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By W. H. Geis

The following pages summarize the causes that led to the suggestion of unit operation of the paloma field, the organization of com-mittees, preparation of the Paloma Operators Agreement and the reasons for rejection of the plan. Introduction Long ago an Austrian physicist observed that under certain conditions the condensation of a liquid from gaseous mixtures resulted from pressure reduction. Some 50 years later he would have known that his research was not in vain. He would have seen a group of serious operators and engineers seeking to apply that principle to a conservation . program for unitized production in the Paloma gas field—but he would also have been saddened to see that forces unsympathetic to the application of science in oil production, with little or no appreciation of modern methods and the advantages of cooperation, so far have prevented the adoption of that program. Soon after the Paloma field was discovered it was realized that all the hydrocarbons in the reservoir existed in the gaseous phase. This condition was confirmed over a large area. Therefore, if the field was to be properly exploited with the greatest ultimate recovery of condensate, the hydrocarbons in the reservoir must be produced in the single or gas phase. They must be cautiously extracted with the least possible reduction of the natural pressure. If this could be accomplished, or if artificial pressure control were utilized, the condensation and underground loss of the valuable distillate would be preventable—otherwise it would not be. Wholehearted cooperation of all oper-ators was required in order to accomplish the conservation purposes of the program. To this end the production engineers of the several companies concerned lent their time and talents. They fully investigated the physical relationships of the products within the complicated gaseous mixture, prepared extensive reports on the subject and drew up a reasonably efficient plan of operations, which now is commonly called the "Paloma Unit Plan" but actually was entitled "The Paloma Operators Agreement." All of the engineers were not in perfect agreement on all the features of the plan, or even on all the engineering principles. However, it is safe to say that on all the important or essential factors there was a unanimity of opinion, particularly as to the objectives. These were fairly simple and reduce to one controlling item, "pressure control" by cycling or recycling. Organization The principal operators initiated the program by calling a meeting of all the lessees in the area, at which an organization was perfected, known as the "Paloma Operators Committee." Various subcommittees were appointed to expedite the work, including an "Engineering Committee." These func-tioned in a businesslike manner, frequently reported to the superior committee and

Jan 1, 1942

By W. H. Geis

The following pages summarize the causes that led to the suggestion of unit operation of the paloma field, the organization of com-mittees, preparation of the Paloma Operators Agreement and the reasons for rejection of the plan. Introduction Long ago an Austrian physicist observed that under certain conditions the condensation of a liquid from gaseous mixtures resulted from pressure reduction. Some 50 years later he would have known that his research was not in vain. He would have seen a group of serious operators and engineers seeking to apply that principle to a conservation . program for unitized production in the Paloma gas field—but he would also have been saddened to see that forces unsympathetic to the application of science in oil production, with little or no appreciation of modern methods and the advantages of cooperation, so far have prevented the adoption of that program. Soon after the Paloma field was discovered it was realized that all the hydrocarbons in the reservoir existed in the gaseous phase. This condition was confirmed over a large area. Therefore, if the field was to be properly exploited with the greatest ultimate recovery of condensate, the hydrocarbons in the reservoir must be produced in the single or gas phase. They must be cautiously extracted with the least possible reduction of the natural pressure. If this could be accomplished, or if artificial pressure control were utilized, the condensation and underground loss of the valuable distillate would be preventable—otherwise it would not be. Wholehearted cooperation of all oper-ators was required in order to accomplish the conservation purposes of the program. To this end the production engineers of the several companies concerned lent their time and talents. They fully investigated the physical relationships of the products within the complicated gaseous mixture, prepared extensive reports on the subject and drew up a reasonably efficient plan of operations, which now is commonly called the "Paloma Unit Plan" but actually was entitled "The Paloma Operators Agreement." All of the engineers were not in perfect agreement on all the features of the plan, or even on all the engineering principles. However, it is safe to say that on all the important or essential factors there was a unanimity of opinion, particularly as to the objectives. These were fairly simple and reduce to one controlling item, "pressure control" by cycling or recycling. Organization The principal operators initiated the program by calling a meeting of all the lessees in the area, at which an organization was perfected, known as the "Paloma Operators Committee." Various subcommittees were appointed to expedite the work, including an "Engineering Committee." These func-tioned in a businesslike manner, frequently reported to the superior committee and

