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By H. M. Kraner, R. C. Devries, K. H. Gee, E. F. Osborn

On the basis of liquidus measurements in the system COO-Mg0-Al2O3-Sio, and previously published data, diagrams have been constructed at 5 pct Al2O3, intervals from 5 to 35 pct Al2O3,. Liquidus temperatures and primary phase fields are shown. The optimum composition of a blast furnace slag for a given alumina content is indicated. At the optimum point, ordinary slags will be entirely liquid and will have maximum desulphurization potential and minimum viscosity. The relation of optimum composition of slags to the "plateau region" of the liquidus surface, and the application of these data on synthetic quaternary slags to actual slag compositions are discussed. Index of refraction of glasses is given as well as composition, temperature, and phase data for each mixture. THE usual blast furnace slag, as a first approximation, can be considered a mixture of the four oxides, CaO, MgO, Also,, and SiO,. Systematic, extensive data for the quaternary system, CaO-MgO-A1,0,-SiO, is therefore required for the understanding of the properties of such a slag as a function of composition and temperature. With sufficient data, it should be possible to fix unequivocably the relative amounts of lime, magnesia, and silica required for a given alumina content to result in a slag composition having optimum properties. Other constituents, such as FeO, MnO, Ti02, and S, have an effect on the properties of a slag, but as long as they are present in small and approximately constant amounts they produce only a second-order effect superimposed upon the major changes in properties of slags determined by the relative amounts of the four major components. Viscosity and desulphurization data have been reported for mixtures approaching blast furnace slags in composition, but systematic liquidus data have not been obtained. Inasmuch as a slag must be all liquid in order to be most effective as well as practicable, clearly the temperature above which a mixture is all liquid (liquidus temperature) is a type of data needed. Such data have been obtained through the study of 446 compositions and are pre- sented in this paper along with a discussion of their bearing on the optimum composition of blast furnace slags. For an orderly presentation of the data, the quaternary system is viewed as a tetrahedron with one component at each apex. Fig. 1 shows a tetrahedron representing the system Ca0-Mg0-A1,0,-Si0,. The base is the ternary system Ca0-Mg0-SiO,, A1,0, is the top apex, and the front face, the system CaO-

Jan 1, 1955

By C. L. Mantell

ALTHOUGH SO common and well known a metal, tin is really a less abundant element than many of those less familiar and usually ranked with the scarce or rare elements, such as cerium, yttrium, lithium, beryllium., titanium, zirconium and vanadium. The color of tin is white, with a slightly bluish tinge. When it is compared with nickel, the latter metal is brown. When placed alongside of tin, chromium is definitely blue. Tin is whiter than silver or zinc. Exceedingly thin films of tin show various shades of brown by transmitted light. The metal has a brilliant luster, and when mirror-polished, has high light reflectivity. The luster depends to a large extent upon the pouring temperature at which the metal is cast. If the temperature be, too high, iridescent colors may show on the surface. These are the result of oxide film formation. If the pouring temperature be too low, the surface is dull. Small amounts of foreign metals, such as lead, arsenic, antimony and iron, decrease the luster of tin and impart a yellowish tinge to the metal. The structure is decidedly crystalline. The cast metal is a mass of crystals. When a bar of tin is bent, it emits a characteristic creaking sound. This is called the "cry" of tin, resulting from the grinding of the crystals one against the other during the bending of the metal. Tin metal may lose its crystalline structure by cold working, but grain growth occurs rapidly under the influence of heat. Metal which has been cast at a low temperature may become amorphous as the result of mechanical work. If such material be heated to temperatures well. below the melting point, say at 110° C. for a half hour or for a few minutes at 150° C. recrystallization occurs. If the surface of tinned plate, tin foil, or tin metal in cast form be etched with hydrochloric acid containing a little free chlorine, attack occurs at the intercrystalline faces. The surface shows patterns resembling the frost flowers on window panes in winter. The etched appearance is called moiré metallique. Fine dendritic surface crystals of tin may be obtained by casting the metal on a surface of polished steel. In commercial tin plate, the intercrystalline boundaries are shown by fine grooves or channels, which result from the method

Jan 1, 1929

By C. G. Grant, Wm. B. Price

This investigation of low copper-nickel silvers was untiertaken to check the work of Lèon Guillet on special brasses and to determine, more accurately, the effect of the addition of nickel on the mierostructure of the binary alloys of copper arid zinc. It was hoped that the results could be successfully applied to the practical production of low copper-nickel silvers. To explain the results of his investigations on special brasses, Lèon Guillet evolved his conception of "fictitious compositions." He states,' in his general conclusions, that on the introduction of a small amount of a third metal to a copper-zinc alloy, it enters into solid solution with the normal constituents up to saturation, but by so doing it brings the ternary alloy into a state microscopically equivalent to a binary copper-zinc alloy of fictitious composition, and physically more nearly like the latter than the brass containing copper-zinc in the ratio actually present. The physical properties of the ternary alloy, when compared to the same properties of an actual brass of the fictitious composition, are modified by the natural properties of the third element. Beyond the point of saturation, a special constituent appears and the above generalization no longer holds. For example, if a 60:40 brass has 4 per cent. of tin substituted for 4 per cent. of zinc, the actual composition would analyze 60:36:4. Assuming that 1 per cent. of tin plays the same part as 2 per cent. of zinc, the proportions of copper and equivalent zinc may be stated as 60 parts of copper and 44 parts of zinc, which, figured to 100 per cent., gives an analysis of 57.7 per cent. of copper and 42.3 per cent. of zinc, the fictitious composition for a 60:36:4 tin brass. The relation between ternary alloys containing copper and zinc together with a third metal, and the microscopically equivalent binary alloy of copper and zinc, may be expressed mathematically.

