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By J. J. Arps

This paper reviews the methods currently in use for estimating primary oil reserves and discusses the principles on which these methods are based. Particular emphasis is placed on how these methods change with the type of information available during the life cycle of an oil property. This paper contains various novel estimating methods and shortcuts heretofore unpublished. INTRODUCTION Estimating oil reserves is one of the most important phases of the work of a petroleum engineer since the solutions to the problems he deals with usually depend on a comparison of the estimated cost in terms of dollars, with the anticipated result in terms of barrels of oil. His recommendations to management regarding the best course of action are therefore normally based on the most favorable balance between these two. Specific engineering problems which require such a knowledge of recoverable oil reserves and a projection of future rates are: [a.] the exploitation and development of an oil reservoir; [b.] the construction of gasoline plants, pipelines and refineries; [c.] the division of ownership in unitized projects; [d.] the price to be paid in case of a sale or purchase of an oil property, and the magnitude of the loan which it will support; [e.] the proper depreciation rate for the investment in oil properties; and [f.] evaluation of the results of an exploration program. This discussion will be confined to the various methods and tools which are currently in use for estimating oil reserves to be obtained during the primary phase of an oil-producing reservoir and for a projection of the future production rates. Reserves which may be obtained by secondary recovery methods or fluid injection programs and gas and gas condensate reserves will not be discussed in this paper. Unfortunately, reliable oil reserve figures are most urgently needed during the early stages when only a minimum amount of information is available. Management's interest in the oil recovery from a property—aside from its use for accounting purposes—usually declines when the property approaches its economic limit, just at the time when the reliability of the estimates is at its best. To illustrate this general idea a chart is presented (Fig. 1) showing the three periods in the life of an imaginary oil property. Time is shown on the horizontal axis, while the cumulative production and estimated ultimate recovery are plotted vertically. No particular units are used and this schematical chart is not to scale. During the first period, before any wells are drilled on a property, any estimates will of necessity be of a very general nature, based on experience from similar pools or wells in the same area, and usually expressed in barrels per acre. This will

Jan 1, 1957

By G. A. Moore, D. W. Williams, C. E. Sims

During the past several years the steel casting industry has made studies of heavy castings in which the test bar has been taken from heavy sections rather than from attached or separately cast coupons. It has been noted that the ductility properties of these heavy sections are often lower than those normally expected. Such lowered ductility is usually accompanied by a spotty test bar fracture and the ductility values often can be greatly improved if a low-temperature aging treatment is given to the casting. A loss of ductility of this type is considered "abnormal," since it is not accompanied by an increase of tensile strength or hardness, and "temporary" when the ductility can be restored by aging, The cure of such an abnormal condition represents a real improvement in the quality of the steel. Some hundreds of previous investigations, largely qualitative in nature, have established beyond reasonable doubt that hydrogen is normally present in newly manufactured steel and that this gas, in small amounts, can cause a temporary ab- normal loss of ductility. The commonly observed association of high gas content and low ductility has given strong evidence for the presumption that hydrogen, possibly assisted by other gases, is the primary cause of the low ductility observed. Accordingly, the Steel Founders' Society of America has, since Nov. I, 1944, sponsored investigations at Battelle Memorial Institute whose primary objective is to obtain quantitative information on the relation of the amount of hydrogen and nitrogen in steel, together with associated methods of steelmaking and treatment, to low-ductility effects and porosity. In order that these investigations might proceed on a quantitative basis, hydrogen analyses of a precision considerably higher than any previously reported in the literature were necessary. 'The method chosen was selected entirely on the basis that it had the highest probability of freedom from uncontrollable errors and will be described in detail in another publication.' Briefly, the method used consisted of the hot extraction of solid pieces of steel weighing from 45 to 50 g in a highly evacuated quartz tube maintained at 1050°C (1925°F) for a period of approximately 40 hr. The greatest precautions were taken to eliminate blanks and insure a sound gas-collection system. vacuum and temperature conditions were maintained automatically. Mercury-filled risers were used for the introduction of samples in order that the System could be degassed thoroughly in

Jan 1, 1949

By C. E. Sims, G. A. Moore, D. W. Williams

During the past several years the steel casting industry has made studies of heavy castings in which the test bar has been taken from heavy sections rather than from attached or separately cast coupons. It has been noted that the ductility properties of these heavy sections are often lower than those normally expected. Such lowered ductility is usually accompanied by a spotty test bar fracture and the ductility values often can be greatly improved if a low-temperature aging treatment is given to the casting. A loss of ductility of this type is considered "abnormal," since it is not accompanied by an increase of tensile strength or hardness, and "temporary" when the ductility can be restored by aging, The cure of such an abnormal condition represents a real improvement in the quality of the steel. Some hundreds of previous investigations, largely qualitative in nature, have established beyond reasonable doubt that hydrogen is normally present in newly manufactured steel and that this gas, in small amounts, can cause a temporary ab- normal loss of ductility. The commonly observed association of high gas content and low ductility has given strong evidence for the presumption that hydrogen, possibly assisted by other gases, is the primary cause of the low ductility observed. Accordingly, the Steel Founders' Society of America has, since Nov. I, 1944, sponsored investigations at Battelle Memorial Institute whose primary objective is to obtain quantitative information on the relation of the amount of hydrogen and nitrogen in steel, together with associated methods of steelmaking and treatment, to low-ductility effects and porosity. In order that these investigations might proceed on a quantitative basis, hydrogen analyses of a precision considerably higher than any previously reported in the literature were necessary. 'The method chosen was selected entirely on the basis that it had the highest probability of freedom from uncontrollable errors and will be described in detail in another publication.' Briefly, the method used consisted of the hot extraction of solid pieces of steel weighing from 45 to 50 g in a highly evacuated quartz tube maintained at 1050°C (1925°F) for a period of approximately 40 hr. The greatest precautions were taken to eliminate blanks and insure a sound gas-collection system. vacuum and temperature conditions were maintained automatically. Mercury-filled risers were used for the introduction of samples in order that the System could be degassed thoroughly in