Jan 1, 1942

By Hiroshi Oikawa, A. G. Guy

Recent experimental evidence has shown that it is often incorrect to neglect the reactions occurring at an interface with respect to the diffusion reactions. By introducing reaction-rate constants and k for the transfer of components 1 and 2 between the a and b phases, a phenomenological description has been devised for the coupled processes of diffusion and in-terfacial reaction. An illustrative example has been analyzed with the aid of a suitable computer program. The results indicate that for kab values on the order of 10'1 cm per sec and Ð values of about 10¯10 sq cm per sec, the interfacial reactions are significant during the first 10 2 to l0 6 sec of a diffusion experiment. Among the observable effects of the interfacial reactions in this case appear to be the burying Kirkendall markers and an anomaly in the initial shifting of these markers. THE study of diffusion between two phases is especially important because of its direct connection to phase transformations. For example, the transformation of austenite to ferrite involves diffusion in the a and ý phases and also an interfacial reaction (trans formation) at the a/? interface. If ferrite and aus-tenite are the two members in a diffusion couple, the same two reactions occur during the diffusion process. The numerical values obtained for the diffusion coefficients and interfacial-reaction constants from diffusion experiments can then be employed to predict phase-transformation behavior. Refinement of the calculations of phase transformation is also suggested by the present method for treating two-phase diffusion. In the recent paper by Nolfi et al.' only the solute com ponent is considered in the interfacial reaction accompanying a phase transformation. The present analysis demonstrates that both components must be considered. It is generally recognized that reactions of some kind must occur at the interface in a two-phase diffusion couple, but usually it is assumed that the interface reaction occurs so rapidly that its effect on the overall process is unobservable because the slower diffusion process determines the kinetics of the process. However, Seith and Heumann 2 pointed out that effects of the interfacial reaction should always occur in the early stages of diffusion, and recently Eifert et al. 3 have shown that interfacial reactions influence the composition and motion of the interface in a/ß Al-Cu diffusion couples during the entire course of prolonged, high-temperature treatments. A general procedure for handling the combined processes of interfacial reaction and diffusion in a binary, two-phase system is to introduce kinetic coefficients for the interface reactions and to develop the system of equations governing the interlinked processes of diffusion and interface reaction. The resulting equations, although not amenable to solution in closed form, can be usefully manipulated by a digital computer. INTERFACIAL REACTIONS IN TWO-PHASE DIFFUSION Consider the general case of diffusion between two solid solutions, a and ß, which are adjacent phases in a binary system, Fig. 1. Two semiinfinite bars having compositions c1 and c0ß are jointed at x = 0. If concentrations are expressed in volume fraction,4

Jan 1, 1970

By P. D. Proctor, M. P. Nackowski

Quantification in recording geologic phenomena and application of well-known geologic principles to engineering works continued at an increasing rate during the year. Highway departments, water resources agencies, private firms and governmental agencies involved in tunnel excavations, dam site locations and construction, consultants and government experts in subsurface liquid-waste disposal, designers of underground storage facilities and city and regional planners all confirmed greater use of applied geology in their planning and implementation of plans. Applications of quantified geologic data to highway locations, slope control of cuts, raw material sources, water sources and water run- off showed a striking increase in number. Environmental geology and geologic hazards became part of the jargon of the geologic profession, and the American public began to realize more fully the significance of where they live, and on what and near what geologic phenomena which might effect their well-being. Tunnel work for water projects of almost dream-like magnitude kept geologic engineers busily engaged in predicting and testing local geologic conditions for construction projects. Disposal of industrial and radioactive liquid wastes continued as problems, but use of stratigraphic data, fluid flow rates and direction of flow helped solve some critical waste disposal problems. Unusual applications of seismic networks, remote sensing methods and X-ray techniques in geological engineering applications added other tools to this increasingly important profession.

Jan 2, 1968

By Ajoy K. Ghose

INTRODUCTION Longwall mining made its debut in Indian coal mining scene around 1900. Despite this headstart, the application of the method has been slow and halting. Currently, there are some 16 operating longwall faces only in different Indian coalfields contributing to perhaps less than 3 percent of the total underground coal production. Ambitious plans for expansion of longwall mining notwithstanding, apprehensions on the cavability of Indian coalmeasure roof rocks and some unsavoury experiences with face collapses in caved longwalla have impeded wider adoption of the technique. Between 1960 and 1983, some 41 caved longwall faces were worked in Jharia, Raniganj, Karanpura and Korba Coalfields in India, of which 6 faces reportedly had collapsed(1). The first powered support longwall face was started in August 1978 at Monidih colliery which marked a major step forward in the introduction of advanced technological system in Indian coal industry. This paper attempts to analyse critically the experiences with longwall ground control in caved longwall faces in India. Experiences from powered support faces at Monidih, Dhemomain and Pathakhera are synthesized to provide an appraisal of the present status of caved longwall faces under the Indian coalmeasure roofs, which thus far have been characterised as “massive”. The geotechnical site factors at the powered support faces are evaluated and conclusions drawn on the pre-assessment of caving characteristics and support resistance required at the faces.