Jan 1, 1924

By N. J. Grant, D. S. Bloom

THE development of high temperature, high stress alloys had proceeded with such rapidity during the war, and for a short time afterward, that our knowledge of the constitution of the alloys had become seriously inadequate. To interpret correctly alloy behavior it is not only necessary to recognize the phases present, but also to know the properties of the phases under all varieties of conditions and treatments. Chromium in these high temperature alloys holds the unique distinction of being the only one element which must be present when an oxidizing or generally corrosive atmosphere is present and when a long life is desired in service. Carbon and nitrogen must also be considered where chromium is present. Carbon is always present, either as an impurity in the raw alloying elements, or as a deliberate addition agent to increase the strength. Nitrogen is generally picked up from the atmosphere during melting or may be added as an alloying element. The effect of nitrogen additions is not too dissimilar to that of carbon additions. As such, chromium carbides and nitrides become of great interest since they are present in a very large number of alloys, including alloy steels, stainless steels, super alloys, and the like. In the chromium-carbon system there are three accepted, carbides: Cr,C, Cr7C8, and Cr3C2. The existence of one more carbide, a still higher carbon form CrC, has been advanced. The phase diagrams of chromium and carbon as published by Friemann and Sauerwald² and by Tofaute, Kuttner and But- tinghaus³ -do not extend beyond the carbide Cr3C2, which contains 13.3 pct carbon; but Hatsuta has extended the diagram up to 20 pct carbon, and in doing so hypothesized, with the use of some questionable experimental results, the compound CrC. This carbide would contain 18.75 pct carbon, 81.25 pct chromium, by weight. It is further known that as the chromium carbides increase in carbon the acid resistance increases but the oxidation resistance decreases4,5 This is of great importance in high temperature alloys where time-temperature stability, as well as oxidation resistance, is of prime importance. The possible existence of a carbide of the formula CrC thus becomes of prime importance and it was considered important to recheck the chromium-carbon binary constitutional diagram for such a compound. In view of the wide spread of values listed for the melting point of chromium (1500° to 1850°C) and 1930°C8, it was considered .that the liquidus temperatures might well be redetermined more ac-

Jan 1, 1951

By J. E. Walstrom

While intensive research continues to promote a more complete understanding of the potential and resistivity measurements that comprise the electric log, it is believed that consideration should also be given to translating these numerous and often widely separated findings into a coordinated and readable body of fundamental facts designed specifically for the petroleum engineer and geologist. Although provision is made through publication for a ready exchange of new theoretical concepts. it is also desirable to provide reviews and appraisals of the more established techniques and methods from the operating standpoint so that an economic and practical application may be realized concurrently with the theoretical progress. With these basic premises as a guide the author reviews the presnt state of electric log interpretation. The paper is directed not so much to the logging or research specialist as to the petroleum engineer and geologist to whom the electric log is only one of the many tools which he employs. Frequently, these persons do not have the time to follow in detail the many specialized contributions that appear and, as a consequence. are not in a position to place these contributions in proper relation to each other, or to the art as a whole. The paper reviews the basic steps in making quantitative determinations from the electric log of the amount of oil or gas present in subsurface formations and also discusses the degree of reliability of these determinations under various conditions. The paper also indicates the trend of future developments in electric logging systems and methods of interpretation. INTRODUCTION The electric log has been used about 20 years as a means for studying the formations penetrated by a well bore. The first half of this period is characterized by the development of suitable logging techniques and equipment. Although progress in this direction is continuing at a satisfactory rate, the last ten years are characterized more by an increasing interest in methods of electric log interpretation. During this period, a large number of fundamental papers have been published, expounding various logging techniques and particular phases of the interpretation problem. Many of these papers represent important contributions, and a few are classic. This paper is an effort to outline as concisely as possible and in simple terms the main course of progress in electric log interpretation. More specifically, it is the purpose of the paper to review the necessary elements and basic steps used in making quantitative determinations of water saturation from the electric log; and to point out the degree of reliability of these determinations under different conditions. It is strongly advised that the operating staffs of the drilling and exploration departments of oil companies cooperate wholeheartedly with both the electric logging service companies and research organizations in the testing and development of new logging systems and interpretation methods. One purpose of the paper is. however, to indicate the degree of caution which must be exercised in placing confidence in new techniques and interpretation methods that have not been thoroughly tested in the field. It is entirely possible to be cooperative in trying new methods and yet reluctant to believe in the results until the methods are firmly established. It is important to define the meaning of quantitative electric log interpretation. In the most general sense, an interpretation of the log has been made when the electrical characteristics of the formations, as portrayed on the log, have been translated into terms describing the formation geometry, rock type, or any other physical characteristics of the formations. The determination that the top of a sand is at a certain depth is an interpretation of the log. Structural determinations made by correlating electric logs from a given area are also interpretations of the logs. The term quantitative interpretation, however, will be used in this paper in the restricted sense to indicate the determination of the water saturation of a formation. This determination defines the fluid content of an oil and gas productive formation only if the porosity is known, and it assumes that the remainder of the pore space contains hydrocarbons. This assumption is believed to be true for most oil and gas productive formations. The quantitative electric log interpretation may he said to be a determination of the fluid content only to the extent which the water saturation, under the conditions given above. defines it. THE BASIC STEPS The fundamental steps in calculating water saturation from the electric log are: 1. Determination of the true resistivity of the formations from the apparent resistivities as recorded on the electric log.

