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By Charles W. Wright

At most mines where large tonnages are handled, "bulldozing" or secondary blasting is an important and costly operation. To reduce the large blocks from primary blasting operations or stoping so that they will be small enough to pass through the chutes into the cars at the haulage level, and not too large for the crushing plant, requires blasting. Often this is done by placing a few sticks of dynamite on top of a block with or without a capping of mud, but to consume less dynamite and to promote safety, most secondary blasting is now done by blockholing, or the drilling of holes 6 to 12 in. long in the blocks, using only a part of a stick of dynamite per hole. Regardless of the method of blasting, however, the term "bulldozing chamber" is applied to the room where this work is done. Bulldozing chambers permit secondary blasting at all times in a safe place without disturbance to the other mining operations. The chambers are usually high above the haulage level and well below the stope level or open-pit floor. In most instances the material is passed through a grizzly in the bulldozing chamber, but sometimes no grizzlies are used. One to four raises extend from the chamber to the stope floor and one or two from the haulage level to the chamber floor. Occasionally large slabs of ore or rock choke the raises above the bulldozing chamber, and these have to be blasted by attaching a bundle of dynamite sticks on the end of a long pole and placing them up in the raise between the pieces causing the choke. This is called "chute-blasting." To give a picture of the progressive developments in the use of the bulldozing chamber, a few typical mines that show the application of this method to both metal and limestone mines have been selected for description here. Limestone mines have been included because many metal miners do not realize to what extent the nonmetallic, or rock, miners' are now applying metal-mining methods successfully in their operations. The bulldozing chamber is the "neck of the bottle" for some mines.

Jan 1, 1937

By R. N. Upadhyay, M. Maleki, I. Fatt

Conventional laboratory core analysis tests on samples of two limestone reservoir rocks indicate that about 20 per cent of PV is in dead-end pores. These tests (electric logging formation factor, mercury injection capillary pressure and miscible displacement) were carried out on 1/4-in. diameter test plugs. Test results show a clear dilference between these samples and sandstone or homogeneous limestone reservoir rock. Although the amount of dead-end pore space can be only roughly estimated, the presence of such pore space seems clearly indicated. Pressure transient studies also show presence of deadend PV. Although they do not give quantitative results, pressure transient data yield a reasonable estimate of the size of the neck connecting dead-end pores to the main flow channels. INTRODUCTION Equations conventionally used to describe reservoir flow behavior contain the implicit assumption that all connected pore spaces contributed to both porosity and permeability. Several authors3-7 have pointed out the changes in pressure transient behavior and in electric log interpretation that may result if this assumption is incorrect and, instead, dead-end or cul-de-sac pores are present. There is a need for laboratory tests that can detect presence of dead-end pores in core samples. With such information on hand the petroleum engineer can make more rational use of the mathematical tools now available for analysis of reservoir flow behavior. This paper describes laboratory studies designed to detect and, if possible, give a quantitative measure of dead-end PV in laboratory-size core plugs. Three reservoir rocks were used, two of which were limestones suspected of having deadend pore spaces and a well-known sandstone, used as a comparison standard, in which there is believed to be little or no dead-end pore space. All the studies were designed to measure the natural dead-end PV; i.e., the pore space which is dead-ended because of rock structure. During multiphase flow in a rock without dead-end pores, some parts of one of the phases can become surrounded by the other, thereby giving (for certain flow behavior) an effective dead-end pV8,9. Such behavior will not be described here.

Jan 1, 1967

By James E. Howard

AT the request of the Council of the Institute, I have the honor to submit the following remarks upon the Program of Tests under which the current work of the Watertown Arsenal Testing Laboratory is carried on, which comprises, among other items, the tests of steel ingot metal and derivative shapes. The intended scope of the tests may be illustrated by extracts from the descriptive part of the program as submitted by the Laboratory under date of April 17, 1907, and subsequently approved by the Chief of Ordnance, U. S. A. Under Item 1, Ingot Metal-Open hearth, acid and basic; Bessemer, acid and basic; crucible; fluid compressed and uncompressed-descriptive remarks were made as follows ; " A thorough, fundamental inquiry into the physical properties of steel necessarily begins with the ingot metal. Investigations, having for their object the improvement of steels, should also begin with the ingot. A knowledge of the ingot structure is essential for judging of the subsequent behavior or appearance of the metal. Under ordinary conditions, so little information is obtained from the ingot in individual cases that practically none of importance is acquired. These remarks have particular reference to the state of physical and structural soundness of the steel. Questions of chemical composition, segregation, piping and the grosser cavities have frequently been given attention. Defects of continuity of structure, which manifest themselves in the working; of the metal, and at the final stages cause distrust in the finished forging, have generally been neglected. ? The range in physical properties in a given composition of metal, as shown in Tests of Metals, 1902 and 1903, is very great. Tests are there found which, when the results are

