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By Bruce W. Gonser, Robert J. Nekervis

EACH metal has a unique combination of properties that distinguishes it from other metal;. Su& a combination may account for applications that cannot be met very well by anything else. This is particularly true of tin, one of the earliest metals used by man. Table i shows the consumption of tin in the United States by usage for the years 1949 and 1950, which may be considered to be generally typical of current usage. The major applications-tinplate, solders, bronze, and babbitt-were well established a century ago. Applications for the metal and (probably later) of tin alloys started more than 5000 years ago. Fortunately for the ancients, tin is one of the metals whose oxide is easily reduced by carbon. Nature further simplified the refining problem by providing only one ore of commercial importance, cassiterite (SnO2). Tin is easily reduced from cassiterite. All that is necessary is high heat in the presence of carbon. It is quite possible that back in the dawn of history, tin was discovered when black alluvial sand was thrown on a fire, either to bank it or to put it out. SOURCES OF TIN All the important tin-producing centers are in the southern hemisphere, far away from the' industrial consuming centers. Fig 1 shows their location and 1950 production. Reserves are adequate, and the industry is able to produce considerably more tin than is

Jan 1, 1953

By AIME AIME

HENRY YONGE WALKER is one of Canada's numerous gifts to the American mining and metallurgical industry, having been born it1 New Brunswick 59 years ago. At eighteen he came to the United States and has since been continuously identified with what are known as the Guggenheim interests. His first position was in the capacity of clerk at the Philadelphia Smelting & Refining Co. plant of M. Guggenheim Sons at Pueblo, Colo. In 1905 he was transferred to the plant of the American Smelting & Refining Co. at Everett, Wash., as assistant manager, two years later going to the Tacoma plant in the same capacity though with added

Jan 1, 1938

By Sir Robert Hadfield

Table 1 gives the composition of the specimens listed by the author. The details of test procedure and the results of the tests on mechanical, magnetic and electrical properties and cor-rodibility of the alloys are published in full in a paper by the same author, "Alloys of Iron and Manganese Containing Low Carbon," presented before the Iron and Steel Institute (of Great Britain) and published in full in their Proceedings for 1927, to which reference should be made. After reporting these tests the author gives the following discussion of results:] The studies here reported do not indicate that any of the series has really valuable or useful qualities for industrial applications, though the demands of industry are so varied that it is unsafe to prophesy that no special use will be found for a given material. The non-magnetic property of manganese steel is due to the association of Fe and Mn, but carbon has also an effect, enabling non-magnetic qualities to be obtained with a much lower percentage of Mn than would otherwise be the case; for example, 16 per cent. Mn is necessary for alloys practically free from carbon, while with 1 per cent. C nonmagnetic alloys may be obtained with as little as 7 per cent. Mn. Carbon, however, is the prime cause of the development of magnetic qualities by heat treatment. (Sec section 8 of the paper referred to above.) These Fe-Mn alloys show a resistance up to 87 microhms per c. c., but. as there are other alloys which have a resistance as high as 130 microhms per C. c., this does not provide any new feature of value. The most marked feature of the series studied is the brittleness in the range 3 to 10 per cent., with a maximum of brittleness at 7 per cent. Material with this percentage, while possessing quite appreciable hard-

Jan 1, 1927

The D'Arcy Exploration Company Ltd. has been granted prospecting licenses in Great Britain to explore four different types of prospect. In the south of England (Dorset, Hampshire and Sussex) the objective lies in Jurassic and Lower Cretaceous beds. In an area of approximately 4470 sq. miles, covering parts of Nottinghamshire, Lincolnshire and Yorkshire, the search is directed to testing Carboniferous rocks. In northeastern Yorkshire a single license covers structures in which the Permian limestone will be explored. In Scotland, southeast of Edinburgh, the company holds another single license where Lower Carboniferous horizons are the objective. Southern England Among the more important "indications" that led D'Arcy Explora-tion Company Ltd. to undertake a testing program in southern England was the discovery of sands in the Wealden (Lower Cretaceous) series of Dorset, impregnated with oil residues. Traces of oil and bitumen were also found in limestones of the Portland and Purbeck beds of the same area. In addition, traces of petroleum had been recorded from Upper and Lower Jurassic beds in borings, more especially those drilled in the course of coal exploration in Kent and Sussex, and an outcropping oil sand was known to occur in Wealden beds near Pevensey in Sussex. Besides these tangible proofs that at least some oil has been generated in this area, _the Jurassic beds, as developed at outcrop in Dorset and elsewhere, include considerable thicknesses of strata that may well be considered as possible source rocks of petroleum. A regional view suggested that these possible source rocks extended, without great thinning, beneath at least the southerly parts of the Weald of Sussex, the South Downs and still farther south beneath the English Channel. It appeared, and still appears, a reasonable conclusion that, where suitable structural conditions occur in this tract of country, an oil accumulation of commercial value may be found. Of the several possible anticlinal structures, those at Portsdown (Hampshire) and between Henfield and Steyning (Sussex) were selected as sites for the first test wells. The groups of strata which at outcrop sug-