Jan 1, 1949

By L. L. Newman

PUBLIC UTILITY GAS PRODUCTION IN 1802, William Murdock first used retort coal gas to light his house and the Boulton and Watt plant where he was employed. For the next three quarters of a century coal served as the principal raw material for the manufacture of city gas for general distribution. Coal continued to hold its predominant position for another half century after Prof. Thaddeus C. Lowe developed the first practical method of enriching water gas with cracked-oil vapors in an integrated operation. This position, however, was no longer maintained through the medium of direct carbonization of coal in retorts but as a result of using anthracite or coke as the generator fuel in carburretted water-gas machines. The early water-gas machines were extremely crude and the consumption of both oil and generator fuel was very high. However, the cost of installation was considerably lower than for any coal-gas system having the equivalent gas-making capacity, the labor involved was small, and the water-gas machine could be started up and shut down quickly. It thus proved very useful as standby equipment and in taking peak loads from the coal-gas plants. The flexibility of the water-gas machine, furthermore, made it possible to change the candlepower of the gas readily to suit the required conditions. Later, when calorific value replaced candlepower as the standard of gas quality, the water-gas machine was found to be equally flexible in keeping the city gas under complete and convenient control. No basic improvements were made in the Lowe carburetted water-gas process until 1898, when means were added to provide for regular reversals of the flow of steam through the fuel bed. By judicious proportioning of the quantities of up-run and down-run steam, it became possible for the operator to control the hardness and position of the clinker to a degree that previously had been unattainable. Also in 1898, the first by-product coke plant in America to supply city gas was built at Everett, Massachusetts. Later many other by-product plants, of greatly improved design and capacity, were built, but not primarily for city-gas production, chiefly because of the relatively high investment cost per unit of gas made. Cheaper plant construction has been the subject of serious study, and some progress is expected, but other factors, such as plant life,

Jan 1, 1953

By A. L. Pranatis, G. M. Pound

Changes in length of copper foils of varying thickness and grain size were measured under such conditions of low stress and high temperature that it is believed that creep was predominately the result of interboundary diffusion of the type recently discussed by Conyers Herring. The surface tension of copper was calculated and results confirmed previous work within the limits of experimental error. Under the assumption of viscous flow, viscosities were calculated as a function of temperature and grain size. Predictions of the Nabarro Herring theory of surface grain boundary flow were borne out fully and the Herring theory of diffusional viscosity is strongly supported. ONLY a relatively few techniques for obtaining the surface tension of solids are presently available. Of these, the simplest and most straight forward is the direct measurement of surface tension by the application of a balancing counterforce. Thin wires or foils are lightly loaded and strain rates (either positive due to the downward force of the applied load or negative if the contracting tendency of surface tension is sufficiently greater than the applied stress) are observed. By plotting strain rates against stress, the load which exactly balances the upward pull is found and a simple calculation yields a value for the surface tension. The technique is of comparative antiquity, and solid surface tension values were reported by Chapman and Porter,' Schottky; and Berggren" in the early part of the century. Later, the filament technique became fairly well established as a method for determining the surface tension of viscous liquids, and Tammann and coworkers,'. " Sawai and co-worker and Mackh howed good agreement between the values of surface tension for glasses and tars obtained by the filament technique and by more conventional methods. With the increased confidence in the technique gained in these experiments, the method was applied to solid metals and the first reliable values of surface tension of solid metals were reported by Sawai and coworkers10' " and by Tammann and Boehme." More recently, Udin and coworkersu-'" have reported the results of experiments with gold, silver, and copper wires. Similar experiments with gold wires were carried out by Alexander, Dawson, and Kling.'" The excellent review articles of Fisher and Dunn" and of Udinl@ should be referred to for detailed criticism of the foregoing work and for discussion of underlying theory. In all the foregoing calculations, it is assumed implicitly that the material contracts or extends uni- formly along the length of the specimen and also that it flows in a viscous fashion, i.e., that strain rates are proportional to stress. For an amorphous material, such as glass, tar, or pitch, the assumptions are quite valid and good agreement is obtained with values of surface tension measured by other techniques. The values reported for metals, however, are occasionally regarded with misgiving, since it can be argued that, because of their crystalline nature, true solids can not deform in a viscous fashion. If this is true, then the results reported for solid metals over a long period of years are of only doubtful value. Thus it is clearly necessary that a mechanism be established that would explain both the viscous flow and the uniform deformation that has been assumed. Such a mechanism has been proposed by Herring."' Briefly, he suggests that, under the conditions of the experiment, deformation takes place by means of a flow of vacancies between grain boundaries and surfaces. This is a direct but independent extension of the theory proposed by Nabarro" in an attempt to explain the microcreep observed by Chalmer~.In a condensed form the Herring viscosity equation is TRL there 7 is the viscosity, T the absolute temperature, R and L grain dimensions, and D the self-diffusion coefficient. In its complete form, all constants are calculable and it includes such factors as grain shape, specimen shape, and degree of grain boundary flow. When applied to existing data, good agreement was obtained between predicted and observed flow rates. The theory received provisional confirmation from the work of Buttner, Funk, and Udin" who observed viscosities in 5 mil Au wire much higher than those in the 1 mil wire used by Alexander, Dawson, and Kling.'" More significant were the completely negligible strain rates found by Greenough" in silver single crystals. Opposed to these observations were those of Udin, Shaler, and Wulff'" who found indications of viscosity decreasing as grain size increased. Thus, complete confirmation of the theory was lacking in that the data to which it could be applied contained only a limited number of grain sizes. Hence, it was proposed that a series of experiments be carried out with thin foils of varying grain size up to and including single crystals, where, according to the Herring theory, deformation would occur only at almost infinitely slow rates.