Mar 1, 1908

By G. Carman Ridland

IN conjunction with a geological investigation of the silver-bearing veins at Contact Lake, Northwest Territories, Canada, a survey was made with a Geiger-Müller counter of the gamma-ray emissions from the rocks in the vicinity of the mine workings. Discontinuous pitchblende veins have been encountered occasionally in the silver-bearing fissures, and the geophysical survey was undertaken with the hope that abnormally high gamma-ray intensities, if detected, might lead to larger and more continuous pitchblende discoveries. Before the instrument was used at. Contact Lake, preliminary tests were made, first with laboratory specimens at Princeton University, and later over known pitchblende deposits at the Eldorado property, LaBine Point, N.W.T. The Geiger-Müller counter, as adapted for field use, is described; the technique of transporting and operating the instrument is outlined; and the general precautions to be observed are discussed. The results obtained at Great Bear Lake show that the instrument is capable of detecting not only a pitchblende ore shoot in a shear zone, but also the mildly radioactive "host rock" at a considerable distance from the ore body. Hence, use of the Geiger-Müller counter is urged, not just for the detailed search for an ore body in a shear zone, but for the detection of possible radioactive "host rocks" in large-scale reconnaissance surveys of unexplored regions made by prospectors and members of federal geological survey parties.

Jan 1, 1944

By A. F. Crawley

THIS communication reports measurements of the densities of dilute liquid alloys of 0.1 and 0.5 pct Ag in Sn over temperature ranges of 170" and 210°C, respectively, above the melting point of pure tin (232°C). The work was earried out to provide accurate density data for some liquid diffusion studies performed by Davis.1 Densities were measured using a pycnometric technique established in this laboratory. Earlier papers2, 4 attest to the accuracy of ±0.05 pct and the reliability of the method. Tin, 99.999 pct pure, and silver 99.99 pct pure, were melted in a graphite crucible in a vacuum furnace and held at temperature for 10 hr to ensure homogenization. Ingots suitable for machining