Jan 1, 1937

By JOHN D. SUMMER

THE Premium Price Plan for copper, lead, and represent, the approach of the Office of Price Administration to the urgent of wartime problem of securing increased output of nonferrous metals. Some of the problems encountered in too operation of the Plan and the considerations which led to it?s adopt it will here he reviewed. The Plan provides for extra payment by the Metals Reserve Co., to mine operators who exceed established quotas of production. Producers are thus directly, compensated for the higher costs of working ores that are not commercial at the ceiling price, although the metal obtained from these ores is directed into regular channels of distribution at the established prices for copper, lead, and zinc. Higher-cost metal is thus available to fabricators and to the government agencies at the regular ceiling price and the dual objective of increased production and table pries is achieved.

Jan 1, 1943

By B. C. Allen, W. D. Kingery

Surface tension and its temperature dependence have been determined for pure liquid Fe, Cu, Co, Ni, and Sn and for Fe-C, Co-C, and Ni-C alloys. The temperature coefficient of surface tension is negative for all these liquids. The surface tension and wetting behavior of tin and tin-titanium alloys on A120,, Si,N,, MoSi,, and Sic, as well as the behavior of titanium-containing nickel alloys on A1 20, have been determined over a wide temperature range. For all the solids investigated titanium additims markedly lower the contact angle. Some limits for the solid-surface energies have been calculated from liquid surface tension and wetting behavior. SURFACE tension and interface energy are important variables in a number of metallurgical and ceramic phenomena, and have been discussed at some length in connection with determining micro-structure of polyphase systems,' solid-state sintering,' thermal etching of grain boundaries, heats of solution and fine powders,'1 grain-growth phenomena,' the mechanical behavior of fine foils and fibers, nucleation, soldering and brazing,' and other phenomenz of academic or practical interest However, until recently few quantitative data have been available for high-temperature systems. Among available data are some indicating positive temperature coefficients for the surface tension of liquid copper,*,11,'2 cast iron,l3 and iron-carbon14 alloys. Although carbon was found to be not surface active in iron at 1570" some preliminary studies had indicated the possibility of a positive temperature coefficient for the eutectic composition at lower temperatures.16 One part of the present study has been largely concerned with determining the temperature coefficient of surface tension for several metals at elevated temperatures, In addition to surface-tension studies, the wetting behavior of alloys containing titanium has been investigated over a wide temperature range. Previous measurements indicated that titanium was selectively adsorbed from nickel at a liquid nickel-solid alumina interface,17 and the use of titanium hydride or titanium-alloy techniques for metal-ceramic soldering is well known. In the present study, previous data have been extended to new alloy systems, and measurements have been carried out with other oxidation-resistant ceramics. EXPERIMENTAL The sessile-drop method was employed to measure liquid surface tension and contact angle between liquid and solid, utilizing apparatus and techniques which have been described previously.'g The shape of a sessile drop depends on equilibrium between forces of surface tension tending to form a spherical surface of minimum area and forces of gravity tending to flatten the drop. Typical sessile drops are shown in Fig. 1. From precise measurements of maximum drop diameter and drop height the surface tension and drop volume were calculated. Four solid materials were employed as supporting plaques for the liquid-metal drops. Aluminum oxide (99.9 pct, J, T. Baker, reagent grade) was pressed and sintered at 1800°C. Molybdenum-disilicide powder (99.0 pct, Electro Metallurgical Co.) was pressed and sintered at 1650°C. Plaques were cut from silicon carbide (99.4 pct, hot-pressed at Alfred University) and silicon nitride (95.1 pct, with Al, Fe, 0 as major impurities, Norton Co.) rods. All plaques were polished, cleaned, and dried prior to use. A number of metals and alloys were employed. Chemical analyses of vacuum-melted ingots of iron, nickel, cobalt (National Research Corp.), commercial nickel-base alloys, electrolytic copper (International Smelting and Refining Co.), and tin (Mal-linckrodt Chemical Works) are given in Table I. Alloys were prepared in the laboratory by vacuum melting the base metal with either titanium hydride (Metal Hydrides, Xnc.) or spectroscopic-grade carbon (National Carbon Corp.). Nickel-titanium alloys contained between 0.001 and 0.005 pct oxygen and the ferromagnetic metal-carbon alloys contained 0.001 pct. Cylindrical metal specimens (1 to 2.5 g) were machined and bevelled at the bottom to insure a uniform advancing contact angle on melting. Before use the samples were acid-etched, cleaned with acetone, and rinsed in petrol ether.