Jan 1, 1956

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was ('Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970

By E. R. Helderman, C. Y. Ang, C. C. Nealey

Beryllium-base alloys have been successfully p7.-epared by the liquid-phase sintering technique. Depending orz the composition and amount of the intended liquid please, microstructures either single -phase or duplex in feature with randomly oriented grains have been obtained. Qualitative and semi-qualitative determination of distribution of alloying elements md microsegregations in some experi)uzental alloys haue been made by electron-micro-probe analysis in conjunction with microliardness testing and standard metallography. Tensile tests reoealed that some conzpositions possess attractive elastic properties with Young's mot1uli greater than 40 X 10' psi. In powder metallurgy, liquid-phase sintering is a process or phenomenon that has proven to be of practical value. For example, the heavy metals such as tungsten-copper-nickel, high-strength heavy gyro alloys,' heavy-duty electrical contacts,' and tungsten carbide tool materials are all products of liquid-phase sintering. Mechanisms involved in liquid-phase sintering, however, are not completely understood. Questions regarding the exact roles played by rearrangement of particles, liquid/vapor surface energy, solution and precipitation, and so forth, have not been completely answered. Evidence has been cited3 that at least volume shrinkage in the densification process is diffusion-controlled. It is possible that the predominant mechanisms for the complete densification and grain growth in a liquid-phase sintered system depend primarily on the alloy systems involved, in addition to processing conditions. Despite the lack of sound understanding of the mechanisms of the process, liquid-phase sintering has been and is being used to advantage either to synthesize microstructures for their special properties or to prepare alloys which are difficult to form by fusion process. Liquid-phase sintering of beryllium alloys was first attempted by Jones and Williams.4 They first tried infiltrating beryllium with magnesium, and then succeeded in preparing the alloy by sintering Be-Mg powder compact in molten magnesium bath. This investigation resulted in the identification of some Mg-Be intermediate phases. Crossley et a1.5 also used liquid-phase sintering technique in an attempt to produce ductile beryllium alloys for structural applications. The major liquid-phase components investigated by Crossley et al. were aluminum and silver with minor additives of germanium, calcium, lanthanum, cerium, and yttrium. The lack of wetting and the bleeding out of liquid phase were the difficulties encountered during experimentation. According to Hodge,6 the two compositions investigated by Crossley, which showed some promise based on compression tests, involved large amounts (over 35 wt pct) of silver, thus making them too heavy to be of practical interest to the aerospace industry and military users. The present investigation was prompted by the search for light-weight (density less than aluminum) beryllium alloys exhibiting small anisotropy in physical properties for precision inertial navigation instrument applications. In addition to isotropy, good structural properties such as high elastic modulus or desirable combination of mechanical and physical properties are also objectives of this investigation. The technique of liquid-phase sintering was chosen for its versatility in producing either duplex or homogeneous microstructures. This report is concerned with the use of copper and aluminum, with or without silicon addition, as the intended liquid phase, and the resultant micro-structures and some physical properties of the beryllium alloys. Qualitative and semiquantitative electron-microprobe analyses of some of the alloys are presented to illustrate the usefulness of this microanalytical technique for the identification of microconstituents and their distribution. EXPERIMENTAL PROCEDURES The beryllium powder used was -200 mesh Brush Beryllium Co. QMV NP-50 grade. Typical chemical analysis of the powder is shown in Table I. Commercial high-purity copper, aluminum, and silicon powders all screened to —100 mesh were used as additions. Mixed powder compositions were ball-milled in ceramic jars for 1/2 hr to ensure thorough blending. Milled powder was loaded either in 3/4-in.-diam button die or in Metal Powder Association flat tensile specimen die and compacted under top and bottom pressure. No lubricant or organic binder was used. Sintering was carried out in a quartz tube under a vacuum of 50 to 100 µ pressure. Surface hardness and some microhardness readings were taken on sintered specimens. Sintered density was

Jan 1, 1965

By Leonard D. Jaffe

In recent years, the advantages of tempered martensite as a microstructure for steel parts have been well established. For parts that must not fracture brittlely when loaded at high rates, at low temperatures, or under conditions of combined stress, tempered martensite is especially desirable. One of the factors that determine whether a steel part will have a martensitic structure after heat treatment is the hardenability of the steel. Despite the large amount of recent research, there are still many unsettled basic questions concerning hardenability and its relation to chemical composition, and, indeed, considerable disagreement among investigators in the field. Much of the uncertainty that beclouds the existing knowledge of hardenability arises from the fact that hardenability is still a wholly empirical concept, and has not been quantitatively related to the more fundamental knowledge of isothermal decomposition of austenite. Hardenability is, essentiaily, a measure of the time required for small percentages of austenite to decompose, during continuous cooling, to pearlite, bainite, proeutectoid ferrite, or proeutec-toid carbide. In the practical heat-treat- ment of steel, also, the decomposition of austenite is usually not isothermal but rather during cooling, or, in general, is not at a single constant temperature. Thus, both hardenability and practical heat treatment involve anisothermal decomposition of austenite. In a previous publication1 the author and his collaborators outlined the principles that govern the relations between isothermal and anisothermal decomposition of austenite, and reviewed the experimental information available in 1945. To avoid repetition, familiarity with that article (Paper I) will be assumed, and attention given primarily to work carried out or published since 1945. The method generally employed was explained in Paper I: anisothermal transformation is studied through investigation of the effect of holding austenite at one temperature upon its subsequent decomposition at another temperature. Both temperatures are below the stability range of the austenite. This paper is confined to studies in which only a small amount of transformation occurred at the first temperature. This is the only case of importance in practical heat treatment when an essentially martensitic structure is sought. Materials and Procedure It was necessary to use different steels for the studies involving proeutectoid ferrite and for those involving proeutectoid carbide, beeause the two constituents have not been found to form in the same steel. Several steels were tried and rejected