Jan 1, 1970

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

The subjects of this study are two corrosion phenomena familiar to operators of aluminum plants employing Soderberg anodes of the vertical type, namely the sul-fide scale formation observed at the steel contact spikes and the corrosion wear observed at the lower edge of the gas collecting skirts. The causes of these corrosion phenomena are discussed on the basis of observations from practice and measurements on commercial cells as well as on laboratory experiments. It is concluded that the anode spike corrosion is mainly due to the attack by sulfur compounds contained in the anodically evolved gases and that this attack is greatly promoted by cracks and pores in the anode carbon embedding the lower spike ends. The corrosion of the gas collecting skirt is mainly attributed to anodic dissolution of the iron during occasional contacts with the melt. ANODE SPIKE CORROSION The visible result of this corrosion is the formation of a brittle loosely adherent scale on the lower ends of the mild steel spikes maintaining the electric contact to the carbon anode, Fig. 1. The thickness of the scale usually varies from 0.5 to 3 mm, but in some cases scale of about 10 mm thickness has been observed by the writers. During the spike pulling, usually repeated every 3 weeks, part of the scale often loosens and remains in the anode carbon, resulting in contamination of the aluminum with iron. This corrosion has been attributed to reaction of the iron with gaseous sulfur compounds originating from the anode paste materials.'-4 This paste usually consists of 70 pct precalcined petroleum coke with 1.2 to 1.4 pct S and 30 pct coal tar pitch containing 0.5 to 0.7 pct S. During operation the gasification of the anode materials takes place in two ways: First, gases are evolved by the gradual baking of the anode paste added on top of the anode. Due to the sealing effected by the upper semifluid zone of the paste, these gases, containing sulfur compounds from the pitch, are forced downward through pores and cracks in the rigid anode carbon. At the temperatures of the zone of the lower ends of the spikes, 700" to 900°C, the original components of the baking gas must undergo decomposition, similar to that taking place with the production of coal gas, resulting in a gas mixture consisting mainly of H2 and CH4 with small percentages of H2S as the main sulfur compound.5 Second, the anodic reaction results in a mixture of C02 and CO, the total quantity of which is about 15 times that of the baking gas. These anode gases must carry the entire sulfur content of the carbon gasified by the anodic reaction. Henry and Holliday6 have shown that COS is the main sulfurous component of the anode gases from Soderberg cells. Soderberg anodes usually exhibit a network of vertical cracks, frequently traversing from one spike to the next one and to the outside of the block and widening downward to the working face of the anode. In addition the anode carbon, particularly that below the spike ends, is rather porous, as indicated in Fig. 1. It therefore seems probable that the anode gases also may partly penetrate to the spike ends. As the anode is partly immersed in the melt, the static pressure of this must forward this penetration. I) SPIKE SCALE COMPOSITION A great number of freshly extracted spikes from industrial plants were inspected and samples of the scale collected for examination. Before analyzing the samples a thin iron oxide layer, formed by air oxidation of the outside of the red hot scale immediately after spike pulling, was removed. On the average the Fe/S ratio found by these analyses corresponded to I the composition FeSl. oo7. X-ray powder patterns showed no oxide and otherwise agreed with those found by Haraldsen7 for iron sulfide with 50.00 at. Pct

Jan 1, 1970

By Edwin H. McKee

Eruption of rhyolitic ash-flow tuffs in the area of the McDermitt (Cordero) caldera began about 17.4 million yr (m.y.) ago and continued for about 1.5 m.y. During this period of silicic eruptions, a circular area about 30 km in diameter collapsed to form a caldera that subsequently filled with sedimentary and volcanic rocks. A total of more than 200 km30f silicic rocks was erupted from the volcano. The final phase of igneous activity, about 15.0 m.y. ago, included resurgent doming and intrusion in the south-central part of the caldera. Three to 4 m.y. later (-1 2 m.y. ago), hydrothermal solutions using the northern part of the caldera ring fractures as conduits deposited silica, cinnabar, pyrite, alunite, and other minerals in tuffaceous lake beds and volcanic rocks accumulated within the caldera. The ore-forming solutions may have been a residuum from the silicic magma, or connate water, or ground water heated by the still-hot resurgent magma in the central part of the caldera. The source of the mercury and other elements has not been identified.