Jan 1, 1960

By L. C. Raymond

Valuations in the mineral industry differ from those of other enterprises because mines and oil wells have a definite life so cannot be considered a perpetuity. This requires that in any mineral-property evaluation the recovery of invested capital is necessary during the life of the property. Capital write-offs for nonextractive industries are assumed to be continuously plowed back to sustain the operation and produce yields on the capital invested. The extractive or mineral industry, however, generally attempts to return to the investor both interest and principal during the life of a property. Normally this is done currently and the dividend includes both items. Where the mineral property possesses large reserves and the life factor approximates a perpetuity, the return on investment is generally comparable to that of industrial stocks. The valuation of a mineral property, at best, is based on educated estimates and judgment factors. This is particularly true as it relates to estimating selling prices over a long term or assessing the quality of management. Also, it is possible to make various assumptions as to rapidity of working out the deposit, varying time for start-up of operations, varying earning rates, so as to obtain different results with the same basic facts. Thus it is not surprising that two engineers, irrespective of their abilities, may not agree exactly even when given the same facts, but their results should be close enough to be used in establishing a fair value for trading purposes. The valuation is no better than the source of basic data and the soundness of judgment factors. Fundamentally the basic principles of mineral valuation are similar for base metals, sulfur, oil, or any other mineral. Each mineral, however, requires an engineer to have a knowledge of such factors as its occurrence, distribution, mining and processing methods, and marketing problems in order to gather and analyze all the facts and data that have a bearing on the earning potential of the property. Present Value of a Mineral Property In essence the present value of a mineral property is a sum of money in today's dollars that future income from the property are worth. It differs from the total anticipated earnings by the amount of the interest that the unrecouped investment could be expected to earn during the period of recoupment. Thus, if one could accurately estimate what a mineral property will earn during its life, after deducting all operating, administrative, capital, interest, and tax charges, the determination of present value would be a relatively simple mathematical calculation. Normally, where the expected life of the mineral property extends beyond 20 or 25 years, the discounted value of earnings beyond this period is relatively small. The petroleum industry generally discounts the annual cash flow of an operation rather than earnings since, for tax-saving purposes, earnings are kept

Jan 1, 1976

By F. Selig, A. S. Odeh

A second-order approximation to the exact solution of the diffusivity equation corresponding to the pressure build-up of a well producing at a variable rate is derived. This approximation is applicable when the well's shut-in time is larger than the total time elapsed since the well was first produced. The resulting equations are compact in form and easy to use. Thus, the need for Horner's' theoretically precise but rather laborious solution to the above problem is eliminated. In addition, these equations apply where the use of Horner's widely known approximate method is questionable. From a practical point of view, the reported method is best suited for analysis of drill-stem tests and short production tests conducted on new wells. INTRODUCTION The utility of drill-stem and short production tests in reservoir studies has long been recognized by the reservoir engineer. If interpreted correctly they could lead to a wealth of information upon which may depend the success or failure of reservoirs' analyses. Initial reservoir pressure and the average flow capacity are two quantities that are normally sought from a drill-stem and/or a short production test analysis. Pressures are the most valuable and useful data in reservoir engineering. Directly or indirectly, they enter into all phases of reservoir engineering calculations. Therefore, their accurate determination is of utmost importance. The flow capacity kh of the reservoir is indicative of its commercial capability. In addition, it can indicate the presence of a darnaged zone around the wellbore and, thus, the necessity for remedial measures. Of the several methods used to analyze drill-stem and short production tests, Horner's' method is by and large the most common. It applies to an infinite reservoir and or a limited reservoir where the effect of production has not been felt by the boundary. Horner's method makes use of the so-called "point-source" solution of the diffusivity equation. The point-source solution is approximated by a logarithmic function and the superposition theorem is utilized to give the familiar pressure build-up equation where is the shut-in time, q is in reservoir barrels per day and the rest of the symbols conform with AIME nomenclature. Eq. 1 was derived for a well which produced at a constant rate q from time zero to time t and was then shut in. In actuality, such a constant rate of production does not normally obtain. Therefore, a correction must be applied to Eq. 1 to account for the varying rates of production. Horner suggested two methods. The first, which results in a theoretically accurate solution, is rather lengthy and laborious and, thus, it is not suited for routine analysis. The second which has been termed a "good working approximation" is the one used by the majority of the reservoir engineers. In the second method, Eq. 1 is modified by simply introducing a corrected time t, and writing where q is the last established production rate prior to shut-in, and t, is obtained by dividing the total cumulative production by the last established rate. Horner's original paper does not give any indication that this method of correction is based on any theoretical justification. In addition, there is a question as to what constitutes the last established rate. In case of a drill-stem test some engineers use the average rate obtained by dividing the total fluid produced by the total flow time, while others calculate the average rate by dividing the total fluid produced by the last flow-period time. Obviously, different results obtain for the different flow rates used. Because of this, a simple method to the varying-rate case was developed which is theoretically sound and which defines clearly the flow rate and its associated time to be used in the calculations. The final equation arrived at is where q* and t* are a modified rate and time, respectively, and can be easily calculated. In addition, it is shown theoretically that Horner's approximate method, if used for a variable-rate case, gives the correct pressure but would not be expected to give the correct flow capacity. MATHEMATICAL ANALYSIS The general equation governing the flow of slightly compressible fluid in porous media may be written as The elementary solution to Eq. 4, representing an instantaneous withdrawal of Q units volume of fluid at the origin at t = 0, is known as the instantaneous sink