Jan 1, 1949

By Leonard D. Jaffe

In recent years, the advantages of tempered martensite as a microstructure for steel parts have been well established. For parts that must not fracture brittlely when loaded at high rates, at low temperatures, or under conditions of combined stress, tempered martensite is especially desirable. One of the factors that determine whether a steel part will have a martensitic structure after heat treatment is the hardenability of the steel. Despite the large amount of recent research, there are still many unsettled basic questions concerning hardenability and its relation to chemical composition, and, indeed, considerable disagreement among investigators in the field. Much of the uncertainty that beclouds the existing knowledge of hardenability arises from the fact that hardenability is still a wholly empirical concept, and has not been quantitatively related to the more fundamental knowledge of isothermal decomposition of austenite. Hardenability is, essentiaily, a measure of the time required for small percentages of austenite to decompose, during continuous cooling, to pearlite, bainite, proeutectoid ferrite, or proeutec-toid carbide. In the practical heat-treat- ment of steel, also, the decomposition of austenite is usually not isothermal but rather during cooling, or, in general, is not at a single constant temperature. Thus, both hardenability and practical heat treatment involve anisothermal decomposition of austenite. In a previous publication1 the author and his collaborators outlined the principles that govern the relations between isothermal and anisothermal decomposition of austenite, and reviewed the experimental information available in 1945. To avoid repetition, familiarity with that article (Paper I) will be assumed, and attention given primarily to work carried out or published since 1945. The method generally employed was explained in Paper I: anisothermal transformation is studied through investigation of the effect of holding austenite at one temperature upon its subsequent decomposition at another temperature. Both temperatures are below the stability range of the austenite. This paper is confined to studies in which only a small amount of transformation occurred at the first temperature. This is the only case of importance in practical heat treatment when an essentially martensitic structure is sought. Materials and Procedure It was necessary to use different steels for the studies involving proeutectoid ferrite and for those involving proeutectoid carbide, beeause the two constituents have not been found to form in the same steel. Several steels were tried and rejected

Jan 1, 1949

By J. S. Marsh

Joseph Priestley prepared oxygen on Aug. I, 1774, and noted with great surprise "that a candle burned in this air with a remarkable brilliant flame." On Aug. 2, 1774, some ironmaker possibly began to wonder if this substance could be used to increase his rate of production; at any rate, there is no disputing the fact that the notion of using oxygen for steelmaking in concentrations greater than that available in great abundance—as air—has been in existence for years. Action was delayed by the lack of enough oxygen at a cost within reach of the steelmaker. Within the last several years enough has been available to permit large-scale tests of its use for both combustion, with which this paper is concerned, and for decarburization. The literature is now enormous and easily available; it is sufficient here to cite three items of historic importance in that all are about 25 years old and in that all are remarkably consistent as far as they go, with what is known today.1,2,3 Significance of High-temperature Heat The principal function of the open-hearth furnace is to supply sufficient high-temperature heat to melt the charge and then to increase its temperature to a range suitable for tapping, ordinarily in the neighborhood of 2900°F. That heat is required to make steel is understood by everybody; however, there seems to be some confusion now and then about the significance of high-temperature heat. Transfer of energy—and heat is energy— is always from a point of higher potential to a point of lower potential and, other things being equal, the greater the potential difference, the greater is the rate of transfer of energy. In the open hearth the flame, of course, is the high-potential source. Perhaps the most satisfactory approach is through the notion of theoretical flame temperature, which is the ratio of heat input to the heat content of the combustion products,* the former is composed mainly of heat of combustion of the fuel plus sensible heat of the fuel plus sensible heat of the combustion air. Thus, flame temperature can be increased by increasing the value of the numerator, by decreasing the value of the denominator, or both. The first method is as old as the open-hearth process and, of course, makes use of preheated air; its possibilities have been by no means exhausted. The second method can be put into effect only by changing the composition of the combustion air, since the combustion of a given quantity of fuel produces a definite quantity of product, and since the denominator includes the non-reactive fraction of the air, principally nitrogen. In other words, the denominator consists of the volume of exit gas multiplied by its heat capacity and that volume consists of carbon dioxide and water vapor as reaction

Jan 1, 1949

By H. T. Bowman

FOR more than 80 years the Bessemer process has depended upon the ability, skill, and judgment of the blower, although as early as the 1860's it was recognized that the process would benefit by some type of instrumental control.1 However, instruments with sufficient recording speeds did not exist, so the end-point determination was always dependent upon the blower's eye. This placed an obstacle in the way of precise experimental work, because of the absence of the necessary records and reference points as reported by Work.2 The use of the photocell provided the instantaneous record of the blow that made this experimental work possible and provided more scientific control for the process as discussed by Graham3' A brief description of the progress of the blow will illustrate the recording function of the instrument. The silicon in the iron is being oxidized during the first minutes of the blow, as pointed out by Henning4 in a table showing the order of metalloid elimination. The product of this oxidation is a solid that remains in the converter, so there is virtually no flame during this part of the blow. This low flame luminosity is illustrated by the flame recording shown in Fig. I, where the silicon blow is plainly marked. The dull flame of the silicon blow gradually gives way to the brilliant carbon flame as the increasing quantities of carbon monoxide formed inside the converter burn to dioxide upon contact with the atmosphere above the vessel. When the carbon reaches some low value under 0.20 per cent, there is insufficient monoxide formed to maintain the dioxide flame, so its intensity drops. Throughout the flame drop carbon continues to burn, until at some value around 0.05 per cent an arrest occurs in the recorded drop. This point has been designated as the end point. The period of time from this end point until the vessel is turned upon its side and blowing has stopped has been called the afterblow. This afterblow is used as a measure of the degree of metal oxidation, and uniformity demands that it be controlled within narrow limits. Iron and blowing conditions are likely to change several times during a turn, necessitating corresponding changes in end-point control. It is the purpose of this paper to discuss these changes, the factors that make them necessary, and their bearing upon the quality of steel. CARBON-FEO RELATIONSHIP In the Bessemer process oxidation relationships are precise. Fig. 2 shows a graph of the carbon-FeO relationship. The familiar "bomb-test" method, described by McCutcheon and Rautio,5 was used for obtaining these and all other dissolved FeO values herein reported, all tests being taken from the converter before deoxidation unless otherwise noted. All tests of 0.10 per cent carbon and above were obtained from metal blown for duplexing. McGinley and Woodworth6 reported iron oxide values for blown metal, but their tests were obtained by a different method than were those