Jan 1, 1977

By G. H. F. Gardner

The velocity and attenuation of elastic waves in sandstones were measured as a function of both pressure and fluid saturation. A large change occurs in these quantities if water is added and the rock is not compressed, but the change is small if the rock is subjected to a large overburden pressure. Measurements were made by vibrating cylindrical samples in both the extensional and torsional modes at frequencies up to 30,000 cycles/sec. Formulas were derived which enable the attenuation of dilatational waves in dry rocks to be deduced from the data. Similar experimental methods were used to investigate the properties of unconsolidated sands. Velocities were found to vary with the 1/4 power of the overburden pressure and attenuations to decrease with the 1/6 power. The effects of grain size, amplitude and fluid saturation were studied. Formulas by which the effects produced by a jacket around the sample may be calculated were derived. The practical application of these results to formation valuation is discussed. INTRODUCTION The attenuation of elastic waves in the earth has been of interest to the seismologist and geophysicist for many years, but only recently to the petroleum engineer. Engineering interest has been brought about by the success of velocity logging devices, for it is possible by modification of these instruments to measure the attenuation of sound waves in addition to their velocity and, hence, deduce the mobility of formation fluids as well as the porosities of the rocks which contain them. The main problem is to decide whether field measurements can be made with sufficient accuracy to be of practical use. This problem can only be solved after we know the magnitude of the attenuations which are typical of the earth at various depths. The logarithmic decrement of a fluid-saturated rock is the sum of a "sloshing" decrement and a "jostling" decrement, the former caused by the mobility of the fluid contained within the rock and the latter by the granular framework of the rock. Sloshing decrements can be calculated' using Biot's theory, but the jostling losses are less well understood. The present paper reports an experimental investigation of jostling losses in consolidated and uncon- solidated sands, particularly with respect to the effect of overburden pressure and fluid saturation. Born' showed that the decrement of a sandstone may increase dramatically when only a few per cent by weight of distilled water is added, and that the additional loss is proportional to the frequency of vibration. His measurements were made with no compressive stress on the framework of the rock. M. Gondouin3 investigated similar phenomena for fluid-saturated plasters but also did not compress the samples. In the present paper it is shown that compression of the framework reduces this effect, so that at depth the jostling decrement of a sandstone may be expected to be almost independent of fluid saturation and frequency. Decrements for many sedimentary rocks have been given by Volarovich,4 but all for the state of zero overburden pressure. Anomalously low velocities have been logged in shallow unconsolidated gas sands. Results of the present investigation confirm that these velocities are not caused by correspondingly high attenuations, because the jostling decrement in a packing of sand grains is small and much less than in a consolidated sandstone at the same depth. Velocities in sands have been measured by Tsareva5 and by Hardin6 as a function of pressure, but the corresponding decrements do not appear to have been measured previously. The widely used "resonant bar method" of measuring velocities and decrements was employed. Comments on variations of this technique have recently been published by McSkimmin.7 The main novelty of the present technique was the application of pressure to the samples. It was found possible to do this by placing the apparatus inside a pressure vessel, provided the conditions leading to large additional losses were avoided. These conditions are discussed below. EXPERIMENTAL TECHNIQUE Cylindrical samples were caused to vibrate in both the extensional and torsional mode of vibration and the amplitude of vibration was measured as a function of frequency in the neighborhood of a resonant frequency. The resonant frequency, fr, is related to the corresponding elastic modulus by the formulas where E and N are Young's modulus and the modulus of rigidity, p is the density of the sample, and A the wavelength of the vibration.

Jan 1, 1965

By K. G. Davis