Jan 1, 1984

By Dorsey Hager

The possibility of oil and gas production in Alabama his been little considered as yet. Gas and some oil have been found in northwestern Alabama, near Birmingham, in the Pennsylvanian beds, but the oil and gas possibilities in the Cretaceous beds are not generally appreciated. The recent activity of oil companies in that State has attracted much attention, and in this paper the main structural and the general strati-graphic features are described. Four favorable areas are outlined. These contain folds of major interest. There are other favorable areas which have not been mapped-l Commercial pools discovered in this area would have the advantage of being near tidewater. Mobile, Ala., on the Gulf of Mexico, would be the logical site for refineries and shipping facilities. A pipe line could readily be laid to that city from the Hatchitigbee and the Jackson areas. The logical outlet for the Geneva and the Gordon areas would be Panama City, Ha., on the Gulf of Mexico. Topography The whole of the area under consideration lies in the Gulf coastal plain and slopes gently to the southwest and west. The elevations vary from 200 to 400 ft. (60 to 121 m.) above sea level. The streams have sunk their channels into this gently sloping plain, the main drainage flowing south or southwest into the Gulf of Mexico. Between the

Jan 1, 1918

By A. W. Ashbrook

There are essentially three main classifications for extractants: acidic, basic, and neutral. The acidic and basic are also referred to as cationic and anionic, respectively. Some extractants are shown in Table 11-1. Acidic Extractants Acidic extractants which are of use, because of cost and/or insolubility in water, are alkylphosphoric, sulphonic, aliphatic monocarboxylic acids and naphthalene derivatives.

Jan 1, 1978

By R. Lingle, E. Hardin, M. Board, H. Pratt, W. Ubbes, M. Voegele, N. Barton

A 2 m. cube of jointed, Pre Cambrian biotite gneiss was subjected to uniaxial and biaxial loading at ambient and elevated temperature. The effects of different boundary conditions on the following rockmass properties were investigated: deformation modulus, joint stiffness, dynamic modulus, coefficient of thermal expansion, thermal diffusivity and conductivity, and joint permeability. Test conditions ranged between 0 and 6.9 MPa uniaxial and biaxial load, and 12° to 74°C mean block temperature. The tests were performed as part of the Office of Nuclear Waste Isolation program for evaluating site charterization test methods for measuring the hydro-thermal-mechanical properties of rock masses. The fracture flow experiments discussed in this paper were described in detail in a similar paper given to this symposium in 1981 (Voegele, 1981). DEFORMATION MODULUS Horizontal deformation measurements oriented parallel to the loading direction were made at the block surface. Several instrument types were employed: surface short-rod extensometers, bonded strain gauges, vibrating wire strain gauges and the Whittemore caliper strain gauge. Two vertical and two slant borehole extensometers measured vertical displacement. Loading history, especially during uniaxial loading, was critical to interpretation of observed deformation and fracture flow data. This important tendency has been observed in other large-scale laboratory (Bandis, 1980) and field tests (Pratt, et al., 1977). Excavation of the block resulted in minimal disturbance to the intrinsic condition of the sample. Even so, permanent, unrecovered "set" was imparted to the block beginning with the first low-stress biaxial load cycle to 3.45 MPa (Table 1). Unloading

Jan 1, 1982

By W. J. Feuerstein

STRUCTURAL imperfections in crystals, in recent years, have received the attention of metallurgists concerned with single-crystal properties. Certain etching solutions cause local variations in the rate of etching at dislocations.' Dislocations are expected to be preferred segregation sites for impurities' and Dash" has shown that precipitation of copper occurs preferentially at edge-type dislocations in silicon. Diffusion rates along dislocations are probably higher than rates through more perfect crystalline regions.' These and other phenomena which may be influenced by dislocations may be studied by revealing dislocations as etch pits. This study was undertaken to develop an etch solution for silicon crystals to reveal low-angle grain boundaries associated with dislocation arrays and also etch pits with good contour definition. Additional etches have been reported by Dash," Vogel and Lovell.T rystals were sectioned on crystal lographic planes at various angles from the growth direction for microscopic examination of the etch pits. Experimental Crystals of 75-100 g mass and 3 cm diam were oriented and cut on crystallographic planes. Crystals were grown by Czochralski technique from a quartz crucible. Lapped wafers were chemically polished in a modified CP-4 etch for 1 min (bromine was deleted from the etch solution). The polished wafer was then etched* at room temperature for 5 min. The use of larger amounts of H2O and/or CH2COOH slows the reaction. The Cu(NO3),.3H2O was added to increase the reaction rate and give more definition to the etch pits developed. Some pertinent features concerning the attack of this etch on silicon can be summarized as follows:

