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By C. Dirksen

This study investigates whether oxygen consumption during segregated forward combustion may be affected by natural convection. Linear theory indicates that thermal instability occurs in a horizontal porous medium when the modified Rayleigh number N 'Ra exceeds a critical value of about 40. Most experimental results, including those described here, indicate this value to be about an order of magnitude smaller. N ', is derived from "differential similarity" and the proper time scale factor is also obtained. The critical value of N'ra for a horizontal, water-saturated porous medium at atmospheric pressure subjected to a uertical temperature gradient was found to be about 3.0. The ambiguity in the value of N'R, arising when fluid properties cannot be assumed constant is indicated. Natural convection was observed for oblique systems below N 'Ra , while simultaneous horizontal flow did not affect N Racrit. The expected range of values for the various parameters pertaining to segregated forward combustion is indicated and the corresponding values of N 'Ra calculated. Only under very favorable conditions, such as high permeability, high pressure and low top temperature, can the critical value of N 'R, be exceeded. Thickness of the convection layer should not become too large, since the time required to obtain significant mixing is proportional to the square of the thickness. For an oblique combustion frant the conditions for significant mixing may be less strenuous. LNTRODUCTION Laboratory1,2 and field314 experiments have shown that a markedly upgraded oil can be produced by in situ forward combustion. Under certain conditions injected air may move through a high permeability, gas-saturated channel over the oil-saturated layer, while combustion takes place, exclusively, at the horizontal interface (Fig. 1). Such a channel may be a natural gas cap, or it may result from a forward combustion process in which injected air and combustion gases fingered through the top of the formation, causing a premature breakthrough at the production well. In this particular case of segregated forward combustion, the air stream moves parallel to the combustion front. Molecular diffusion and transverse mechanical dispersion will be insufficient to cause all the oxygen in the air stream to reach the combustion front. When the oxygen in the air stream is not completely consumed in the combustion process, it will reach the production well and create a serious fire hazard. In addition, the reduced efficiency may make the process economically unprofitable while also serious corrosion problems may be experienced in the production we11.3 This undesirable situation should, therefore, be prevented. However, in a situation as depicted in Fig. 1, an unstable temperature gradient exists in the gas phase. The combustion is taking place at the lower boundary at a nearly constant temperature that may be anywhere from 600 to 1,200F, depending on the conditions. The upper boundary of the gas phase is overlying, impermeable rock; its temperature might be around 100F, but may increase to 300F or higher due to conduction and convection as the combustion process continues. This represents a steep temperature gradient and it is conceivable that under those conditions free or natural convection will take place in the gas

Jan 1, 1967

By John C. Draper

The principal object of an underground coal mine transportation system is to move coal from the face where it is produced to the outside of the mine where it is prepared for market. In addition to the movement of coal, a transportation system must also move supply materials to the inside ; it must move men in and out of the mine ; and it must move rock and other debris out of the mine for disposal. Usually, mine haulage is divided into three categories named for the various areas of the mine served : 1) Pace Haulage. This is used at face from the mining machine to the intermediate transport system. 2) Intermediate or Secondary Haulage. Generally this is used between face haulage and main haulage. Sometimes this is merely an extension of the main haulage. 3) Main Haulage. This extends from the secondary haulage to the outside and is usually either a track or conveyor system, sometimes a combination of both. Transportation modes of coal in the various areas pose different problems, but the whole system must be synchronized. For instance, at the face the coal should be removed quickly from the various places to facilitate the movement of machines, whereas the intermediate system just passes the same coal on to the main transportation system. Selection of the transportation system must be based on the seam height, mining methods used to extract the coal, capacity required, ease of coal handling, and haulage efficiency. When driving rooms, mine cars can be used. They often simplify supply haulage and rock handling because they can also handle these items. Conveyors could be used and would have a greater haulage capacity but they cannot handle supplies easily or segregate the rock. When using a different mining method, such as longwall, mine cars cannot be used because there is not sufficient space to move the cars at the face nor can the cars haul the coal without delays which would cause excessive losses in production. As for ease of handling