Jan 1, 1952

By K. A. Jackson, J. D. Hunt

A new classification of eutectics is proposed, based on tlze entvopies of wzelting of the tuio eutectic phases. The clnssification was used to predict suitable tvansparent analogs of the metallic systems. Experimental confir?nation loas obtained for the theovetical shape of the lamellar solid-liquid interface, fov the fault mechanisms of lanzellar spacing changes, and for the development of low-energy solid-solid boundaries between the lamellae. An explanation is presented to account jov the irvegular and coinplex regular structures zrhich are found in some eritectic systems. FrOM experimental observations, single-phase materials can be divided into two groups according to their solidification characteristics, those that grow as faceted crystals and those that do not. acksonl' showed from thermodynamic reasoning that the type of growth depended on a factor a which was almost thg entropy of melting. Most nonmetals have high entropies of melting (a greater than 2) and grow with crystalline facets. Most metals have low entropies of melting (CY less than 2) and grow almost isotropically with no facets. The authors propose that eutectics may be classified in a similar manner. There are three groups of eutectics, those in which both phases have low entropies of melting, those in which one phase has a high and the other phase has a low entropy of melting, and those in which both phases have high entropies of melting. Lamellar or rodlike structures are formed in systems in which both phases have low entropies of melting. In these alloys dendrites of either phase may be formed, when the alloy is rich in the relevant component. Examples are Pb-Sn, Sn-Cd, Pb-Cd, Sn-Zn, Al-Zn. Irregular, Fig. 14((), or complex regular, Fig. 14(b), structures are formed in alloys in which one phase has a high entropy of melting and the other has a low entropy of melting. Examples are A1-Si, Zn-MgzZnll, Pb-Bi, Sn-Bi. When the alloys are rich in the low entropy of melting phase, dendrites are formed; when the alloys are rich in the high entropy of melting phase, faceted primary crystals are produced. These crystals are sometimes called hoppers or pseudodendrites. In this work the term dendrite will only be used to describe nonfaceted primary crystals. Dendrites are not formed during solidification in high entropy of melting single-phase materials. The third group of eutectics includes alloys in which both phases have high entropies of melting. Each phase grows with a faceted solid-liquid interface. Since most metals do not have high entropies of melting, metallic examples in this eutectic group are rare. However they may occur between some intermetallics and semiconductors or semimetals such as silicon, germanium, and bismuth. Attempts have been made to study eutectic solidification visually by watching the growth process.374 Since metals are not transparent, the observations had to be made on external surfaces. This difficulty can be overcome by using transparent analogs of the metallic systems. As was mentioned earlier, most single-phase compounds have entropies of melting greater than 2 and so grow as faceted crystals. Recently organic materials with entropies of melting less than 2 were investigated.' These materials grow in exactly the same way as the low entropy of melting metals. When the materials are pure, they grow with a solid-liquid interface parallel to an isotherm; when they are impure, cells or dendrites are formed. Since these materials are transparent, have low melting points, and even have cubic structures, they should be ideal for making up transparent analogs of the metallic eutectics. The purpose of the present work was to investigate these organic eutectics and to see whether this quite different series of eutectics could be classified in the same way as the metallic systems. The observations made on the organic alloys are also discussed with reference to the current theories of lamellar growth. Explanations are proposed to account for the structures formed in the other eutectic groups. EXPERIMENTAL Thin cells containing the organic alloys were uni-direction ally solidified on a specially constructed microscope stage.' Uniform growth rates were obtained by moving the cells, with a motor drive, through a fixed temperature gradient, so that the solid-liquid interface remained stationary with respect to the microscope objective lens. The cells were made by fusing two microscope cover slides 7/8 by 7/8 by 1/100 in. together on three sides, leaving a gap of 1 to 3 mils between the slides, and these were filled by surface tension. A preliminary investigation of the phase diagram between two components could be made very rapidly. One side of the cell was filled with component A and the other side with component B. Since only a small amount of mixing could occur every composition from pure A to pure B was present in the cell. When the cell was placed in the temperature gradient a pictorial representation of the phase diagram was obtained. Eutectics, peritectics, "interorganics", and solid -solid transformations could be readily detected. Fig. 1 shows part of a eutectic phase diagram. The Sample was first grown slowly then stopped. The two

Jan 1, 1967

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.' At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir's work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.' Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By Jr. F. M. Perkins.

