, sizes smaller than pea, such as No. I and No. 2 buckwheat, were developed and used. Accu¬mulations of piles from current mining operations were still increasing; that is, the smaller sizes were still being discarded. It was not until after World War I that preparation of the so-called steam sizes began commercially. This was largely No. 3 buckwheat, which is screened through a 3f 6-in. round-hole screen and over a 332-in. or a M 6-in. round-hole screen. USE OF SMALLER SIZES The earliest recorded experience in burning the small sizes of anthracite for steam production, other than in a previous small experiment, was in the year 1913, when a size known as "boiler fuel" was introduced-a mixture of rice and barley (No. 2 and No. 3 buckwheat). At that time, there was still no method known for burning the still smaller sizes. TABLE I.-Screen Sizes Used for Small Sizes of Anthracite [ ] At the present time, various sizes down to and including No. 5 buckwheat are being prepared (Table I) from current mining and bank-reclaiming operations. The sizes of No. 4 and No. 5 buckwheat and smaller are generally being used for steam production in large boilers. The Pennsylvania Power and Light Co., following World War I, used 680,000 tons of anthracite per year, burned largely on stokers for production of steam, whereas for the year 1943 it used 1,940,000 tons of stoker sizes and 400,000 tons of smaller sizes for grinding and burning in pulverized form. This company has taken a very large part in the research and development of ways and means of burning these smaller sizes of anthracite, including the grinding of the very small sizes. This paper is particularly concerned with the latter feature.

Jan 1, 1946

By E. A. von Hahn, T. R. lngraham

Cementation rates ulere studied by rotating an elec-tropolished or etched copper strip in aqueous solutions, of either perchloric acid or alkaline cyanide, containing silver ions. The rates of cementation were more rapid in acidic media than in cyanide media. In both, the rates varied with the rate of rotation of the copper strip. The deposits formed in the acidic solutions were finely divided, loosely adhering powders. Those formed in the cyanide solutions were dense and adherent. The presence of the deposits influenced the cementation rates. In the acidic solutions the rate was enhanced, possibly because of the increased cathodic area. In the alkaline solutions the rates were decreased in the presence of the deposits. This has been attributed to restricting the diffusion of the copper ion from the rnetal outward into the bulk of the solution. In an earlier paper1 the authors described a kinetic study of the cementation of palladium on copper in perchloric acid solutions. That work indicated that there were two stages in the palladium cementation process. The first, more rapid stage was consistent with rate control by the diffusion of Pd11 ions to the copper surface and/or by chemical reaction at the surface. The second stage was consistent with rate control by the diffusion of copper ions from the copper surface, through the deposit, out into the main body of solution. The effect of the type of deposit on the rate of cementation is of particular interest because it may be one of the primary features involved when large quantities of metal are to be cemented from solution. No substantial investigations of the effect seem to have been made. Accordingly, an extension of the previous work was arranged to study the cementation of silver on copper. This system was selected because of the convenience of the analytical methods, the previously established technology with copper, and the fact that the system could be studied in both acidic and alkaline media. By selecting perchloric acid and alkaline cyanide solutions as the media, it was hoped that some assessment might be made of the effects, on cementation, of having the silver ion present in a virtually uncomplexed state and in a highly complexed state. EXPERIMENTAL The cementation rates were studied, as previously described,&apos; by rotating a copper strip (1.0 by 23.2 cm) clamped to the peripheral surface of a lucite cylinder. The solutions were kept at constant temperatures (±0.05°C) under an atmosphere of purified nitrogen, and samples were taken periodically for analysis. The initial solution volume was 1000 ml and the sample volume 5 ml. The initial silver(1) ion concentrations were made low (0.5 to 1.0 x 10-4 moles per liter) to minimize the influence of the cemented deposit on rates. The solutions were prepared by dilution of suitable aliquots of silver perchlorate and silver cyanide stock solutions. Both stock solutions were prepared from purified silver powder (Johnson, Matthey, and Mallory Ltd.) with redistilled deoxygenated water, and they were kept under an atmosphere of purified nitrogen. To prepare the stock solutions, weighed amounts of silver powder were dissolved with nitric acid. For the AgC104 stock solution the silver nitrate solution was evaporated twice to near dryness with perchloric acid and then made up to volume: For the NaAg(cN)2 stock solution, the silver ions were precipitated with sodium hydroxide solution. The precipitate was filtered, washed thoroughly with redistilled water, dissolved with 1.1 times the required stoichiometric amount of sodium cyanide solution, and made up to volume. The small amounts of free perchloric acid and sodium cyanide present in the stock solutions were disregarded in the preparation of the solutions. The copper strips were cut accurately from 0.025-in. sheet (American Metal Climax OFHC brand) and annealed for 1.5 hr at 470°C in a stream of nitrogen. Analyses of the solution samples for silver and copper were done with a Techtron Model AA-3 atomic absorption spectrophotometer. Calibration standards of the same composition as the experimental solutions were prepared and analyzed simultaneously with the samples. No difficulty was experienced in the analyses, and the reproducibility was within 1 to 2 pct in both alkaline cyanide and perchloric acid solutions.