Jan 1, 1981

By J. W. Hickman

Most of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.' In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,~ nickel,= chromium,= copper,z tungsten,s molybdenum,3 beryllium,' uranium,' thorium,' titanium6 and zirconium6 while investigations are in progress on tantalum and columbium. The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally. Examples of solid solutions which may present difficulties are MOO* and WOp, Fe304 and FeO.CrnOa since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of loglo Kg for the several temperatures. AF"B = -RT In KR AF°R and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the the given in I 1 to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium oxide to form

Jan 1, 1949

By Theodor Zuschlag

Electrical prospecting is the art of exploring the structure of the subsoil in regard to conductivity variations and interpreting the results of such exploration as to their geological meaning. Electrical prospecting has been applied during the last few years with outstanding success, not only to prospecting1 for ore but also to structural studies.2 Both applications have proved helpful to the geologist, and the latter application especially promises to become of still greater importance in the future. The mapping of structures is the most important function of the oil geologist. Oil is lighter than water, therefore in water-bearing beds it will migrate upward until the migration is stopped by a bed impermeable to the oil. Geologic structures such as domes, anticlines, faults and terraces, offer good prospects in the search for oil accumulations and can be traced easily by electrical prospecting, provided they are composed of a series of sedimentary layers of which at least one possesses fair electrical conductivity and follows the general trend of the structure. Conditions for Successful Mapping The first condition, fair electrical conductivity, is met in almost any oil-bearing series, because generally the electrical resistance of a sedimentary bed is identical with the resistance of the more or less saline waters, filling partly or entirely the pores of the rocks.3 Briefly, the electrical resistivity of a bed can be expressed for all practical purposes by the product R X P, where R is the specific resistance of the waters in the rock pores and P a factor depending upon the percentage of water by volume in the rock. The specific resistance of any solution can be computed from the chemical analysis, being primarily a function of the

Jan 1, 1932

By C. W. Parmelee

THE ideal fuel for burning ceramic wares is the one that, among other characteristics, has little or no sulfur. For that reason wood was long considered the most desirable fuel but its high cost has practically eliminated its used except in regions where it is very abundant or other circumstances warrant its choice. The fuels commonly employed are natural and producer gas, oil, and coal. The last named is undoubtedly the most important, not only in this country but abroad. Occasionally anthracite is used but the larger part is bituminous. The quality of the coal used depends on the kind and the value of the products being manufactured. For some materials, such as common brick, hollow block, etc., the quality of the coal is of less importance than in the manufacture of polychrome terra cotta, pottery, porcelain, etc. It is obvious that in burning clays that contain notable amounts of pyrite, marcasite or gypsum, as is the case with many common clays, the sulfur content of the fuel is of much less importance. The permissible amount of sulfur in the coal used will depend on the kind of product being manufactured. "A good sample' of coal commonly used in pottery ovens has something like this quantity of sulfur." PER CENT. Total sulfur 1.20 Sulfur in the ash 0.11 Volatile sulfur a 1.09

Jan 9, 1919

By R. S. Busk, R. F. Marande

The magnesium-aluminum-zinc 'system contains most of the magnesium-base alloys used commercially, although in practice the ternary alloys are usually modified by the addition of a small amount of manganese. Table I contains the magnesium-base commercial sand-casting alloys most widely used throughout the world, together with their typical tensile properties. These alloys may be regarded as a single family of varying aluminum and zinc content, disregarding manganese. A concise means of presenting data for them is by means of iso-property lines plotted on triangular coordinate paper. Constitutional, casting, and mechanical properties are presented in this manner. The data are given with the obiect of providing reference material, and to aid in the choice of a commercial alloy to serve a particular purpose. Detailed, critical analysis of the commercial alloys has been covered in a previous paper.' All alloys reported were made in rj-lb. melts, superheated to r700°F. for 15 min., cooled to r400°F. and poured in sand molds. The test bars produced had a 1/2-in. reduced section and were about 6 in. long. Except for the data represented in Figs. I and 3 the alloys used were of commercial purity and contained 0.1 to 0.2 per cent Mn in addition to the aluminum and zinc. Constitutional Data Under the heading of Constitutional Data are included all known data on con-