Capillary forces play a controlling role in water-drive displacement processes both in laboratory experiments and in actual reservoirs, but their quantitative importance may be quite different in the two cases. Because of the importance of conducting laboratory experiments which are representative of field conditions, it is necessary to understand exactly the role of capillary forces in the displacement process. Though a number of experimental investigations related to this subject are contained in the literature, there appears to be a lack of information pertaining to unsteady-state experiments in water-wet media. This experimental study was conducted to obtain additional laboratory data to clarify further the role of capillary forces in both the macroscopic and microscopic flow of oil and water in porous materials. THEORETICAL CONSlDERATlONS The capillary pressure is defined as the difference in pressure between a continuous oil phase and a continuous water phase in a porous material.' The magnitude of this pressure difference depends on the interfacial curvature and the interfacial tension. The interfacial curvature is determined by the geometry of the pore spaces, the wettability of the rock surfaces, and the quantity of cach phase present. Capillary forces are involved in a water-drive displacement process in that they exert a controlling influence on the microscopic fluid distribution which in turn is reflected in the saturation or macroscopic flow behavior. Microscopic Fluid Distribution Because of the microscopic nature of the displacement of oil by water, it is necessary to consider the flow and the fluid distribution in individual pores. On this microscopic scale the capillary Forces, which act over a distance of one or two sand grain diameters, control the distribution of oil and water under static equilibrium conditions. When an external force is applied to the fluids, such as in a water-injection experiment, the applied forces tend to distort the oil-water interfaces. However, in most fine-grained, water-wet sands, the applied pressure difference across one or two grain diameters is usually several orders of magnitude less than the capillary pressure difference. These con-siderations lead to the theory' that even during flow the capillary forces continue to control the microscopic distribution of oil and water within the pores of a porous material for all practical reservoir and laboratory flow rates. This concept of capillary forces controlling the microscopic distribution of fluids has been substantially verified by other investigators3-7 who have found a lack of dependence of relative permeability and residual oil saturation on rate of fluid injection. Macroscopic Distribution The microscopic influence of capillary forces cannot be observed easily and only the effect on the macroscopic or average saturation can be detected. The saturation, of course, is really the point of interest. During a water flood, large differences in saturation at the flood front cause large capillary pressure gradients. This, in turn, causes water to advance ahead of the flood front thereby reducing the capillary pressure gradient in this region. The result is that in homogeneous porous media capillary pressure gradients tend to cause a diffuse displacement front. At low rates in laboratory columns, the front may extend over the entire column length. When the advancing water first reaches the outflow face of a core, the water, which is the wetting phase, cannot be produced because the pressure in the water just inside the core is lower than the pressure in the oil-filled space around the outflow face. This difference in pressure is equal to the capillary pressure for the water saturation existing at the outflow face. Water, therefore, accumulates at the outflow end of the core which causes a reduction in the capillary pressure. Because the capillary pressure does not vanish except at the residual oil saturation,7,8,9 water will not be produced until the residual oil saturation exists at the outflow face. This entire effect,"' which is called the "boundary effect", results in a region of relatively high water saturation near the outflow face. At low rates of injection in a short column, this region of high water saturation may extend over a considerable portion of the column. The influence of capillary forces on the macroscopic flow of oil and water have been described by Leverett.10 For unidirectional, viscous flow in the absence of gravity segregation, the expression in dimensionless form for the fraction of water in the flowing stream, f, is

Jan 1, 1958

G. O. SMITH,* Washington, D. C.—This program is itself a demonstration of the widespread interest in the subject of more efficient development and operation of oil fields. The statements of fact already presented and the views expressed are sufficient evidence that the engineering and economic principles fundamental to the idea of unit operation are much more generally accepted than they were even one year ago. And real progress has been made in putting these principles to the test. No one realizes better than I that the fight against waste, whether physical or economic, must be waged in the front-line trenches: Washington at best is only an observation post. Yet viewed from this distance the advance made in the last few months has been notable and to a high degree encouraging. Five years ago the Federal Oil Conservation Board, in its first contacts with the industry, raised the question, "How can new pools be explored without exploitation until new production is warranted by the country's needs?" Three and one-half years ago the Board, in its first report to the President, paid largest attention, among what it listed as fundamental conservation measures, to "cooperative methods in sane development of new fields." A year ago, in its third report, the Board again endorsed as the essential factor in conserving the nation's reserves of oil, "full cooperation in unit control, whether by voluntary agreement or by state enforcement." The function of this federal agency has been purely fact-finding and educational. The Oil Conservation Board early declared that the major part of its task was to help the industry "formulate the broader by-laws in the sense of conservation." And now, after these five years of eventful history in the oil industry, may I size up the situation as I see it from the Washington point of view? First of all, and fundamental to a successful issue, I have observed in the industry a gradual acceptance of technical opinion as the guide to executive action; and this has at last led to some agreement as to what procedure offers most promise. Analyzed in more detail, this highly desirable progress has consisted in "self-restraint actuated by enlightened self-interest." We see emerging the general desire of oil producers for efficiency in operation, which means low costs and high recovery. As shown by facts presented at this meeting, competition in drilling is in direct opposition to efficiency in oil production, in that such competition increases costs and lowers recovery. The only route to conservation of this natural resource and also of the capital and labor involved in making it available is through unit control, which substitutes cooperative, well-planned action for competitive, unregulated activity, forced by the individualism of a small minority of landowners or perhaps by a single operator. Or, in terms of actual experience, development of an oil field and its subsequent operation under unit control means the substitution of majority rule for minority rule, yet the minority enjoys to the full the resulting economic benefits. So far as it affects the public interest, unit operation of oil properties deserves unqualified approval. It means more oil from the same area over a longer period