Jan 1, 1968

By Robert B. Bossler, Parke A. Dickey

The presence of connate water in oil sands is of far greater practical significance in secondary oil-recovery operations than it is in primary operations. The percentage saturations of oil, water, and gas in a depleted field determine whether it will be economically possible to recover oil by secondary methods, and whether water-flooding or gas-driving, or either, will be successful. It is suggested that economic recovery of oil by secondary water-flooding can occur only when a rich bank of oil is formed by the encroachingm water. If the sand has a greater effective permeability to water than it has to oil before flooding, a bank will not be formed, and water-flooding will not be successful, although gas-driving may be. Published results of laboratory work indicate that the effective permeability of a sand to oil and water depends primarily on the saturation of the sand by these phases. They also indicate that a small difference in relative saturation produces a large difference in effective permeability to the phase in question. There thus exists a critical range of saturations, wherein a small change in oil and water content of the sands will make water-flooding possible or impossible. In gas-drive operations the water saturation is less critical but no less important. The presence of connate water in a sand increases the proportion of the residual oil that may be recovered by gas drive. Sands containing oil saturations too low and water saturations too high to make water-flooding possible can often be subjected to gas drive with economic recovery of oil. The results of laboratory work on test samples that do not contain water cannot be applied to normal field operations. More tests on cores containing water as well as oil are desirable, and the improvement of coring technique is necessary. However, sufficient data are already available to enable an operator to use core data intelligently in estimating the chances of a secondary oil-recovery program. Introduction In recent years laboratory work has led to a much better understanding of the principles of oil-reservoir performance. The general principles of the expulsion of oil from sandstone by gas or water were developed by geologists of the Second Geological Survey of Pennsylvania in the 1870lsl but only recently has the mechanism of gas or water drive been intensively investigated. Most published articles have large the facts established in the labora tory to the primary production of oil from flush fields- This Paper is not based on any new observations, but is an attempt to apply some of the conclusions obtained in the laboratory and described in the literature to the recovery of oil from depleted pools by secondary methods. One of the most important factors that determine whether or not a secondary-recovery operation is economically successful is the ratio of injected fluid to oil recovered. This ratio may be expressed as the over-all or cumulative gas-oil ratio if gas is the driving medium, or water-oil ratio if water is the driving medium. Recent theoretical and experimental work has shown that the relative amounts of

Jan 1, 1944

By Parke A. Dickey, Robert B. Bossler

The presence of connate water in oil sands is of far greater practical significance in secondary oil-recovery operations than it is in primary operations. The percentage saturations of oil, water, and gas in a depleted field determine whether it will be economically possible to recover oil by secondary methods, and whether water-flooding or gas-driving, or either, will be successful. It is suggested that economic recovery of oil by secondary water-flooding can occur only when a rich bank of oil is formed by the encroachingm water. If the sand has a greater effective permeability to water than it has to oil before flooding, a bank will not be formed, and water-flooding will not be successful, although gas-driving may be. Published results of laboratory work indicate that the effective permeability of a sand to oil and water depends primarily on the saturation of the sand by these phases. They also indicate that a small difference in relative saturation produces a large difference in effective permeability to the phase in question. There thus exists a critical range of saturations, wherein a small change in oil and water content of the sands will make water-flooding possible or impossible. In gas-drive operations the water saturation is less critical but no less important. The presence of connate water in a sand increases the proportion of the residual oil that may be recovered by gas drive. Sands containing oil saturations too low and water saturations too high to make water-flooding possible can often be subjected to gas drive with economic recovery of oil. The results of laboratory work on test samples that do not contain water cannot be applied to normal field operations. More tests on cores containing water as well as oil are desirable, and the improvement of coring technique is necessary. However, sufficient data are already available to enable an operator to use core data intelligently in estimating the chances of a secondary oil-recovery program. Introduction In recent years laboratory work has led to a much better understanding of the principles of oil-reservoir performance. The general principles of the expulsion of oil from sandstone by gas or water were developed by geologists of the Second Geological Survey of Pennsylvania in the 1870lsl but only recently has the mechanism of gas or water drive been intensively investigated. Most published articles have large the facts established in the labora tory to the primary production of oil from flush fields- This Paper is not based on any new observations, but is an attempt to apply some of the conclusions obtained in the laboratory and described in the literature to the recovery of oil from depleted pools by secondary methods. One of the most important factors that determine whether or not a secondary-recovery operation is economically successful is the ratio of injected fluid to oil recovered. This ratio may be expressed as the over-all or cumulative gas-oil ratio if gas is the driving medium, or water-oil ratio if water is the driving medium. Recent theoretical and experimental work has shown that the relative amounts of