Jan 1, 1946

By R. F. Marande, R. S. Busk

The magnesium-aluminum-zinc 'system contains most of the magnesium-base alloys used commercially, although in practice the ternary alloys are usually modified by the addition of a small amount of manganese. Table I contains the magnesium-base commercial sand-casting alloys most widely used throughout the world, together with their typical tensile properties. These alloys may be regarded as a single family of varying aluminum and zinc content, disregarding manganese. A concise means of presenting data for them is by means of iso-property lines plotted on triangular coordinate paper. Constitutional, casting, and mechanical properties are presented in this manner. The data are given with the obiect of providing reference material, and to aid in the choice of a commercial alloy to serve a particular purpose. Detailed, critical analysis of the commercial alloys has been covered in a previous paper.' All alloys reported were made in rj-lb. melts, superheated to r700°F. for 15 min., cooled to r400°F. and poured in sand molds. The test bars produced had a 1/2-in. reduced section and were about 6 in. long. Except for the data represented in Figs. I and 3 the alloys used were of commercial purity and contained 0.1 to 0.2 per cent Mn in addition to the aluminum and zinc. Constitutional Data Under the heading of Constitutional Data are included all known data on con-

Jan 1, 1946

By Richard Miller

WORK was undertaken two years ago at the Hammond Laboratory for the purpose of determining the magnitude of the elastic range in single crystals of pure metals by means of creep tests, the assumption being made that if a true elastic range exists, the elastic limit represents the maximum stress for no creep. A sensitive extensometer was constructed, and creep tests were made on zinc single crystals at a variety of loads and temperatures1. It was soon discovered that there is tip measurable elastic limit in ductile zinc single crystals at, or above, room temperature. The inference that pure metallic single crystals may not possess a definite elastic range was not justified, however, since zinc had been tested in creep only above its recrystallization temperature, and several investiga-tors2,3,4 had already shown that above the recrystallization temperature polycrystalline metals will flow under very small stresses, while below that temperature stresses of a much larger magnitude are required. For that reason, it was decided to extend the study of the elastic limit to other metals having a higher recrystallization temperature than zinc. Aluminum and silver were selected, because of the ease of obtaining pure materials and of preparing large single crystals, and because the crystallo-graphic glide system of these metals is well known. Owing to the limited time available, the elastic range was investigated by slow tensile tests rather than by creep tests.

Jan 1, 1937

By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757' and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick 'needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,' are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed' by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke's law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967

By O. B. Bucklen, P. G. Meikle

INTRODUCTION The trend in the coal industry for many years has been to make every- thing "bigger and faster." This also held true for loading and storage facilities. Where once a million ton per year mine was rare, three to five million ton per year mines are not uncommon today in the bituminous industry. This greatly increased production, made possible through mechanization, required greatly improved loading facilities just to get the coal away from the mine. Also, there is a trend toward combining production from more than one mine and cleaning it in a single preparation plant. In addition to increased loading capacity, this frequently necessitates raw coal storage and blending facilities. The development of the unit train with its attendant economics, more than any other factor, has contributed to the widespread construction of storage and high-speed loading facilities. In the export market, the construction of ever larger coal colliers has contributed to a need for faster and larger loading facilities. In this climate of rapidly changing technology, any written account is faced with the possibility of obsolescence before its appearance. Thus, this chapter seeks to define the common and current practice in coal loading and storage facilities with the full knowledge that this practice is an ever-moving target. FUNDAMENTALS OF COAL STORAGE Storage of coal is becoming an increasingly important part of coal handling systems at mines, particularly since the advent of the unit train concept in transportation. In order to take advantage of reduced transportation rates on trainload shipments of coal offered by unit train movement, operators have found that storage is an economic necessity. In unit train practice large predetermined quantities must be loaded in relatively short periods of time as opposed to conventional practice where coal is loaded at a speed dependent on the production capacity of the mine and/or the cleaning capacity of the preparation plant. Two surveys of storage practices at mines reveal several objectives for storage.1, 2 Raw and/or clean coal storage is generally practiced in order to accomplish one, or a combination, of the following objectives: 1. To improve plant efficiency by distributing plant feed over the entire operating time, or to allow a preparation rate different from the production rate. 2. To limit interruptions of supply, ie, allow mine and plant to function independently with delays in one not affecting the operation of the other.