Jan 1, 1959

By D. R. Parrish, V. J. Berry

Reverse combustion is one thermal method of recovering hydrocarbons from porous undergrortnd formations containing oil or tar. In applying this method, air is introduced via an injection well and the mixture of air and hydrocarbons is ignited in the production well. A combustion zone then recedes toward the injection well, counter-current to the air flow. If the combustion-zorie temperature is sufficiently high, the oil or tar irz place is distilled arid cracked. The hydrocnrhon flows as a vapor to the production well and subsequently is condensed at the surface. Maximum temperature and velocity of morcment arc the two dependent variubles defining the progress of the combustion zone. A theoretical analysis has been made of heat flow in the reverse-comhustion process as.srtrning linear flow in a homogeneous system. The differentirll equatious, which include the oxygen-hydrocar-hon rctrction rate, have been solved numerically. Rescllts indicate that the maximum temperature reached and he cornbustion-zone relocity both increase with an incrense in air-injection rote. Heat loss to surroundings has little effect on the maximum comhustion-zone ten?perature achieved, but it is reflected in a reduced com-bustion-zorzc, velocity. It is also predicted that an increase in the oxygen-hydrocarbon reaction rate results in a reduction in the maximum temperature reached. The calculated results are in agreement with results from reverse-combustion experinments using samples of a tar sand. INTRODUCTION Reverse combustion is one thermal method of recovering hydrocarbons from porous underground forma-tions containing oil or tar.' In applying this method, air is introduced into the underground formation via an in-jection well. In one or more adjacent production wells, the mixture of air and hydrocarbons is ignited at the sand face. The combustion zone thus formed recedes toward the injection well, counter-current to the air flow (Fig. 1). Under certain conditions, the rate of recession of the combustion zone is sufficiently rapid that only a small fraction of the hydrocarbon at any point in the formation is consumed by combustion. If the combustion-zone temperature is sufficiently high, the uncon-sumed oil or tar in place may be partially distilled or cracked. This material then can flow as a vapor with the gaseous combustion products to the production well and subsequently be condensed at the surface. Under other conditions, the combustion-zone temperature may be so low that little, if any, of the hydrocarbon is vaporized. Nevertheless, the viscosity of the hydrocarbon may be reduced enough so that other recovery methods subsequently can be applied to produce oil at attractive rates. The maximum temperature achieved in the combustion zone and the velocity of movement are the two dependent variables defining the progress of the combustion zone. Presumably. knowledge of these factors will permit estimates to be made of oil recovery efficiency, oil and gas producticn rates and average amount of injection air required per barrel of oil recovered. The maximum temperature and combustion-zone vclocity are, in turn, expected to be dependent upon air flow rate, heat losses to surrounding formations, physical properties of the rock and the hydrocarbon. the extent to which the porous formation is saturated with the hydrocarbon, the rate of oxidation of the hydrocarbon and the amount of heat released. It is desirable that the relative importance of each of these factors be understood so that the results of laboratory tests of oil recovery by reverse combustion can be properly interpreted in terms of expected field performance. It is particularly desirable to assess the importance of heat lcsses because these are difficult to control or eliminate

By Gilbert P. Moore

The production of petroleum in Argentina during 1932 was greater than in any preceding year. The total amount produced was 13,012,-756 bbl. This figure represents a decided increase in the production of oil in Argentina and can be attributed largely to the increased activities of the Royal Dutch operations at Kilometer 27 in the Comodoro Rivadavia district and those of the Standard Oil Co. of Argentina in the Salta region. Production from the Royal Dutch wells amounted to considerably more than 10,000 bbl. per day over quite a long period during the year. Of the 13,012,756 bbl. of oil produced during 1932, the Government Agency (Y. P. F.) was responsible for some 5,578,954 bbl., while 7,433,-802 bbl. were produced by private companies. Although in 1930 the Y. P. F. produced about 55 per cent of the total production and in 1930 50 per cent of the total, in 1932 its production had fallen to about 42 1/2 per cent of the total. This decrease in the proportion produced by the Y. P. F. was not due to a decrease in its production but to the decided increase in the production of private companies, particularly those two whose names are given above. One new discovery was recorded during the year. This was a well drilled by the Y. P. F. at Cacheuta in the province of Mendoza which came in pumping 80 bbl. of 15" gravity oil from a depth of 673 meters. This well was completed at approximately the same time that the provincial government of Mendoza granted a concession to the Y. P. F. and declared the whole province as a reserve in which no concessions may be granted for a period of 10 years. Under these conditions, the federally operated Y. P. F. will have no competition in the Cacheuta area from private companies such as they have in the other three fields of the republic. The Y. P. F. wildcat west of Comodoro Rivadavia at Pampa Maria Santissima on the Rio Senguerr was completed as a dry hole during 1932. This we11 was reported as a producer in 1930 by persons returning to this country from Argentina but it appears that they had been misinformed. The site of this test has been abandoned and a new location made north of the Rio Senguerr.