Jan 1, 1944

By Laurence C. Hicks

Consideration of the past work on the subject of the diffusion of chromium into iron suggested that additional information might be given by the use of X-ray spectroscopy in following the concentration changes through the diffusion zone. Grube and Fleischbeinl packed rods of electrolytic iron in a mixture of alumina and chromium. These specimens were heated in an atmosphere of purified hydrogen for varying lengths of time. After treatment the specimens were examined metallographically and showed the usual structure, consisting of a border of radially oriented columnar grains ending in a sharp boundary line. Reference is made to the fact that etching with certain reagents will attack only the material inside the border of columnar growth and also to the fact that polishing seems to develop a ridge at the position of the boundary between the etched and unetched areas. By chemical analysis of thin layers turned off on a precision lathe, the authors were able to obtain depth-concentration curves. These curves, reproduced in Fig. 1, show that in most cases a pronounced change of slope occurs, corresponding to the position of the boundary of the columnar grains. In a laler paper Grube extends his work to other systems which show the same characteristics.~ He concludes that the reason for the break in the curve is that a hindrance of diffusion occurs at the place where the regularly oriented grains of the diffusion zone meet the random grains of the interior portion, on the assumption that the diffusion velocity in one direction in a grain may be greater than in another direction, and that the grains in the diffusion zone orient themselves so as to give the maximum diffusion rate. Kel1ey" points out that Grube has failed to note that the boundary line does not consistently cross all grains and

Jan 1, 1934

By T. K. Perkins, L. E. Bartlett

Values of rock surface energy (i. e. energy required to form a unit area of new surface) are useful for interpretation of drilling and fracturing phenonema This paper describes the adaptation of a cleavage technique (splitting of large rocks under controlled conditions) for measuring surface energies. Values of surface energy obtained at room temperature and at low crack extension rates are reported for a variety of sandstones and limestones. Elastic moduli, tensile strengths and compressive strengths of the samples are also reported. The values of Young&apos;s moduli (measured in bending) are relatively low, probably because of the low stress levels imposed. Measured values of surface energy me generally higher than anticipated and probably reflect inelastic yielding near the extending tip of the crack. INTRODUCTION The technology of petroleum production includes many operations such as drilling and fracturing, which involve rock breakage. One of the fundamental properties of a rock needed to fully explain breaking and fracturing phenomena is the surface energy (i. e. the energy required to form a unit area of new surface). In this paper we describe an adaptation of the cleavage method (splitting of the rock under controlled conditions) to utilize large rock samples. Application of the theory of elastic cantilever beams and the Griffith concept of mechanical stability permits the calculation of surface energies from simple measurements. Values of surface energies obtained at room temperature on dry samples and at low crack extension rates are reported for a variety of sandstones and limestones. Measured values of Young&apos;s Moduli, compressive strengths and tensile strengths are also reported for the rocks. THE EXPERIMENTAL METHOD Equipment designed to cleave large rock samples is shown on Fig. 1. This equipment consists essentially of two steel blocks cemented to a rock sample and forced apart with a steel rod. A ball joint and a pivot prevent bending stresses in the rod. A differential thread arrangement permits the rod to advance only 0.012 in./revolution of the driving nut. The axial force in the rod is measured with type FA-50-12 Baldwin Lima Hamilton strain gauges and a BLH type 20 strain gauge reader. Separation of the blocks is measured with a Starrett 656617 dial gauge. The massive nature and design of the equipment minimize the amount of elastic energy stored in the steel parts as the stress in the rod is increased. This will permit the rock to split under controlled conditions as will become clear later. Fig. 2 shows a sketch of the rock sample during cleavage. Guide slots are cut longitudinally along the rock sample as suggested by Berry.1 An initiating slot is also cut across the top of the block to a depth of 1 to 2 in. During cleavage, elastic energy is stored in the flexed beams of rock of length C. If the length of steel rod L is held constant and the crack extends in length, then the elastic potential energy stored in the rock decreases. However, surface energy must be supplied as the crack extends in length. Griffith6 has proposed the following criteria for mechanical stability. The crack will extend as long as the potential energy available is greater than the surface energy required. However, the crack will stop extending when the change in potential energy with change in crack length is just equal to the change in surface energy with change in crack length. See Eq. 1.