Jan 1, 1968

By J. A. Woolf, E. S. Leaver

The presence of soluble base metals in precious-metal ores usually precludes cyanidation as the best method of treatment. The laboratory experiments described in this paper show the possibility of cyanidation of gold-silver ores containing less than 0.5 per cent. of cyanide-soluble copper and the effect of zinc in the cyanide solution. Part I.—Copper in Cyanidation The proposed process of cyanidation of precious-metal ores containing copper is based on the regeneration of about 80 per cent. of the cyanide used in the dissolution of the copper. The method of regeneration involves a combination of the sulfide and the acid precipitation of the copper and silver. The resultant solution is made alkaline with lime, and the gold is precipitated with zinc dust. Solubility of Copper Minerals in Cyanide Solution In order to determine the solubility of copper minerals, including metallic copper, under the usual conditions for cyanidation, experiments were conducted with synthetic ores. Each ore sample was prepared by mixing the particular pure copper mineral with barren sea sand. Both the mineral and sand were ground to pass 100 mesh before they were thoroughly mixed. The percentage of copper in each head sample was determined by direct assay, excepting the metallic copper sample, which was computed on weights before mixing. Table 1 gives the results. Azurite, bornite, chalcocite, cuprite, malachite and finely divided metallic copper are readily and completely soluble under the usual conditions for cyanidation. Enargite and tetrahedrite are sufficiently soluble to cause an excessive loss of cyanide, and they also cause fouling of solutions with arsenic and antimony. Precious-metal ores containing small percentages of chalcopyrite or chrysocolla may give satisfactory returns with the usual cyanidation.

Jan 1, 1930

By Allen D. Garrison

THE chemistry of clays and shales has been assuming increasing importance in the petroleum industry, and two factors have greatly influenced this trend. The first has been the growing evidence that the marine shales are source beds, and that the petroleum compounds have migrated to the sand reservoirs overlying or underlying these shales: the second has been the demand for drilling fluids better adapted to penetrate these marine shales without difficulty and expense. ORIGIN AND GENERAL COMPOSITON OF CLAYS AND SHALES Clays, shales and surface soils are all closely related materials. They are mixtures of finely divided compounds formed during the weathering of the solid crust of the earth. Their nature is essentially colloidal; that is, their behavior is determined by the state of division of the materials and the surface reactions of the smallest grains. Many of their chemical changes affect only the exposed areas and do not involve the interior of the grains of matter. The extent of these reactions is more nearly proportional to the area of the substances than to their mass, therefore it is possible for a small amount of a material in an extremely fine state of division to completely dominate the character of the mixture. More than 83 per cent of the crust of the earth is composed of three elements-oxygen, silicon and aluminum. Consequently, the corrosion products of the crust are predominantly aluminosilicates, or compounds of aluminum, silicon and oxygen. If we add the compounds of six elements-iron, calcium, sodium, potassium, magnesium and hydrogen-more than 98 per cent of the crust has been accounted for. These six elements, together with the first three, also appear in soils, clays and shales. But direct chemical analysis is of little value in describing the nature of such materials. Many chemical individuals may be present in variable amounts, and the extreme subdivision of any one of the individuals may contribute qualities that dominate the mixture.