By Kefton H. Teague

Olivine is a mineral containing a mixture of forsterite (Mg2SiO4) and fayalite (Fe2SiO4) in solid solution. The name olivine was first applied by Werner in 1790 (Hunter, 1941) because of the olive-green color of the mineral. Olivine is the principal component of the rock dunite, which itself is a member of the peridotite group of ultrabasic igneous rocks. European uses of the terms olivine and dunite are somewhat different than US usage. In commerce European usage defines dunite as containing 36 to 42% MgO, 36 to 39% SiO2, and loss on ignition of approximately 10%. The term olivine is used to designate a material containing approximately 85% forsterite, with a chemical composition of approximately 45 to 50% MgO, 40 to 43% Si02, 5 to 8% Fe2O3, and ignition loss of 1 to 2%. Uses The principal use of olivine is in various applications involving hot metal. Table I shows the best estimate available as to the amount of olivine consumed by various industries worldwide. In excess of 90% of world uses involve hot metal, with approximately 75% as a slag conditioner in the blast furnace production of pig iron. Approximately 15% of total olivine usage is as a special foundry sand in mold making for the brass, aluminum, magnesium, and manganese steel foundries (Schaller, 1957, 1958; Snyder, 1957; Anon., 1977). Olivine was first used as an industrial mineral in the early 1930s for a refractory material (Anon., 1970; Hunter, 1941). As a refractory raw material, olivine was first introduced in the United States as hand-cobbed, selected, shaped blocks of crude olivine. This use met with limited success. More recently, finely ground olivine blended with MgO and pressed into bricks, which are then fired, has found use in glass tank furnaces and open-hearth furnaces. Ramming or gunning mixes for basic furnace linings also utilize olivine. Olivine has been used in ladle linings with varied success. In Europe, substantial tonnages of olivine are utilized in refractory brick for night storage heaters (Anon., 1970). A limited amount of olivine has been used in the past as a fertilizer (magnesium source) and has been fused with rock phosphate to produce a magnesium phosphate as a plant food. The relatively high magnesia (MgO) content of olivine also attracted attention to it as a potential source of both magnesium compounds and as a source of metallic magnesium (Bengston, 1956; Hunter, 1941). The use of olivine as an additive in the blast furnace is relatively new, having been developed during the last decade. J.W. Currier (Private communication, 1978) describes the behavior of olivine in the blast furnace as follows: Olivine (Mg, Fe2, Si04) represents a unique lime-free source of magnesia and silica as a blast furnace charge component. Only recently has the magnesia-rich mineral been recognized as beneficial cleaner for blast furnace experiencing the problems associated with excessive alkali inputs and/or low coke stabilities. For some time it has been known that alkalis tend to recycle and accumulate in blast furnaces. In the high temperature region of volatilization the elemental alkalis formed attack the integrity of the graphite structure. This alkali attachment is enhanced when poor coke is used. Higher in the furnace stack volatile alkali cyanides condense and oxidize. This accumulation of alkalis tends to agglomerate the burden materials, producing scabs and scaffolds. These structures not only inhibit the downward movement of burden materials and the upward passage of wind, but also lead to erratic furnace performance