Jan 1, 1933

By H. Rush Spedden

Antoine M. Gaudin was a vigorously creative man and throughout his career an internationally respected leader of his chosen profession of mineral engineering. To his professional colleagues and clients and to his former students he was both "Professor Gaudin," their wise, inspiring, and enthusiastic teacher, and "Tony," their, warm and beloved personal friend. Thus, his teachings and his unique inquisitive-creative approach to problems live on and grow in the accomplishments of his students. Antoine Gaudin was born at the turn of the century in Smyrna, Turkey, where his father was general manager of a French-owned railroad. It was there that he spent his earliest years, literally in the shadow of classic marbles from diggings at the site of Aphrodesias, which his father had rediscovered. From this, Tony developed an appreciation of the arts. He eventually surrounded himself with art treasures; he reveled in the beauties of nature, and he cherished his choice collection of rhododendron and azaleas. His artistic traits led him to take up painting when his daughter, Elinor, sought his help in blending her tints for a water color. In typical fashion he was not satisfied until he had become adept with pastels in capturing the muted tones of distant landscapes and the technical properties of light and color. Unfortunately not many paintings were produced. His paternal grandfather was Marc-Antoine Gaudin, for many years secretary of the Academie des Sciences in Paris, and a well known chemist and mineralogist whose primary interests included the synthesis of precious stones. In an autobiographical sketch written in 1939, Dr. Gaudin recalled: "As a child I saw many of the original synthetic sapphires and rubies which my father had inherited. This, coupled with my father's avocation of mining ventures and archaeology, early decided that I would become connected with the mineral industry." One can speculate that the archeological activities of his father, the mineral systhesis experiments of his grandfather, and his own early studies of mineralogy and geology formed a base from which his special talents as an experimentalist were to develop. Laboratory research under Professor Gaudin's personal guidance was often an intensive, fast-moving, and exciting experience--especially to a new graduate student. First of all, Professor Gaudin was a highly skilled observer with seem-

Jan 1, 1976

By Michael F. Dunn, Francis S. Kendorski

The fall of rock from strip coal mine highwalls continues to be the largest single source of fatal accidents, so methods to improve highwall stability through improved blasting practices were investigated in the field. This paper covers the results of a project to improve, using existing and proven technology, unstable highwall conditions through better blasting practices in Appalachian strip coal mines. Better borehole blasting agent distribution and optimization of burden, spacing, and delay periods allowing satisfactory breakage with minimal backbreak were the objectives. At a selected field site, geologic conditions were closely examined with regard to joint orientation and spacing, and resulting slope stability considerations. Utilizing surface blasting concepts of trying to achieve flexural failure of the rock mass both horizontally and longitudinally by appropriate relationships between burden, spacing, and hole length, as well as delay time sequence to achieve optimal confinement and breakage, successful results were achieved. A test series of eight blasts was completed and the resultant highwall monitored by repetitive photography. Actual blockfalls could be measured and the stability for each blast design thus quantified. The study of drilling and blasting economics along with equipment performance led to an economic model of blast parameters and the identification of blast design cost benefits. The work demonstrated that small strip mining companies are able to achieve a more stable highwall excavation utilizing presently available technology, equipment, and explosive products at improved operational cost and safety.