Jan 1, 1939

By P. J. Jacquard, C. Jain

Interpreting pressure measurements is one of the fundamental problems in the operation of oil reservoirs. The principal methods and means of study zuhich are currently used are reviewed. Emphasis is placed on the necessity of improving the quality of the information to turn it to the best possible account. One of the important aspects of the problem is the development of a system of automatic interpretation of the pressure measurements. The proposed method aims at this objective: starting from the relation which exists between a local perturbation of permeability and its effect on the velocity potentials in the wells, we determine by successive approximation the modifications to be made to the permeability map by fitting the least squares between the measured pressures and the pressures indicated by the mathematical model. The method has already been successfully employed in the case of heterogeneous reservoirs of radial- circular symmetry. Its application is extended here to the two-dimensional case, and is illustrated by two examples, for which the results are presented. The conditions required for the method to become fully operational are likewise analyzed. I — INTRODUCTION One of the basic problems of production and recovery from oil fields is interpreting pressure measurements made in wells in the single-fluid-phase regime. Simplifying assumptions, for example supposing the reservoir to be homogeneous, make it possible to use more or less simple methods which permit the estimation, from these pressure measurements, of a mean value of the permeability around the wells. Considering the actual heterogeneity of the majority of reservoirs, and the phenomena of interference between wells, these methods are only indicative. Much has been published on the studies of different cases of comparatively simple heterogeneity: some have discussed the radial heterogeneity around a single wel1,l or vertical heterogeneity.2 The results of these works have shown the influence of variations of permeability on the pressure, but unfortunately they are not very useful in practice because they all are concerned with the phenomena around a single well, without interference between wells, and they correspond to relatively simple and theoretical schemes. These studies of reservoirs or parts of reservoirs on a larger scale are made by the electric analyzer or digital model. We define a permeability map and a porosity map, then reproduce the production history of the wells on the wells of the model, and note the corresponding pressures. These pressures are then compared with actuality, and the discrepancies observed are analyzed. From this analysis we deduce the modifications to be made to the maps of permeability and porosity, and repeat until the coincidence between the pressures indicated by the model and the actually observed pressures is considered adequate. We have adjusted the model. Obviously, in this method of investigation, everything depends on the formula which permits the modification of the permeability to approach the adjustment. Considering the complicated nature of the problem, some oversimplified formulas are poorly adapted to reaching a good adjustment. For example, we have shown that the elementary operation of increasing the permeability not far from a producing well to compensate for too low pressures in the well can, in certain cases, express itself by an effect exactly opposite. 3 The project described here is for a system where we begin with the pressure measurements and the several known parameters of the reservoir, and develop the most probable permeability map, taking account of the measurements available and a subdivision of the reservoir fixed a priori. Ideally, this system is conceived as one in which no manual intervention would be necessary. The model simulating the reservoir is only one part of the whole system, and it is neither the longest nor the most complex part. The need to integrate the model into an aggregate of much more extensive processes has led to the adoption of the digital solution, even though a solution combining the digital and the analog is perfectly conceivable. The simulating model is in that case no more

Jan 1, 1966

By R. J. Schilthuis

In 1929, Coleman, Wilde, and Moore1 undertook an investigation of the theoretical decline in reservoir pressure as related to the production of oil and gas. The most important part of this work was presented in an equation defining the relationship between the reservoir pressure, the quantities of oil and gas produced, the oil and gas content of the reservoir, and the properties of the reservoir fluids. With this equation, it appeared that, with sufficient data, it would be possible to calculate the oil content of the reservoir and predict quantitatively the effect of gas-oil ratio on the decline of reservoir pressure. Needless to say, such an expression would be highly important in evaluating fields and in arriving at a choice of production methods to be used. Unfortunately, at the time these investigators published their work, there were not sufficient data available to permit application of the equation. The technique of measuring reservoir pressures had not been developed, gas measurements were uncommon, oil and water production records were in most cases inadequate, and little was known of the properties of the complex hydrocarbon mixtures making up the oil and gas in the reservoirs. For these reasons, little additional work of a similar nature could be done. However, during the past four years many data have been systematically accumulated on reservoir pressures and the properties of oil and gas, and it is now possible to use these data in furthering the studies on the behavior of oil and gas reservoirs. It is the purpose here: first, to present the derivation of a modified form of the equation given by Coleman, Wilde and Moore, which will permit the calculation of what later will be defined as the "active oil" content of a reservoir; second, to derive formulas for calculating the reservoir-energy changes that occur during the course of production, and finally, to discuss the limitations and application of the equations developed.

Jan 1, 1936

By R. J. Schilthuis

In 1929, Coleman, Wilde, and Moore1 undertook an investigation of the theoretical decline in reservoir pressure as related to the production of oil and gas. The most important part of this work was presented in an equation defining the relationship between the reservoir pressure, the quantities of oil and gas produced, the oil and gas content of the reservoir, and the properties of the reservoir fluids. With this equation, it appeared that, with sufficient data, it would be possible to calculate the oil content of the reservoir and predict quantitatively the effect of gas-oil ratio on the decline of reservoir pressure. Needless to say, such an expression would be highly important in evaluating fields and in arriving at a choice of production methods to be used. Unfortunately, at the time these investigators published their work, there were not sufficient data available to permit application of the equation. The technique of measuring reservoir pressures had not been developed, gas measurements were uncommon, oil and water production records were in most cases inadequate, and little was known of the properties of the complex hydrocarbon mixtures making up the oil and gas in the reservoirs. For these reasons, little additional work of a similar nature could be done. However, during the past four years many data have been systematically accumulated on reservoir pressures and the properties of oil and gas, and it is now possible to use these data in furthering the studies on the behavior of oil and gas reservoirs. It is the purpose here: first, to present the derivation of a modified form of the equation given by Coleman, Wilde and Moore, which will permit the calculation of what later will be defined as the "active oil" content of a reservoir; second, to derive formulas for calculating the reservoir-energy changes that occur during the course of production, and finally, to discuss the limitations and application of the equations developed.