Jan 1, 1983

By T. D. Tiemann

The extraction of iron oxide from several types of siliceous iron ore by digestion in sulfuric acid solutions was investigated in the temperature range from 80 to 258°F at concentrations from 10-60% H2SO4. Degree and rate of extraction were found to be critical with respect to both temperature and acid concentration, requiring temperatures in excess of 250° F and acid concentrations of 50% to effect 80-90% extraction of iron oxide in 60 min. Rate of extraction is directly related to surface area and apparently controlled by the rate of chemical reaction. The activation energy was found to be approximately 25,000 cal per g mol. Extraction characteristics of the several ores were found to be similar. The Department of Minerals and Metals Engineering at the University of Wisconsin conducts a continuing research program to develop processes for the utilization of low-grade iron ore deposits such as the nonmagnetic taconites of the Wisconsin Gogebic range. Methods under study include high-intensity magnetic and high-tension electrical concentration, flotation, direct reduction and chemical extraction. Concentration of a number of low-grade siliceous iron ores by the extraction of silica in sodium hydroxide solutions has been reported by the writer and others in the literature.1,2,3,4 Residual concentrates containing as much as 65% iron have been obtained from taconites containing less than 30%. Currently an alternative approach is under study, namely the dissolution of iron oxides from siliceous gangue by extraction in acid, with subsequent recovery of the iron from solution. Such a process for extracting iron oxide from the low-grade oclitic deposits of Alberta with hydrochloric acid was investigated and described by Gravenor, Govett and Rigg.5 The current investigation, which is entirely devoted to extraction with sulfuric acid, is the subject of this paper. In part, the objective of this research was to determine the possibility of leaching iron ores in situ with sulfuric acid. The investigation of a recovery method is left to later research. The ores investigated contained hematite (Fe2O3) as the principal iron-bearing mineral and minor amounts of goethite (Fe2O3 .H2O), magnetite (Fe3O4), and iron-bearing silicates. The gangue was essentially quartz occurring as single crystals and microcrystalline aggregates. Detailed description of the ores may be found in the literature.1,2,4,6 A comparison of the specific ores used in this investigation is shown in the partial analyses of Table I. EXPERIMENTAL METHODS All extractions were made at atmospheric pressure using beakers with a mechanical stirrer for those tests run below the boiling point, and Erlenmeyer flasks for those at the boiling point. A thermostatically controlled hot plate was used for heating, and this maintained the mean temperature within the solution to within ±3°F during extraction. The sample of ore for extraction was weighed to + 0.02 g. For tests below the boiling point, the sample was added to the beaker containing the sulfuric acid solution at the desired temperature. For the boiling-point tests, the sample was added to the Erlenmeyer flask followed by distilled water and the

Jan 1, 1968

By Dubois Eastman

BEHIND the contrasting liquid-fuel technologies of Germany and the United States lie the basic differences of scarcity and abundance. The chemists and engineers of each nation have developed processes that accommodate available raw materials. In the United States, processing is based on an abundant supply of petroleum, which is refined into a variety of fuels and lubricants. Germany has little indigenous petroleum but has a readily available supply of coal that can be converted into liquid fuels and lubricants. As a result, in Germany several basic processes have been developed for the conversion of coal into synthesis gas (carbon monoxide and hydrogen). In turn, this gas is processed into products. As a normal function of its researches into petroleum processing, the petroleum industry in the United States has made careful studies of various conversion and synthesis techniques. A number of oil companies are carrying out independent development programs with the aim of synthesizing hydro- carbon products that can be marketed at a price that will compete with the price of refined petroleum products. American oil companies hope to perfect synthesis processes that will directly benefit the consumer. A good example of progress in these terms is the synthesis plant at Brownsville, Texas, which is based on the conversion of natural gas to synthetic fuels and other valuable products. When this plant is operated at near capacity, it is expected that the products will be able to compete favorably for the consumer dollar. The complete gasification of coal is a technique well rooted in history. As a controlled process on a small scale, it goes back centuries. As a practical technique on a commercial scale, it dates back to 1839, when "producer gas" appeared in Germany for limited industrial use. By 1873, "water gas," or "city gas" as it is sometimes called, was being manufactured commercially in the United States for use in heaters and stoves. The water-gas process was the cornerstone for modern synthesis. To older methods that were concerned only with carbon and oxygen reactions, it added hydrogen by means of steam. Thus far the goal of conversion was to produce gas for heating, lighting, industrial use, and cooking. The long step forward to synthesis was made in 1927, when Germany started to make gasoline from coal by means of the revolutionary Bergius hydrogenation process. A year earIier, Franz Fischer and Hans Tropsch had announced their process, which finally reached the