Jan 1, 1983

By J. F. Smith

ELASTIC constants of yttrium and eleven of the rare earth elements have been measured. This has been accomplished by measuring the propagation velocities of ultrasonic pulses. The velocity measurements were made by noting the elapsed time between an applied pulse and the appearance of successive echoes. The pulse-echo technique has become relatively common, and the basis of the measurement is outlined in several standard tests, e.g., Heuter and Bolt.1 Two important assumptions are made when using this method for the determination of elastic moduli. First, the pulse is assumed to propagate as a plane wave. To justify this assumption, the cross section of the test specimen should be large compared to the wave length of the transmitted pulse. For these measurements on the rare earth elements the minimum cross section wave length ratio was about 20. A second assumption which must be made when using polycrystalline specimens is that the grains are sufficiently numerous and randomly oriented so that the specimen may be approximated as elasti-cally isotopic. The grain size in the as-cast specimens which were used is believed to be sufficiently fine for this approximation, and the degree of preferred orientation is believed to be small. Supporting this viewpoint is the fact that elasticity measurements by the pulse-echo technique on as-cast specimens of other metals give results which are in satisfactory agreement with values obtained by other techniques. Hence, it is believed that the measured elasticity values for the rare earth elements are not apt to be seriously in error due to the assumption of elastic isotopy. The apparatus used in this determination was a modified Sperry Reflectoscope with a precisely calibrated time base circuit. Piezoelectric transducers were used both to generate the pulse and to detect the echoes. X-cut quartz crystals were used for the longitudinal modes, and Y-cut quartz crystals were used for the shear modes. Frequencies of 2.25 and 5 megacycles per sec were employed. Most of the specimens were 2.5 to 5.0 cm in length. Results Table I is a tabulation of the measured propagation velocities of longitudinal waves and of shear waves, together with densities obtained by Sped- ding, Daane, and Herrmann2 from lattice parameter measurements. The shear modulus, Poisson's ratio, and Young's modulus were calculated from the data in Table I through use of the following relationships: µ = pv32 [1] s=2-(vb/vs)2/2[1-(vb/vs)2] [2] and Y= 2µ(l+s) [3] where s is the shear modulus, Y is the Young's modulus, s is Poisson's ratio, p is the density, V0 is the longitudinal wave velocity, and v, is the shear wave velocity. The calculated quantities are shown in Table 11. Compressibility values can be computed from the relationship and the computed values may be compared with measured values obtained by Bridgman.8 Table III lists the data for such a comparison. The agreement is satisfactory, being particularly good for neodymi- um and gadolinium, poor for samarium, and intermediate for the other elements. Some variation is expected since Bridgman's measurements are isothermal, whereas the present measurements are adiabatic. In addition there may be some effect due to small variations in purity. Though most of the rare earth metals measured by Bridgman and all of the metals used in the present measurements were prepared at this laboratory, minor purity variations might exist since the samples came from different lots. Also, any imperfections such as dislocations, vacancies, voids, grain boundaries, microcracks, etc., should contribute to the volume change of a com-

Jan 1, 1958

By Peter M. Fozzard

The San Bartolomt silver deposit was discovered by a United Nations team of geologists working with a counter- part team of staff of the Ecuadorian Government's General Directorate of Geology and Mines (DGGM). The Phase I project over five areas of operation during which this discovery was made was financed through a United Nations Development Program contribution of $860,000 and an Ecuadorian Government participation of about $680,000 equivalent. Existence of mineralization at San Bartolomé was first recognized in 1966 when a reconnaissance geochemical stream-sediment program was carried out over a 10 500 km2 (4,054 sq mile) area centered around the city of Cuenca in southern Ecuador. Over the course of this project more than 10,000 samples of stream-sediment, soil, and rock materials were collected. Average costs per sample were $10.00, as follows: collection, $5; sample preparation, $1.60; assay work, $3.40. Initially in the program (1965-1966) sediments were collected along all motorable roads and tracks. Routine analyses, originally by colorimetry and later by AAS, were for Cu, Pb, Zn and occasionally As, Ni, and Co. Discovery geochemical samples from the San Bartolomé drainage area were among the first to be taken in 1965. As luck would have it, the road along which this traverse was taken passes only some 100 m (328 ft) downstream from the mineralized suboutcrop. The relevant two streams sampled are of inconsequential size, some 1 m (3.3 ft) in width, with a limited flow volume throughout the year. Original anomalies were recognized through cold-extractable Cu/Zn analyses. The pH of all river waters was also recorded at sample sites. Resampling the discovery sediments when AAS became available showed total extractable values of between 150 ppm-300 ppm Zn, 550 ppm Pb, and 10 ppm Ag. In 1967 the first followup was by rough-and-ready means. Dithizone field-kits (THM) were used to rapidly test soils from the surrounding area. The area has no outcrop. This work allowed the definition of an area of interest of some 2 km (1.2 miles) x 500 m (1640 ft). Six approximately 1 km (0.6 mile) to 1.5 km (0.9 miles) lines spaced at approximate 250 m (820 ft) intervals were established and used for IP surveys and soil sampling at 50 m (164 ft) intervals. Where one of the lines crossed the westernmost geochemical discovery creek a first-priority geophysical anomaly coincided with a major Zn/Pb (and later Ag) soil anomaly. A pit was sunk and encountered mineralized vein material at a depth of 1.5 m (5 ft). This lucky glory hole confirmed the geochemical discovery and prompted systematic followup. Immediately, costeaning of the west bank of the discovery creek, the Quebrada Ocashuaico, was carried out and exposed weathered and leached mineralization. Nearly 100 mineralized veinlets ranging in thickness from 0.5 cm (0.2 in.) to 8 cm (3 in.) were exposed across the 180 m (59 1 ft) costean. Sixty mineralized veinlets were determined over a 90 m (295 ft) wide zone. Sampling delineated minable widths averaging between 0.16 and 0.31 kg/t (5 and 10 oz per st) Ag with associated copper (very sporadic) lead and zinc. Over the period 1968- 1972 a considerable amount of detailed work was completed: detailed IP, EM Turam, magnetic and mise-a-la-masse geophysics, very detailed soil- sampling, trenching, drilling and glory-hole drifting, and cross-cutting. Numerous problems were encountered: the area was found to be a most difficult geoelectrical target; zero outcrop; pyrite (nonargentiferous zones) associated with faulting; mineralized groundwater; extensive clay development; loss of diamond drill-core, and no two-dimensional surface information. As the program developed the complexity of the structure was slowly unravelled, using a degree of good guesswork. Apart from photogeological and ground geological mapping at various scales, the following