Jan 1, 1942

By R. L. Fullman

Relationships are derived between average dimensions measured on a polished cross section and the spatial dimensions of particles dispersed as uniform cylinders. The equations are applicable to the measurement of rods or plates without the stipulation that they be extremely thin. QUANTITATIVE analysis of the elements of mi-crostructures has been limited by a lack of knowledge concerning the relationships between observations on plane surfaces and the spatial nature of the structure. This paper is an extension of previous efforts to establish equations suitable for the quantitative investigation of microstructures. The equations derived fill two gaps in the range of particle shapes for which measurements may be required, namely those shapes lying between extremely thin plates and equiaxed particles (approximately spherical), and those intermediate between equiaxed particles and extremely thin rods or needles. In a previous paper' equations were developed relating dimensions measured on a polished cross section to the average spatial dimensions of particles in the form of spheres, extremely thin plates, and extremely thin rods. For extremely thin rods the dimensions measured on a polished cross section were found to depend on the radius only, so that no information concerning the rod lengths or number of rods per unit volume could be obtained from observations on a cross section. In this paper equations are derived relating dimensions measured on a polished cross section to the spatial dimensions of particles in the form of identical cylinders. These equations may be used to evaluate the dimensions of rods, as well as the dimensions of plates, without the stipulation that the plates or rods be extremely thin. The impossibility of evaluating the length of extremely thin rods from planar measurements appears as an increase in the amount of data required for a given precision, as the length-radius ratio increases. Consider a sample containing particles of a phase in the form of cylinders of uniform radius T and height t. If the cylinders are randomly oriented, as in a sufficiently large sample of a fine grained poly-crystalline material, area and lineal analysis may be carried out with parallel cross-sectional planes and lineal traverses. If the cylinders are not randomly oriented, it is necessary to randomize the orientations of the cross-sectional planes and traverse lines. Let a unit cube be cut from the sample, and a cross-section plane be passed through the cube parallel to one of the cube faces. The number of particles N, cut by the cross-sectional plane per unit area is equal to the number of particles N, per unit volume times the probability p1 of a plane intersecting a single randomly positioned and randomly oriented cylinder in the cube. Let J be the maximum cylinder dimension in the direction normal to the cross-section planes, as shown in Fig. 1. Since, of the various possible positions for the cross-sectional plane over the unit length from top to bottom of the cube, only those positions existing over the length J

Jan 1, 1954

By J. S. Marsh

Joseph Priestley prepared oxygen on Aug. I, 1774, and noted with great surprise "that a candle burned in this air with a remarkable brilliant flame." On Aug. 2, 1774, some ironmaker possibly began to wonder if this substance could be used to increase his rate of production; at any rate, there is no disputing the fact that the notion of using oxygen for steelmaking in concentrations greater than that available in great abundance—as air—has been in existence for years. Action was delayed by the lack of enough oxygen at a cost within reach of the steelmaker. Within the last several years enough has been available to permit large-scale tests of its use for both combustion, with which this paper is concerned, and for decarburization. The literature is now enormous and easily available; it is sufficient here to cite three items of historic importance in that all are about 25 years old and in that all are remarkably consistent as far as they go, with what is known today.1,2,3 Significance of High-temperature Heat The principal function of the open-hearth furnace is to supply sufficient high-temperature heat to melt the charge and then to increase its temperature to a range suitable for tapping, ordinarily in the neighborhood of 2900°F. That heat is required to make steel is understood by everybody; however, there seems to be some confusion now and then about the significance of high-temperature heat. Transfer of energy—and heat is energy— is always from a point of higher potential to a point of lower potential and, other things being equal, the greater the potential difference, the greater is the rate of transfer of energy. In the open hearth the flame, of course, is the high-potential source. Perhaps the most satisfactory approach is through the notion of theoretical flame temperature, which is the ratio of heat input to the heat content of the combustion products,* the former is composed mainly of heat of combustion of the fuel plus sensible heat of the fuel plus sensible heat of the combustion air. Thus, flame temperature can be increased by increasing the value of the numerator, by decreasing the value of the denominator, or both. The first method is as old as the open-hearth process and, of course, makes use of preheated air; its possibilities have been by no means exhausted. The second method can be put into effect only by changing the composition of the combustion air, since the combustion of a given quantity of fuel produces a definite quantity of product, and since the denominator includes the non-reactive fraction of the air, principally nitrogen. In other words, the denominator consists of the volume of exit gas multiplied by its heat capacity and that volume consists of carbon dioxide and water vapor as reaction