Jan 1, 1953

By Wei-Kao Lu, G. Bitsianes

An improved general rate equation for a one-ditnensional gas-solid system has been derived. Fov the veversihle interfacial chemical reaction, there are concentrations of gaseous reactant and product at the reacting zone to be considered. They have been calculated with the velations fuvnished by the constraints on the system, namely, quasi-steady state and equimolal counterdiffusion of the gases. The results of the diffusiori study of Evans, Watson, and ,Mason based on the "dusty gas" model have been applied here. The interfacial chemical reaction is taken as first-order with respect to the concentration of the gases involved. The equation has proper dependence on gas composition and on solid structure through the relative values of Knudsen and normal diffusivities. The existence of the total pressure gradient inside the specimen has been predicted and confirmed experimentally. In a previous communication' we introduced a general rate equation for gas-solid reactions by considering the contributions of chemical reaction at inter- phase boundaries and diffusion through the solid product layer simultaneously. These equations, for one-dimensional and spherical specimens, take care of the whole range continuously from purely diffusion control to purely chemical reaction control. In this paper we study only the one-dimensional system. The corresponding rate equation is reproduced here: Of the two terms on the right-hand side of Eq. [I], the first represents the contribution of interfacial chemical reaction and the second that of gaseous diffusion. The shortcomings of Eq. [I] are that in its derivation the interfacial chemical reaction was assumed to be irreversible and the diffusion rate of gaseous product was not considered. Any pressure effects building up within the porous media were also neglected. Evidently. these simplifying assumptions will limit the general applicability of these equations. The rate of reduction of iron oxide by hydrogen, for instance, is very sensitive to the concentration of water vapor in the main gas stream, as has been reported by cewan' and by Quets et a1.3 Furthermore, the gaseous phase at the reacting interface will contain an appreciable amount of the gaseous product of reaction. If this were not true, a sufficiently high concentration gradient for the outward diffusion of the gaseous product could not be maintained. With these shortcomings in mind, Eq. [1I cannot be rigorously ap-

Jan 1, 1967

By J. E. Warren

To clarify the specific questions raised by J. E. Warren's discussion, the following remarks are offered. 1. It is correct that stratification is assumed in the application of the statistical zonation technique, but this does not constitute a limitation. If, in fact, the reservoir is not stratified the zonation technique will show it. The reservoir is then considered as one zone with a particular distribution of permeabilities. 2. The statistical zonation technique was intended as wells may not be an adequate measure of the lateral permeability changes; e.g., if the data presented in Table A-4 of the subject paper are evaluated on the basis of two crossed classifications with interaction, the variation between zones is significant with a probability greater than .99; however, the variation betwen wells is also significant with a probability greater than .87. It is apparent that the technique suggested by the author can be generalized to provide a powerful method for describing petroleum reservoirs. This generalization can be achieved by treating the core data as a two-way classification to determine the between-zones and the between-wells variations; then, the build-up permeabilities can be analyzed, perhaps on at least-squares basis, to establish the probable distribution of the permeabilities within the zones associated with the individual wells. an additional tool for the reservoir engineer to use together with other techniques and all available information. If pressure build-up permeabilities are available, they should certainly be included. Pressure build-up tests were not available for the reservoir considered in the paper. 3. The proposed correlation of zones between adjacent wells was the best of the techniques that I examined. It is not so much a "measure" as an indication of lateral permeability changes, regardless of whether they are seemingly random or form an obvious trend.

By Sidney A. Swensrud

The writer has been interested for some time in trying to appraise our industry's prospects for gasoline consumption over the next half dozen years or so. Anyone who has even approached the problem knows the intimate relationship to it of the number of automobiles in use— by automobiles I mean both passenger cars and trucks. Probably at least 90 per cent of our gasoline is used in automotive vehicles. Some recent estimates secured from the Department of Commerce show the following breakdown: Per Cent Passenger cars............................................ 60.0 Trucks................................................... 27.4 Busses................................................... 2.9 Taxicabs................................................. 2.2 Subtotal............................................... 92.5 Aviation, motor boats and railroads......................... 0.5 Agricultural: farm tractors, etc.............................. 3.3 Balance (manufacturing, government use, construction, etc.)... 3.7 100.0 Up to the beginning of the depression there was, of course, a constant annual increase in the number of automobiles in use, for each year the industry added to the total inventory or ''population" more new units than were being scrapped, as may be seen in Fig. 1. Few of us in the oil industry needed to give much attention to the detailed figures, although the automobile industry seemed to interest itself in all sorts of calculations of replacement demand vs. new car demand, the average life of the car, the number scrapped, and the like. Probably many people in the oil industry, as well as outside it, were surprised at the way in which automobile registrations and gasoline consumption held up during the early years of the depression. Nor were they greatly perturbed when, as in the last two years, both registrations and consumption began to fall somewhat. That was natural enough; it