Jan 1, 1985

By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria 'Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

By W. L. Crentz, E. E. Donath, D. Doherty

IN 1948, the United States used nearly six million barrels of petroleum products every day. Although substitution of synthetic fuels for the natural petroleum product is not here yet, large quantities of special-purpose coal will be required in ever-increasing volume as the domestic production of oil from other sources fails to meet demand and the production of synthetic fuels begins. Petroleum economists do not agree as to when the shortages of domestic oil will appear; but the increasing per capita consumption of oil, coupled with a constantly growing population drawing on a potential domestic oil supply estimated to be 85 billion barrels, sooner or later will result in demand exceeding domestic supply. When this situation comes about, the excess demand will be either eliminated by curtailment of consumption or the demand met by increasing importation of foreign oil or by the production of synthetic fuels. The first recourse would definitely retard the heretofore unbroken rise in American living standards, while dependence upon a foreign oil supply during a war or other emergency would be dangerous. On the other hand, the enormous coal reserves in the United States, plus sizable deposits of oil shale, indicate adequate means of augmenting a diminishing domestic oil supply. Some idea of the impact of an expanding synthetic liquid fuels program on the coal-mining industry may be gathered when it is considered that to supply just half of our present-day petroleum needs synthetically from coal would increase the coal output by about 500 million tons annually, using an 11,900 Btu bituminous coal as the plant feed. If either a subbituminous coal or lignite were used, the quantity required would be materially increased. Synthetic Fuel Processes: The principal synthetic fuel processes using coal as a raw material are the Bergius, or coal-hydrogenation process, and the Fischer-Tropsch, or gas-synthesis process. These two processes not only produce different end products, but the preparation of the coal used in each presents its own individual problem to the coal-preparation engineer. The hydrogenation process brings together a mixture of dry, finely powdered coal, catalyst, and heavy oil to form a paste. Addition of hydrogen under rather high pressure and temperature conditions brings about transformation of the coal to a liquid product, from which a high-grade gasoline and other motor fuels may be obtained. The Fischer-Tropsch process requires the production of synthesis gas, a mixture of carbon monoxide and hydrogen. At the Bureau of Mines Louisiana, Mo., demonstration plant, this gas is being made by reacting dried pulverized coal with carefully controlled volumes of oxygen and superheated steam. After purification and in the presence of the proper catalyst and suitable conditions of pressure and temperature, the hydrogen and carbon monoxide components of the synthesis gas react to form motor fuel. The two processes are not competitive but rather com-

Jan 1, 1951

By E. E. Donath, W. L. Crentz, D. Doherty

IN 1948, the United States used nearly six million barrels of petroleum products every day. Although substitution of synthetic fuels for the natural petroleum product is not here yet, large quantities of special-purpose coal will be required in ever-increasing volume as the domestic production of oil from other sources fails to meet demand and the production of synthetic fuels begins. Petroleum economists do not agree as to when the shortages of domestic oil will appear; but the increasing per capita consumption of oil, coupled with a constantly growing population drawing on a potential domestic oil supply estimated to be 85 billion barrels, sooner or later will result in demand exceeding domestic supply. When this situation comes about, the excess demand will be either eliminated by curtailment of consumption or the demand met by increasing importation of foreign oil or by the production of synthetic fuels. The first recourse would definitely retard the heretofore unbroken rise in American living standards, while dependence upon a foreign oil supply during a war or other emergency would be dangerous. On the other hand, the enormous coal reserves in the United States, plus sizable deposits of oil shale, indicate adequate means of augmenting a diminishing domestic oil supply. Some idea of the impact of an expanding synthetic liquid fuels program on the coal-mining industry may be gathered when it is considered that to supply just half of our present-day petroleum needs synthetically from coal would increase the coal output by about 500 million tons annually, using an 11,900 Btu bituminous coal as the plant feed. If either a subbituminous coal or lignite were used, the quantity required would be materially increased. Synthetic Fuel Processes: The principal synthetic fuel processes using coal as a raw material are the Bergius, or coal-hydrogenation process, and the Fischer-Tropsch, or gas-synthesis process. These two processes not only produce different end products, but the preparation of the coal used in each presents its own individual problem to the coal-preparation engineer. The hydrogenation process brings together a mixture of dry, finely powdered coal, catalyst, and heavy oil to form a paste. Addition of hydrogen under rather high pressure and temperature conditions brings about transformation of the coal to a liquid product, from which a high-grade gasoline and other motor fuels may be obtained. The Fischer-Tropsch process requires the production of synthesis gas, a mixture of carbon monoxide and hydrogen. At the Bureau of Mines Louisiana, Mo., demonstration plant, this gas is being made by reacting dried pulverized coal with carefully controlled volumes of oxygen and superheated steam. After purification and in the presence of the proper catalyst and suitable conditions of pressure and temperature, the hydrogen and carbon monoxide components of the synthesis gas react to form motor fuel. The two processes are not competitive but rather com-