Jan 1, 1949

By D. E. Etter, J. E. Selle

The Pu-Ce phase diagram was determined by differential thermal analysis, metallography, and elechm-nricroprobe analysis. The dingram is chararterized by a eutectic with extensive solid solubility in the cubic Phases of both cerium and plutonium. No intermediate phases were found. Cerium is soluble in e plutonium to 16.0 at. pet Ce at 626OC nnd in d plcltoniurn to 23.0 at. pet at 613 "C, decreasing to 17.5 at. pet at room temperature. No solubility in the a, ß, or ? phases was jound, and the mininum cerium required to stabilize 5 plutonium to room temperature is 3.2 at. pet. The maximum solubility of plutonium in 6 cerium is 19.5 at. pet at 721OC, and the maximum soluhility of plutonium in ? cerium is 34.5 at. pet. Invariant points in the system are: a) eutectic at 626oC, L16.5 = E Pu16.0 + y Ce65.5; b) peritectoid at613oC, e Pu13.5 -y Ce65.5- d Pu23.0. AS part of a program aimed at the determination of the phase equilibria in the Pu-Ce-Cu ternary system, preliminary investigations were made of the three binary systems. A survey of the Pu-Ce binary system by differential therma1 analysis indi- cated several areas of disagreement with the published diagram,' primarily in the shape of the liquidus surface. Consequently, a thorough investigation of the system was undertaken, and this report presents the results of the study. EXPERIMENTAL PROCEDURE Three methods of investigation were used: differential thermal analysis (DTA), metallography, and analysis with electron-microprobe X-ray analyzer (EMX). The EMX analysis was particularly useful for the determination of solvus lines. The DTA method was most useful for the determination of the liquidus curves. Metallography complemented both of these techniques. Materials. The cerium metal used for most of this work had a freezing point of 805°C. This material showed 15°C premelting, and was found metallographically to contain some unidentified in~lusions.2 The temperature of premelting is defined as the point at which the DTA curve breaks away from the base line, analogous to a curve obtained from a solid-solution alloy. Several compositions were prepared near the cerium end of the diagram with higher-purity material which had a freezing point of 800°C. etallographic analysis showed this material to be relatively free of inclusions and only 8°C premelting was observed. Major impurities were found by spectrographic

Jan 1, 1964

By F. S. McNicholas, M. S. Walker, V. C. Rogers

During the year of 1944 and the first half of 1945, the Climax Molybdenum Co. made a study of some of the problems in block and panel caving, with the use of a scale model. The experiments dealt essentially with the type of rock and conditions at Climax, but some experiments were carried out to simulate conditions found in other mines. Most of the previous experiments on the caving characteristics of rock have dealt with sedimentary or broken igneous material. The series of experiments described here was designed to show the caving action of unbroken igneous rock. Con- siderable difficulty was experienced in duplicating unbroken material in the model. The results obtained are believed to be relatively correct, but verification must necessarily come from future mine operation. Observations in the mine and glory hole, together with statistical data, were used as criteria for creating similar conditions in the model. In 1913, George R. Lehman' experimented with broken material in a model for the Inspiration Consolidated Copper Co. and, more recently, P. B. Bucky2 experimented with broken material with a capping of mill tailings. Mr. Lehman's model represented a maximum ore height of 70 ft. capped by 55 ft. of waste. He varied the draw-hole spacing from 6¼ ft. to 8? ft. and 12½ ft. The material used graduated from fines to 30-in. maximum size. Some of his conclusions were: "(I) The less the distance between chute centers, the greater the extraction (Fig. I); (2) the higher the ore column, the greater the extraction; (3) the less the amount drawn at a time from each chute, uniformly, the greater the extraction of clean ore before the capping appeared, but not the greater the total extraction to a I per cent copper final product." (Fig. 2.) Professor Bucky concluded, in part: "(I) Drawing of ore may take place at any time from any finger and in any amount without affecting materially: (a)

Jan 1, 1946

By Gerald Edmunds

Castings of pure metals and many alloys usually have a coarse-grained structure characterized by long columnar grains throughout the main body of the casting. Frequently, the surface exhibits finer, sometimes nearly equiaxed grains, and such grains may also compose other parts of the casting. This paper deals .primarily with determinations of the grain-orientation textures of the columnar and surface grains of polycrystalline zinc castings. It includes some results upon a cadmium casting and a magnesium casting. A hypothesis is developed to account for the observations on columnar grains and to use as a basis for predicting orientations in other cast metals. A general description of the position of the columnar grains in castings is that their long axes are approximately parallel to the direction of the thermal gradient during crystallization. Thus, in cylindrical castings the columnar grain axes tend to be radial, and in large flat castings where most of the cooling is through one or both of the large mold surfaces they tend to be perpendicular to the mold surfaces. At the edges and corners the direction of heat flow and therefore the position of the grains is more cornplex. Actually observation shows that even in castings made in flat molds the cooling seems to be somewhat irregular, since columnar grains tend to emanate from certain areas of the cooling surface, indicating that thermal contact was better there than in neighboring areas. The nucleus from which a columnar grain grows may be so oriented that its direction of maximum growth rate does not coincide with the direction of the thermal gradient. In this case the long axis of the grain probably assumes an intermediate position. Notwithstanding these minor irregularities, the situation does exist that the long axes of the columnar grains are generally disposed approximately perpendicular to the mold surface. Schmid and Wassermanl and Nix and Schmid2 have determined the orientation texture of columnar grains in castings of several cubic, tetragonal, hexagonal close-packed and rhombohedra1 metals. For zinc and cadmium, they report the basal plane to be parallel to the columnar grain axes, with no preference for any particular direction in this plane to coincide with the grain axes. This texture, termed a ring fiber texture,3 is uncommon in metals; zinc and cadmium are the only ones reported to exhibit it. Generally, it is stated, a simpler texture exists in which a principal, though not necessarily the most closely packed, crystallographic direction is parallel to the direction of heat flow. In cast magnesium (also hexagonal close packed) they report a digonal axis I, [100] direction, parallel to the direction of heat flow. The writer is not aware of any other orientation-texture determinations on cast polycrystalline hexagonal metals. In view of the observations reported in the present paper it is of interest also to note that Nix and Schmid stated that a