Dilute alloys of silver and of thallium in tin have been solidijzed unidirectionally under controlled conditions, to study the segregation associated with a cellular interface under conditions where both thermal and solute convection are present. Autoradiography and radioactive tracer counting techniques were combined with electron-probe microanalysis to study both macro- and microsegregation. It was found that, for concentrations giving only small amounts of constitutional supercooling, cell formation had little effect on the macroscopic distribution of solute along the specimen. At higher concentrations the effective distribution coefficient was higher than that expected for a smooth interface. Node spacing was independent of initial solute content at lower concentrations, becoming greater as keff increased. Silver content at the segregation nodes of silver in tin alloys was independent of initial concentration and considerably in excess of the eutectic composition. SINCE the investigation of cell formation at advancing solid-liquid interfaces by Rutter and Chalmers,' a large volume of work has been dedicated to the determination of solidification conditions under which a planar interface will break down into cellular form. Early experiments were explained satisfactorily by the concept of constitutional supercooling,2 but, due to poor measurement of temperature gradients in the liquid, lack of accurate data on liquid diffusion and equilibrium distribution coefficients, and uncertainty about the effects of thermal and solute convection, these experiments cannot be used as proof for the theory. More recent work, however, has shown that under conditions where convection is eliminated or can be ignored good correlation is observed.3,4 Investigations into segregation at cell caps5 and at cell nodes6-'' have been made, but no measurements appear to have been done on the overall, macroscopic segregation down a unidirectionally solidified rod of material which has solidified with a cellular substructure. This has practical importance in casting, where regions of material with cellular substructure are often encountered, and also in zone refining where the thermal conditions necessary for a planar interface are unattainable. Further, as will be shown, the macroscopic segregation can give information on the following question. Granted that a cellular solid-liquid interface develops from a planar one when the conditions for constitutional supercooling are exceeded, how much supercooling is present after the cells have formed? EXPERIMENTAL PROCEDURE AND RESULTS Specimen Preparation. Specimens 25 cm long with a square cross section 0.6 by 0.6 cm were grown in graphite boats by solidification from one end. Alloy compositions are given in Table I. Two specimens of each composition were grown. The tin was 5-9 grade and the silver and thallium both 4-9 grade. Ag110 and Tl204 were used as tracers. Each composition had the same quantity of tracer so that auto radiographs of specimens containing different concentrations of the same element could be easily compared. Thermocouples inserted through the lid of the boat into a dummy specimen showed that, over the first 10 cm of growth, thermal conditions were quite steady, with a rate of interface advance of 5.8 cm per hr and a temperature gradient in the melt ahead of the interface of 3.0°C per cm. The specimens were seeded from tin crystals of a common orientation to eliminate orientation effects. Dilution of the specimen by seed material was minimized by the provision of a narrow neck between specimen and seed crystal. Macrosegregation. After growth, the specimens were sectioned with a spark cutter. The rods of silver alloy were cut into 1-cm lengths and analyzed for Ag110 using a y -ray counter with fixed geometry. The specimens containing thallium were cut into 2-cm lengths and analyzed for T1 204 by taking 13 counts from each end of the cut lengths through an aperture in lead sheet approximately 0.4 cm square. The results are summarized in Figs. 1 and 2. To find the effective distribution coefficient for the silver in tin alloys under smooth interface conditions, the region of substructure at the bottom surface of one of the 10 ppm specimens, see Fig. 3, was removed by spark machining before counting. Autoradiography. For both alloy systems the samples were polished on sections taken alternately parallel and perpendicular to the growth direction, and autoradiographed by placing the polished surfaces in contact with Kodak "Process Ortho" film. Figs. 3 and 4 show the structures revealed. The alloy containing 10 ppm Ag showed substructure only after a few centimeters of growth, and then substructure was limited to a narrow layer at the base. The "speckled" substructure reported previously in this system4 is here clearly seen to be an intermediate stage between planar and cellular interface conditions. The other samples show a remarkable similarity considering