Jan 1, 1930

By J. R. Elenbaas, J. A. Vary, D. L. Katz

The development of gas fields, oil fields and aquifers for storing natural gas is treated from two main vieu.-points: (I) the volumetric storage capacity for gas in a given situation and (2) the prediction of the number of wells required for the delivery of gas. Other experiences in the design and operation of storagc fields are incluclerl INTRODUC TION Storage of natural gas in underground reservoirs near the terminus of long distance pipelines has been the prime factor in opening the space heating market to the natural gas industry. Storagc has permitted a major. increase in both the load and the load factor of pipe-lines; some are now operating at steady load throughout the year. Thus, underground storage has been responsible for the rapid increase in demand for natural gas in recent years. Three types of reservoirs have been used for gas storage: natural gas reservoirs, oil reservoirs, and waterbearing sands or aquifers. This paper presents the factors to be considered when developing gas storage reservoirs of these three categories. There are two prime considerations tor any storage reservoir: (1) the volume of gas which a given reservoir will store advantageously and (2) the number 01 wells needed to provide the required peak deliverability. These two problems will be considered for the three types of reservoirs just noted STORAGE IN PARTIALLY DEPLETED GAS FIELDS Early storage operations consisted of replenishing the natural gas in a depleted gas field situated adjacent to the market. Today, newly discovered fields near the market may be considered for storage, and this discussion applies equally to both types of reservoirs. For reservoirs originally containing gas or oil, the question of the impermeability of the cap rock nor-mally does not arise. However, such fields are likely to have many wells drilled either to or through the reservoir under consideration. Positive assurance must be obtained that such wells are or can be made mechanically tight. Corroded casings may need to be lined or permanently plugged. Abandoned wells should bc reopened and properly cemented. The volumetric capacity for gas storage depends upon space available in the porous rock as well as pressure and temperature of the gas in the reservoir. The production-pressure decline data on partially depleted gas reservoirs without water drive permit calculation of the reservoir space for gas. Isopachous maps of sand volume and porosity data for the reservoir rock provide an alternate method of calculating the pore volume for water-drive reservoirs. The pressure range selected for the storage cycle depends upon ()) the safe upper limit of pressure. 2) the flow capacity of wells and (3) compression requirements when injecting gas into the reservoir or delivering to market. Normally, gas and oil fields have pressures at discovery in the range of 0.43 to 0.52 psi/ft of depth. Pressures of around 1.0 to 1.2 psi/ft of depth appear to lift the overburden1-3 and invite uncontrolled movement of fluids in the porous rock. Some top pressure is normally selected for a storage reservoir ranging from below discovery pressure for deeper reservoirs to 0.65 psi/ft of depth for shallower reservoirs. Pressures to 0.66 psi/ft have been experienced without difficulty. The lower pressure limit is set by water intrusion accompanying low pressures, reduced flow capacity for wells at lower pressures and compression requirements. Depletion-type gas reservoirs often encounter water problems in the later stages of gas production. Such water intrusion may be due to movement from the surrounding aquifer. Accordingly, displacement of this water back into the aquifer by gas pressure and subsequent surges of water corresponding to the gas storage pressure cycle must be considered. Storage fields often produce in four months a volume of gas equal to its initial content. Rapid decreases in reservoir pressure occur, such as 20 psi/day. Accordingly, closed-in pressure observation wells which reflect the pressure in the bulk of the reservoir are required for following the operation of the reservoir. It has been found that a plot of observation wellhead pressures against gas content, Fig. 1, is very useful in observing operation of the field, checking the inventory and predicting future behavior. The plot is based on a given quantity of base or cushion gas in place. The injection and withdrawal curves may spread depending upon the homogeneity of the reservoir rock. permeability of the rock, well spacing and flow rates.