Jan 1, 1941

By Gerald Edmunds

Castings of pure metals and many alloys usually have a coarse-grained structure characterized by long columnar grains throughout the main body of the casting. Frequently, the surface exhibits finer, sometimes nearly equiaxed grains, and such grains may also compose other parts of the casting. This paper deals .primarily with determinations of the grain-orientation textures of the columnar and surface grains of polycrystalline zinc castings. It includes some results upon a cadmium casting and a magnesium casting. A hypothesis is developed to account for the observations on columnar grains and to use as a basis for predicting orientations in other cast metals. A general description of the position of the columnar grains in castings is that their long axes are approximately parallel to the direction of the thermal gradient during crystallization. Thus, in cylindrical castings the columnar grain axes tend to be radial, and in large flat castings where most of the cooling is through one or both of the large mold surfaces they tend to be perpendicular to the mold surfaces. At the edges and corners the direction of heat flow and therefore the position of the grains is more cornplex. Actually observation shows that even in castings made in flat molds the cooling seems to be somewhat irregular, since columnar grains tend to emanate from certain areas of the cooling surface, indicating that thermal contact was better there than in neighboring areas. The nucleus from which a columnar grain grows may be so oriented that its direction of maximum growth rate does not coincide with the direction of the thermal gradient. In this case the long axis of the grain probably assumes an intermediate position. Notwithstanding these minor irregularities, the situation does exist that the long axes of the columnar grains are generally disposed approximately perpendicular to the mold surface. Schmid and Wassermanl and Nix and Schmid2 have determined the orientation texture of columnar grains in castings of several cubic, tetragonal, hexagonal close-packed and rhombohedra1 metals. For zinc and cadmium, they report the basal plane to be parallel to the columnar grain axes, with no preference for any particular direction in this plane to coincide with the grain axes. This texture, termed a ring fiber texture,3 is uncommon in metals; zinc and cadmium are the only ones reported to exhibit it. Generally, it is stated, a simpler texture exists in which a principal, though not necessarily the most closely packed, crystallographic direction is parallel to the direction of heat flow. In cast magnesium (also hexagonal close packed) they report a digonal axis I, [100] direction, parallel to the direction of heat flow. The writer is not aware of any other orientation-texture determinations on cast polycrystalline hexagonal metals. In view of the observations reported in the present paper it is of interest also to note that Nix and Schmid stated that a

Jan 1, 1941

By S. C. Sun, John A. L. Campbell

Objective of the ittvestigation was to determine the electrokinetic differences, if ally, of anthracite lithotypes and thus establish the feasibility of making a coqlstituent separation by froth flotation or other surface-dependent processes. The elec-trokinetic properties were determined by streaming potential methods. In addition, chemical and physical analyses of the lithotypes were made to establish nonsubjec-tive parameters for their diflerentiation. Electrokinetic results indicate a difference in the characteristics of the lithotypes. The isoelectric points of 4 anthracites and 12 lithotypes were obtained. It was suggested that the relative flotation rates of the lithotypes were pH dependent and that the maximum flotation rate of anthracite occurs in an acidic circuit. Although there has been an increased interest in the electrokinetic properties of coal,' research on the subject is still in an early stage of development."' To the authors' knowledge, no electrokinetic studies have been made on coal lithotypes, particularly anthracite litho-types. This paper presents the results of an investigation of the double layer properties displayed at the anthracite/water interface (whole coal and lithotypes) as determined by streaming potential methods. It is hoped that this investigation and related future investigations will provide correlations from which the surface properties of any coal can be predicted and then related to surface-dependent processes such as froth flotation and flocculation. Another aspect of this research, undertaken to determine the physical and chemical parameters necessary for anthracite lithotype differentiation, was previously published.? The number of parameters involved, lithologic, organic and inorganic, and the wide divergence of these parameters within an individual coal limits the practical utilization of the results; however, the result? are of value and of interest in guiding theoretical developments. Keeping the limitations in mind, the results are analyzed in terms of their application to froth flotation processes and are used to indicate the feasibility of making a lithotype separation by flotation. Experimental Procedure Prior to discussing the experimental work per se, it would be of value to establish an understanding of anthracite lithology. Anthracite Lithology: Coal seams display two different modes of variation, rank and type. A coal's position in the continuous series ranging from peats through anthracites determines its rank. The rank of the material under consideration is anthracite. The different bands of coal which constitute a coal seam are distinctly contrasted in regard to physical properties and chemical composition. These megascopic bands are the coal types and are termed lithotypes., A megascopic examination of 11 anthracites revealed three distinct, homogeneous, lithotypes. The classic description of bituminous coal lithotypes as proposed by Stope" was found to be quite adequate for recognizing the three lithotypes in anthracite, namely vitrain, durain, and fusain. The term vitrain describes the brilliant constituent of coal; durain describes dull coal; and fusain is the term applied to fossil charcoal. The anthracites studied were generally found to contain 60-80% vitrain, 10-30% durain, and 1-10% fusain. A complete description of the physical characteristics and chemical composition of the studied lithotypes can be found in a previous publication.' Sample Preparation: Nine of the anthracites used in the investigation were from Pennsylvania, one was from Russia, and one from Wales. Table 1 shows the various designations and sources of the employed anthracites. The letter V, D, or F added to the whole coal designation indicates respectively the vitrain, durain or fusain lithotype of that coal. The samples were carefully collected to avoid contamination. To insure against oxidation, the samples were obtained as fresh as possible and stored under nitrogen or water. Generally a representative sample of the seam and samples containing high concentrations of one or another of the petrographic constituents were secured for each coal. Pure lithotypes were prepared by manual separation and selection. The pure lithotypes and representative samples were ground to —35 mesh and screened to 35 x 48 mesh. The 35 x 48-mesh fraction was then passed over a magnet to remove iron contamination, washed with doubly