Jan 1, 1933

By I. H. Pratt

The results of a study on the preparation of thin-film capacitor structures are discussed. The dietectric source material was quartz which was sputtered and deposited onto aluminum electrodes and counter-electroded to complete the metal-oxide-metal structures. This configuration was utilized to evaluate the dielectric, the device characteristics, and related process parameters. The effect of gas sputtering pressure, magnetic field strength, source-to-substrate distance, and power density on the rate of deposition is shown. Increased film thickness uniformity over a 3 by 3 in. area by optimum substrate positioning is indicated. Dielectric constant, dissipation factor, dielectric breakdown strength, insulation resistance, heat treatment, capacitance, and dissipation over the range 400 Hz to 5 MHz are reported. In the fabrication of silicon-integrated circuits, silicon dioxide has found use as a material suitable as a diffusion mask, for surface passivation of the silicon, and for protection of conductive films used for interconnections. Its use as a dielectric for thin-film capacitors in film hybrid circuits has been limited, to a degree, for lack of a compatible processing technique and because of its relatively low dielectric constant. With the recent advent of practical metal-oxide-semiconductor (MOS) field effect devices, the material is now being used to insulate the gate electrode from the conducting channel in the silicon. In this latter application, more stringent requirements have been imposed on .the oxide. A comprehensive resume of the use of silicon dioxide in integrated silicon device technology has been compiled including oxide film and bulk properties, method of oxide formations, and their applications.' A relatively new process to deposit SiO, and other dieIectrics is by rf sputtering, and the purpose of this paper is to describe the behavior of capacitors fabricated with a dielectric which has been sputtered from a quartz target and to indicate the relative effect of several of the process parameters on the film deposition. Work on rf sputtering of SiO2 and other dielectrics has been reported utilizing a triode type of sputtering system as described herein or a diode self-sustained glow discharge system. 2-8 SPUTTERING The process occurs during an electrical discharge in a gas plasma which provides the ions for acceleration to the target to produce the desired sputtering. The necessary plasma can be generated by a dc glow discharge through application of a high potential between two electrodes at approximately 2 to 10 x 10-2

Jan 1, 1969

By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.' This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",' and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,' and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,' part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,' in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,' again in agreement with the idea that oxygen is transported,

Jan 1, 1963

By J. F. Myers, F. M. Lewis

C. G. McLACHLAN*-I have read this paper with considerable interest and wish to congratulate the authors on the care with which they carried out their experiments and for the detailed sizing data they have presented. 011 the other hand I do not feel that these data establish their contention that "with other factors the same, the work accomplished in a fine crushing rod mill is directly proportional to the rotating speed." My reason for making this statement is that their conclusion is based on the percentage of minus 65 mesh material produced at each of the speeds at which their tests were run. The rod mill is, however, not a fine grinding machine and therefore figures based on minus 65 mesh production are figures outside the range at which it operates to best advantage. Further, if rod mill performance is to be judged on the production of such material it should have been established that a rod mill will produce it as effectively as a ball mill. To check this last point I have gone over some of the rod and ball mill grind-ing figures for our Waite-Atnulet operation and find that the ball mill at that property produces more minus 65 mesh material per horsepower than the rod mill. Moreover, this comparison is even more favorable to the ball mill if it is limited to minus 100 mesh production. It therefore seems to me that the most satisfactory basis on which to try to com-pare the performance of the rod mill in the present case is by taking a weighted average of all the new surface produced per horsepower. W. H. Coghill3 has published data which can be applied to the sizing figures presented by the authors, and if this is done the units of new surface per horsepower produced in the Tennessee tests are as follows: Admittedly the increment of increase in new surface per horsepower shown in the foregoing figures is not great, but its trend is nevertheless definitely in favor of slower speed operation, for the conditions under which these particular tests were run. I also feel that some information regarding liner contour should have been given as I think it will be found that a mill which is equipped with liners which lift the rod load can be run at a slower speed than a mill in which the liners are comparatively smooth. J. F. MYERS and F. M. LEWIS (authors' reply)—The position taken by Mr. McLachlan is to be respected even though we are all aware of the faults of surface considerations. As he points out. the increment of increase is very small. It is so small in fact that for all practical purposes it does not conflict with the conclusions of the paper. The authors appreciate Mr. McLachlan's comprehensive study of the data.

Jan 1, 1950

By JOHN JANNEY

STABILIZATION of the adjustment of normal consumption to normal production of world commodities is quite different from reducing production until visible surpluses are consumed. The first means restoration and maintenance of prosperity, the second means merely a temporary alleviation of a condition with the prime cause remaining uncorrected. Overproduction of foodstuffs in some sections of the world while millions starve in other sections represents not so much overproduction of foodstuffs as mal-distribution of foodstuffs. The flour mills of Washington and Oregon normally ship quantities of flour to China. Now, the wheat that would make this flour goes East instead of West. Is this overproduction, or is there something wrong that calls for study, analysis and correction? Can the plan used by the ostrich of hiding its head in. the sand get us by this present world tragedy, or must the challenge to solve this problem be met, constructively? Can we not make out of this breakdown in the world's economic system an opportunity? And use it as the stimulus for remedying the basic cause of the trouble and not content ourselves with devising temporary expedients that aim at remedying this or that of the obvious conditions, in themselves not causes at all but rather the evidence of causes, or that are the symptoms of the real trouble.