Jan 1, 1951

By B. G. Reisdorf

This paper describes the microstructural changes that occur when quenched ultrahigh-strength steels containing OA pet C and various amounts of nickel, silicon, and cobalt are tempered. The changes that occur in hardness, yield strength, and martensite diffraction-peak widths when these steels are tempered are related to the precipitation of the carbide phases. An unea$ectedly high silicon content (about 30 pct) was found in the E -carbide phase in a steel containing only 1.5 pct Si. TEMPERED martensitic steels have such wide-spread utility that they have been the subject of numerous investigations, and a sizable amount of literature has developed on this subject.M This investigation, which is a part of a larger program to correlate microstructure with mechanical properties at a variety of strength levels, is limited to the microstructural changes that occur when a quenched 0.40 pct carbon steel (USS Airsteel X-200 steel) is tempered, and to the effects of the alloying elements—nickel, cobalt, and silicon—on these microstructures. Used in this investigation were electron microscopy, electron-diffraction identification of the carbide phases, electron-probe micro-analysis of the carbides, X-ray determinations of retained austenite, and measurements of martensite X-ray diffract ion-peak widths. MATERIALS AND METHODS The chemical analyses of the eight heats examined eats No. 30 through 37) are shown in Table L Heat No. 30 has the chemical com~osition of Airsteel X-200, and the remaining seven heats contain various amounts of nickel, chromium, cobalt, and silicon. The heats were air-melted in an induction furnace and cast into 8 by 8 in. ingots that were subsequently heated to 2300 and rolled to 1-in.-thick plate. Oversize 0.505-in.-diam tensile specimens were rough-machined from the plates and austenitized in air at 1700° F for half an hour and oil-quenched. The specimens were then tempered in air at temperatures of 400° to 1000 for tempering times of 1, 4, and 16 hr, and finish-machined to 0.505-in.-diam tensile specimens. Electron micrographs were prepared from Formvar replicas of the midthickness of tensile-specimen shanks that had been electrolytically polished and etched in nital. Electron-diffraction patterns were obtained from carbon-extraction replicas. The replicas were prepared by etching the sample surface in the same manner as for microscopy, evaporating carbon on the etched surface, and re-etching the sample to free the carbon film and the precipitate particles. Electron-probe microanalysis was performed on some of the extraction replicas. To obtain adequate fluorescent X-ray intensities, several thicknesses of replica were exposed to the electron beam so that the results represent an average composition of the extracted particles rather than an analysis of single precipitate particles. The retained austenite contents of the specimens were determined by an empirical X-ray diffraction

Jan 1, 1963

By Joseph A. Holmes

(Pittsburg Meeting, March, 1910.) AT the Mining Experiment Station of the U. S. Geological Survey, in Pittsburg, an investigation of the process of combustion is being carried on in a specially-designed furnace having an unusually long combustion-chamber. This work is conducted by a committee consisting of H. Kreisinger, mechanical engineer; Dr. J. C. W. Frazer, chemist; and Dr. J. K. Clement, physicist. The problem, essentially one of physical chemistry, is extremely interesting to all who are concerned in the burning of coal or the construction of furnaces. The main object of these experiments is to ascertain the relation between the amount of the volatile combustible driven from the coal and the combustion-spaces necessary to burn it completely. Our best steam-coals vary from 15 to 45 per cent. of fixed combustible. The greater part of the latter is burned on the grate; but the volatile combustible leaves the freshly-charged coal and must be burned in the combustion-space. If this space is not large enough, the volatile combustible will leave the furnace only partly burned, and the result will be a considerable heat-loss and a smoky stack. Strictly speaking, the factor which determines the completeness of combustion of the volatile matter, after it has been mixed with a certain amount of air, is the length of time the mixture is allowed to remain in the combustion-space; but this length of time depends on the extent of the space itself. Let us suppose, for instance, that, when a given coal is burned at a certain standard rate, the volume of the volatile combustible driven off per second is 10 cu. ft. Adding, say, 10 cu. ft. of air, the volume of the resulting burning mixture is increased to 20 cu. ft. If the combustion-space is 20 cu. ft., the burning mixture will stay in it,

May 1, 1910