Jan 1, 1936

By Roy J. Greenfield, Charles H. Stoyer

A geophysical survey was made in Kylertown, Pa., in an area where the ground water is polluted with acid mine drainage. Since acid mine water is a good electrical conductor, both direct-current electrical and electromagnetic loop methods were examined for their ability to determine the subsurface electrical conductivity structure and from this to imply the location of the acid water. Consistent results were obtained with the two methods and the interpreted subsurface resistivities were consistent with the electrical resistivity measured for water samples. It was demonstrated that fracture traces which act as conduits for ground water flow can be located with electromagnetic surveying methods. Thus geophysical methods for measuring subsurface electtrical resistivity can be used to advantage for monitoring the environmental impact on the ground-water system of acid mine water.

Jan 1, 1977

By R. Woodward Moore

A graphical method of analyzing the data obtained from shallow earth-resistivity depth tests is presented. The method is based upon empirical results and has no theoretical basis. The usual apparent resistivity-electrode spacing curve is used together with a cumulative resistivity-electrode spacing curve plotted on the same sheet. The greatly reduced scale required for plotting the cumulative values of resistivity together with the effect of the summation of the individual resistivity values serves to minimize the effect of purely local surface anomalies and inadvertent errors of measurement. The point of intersection of tangents or straight lines drawn to intersect at zones of maximum curvature in the cumulative curve indicates the depth to the underlying material. Numerous figures are presented in which data from published reports and from recent field studies are analyzed and the results compared with actual depths established by borings or with depth values obtained by the use of theoretical methods of analysis. Smoothly rounded curves of apparent resistivity such as are often obtained in the field, and which have been a serious drawback to attempts to analyze the data empirically heretofore, appear to be susceptible to rather accurate analysis by the method described. The method is best suited to analyses involving shallow two-layer formations. It has been applied successfully, however, in analyzing the data obtained from tests made over shallow three-layer formations. As with most empirical methods, its chief advantage is its simplicity and ease of application. There have been published many papers that discuss the interpretation of data obtained from earth-resistivity tests when using the four-terminal method of electrode spacing developed by Wenner.' The majority of these have dealt with theoretical analyses for two-layer and three-layer formations. Some sets of "master curves" have been presented for use in analyzing field data to determine the depth to the first and possibly the second horizon below the earth's surface. Although practically all of these theoretical methods of analysis have appeared to have particular merit and some have been used successfully in practice, they have been found to be of little value where the local conditions surrounding the test failed to conform to those assumed in the theory. In certain fields, particularly in civil engineering, relatively shallow explorations are often involved and geophysical methods of test must compete with the direct methods of exploration ordinarily used. Only when it can be demonstrated that geophysical methods of test can materially reduce the time and cost of a given exploration project will the civil engineer abandon direct methods in favor of the interpretations of geophysical exploration data. Empirical methods of analyzing earth-resistivity data have been used in many instances in the past. Such methods have been employed for a number of years by the Public Roads Administration in research work relative to the application of