Jan 1, 1971

By Charles E. Mann, Douglas J. Lootens, Rufino B. Bomasang

INTRODUCTION The economy of the Philippines, like that of many other developing nations, has been severely strained by the rapid escalation of imported crude oil prices over the past decade. In an effort to reduce its dependence on imported crude, significantly increased emphasis, both in the public and private sectors, is being placed on the rapid development of Philippine coal resources. This paper is designed to present an overview of the Philippine coal industry, its historical development, present status, and future potential. COAL RESOURCES AND RESERVES In 1977, a British consulting firm collated all available data on Philippine coal resources and estimated the total coals potential at about 0.9 to 1.4 billion metric tons (mt). In 1981, using more recent data the Philippine Bureau of Energy Development (BED) estimated the potential at 1.7 billion mt. The BED estimated the proven coal reserves at 257 million mt. These coal resources are scattered throughout the major islands comprising the Philippine archipelago. However, about 52 percent of the currently proven reserves are located in the tiny island of Semirara between the islands of Mindoro and Panay. About 25 percent is located in the Cagayan Valley in northeastern Luzon while 13 percent is located in Mindanao. The remaining 10 percent is scattered in the islands of Cebu, Samar, Mindoro, Negros, Polillo, Batan, and Catanduanes. The bulk of Philippine coal is sub-bituminous in rank. Some bituminous coal with coking properties has been reported in Malangas, Zamboanga del Sur in western Mindanao, and in Catanduanes, but the exact tonnages have not been accurately established. It is believed, however, to be at most 5 million tons. A little semi-anthracite coal exists in Malangas with the remaining unmined reserves estimated at a little more than one million tons. Table 1 shows the quality ranges of Philippine coal deposits.. Figure 1 shows the distribution of known Philippine coal resources PHILIPPINE COAL PRODUCTION In 1981, total coal production was 330,720 mt. Though modest by world standards, this was the highest production figure in Philippine coal mining history. This came from 25 mines, mainly small scale underground mines of capacities varying from 10 to 100 tons per day (tpd). The actual production capability was about 800,000 mt in 1981, but the producers had to scale down production to the level of local demand. Even then, some 50,000 tons of coal remained unused by year-end. The 1981 production came from the following areas: Cebu 224,751 mt (68%) Zamboanga del Sur 57,095 mt (17%) Semirara 13,222 mt (4%) Polillo 17,132 mt (5%) Cebu has always been the main source of Philippine coal production. Coal mining has been carried out in Cebu for the last 50 years, although it has been characterized by a very crude mining technology. Due to the limited size of coal deposits and complicated geology, however, Cebu's share of the total national production is expected to go down to only 10 percent by 1985. Except for Semirara's open-pit production, the balance of Philippine coal production comes from underground mines. These underground mines generally use room-and-pillar methods, except for those at Zamboanga del Sur and Polillo which use modified longwall methods patterned after those used in Taiwan. Due to the much higher mining recovery, most underground mines are now planning on switching to longwall. At Semirara, an open pit mine is now being developed for a one million ton per year capacity by 1984, and will then be the largest Philippine coal mine. While present earthmoving work is done with bulldozers, loaders, and trucks, the main coal extraction equipment will be bucket wheel excavators imported from Austria. PRESENT COAL UTILIZATION Existing coal production is sold mainly to coal- fired cement plants and power plants. The balance is sold to a sugar central, a coconut oil mill, a food processing plant, and two plants producing carbide and ferro-silicon alloys.

Jan 1, 1982

By P. Hazebroek, C. S. Mathews, E. E. Allen, H. C. Lefkovits

A rigorous study was made of the behavior of reservoirs composed of horizontal layers, unconnected except at the well and filled with a compressible fluid. The report is presented in two parts. Part I deals with the practical implications of the results obtained; Part 11 contains the mathematical derivation of the solution. The main portion of Part I is concerned with application of the results to reservoirs composed of two layers. Relative rates of depletion of the layers are studied, and it is shown that differential depletion between layers exists in the transient stage of the reservoir, which generally is of an order of magnitude longer than the transient stage in a single-layer reservoir. In the transient stage, the more permeable layer is depleted faster than the less permeable. However, the reservoir approaches a steady-state situation where both layers contribute equally to production. Theoretical build-up curves from such reservoirs are presented, and the influence of a skin effect and flow into casing and tubing are also evaluated. The build-up curves are predicted to have, first, the familiar logarithmic straight-line section and, subsequently, a rising and flattened section. The results found are compared with an extension of an approximate theory, and it is found that this simplified theory is applicable over most of the life of the reservoir. Extensions to reservoirs containing more than two layers are indicated, and examples of the performance and build-up curves for three-layered reservoirs are presented. The theoretical results on build-up curves were applied to field examples of such reservoirs, and satisfactory results were obtained. From the build-up curve, the pemeability-thickness product, the wellbore damage and the static pressure are obtained. However, it apparently is not possible to determine the properties of the individual layers from the combined build-up curve. A large number of reservoirs have been found where the producing formation is composed of two or more layers of differing physical characteristics, such as permeability and porosity, and where also the thicknesses of the layers differ. Since in general a differential depletion should exist between the layers of such reservoirs, it would be advantageous to know the amount of the differential depletion under a given production history. It also would be valuable to know the pressure behavior, because it could be undesirable to produce a reservoir in such a manner that the pressure in one of the layers would have fallen below the bubble point of the oil at a time when another layer might still be virtually undepleted. The determination of static pressures in shut-in wells with slow build-up is another feature of importance in layered reservoirs. If the behavior of the reservoir differs appreciably from the predicted behavior of a single-layer reservoir, the type of analysis for build-up curves suggested for single-layer reservoirs is not applicable. Several authors have treated the problem of finding the pressure and production characteristics of multilayer reservoirs. Horner treated the problem of n layers in an infinite field, the layers being connected only at the well. Tempelaar-Lietz2 has presented an approximate treatment of the characteristics of a bounded reservoir composed of two layers of different permeabilities and equal thicknesses. Homer gave no information on differential depletion between layers, and the treatment of Tempelaar-Lietz was not applicable for prediction of pressure build-up behavior. In addition, it was thought that a more rigorous treatment than the one by Tempelaar-Lietz would be valuable in determining the range of validity of this solution. The present study, therefore, was made of a bounded reservoir composed of two or more layers,