By K. G. Davis, P. Fryzuk

VALUES for the equilibrium distribution coefficient, ko, are required for solidification studies. The procedure generally adopted1-3 is to progressively solidify alloy rods over a range of growth rates, under conditions where a high degree of convective mixing is present in the melt. The measured effective distribution coefficients are plotted as a function of growth rate, and the extrapolated value at zero growth rate is taken to be the equilibrium ko. The method is limited by the experimental difficulty in obtaining steady growth rates less than approximately 10-4 cm per sec. Extrapolation from rates greater than this can lead to inaccuracy. In the present investigation, an alternative method for determining ko, previously used by the authors for the Ag-Sn system,' was applied to alloy of thallium in tin. Specimens were grown under conditions where convective mixing was absent, and experimental concentration-distance curves in the region of the initial transient were compared with curves calculated for trial values of ko. The ko which gave the best fit was taken as the correct value. To obtain the calculated curves, a value for the diffusion constant in the liquid near to the melting point was needed. This was determined by the capillary-reservoir method. Diffusion Constants. Details of the experimental procedure used by the authors in the capillary-reservoir technique have been described in previous papers,5'6 the only variation being in the use of Tl204, a ß emitter, as tracer, in contrast to previous work where ? emitters were used. The activity of a ß-emitting sample, as measured in a Geiger counter, is proportional to the surface area. To measure the concentration of thallium along the capillary after diffusion had taken place, the solidified capillary (1 mm diam) was cut into 2.5-mm lengths and each length compressed between parallel steel plates to form a disc approximately 5 mm in diam. The discs were placed in a flat-bottomed dish, covered by a thin lead shield with a central aperture, and counted in a 0 counter with fixed geometry. Each disc was etched lightly in a dilute solution of nitric and hydrochloric acids a short time before counting, to eliminate sur-

Jan 1, 1968

By Paul Munoz

TRINIDAD, which has never been. seriously consid-ered as a large oil producer, has recently taken a new lease on its oil life through active development work being carried on by a newly organized American company that has been conspicuously successful in the short time in which it has operated on the island. From an oil operator's point of view Trinidad pos-sesses numerous natural advantages which are not found in any other oil producing country. The climate, while tropical, is healthy. The nights are always cool. Deep-water shipping ports in protected waters are available within short pipe-line distance from the pro-ducing fields. The distance from Trinidad to the At-lantic seaboard of the United States is less than from the Gulf Coast or from Mexico. The labor supply is abundant and can be had at reasonable rates. The island enjoys a good, stable government under British rule and is traversed by a net-work of excellent govern-ment roads. From a production standpoint the fields being de-veloped by Trinidad Oil Fields, Inc., the company re-ferred to above, present interesting problems which are being successfully solved. The oil sands are extremely fine; some of them having over 50 per cent passing 100- mesh screen and, with the exception of the Palo Seco field, the sands are loose, with shale-breaks and shale capping and with rock pressures running up to 600 lb. per square inch. Rotary drilling is universal, as the formations encountered are soft Tertiary shales, clays, sandy shales and sands, with occasional sandstone and lime shells, which are easily drilled with the rotary. As high as 600 ft. of hole in 24 hr. has been made in some of this company's wells. Production is at present obtained at depths ranging from 500 to 2500 ft. but further development will probably result in deeper pro-duction being obtained. The oil being produced ranges from 21 deg. to 37 deg. Bé gravity and is all asphaltic base oil.

Jan 7, 1927

By G. E. Steudel

THE study of the possibility of effecting a lower cost in the manu-facture of pig iron reveals the importance of the ever present question of slag chemistry and volume. Factors that determine slag chemistry and volume are the impurities in the ore available, the ash-sulphur content of the coke, and a flux material necessary to promote removal of sulphur. Of these, the ores present by far the major source of impurities and what may prove to be the lowest practical slag volume with desired chemistry in one locality may be considered low or high in some other center of iron manufacture. The Chicago district is not only blessed with ores of high quality, but with excellent coke and flux materials as well. It is the intent of this paper to discuss slag problems at the South Works only, where burdens consist of Mesabi ores, Michigan stone, and coke ranging from 7 to 9 per cent ash and containing an average of 0.57 per cent sulphur. Early in the development of modern blast-furnace practice, the con-sideration of slags was secondary to the many adjustments of mechanical difficulties, such as furnace lines, stock distribution, stove design for obtaining higher blast temperatures, improved chemical segregation and size of raw materials. Furnace operators, after making these improve-ments, turned their attention to the study of other refinements in practice, of which slag chemistry appeared to be the most important. It is only within the last two decades that operators have become familiar with the various aspects of slag compositions. The industry, while rather slow in its recognition, is indebted to such investigators as Rankin,1 Wright,1 Feild,2 Royster,2 McCaffery,3 Kinney,4 Holbrook,5 and Joseph5, whose researches concerning the elimination of sulphur within the blast furnace and the effect of slag composition upon melting point, viscosity, and desulphurizing power have established criteria for the selection of slags of the requisite quality.