Jan 1, 1946

By R. Woodward Moore

A graphical method of analyzing the data obtained from shallow earth-resistivity depth tests is presented. The method is based upon empirical results and has no theoretical basis. The usual apparent resistivity-electrode spacing curve is used together with a cumulative resistivity-electrode spacing curve plotted on the same sheet. The greatly reduced scale required for plotting the cumulative values of resistivity together with the effect of the summation of the individual resistivity values serves to minimize the effect of purely local surface anomalies and inadvertent errors of measurement. The point of intersection of tangents or straight lines drawn to intersect at zones of maximum curvature in the cumulative curve indicates the depth to the underlying material. Numerous figures are presented in which data from published reports and from recent field studies are analyzed and the results compared with actual depths established by borings or with depth values obtained by the use of theoretical methods of analysis. Smoothly rounded curves of apparent resistivity such as are often obtained in the field, and which have been a serious drawback to attempts to analyze the data empirically heretofore, appear to be susceptible to rather accurate analysis by the method described. The method is best suited to analyses involving shallow two-layer formations. It has been applied successfully, however, in analyzing the data obtained from tests made over shallow three-layer formations. As with most empirical methods, its chief advantage is its simplicity and ease of application. There have been published many papers that discuss the interpretation of data obtained from earth-resistivity tests when using the four-terminal method of electrode spacing developed by Wenner.' The majority of these have dealt with theoretical analyses for two-layer and three-layer formations. Some sets of "master curves" have been presented for use in analyzing field data to determine the depth to the first and possibly the second horizon below the earth's surface. Although practically all of these theoretical methods of analysis have appeared to have particular merit and some have been used successfully in practice, they have been found to be of little value where the local conditions surrounding the test failed to conform to those assumed in the theory. In certain fields, particularly in civil engineering, relatively shallow explorations are often involved and geophysical methods of test must compete with the direct methods of exploration ordinarily used. Only when it can be demonstrated that geophysical methods of test can materially reduce the time and cost of a given exploration project will the civil engineer abandon direct methods in favor of the interpretations of geophysical exploration data. Empirical methods of analyzing earth-resistivity data have been used in many instances in the past. Such methods have been employed for a number of years by the Public Roads Administration in research work relative to the application of

Jan 1, 1946

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

By M. Muskat

A theory has been developed describing the behavior of wells and reservoirs producing by the action of bottom water drives. It is assumed that the pressures are maintained above the bubble point, and that the permeability to viscosity ratio of the water in the flooded zone is the same as for the oil in the oil-saturated pay. Accordingly, the treatment is based on the homogeneous fluid potential theory. The effect of the difference in density between the oil and water is neglected. .4fter deriving the proper potential distrihutions, the nature of the rise of the water-oil interface below the producing wells is calculated. The primary clean-oil-production phase is expressed in terms of the displacement efficiency, defined as the fraction of the pay flooded out by the rising water table at tlle time of first water entry. The variation of this displacement efficiency is calculated as a function of the well spacing, pay thickness, the ratio of the horizontal to vertical permeability, and the well penetration. The important parameter, other than the well penetration, is found to be the ratio of the well separation to the thickness of the oil pay multiplied by the square root of the ratio of vertical to horizontal permeability. It was found that the displacement efficiency continually decreases as this parameter increases, and for values of the latter >3.5, the efficiency varies inversely as the square of the parameter. It also increases with decreasing well penetration. Perhaps the most striking result of this phase of the analysis is the conclusion that in order to explain the delay in entry of water in wells producing by bottom water drives for periods longer than a few days normal production, with drawdowns large compared with the differential density head between the oil and water, it is necessary to assume that the vertical permeability is a very low fraction of the horizontal permeability. An analysis is also given of the production history after the water has broken through, on the assumption that the production mechanism and details of the flow distribution continue to be the same as during the phase of clean-oil production. As is to be expected, it is found that the water cut will increase at an accelerated rate as production proceeds. However, the initial differences between systems of different well penetrations or well spacings with respect to the total clean-oil production gradually decrease in terms of the variation of the water-oil ratio with cumulative production. In particular, by the time the water-oil ratio has reached values of the order of 5 or greater the cumulative recoveries will generally differ much less among various producing systems than their corresponding clean-oil recoveries. Introduction On the basis of elementary geological principles, one may classify effective water-drive fields in two groups. In the first, the entry of water into the oil-producing formation may be characterized as an edge-water encroachment. This term is used to suggest that the motion of the water proceeds largely in a direction parallel to the planes of stratification. This type of water intrusion occurs usually in thin producing zones and in strata lying along structural flanks of appreciable dip. In the second group—"bottom water-drive" fields—the water-oil interface lies in a plane of zero or slight inclination to the

Jan 1, 1947