Jan 1, 1931

By W. H. Morris

I have been requested to present a paper on the slag from the basic Bessemer process, as prepared for fertilizing. Since Professor W. B. Phillips presented at the Birmingham meeting, in May, 1888, an able paper* on this subject, as it had been developed up to that time, there is little for me to add. Perhaps later practice may be best expressed by the homely proverb, " The proof of the pudding is in the eating." As the Pottstown Iron Company is the only concern manufacturing basic Bessemer slag in this country, the writer's personal experience in the use of it may be interesting. Our slag averages: P2O5, 21.37; SiO2,, 5.10; MgO, 5.90; Al2O3, 4.01; MnO, 5.56 ; FeO, 12.00; Na2O and K2O, 0.80; CaO, 45.26; total, 100.00. This gives over 76 per cent. of phosphoric acid and lime. In using this material for several years past on my lawn and garden, I have found it better than anything else I have ever tried ; and I am sure that any of you who had seen my green grass last month (January), wherever the ground was bare from snow, as bright as in early fall, would be forced to acknowledge the advantages of this soil-enricher. The grass on my private lawn, and around the company's office, is green the whole winter; and we have raised very good sod, by the use of this phosphate, where, without it, we were unable to get the grass to grow either from seed or by repeatedly sodding. The same statement applies to garden-truck; when the soil was first broken up, a good crop of vegetables was easily raised. My own gardener has had several premiums from Philadelphia seedsmen (notably, last year, the first premium for sugarcorn raised in the first part of July, being the first sample sent them). Our method of applying this material is to grind the slag very finely, so that at least 60 per cent. of it will go through a 150-mesh screen (i.e., say, 22,500 meshes to the square inch), and 90 per cent. through a 100-mesh screen (i.e., 10,000 meshes to the square inch). This fine grinding seems to be the main condition of success.

Jan 1, 1893

By Charles H. Jacoby

In 1774 a Swedish chemist, C. W. Schule, first recognized manganese as an element. That same year Schule's associate, J. G. Gahn, isolated the element manganese for the first time. In 1856 the Bessemer process of steelmaking gave birth to the economic importance of manganese. Later, in 1882, Robert Hadfield discovered high manganese steels. Although the primary use of manganese is in the ferroalloy industry, two additional important uses for manganese are making chemicals and dry cell batteries. Manganese is also vital to plant and animal life. Various chemical compounds of manganese are used in fertilizers, feeds, glass manufacture, paints, varnishes, and for numerous medicinal and chemical purposes. For the study of industrial minerals and rocks, only the chemical and battery grade material is of- concern, but for the sake of comparison, metallurgical aspects are included in this presentation. Although currently the world's largest consumer of manganese, the United States is producing only minor amounts of ore at the present time. This is due primarily to the fact that although huge deposits of manganese occur within our borders, all are of such low grade as to be economically unfeasible to mine. For many years various government agencies and segments of private industry have devoted sizable sums of money and time in an attempt to upgrade ores from the various deposits, and also in an attempt to recover manganese from blast furnace slags. In view of current world prices, and the quantity of high grade material available, there is little likelihood that any of these approaches will be found to be economically feasible in the near future. Geology and Mineralogy Mineralogy There are over one hundred minerals that contain manganese. These minerals vary from those with compositions that are predominantly manganese to those having only minor percentages. [Chemical Mineral Composition % Mn Hausmannite Mn304 72 Polianite MnO2, 63.1 Pyrolusite MnO24 60-63 Cryptomelane KR8O16R (R=Mn) Variable PsilomelaneBa Mn Mn8O16 (OH).45-60 CoronaditePb R8O16R (R=Mn) Variable Hollandite Ba R8O16R (R=Mn) Variable Manganite Mn2O3•H20 62 Braunite 3 Mn2O3•MnSiO3 62 Tephroite 2 MnO•SiO2 54.3 Rhodochrosite MnCO3 47 Rhodonite MnSiO3 42 Spessartite 3 MnO•AI2O3•3SIO2 33.3 WadHydrous Mn OxidesVariable Franklinite(Fe Mn Zn)O(Fe Mn)sO3 Variable Asbolan Cobaltiferous wad Variable AlabanditeMnS63.14] Geology From a geological standpoint most manganese deposits are complex. In general, it can be said that all primary deposits of manganese are carbonates or silicates. The most productive and profitable have been those of sedimentary origin and residual concentrations. Examples of these residual types of deposits are associated with the metamorphosed lodes of Madhya, Pradesh, India, and the lateritic deposits of Orissa and Bihar, India; nodules in the residual clays of the Philippine Islands, US southern Appalachians and Arkansas, Ghana, and Brazil. Sedimentary manganese deposits are best exemplified by the Nikopol district of Russia and the Tchiatouri area of Georgia, USSR. Hydrothermal replacements are characterized by the rhodochrosite deposits of Butte and Phillipsburg, MT. In general, the hydrothermal type deposit has not resulted in any large tonnages being produced, but may have given

Jan 1, 1983