Jan 1, 1939

By John Blatchford, H. O. Hofman

The leading antimony mineral is stibnite. In smelting stibnite ore two processes are available, precipitation and roasting-reduction. The former is suited only for high-grade ores. As low-grade ores are more common than high-grade, roasting-reduction is of greater importance than precipitation. In the roasting process the aim may be to leave the oxidized antimony in the ore, or it may be to volatilize as much of the antimony as possible, collect the volatilized oxide as a rich intermediary product and smelt it for antimony, leaving the gangue poor enough to be considered a waste product. Whichever way the roast is conducted certain difficulties inherent in stibnite are encountered. These are: 1. The low melting point of stibnite which, according to Pélabon,' is 550°C., according to Wagemann2 540°C., and according to Borgstroma 546°C. 2. The ignition temperature: According to Friedrich,4 stibnite, if heated in air, begins to oxidize at 290°C. if the size of a grain is 0.1 mm. in diameter; at 343", if 0.1 to 0.2 mm.; and 430" if 0.2 mm. 3. The fusibility of a mixture of Sb2S33 and Sb203 which in the form of kermesite (Sb2S3)z.Sbz03 melts at 517°C.6 4. The volatility of Sb2Ss and SbzOs, for which no numerical data appear to exist, although practical experience has shown that they are volatile at low temperatures. As regards the oxidation of metallic antimony, we have the experimental evidence of C. F. Plattner6 that when fused and brought to a red heat, it burns with a bluish-white flame to Sb2Oa which passes off as a

Jan 1, 1916

By C. L. Dake

Many proposals have recently been made regarding the broadening of engineering education, often with little consideration of the problems their application involves. The chief purpose of this paper is to point out how many and how complex are the questions that absolutely must be answered, in any conscientious effort to solve the problem of liberalizing engineering curricula. Among proposed additions, more training than is now given has been urged in public speaking, report writing, business law and contra s, general finance, money and banking, scientific management, gene ' economics, economic and financial history, social problems, labor pre lems, public ownership, psychology and similar related subjects. T urge in this direction is widespread and persistent. In discussing the blem, the following questions must be given careful consideration, an he absolutely definite conclusion reached: 1. The Present Curriculum Load.—Is this load actually too heavy? In the face of this load, is there room to add broadening subjects to our curricula? Can elimination of present subject matter make room for such additions? Can an elective system accomplish the desired end? 2. Problem of Early Specialization.—Is early specialization a weak ness? Is industry forcing early specialization? Do our varied degrees demand early specialization? Can broadening be harmonized with the present degree of specialization? 3. Graduate Work to Solve the Broadening Problem.—Can we add the desired work in the graduate school? Are the proposed additions of graduate caliber? Is it desired to reduce graduate standards? Can present undergraduate work be removed to the graduate school, to make room for desired broadening courses? Is graduate work normally broadening, or is it specialization ? 4. Importance of Proposed Additions.—Will they increase entrance salaries? Will they increase the engineer's efficiency? Will they raise

Jan 1, 1934

By Leah L. Naugle, H. G. Landau, H. H. Lowry

EVIDENCE has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its "Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,1-12 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends-including coals numbered I to 55b, inclusive -which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or I8-in. cylindrical retorts." In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash; from 2.1 to 15.9 per cent, in moisture from o.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the go coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1941

In his paper, Sastry proposes the use of flotation methods other than the "conventional flotation!' process as possible economical methods of removing mineral fines, The practice of Liquid/Solid separation employing microbubbles to assist or induce the flotation of suspended solids is common to both municipal and industrial waste- water treatment; and is also used as a separation step in some processing industries. The pretreatment (if any) of the stream prior to flotation, the source of the microbubbles, and the design of the separation vessel depend on the application. For example: a metal finishing plant would use an elaborate chemical conditioning scheme to precipitate metal hydroxides for removal by a dissolved air flotation unit operating in the effluent recycle mode, while some oily waste can be separated using a dispersed air flotation cell with no chemical conditioning. At the present time, the "conventional flotation" process employed by the mineral processing industry makes use of mechanical agitation and aeration to generate certain sizes and quantities of bubbles and to mix these bubbles with the pulp. Specific types of chemical conditioning are used to obtain the desired results. For the separation of mineral fines, the type of chemical conditioning, bubble generation and separation device needed to obtain optimum results will have to be determined through research. The point to be made is that while the principles of flotation separation can be applied to a wide variety of applications, the specifics of the flotation process may vary with each application. Sastry's paper has dealt with the many areas of research required to fully understand and utilize the flotation process for the beneficiation of mineral fines.

Jan 1, 1979

By W. H. Fitch

HAVING been asked to make some remarks after the reading of Mr. Dyrssen's paper, I regret that a test started some months ago has not yet been completed, but some of the things which I can tell you at this time seem interesting and shed a little different light on the idea of a recuperator. The device referred to is becoming more than. a recuperator, largely taking the place of a regenerator. I assume there is familiarity with the sketches that I presented in October, 1926, before the Engineers' Society of Western Pennsylvania, describing our re-cuperator combination with checker chambers, and I have additional ones to show at this time. The follow-ing remarks will deal with modifications that have been made. At that time I suggested the gases leaving the regenerators at, say, 1400°, be reduced to 500° F. The opinion of the operating men consulted since that time is that, under the best operating conditions, the tem-perature may be 750° to 800° F. after the recuperator and on entering the stack. While the lowest final temperature of the gases en-tering the stack is important from the economic stand-point of fuel burning, and operating in general, it is not the whole story. The method of getting the heat out of the checkers is important. It is believed by many with whom we have talked that a better way is by a combination of checkers and a carborundum re- cuperator of the type described as it will stand all tem-peratures met in practice and might be called a super-refractory.

Jan 1, 1928

By Howard N. Eavenson

Waste of coal, or perhaps more properly the percentage of its recovery in mining, has keenly interested me during an experience of over a half century in coal mining. In the early part of that time and until a few years after World War I the use of better mining plans and supervision resulted in an increased recovery. Since then, and particularly since controlled prices have been effective and mechanized mining has been extensively practiced, the tendency has all been toward lesser recovery in mining. The purpose of this paper is not to criticize the methods being used, which after all are the result of economic forces, nor to point to any particular mining method or to any locality where the best recovery is obtained, but to call attention to the tremendous waste of our national coal resources that is constantly continuing. A possible method of reducing this loss will be suggested, but without any illusions that it will be followed or that such attention will be paid to it. Average Recovery The actual average percentage of recovery of coal in the ground is not known. Many papers giving figures of recovery have been published but no definite base of measurement has been agreed upon by those presenting the data. As an example, the Pittsburgh bed can be considered—it has produced a greater output than any other and has been sold or leased at higher prices in place than any other coal bed. Over a large part of its area where high prices have prevailed it has been customary for many years to draw pillars. In these mines it has been usually assumed that the average recovery was higher than in other beds and percentages of recovery of 85 to 95 per cent are usually said to be realized. In all of these mines, however, it has been customary to leave from 4 to 8 in. in the bottom, and 10 to 16 in. in the roof; thus from 14 to 24 in. of coal has been left in the mines out of a total seam thickness of about 96 in., or 15 to 25 per cent of the total coal. No attempt is made to mine this coal for metallurgical purposes, owing to its impurities, although this unmined coal is of excellent quality and better than much of the coal used for steam purposes. If we add to this discard the coal usually lost in mining and those parts of the bed 'that must be left because of bad seam conditions, barrier pillars, reservations for buildings, gas and oil wells, one can easily see that the actual recovery from this bed cannot be more than 65 to 75 per cent. In addition, the rooster or rider or wild coal over the mining bed—often 3 to 4 ft. of coal, high in ash and sulphur but still good steam coal—is hardly ever mined, nor is any attempt made to mine it. It is safe to say that from a broad economic viewpoint not more than 50 to 60 per cent of the fuel value of this great seam is actually being recovered.

Jan 1, 1947

By Howard N. Eavenson

Waste of coal, or perhaps more properly the percentage of its recovery in mining, has keenly interested me during an experience of over a half century in coal mining. In the early part of that time and until a few years after World War I the use of better mining plans and supervision resulted in an increased recovery. Since then, and particularly since controlled prices have been effective and mechanized mining has been extensively practiced, the tendency has all been toward lesser recovery in mining. The purpose of this paper is not to criticize the methods being used, which after all are the result of economic forces, nor to point to any particular mining method or to any locality where the best recovery is obtained, but to call attention to the tremendous waste of our national coal resources that is constantly continuing. A possible method of reducing this loss will be suggested, but without any illusions that it will be followed or that such attention will be paid to it. Average Recovery The actual average percentage of recovery of coal in the ground is not known. Many papers giving figures of recovery have been published but no definite base of measurement has been agreed upon by those presenting the data. As an example, the Pittsburgh bed can be considered—it has produced a greater output than any other and has been sold or leased at higher prices in place than any other coal bed. Over a large part of its area where high prices have prevailed it has been customary for many years to draw pillars. In these mines it has been usually assumed that the average recovery was higher than in other beds and percentages of recovery of 85 to 95 per cent are usually said to be realized. In all of these mines, however, it has been customary to leave from 4 to 8 in. in the bottom, and 10 to 16 in. in the roof; thus from 14 to 24 in. of coal has been left in the mines out of a total seam thickness of about 96 in., or 15 to 25 per cent of the total coal. No attempt is made to mine this coal for metallurgical purposes, owing to its impurities, although this unmined coal is of excellent quality and better than much of the coal used for steam purposes. If we add to this discard the coal usually lost in mining and those parts of the bed 'that must be left because of bad seam conditions, barrier pillars, reservations for buildings, gas and oil wells, one can easily see that the actual recovery from this bed cannot be more than 65 to 75 per cent. In addition, the rooster or rider or wild coal over the mining bed—often 3 to 4 ft. of coal, high in ash and sulphur but still good steam coal—is hardly ever mined, nor is any attempt made to mine it. It is safe to say that from a broad economic viewpoint not more than 50 to 60 per cent of the fuel value of this great seam is actually being recovered.

Jan 1, 1947