Jan 1, 1969

By J. E. Dutrizac, R. J. C. MacDonald, T. R. lngraham

When sintered disks of synthetic chalcopyrite (CuFeS2) were leached in acidified aqueous solutions of ferric sulfate, the following reaction stoichiometry was obtained: CuFeS2 + 2Fe2(SO4)3 = CuSO4 + 5FeSO4 + 2S Over the temperature range from 50º to 94ºC, the reaction displayed parabolic kinetics. The parabolic rate constant for the dissolution of copper is given by the equation: log.k(mg2/cm4-hr)= 11.850 - 3780/T The activation energy for the dissolution process is 17 ± 3 kcal per mole. The parabolic kinetics have been attributed to the progressive thickening of a sulfur film on the surface of the chalcopyrite. When the leaching solutions contain less than 0.01 molar Fe+3 , the Fe concentration influences the rate of leaching, probably through a mechanism involving the diffusion of ferric sulfate through the sulfur layer. At higher Fe+3 concentrations, the rate control in the leaching. reaction has been attributed to the diffusion of ferrous sulfate through the sulfur. The rate of reaction is insensitive to changes in acid concentration and in disk rotation speed. ThE reaction of acidic ferric sulfate solutions with various sulfide minerals is of practical interest for both bacterial and heap leaching. This leaching medium is generally used with low-grade ores that cannot be treated profitably by conventional means. In both bacterial leaching1-3 and heap leaching, the active agent for sulfide dissolution is ferric sulfate. Although the reactions of ferric sulfate with chalcocite, covellite, and bornite have been investigated,4*7 the kinetics of leaching chalcopyrite with ferric sulfate have not been thoroughly studied. This paper reports a study of that reaction. EXPERIMENTAL Reagent-grade sulfur was purified by the method of Bacon and FanelliB and then it was vacuum-distilled to remove any soluble magnesium salts that had been introduced during the purification procedure.9 From stoichiometric quantities of the purified sulfur and hydrogen-reduced electrolytic copper sheet (99.90 pct Cu), CuS was synthesized at 450°C in a vacuum-sealed, pyrex vessel. About 24 hr was required for the completion of the reaction. A similar procedure involving hydrogen-reduced iron wire (99.90 pct Fe) was used to synthesize FeS1.002. A 2-furnace arrangement was required. The iron was heated to 800°C while the sulfur was maintained at about 400°C. Although the reaction to consume the sulfur was rapid, the material required additional heating (1 week) in a sealed silica ampoule at 800°C before it was homogenized. X-ray powder diffraction analysis confirmed that the copper sulfide was covellite and that the iron sulfide was troilite. The composition of the iron mineral was confirmed by wet chemical analysis. The two sulfides were ground to minus 100 mesh, weighed in equimolar amounts, mixed thoroughly, and pressed into pellets at 80,000 psi. The pellets were vacuum-sealed in pyrex ampoules and then sintered for 3 days at 550°C after an initial heating at 450°C for a few hours. The pellets were then cooled, polished with 3/0 emery paper, rinsed in acetone, and stored. The material had the characteristic brassy color of chalcopyrite and was shown by X-ray diffraction to be CuFeS2. Microscopic examination of the polished surfaces revealed small inclusions of pyrite (approximately 0.5 vol pct) as the only impurity. The presence of small amounts of a second iron compound will not alter the amount of dissolved copper but might increase the amount of ferrous ion slightly. It was calculated that dissolution of all of the pyrite and 100 mg of Cu (a typical value) would change the expected ferrous concentration by only 4 pct. Microscopic examination of a pellet after leaching revealed that the pyrite was not preferentially solubilized; only those pyrite grains at the surface were attacked. Hence, the pyrite is unlikely to alter the rate of copper dissolution. The chalcopyrite disks were about 1.7 mm thick and 27 mm in diam. They were about 80 pct of theoretical density, and for this reason their true reaction area was somewhat larger than the 5.8 sq cm area presented by the polished face. The disks were cemented to lucite cylinders in such a way that only the polished face was exposed. The disks were then leached by methods previously described.6,7 RESULTS AND DISCUSSION Stoichiometry and Kinetics. The initial experiments were directed to the problem of resolving the stoichiometry of the leaching reaction. Disks of CuFeS2 were leached at 80°C for various periods of time in acidified ferric sulfate solutions that were protected from oxidation by a cover of flowing nitrogen. When the disks had been partly leached, they were removed, their soluble salts were washed out, and then they were treated with CS2 in a Soxhlet extraction apparatus. The ratio of elemental sulfur to dissolved copper thus obtained was approximately 2 to 1. After the extraction of elemental sulfur from the pellet, the residue consisted of unreacted chalcopyrite only. For runs in which an appreciable amount of copper was dissolved, the ratio of ferrous ion to cupric ion in the solution was

Jan 1, 1970

By H. H. Evinger, M. Muskat

A methoD of calculating productivity factors for oil, gas, and water systems in the steady state is presented as an illustration of the quantitative application of the fundamental data on the flow properties of heterogeneous fluid systems. While the numerical results of the calculations cannot be applied directly to field conditions, because they are based on permea-bility data for unconsolidated sands and involve specific assumptions regarding the nature of the reservoir fluids, the methods of analysis and interpretation should havc significance in considering certain specific field situations when the necessary field and laboratory data become available. Moreover, it is felt that even under the idealized conditions to which the numerical calculations refer they should serve to give at least the orders of magnitude of the effects of gas-oil ratio and connate water on observed productivity factors. Within the indicated limitations, the computations imply that the foregoing factors can explain only a part of the apparent discrepancy between the homogeneous fluid productivity factors and those obtained recently in field measurements on the West Coast. IntroductioN Sufficient laboratory research has been carried out in the last several years on the fundamental features of the flow of heterogeneous fluids through porous media to call for consideration of what can be done with this type of information. It has, of course, already led to a, much clearer general understanding of the mechanics of oil production. However, examples of the quantitative application of the results of such laboratory studies are few in the literature. part of the explanation for this fact lies undoubtedly in the lack of sufficient laboratory data relating to practical fluids and sand systems such as would occur ill actual oil reservoirs. However, unless it can be shown that if such data were obtained quantitative applications could be made, serious doubt may be cast upon the desirability of carrying on further extensive experimental research work on fluid flow. The purpose of this paper is to present one approach to the problem of quantitative application of laboratory data to practical field problems. Because the published results on the basic experiments with three-phase fluid systems in porous media are limited entirely to uncon-solidated sands, the numerical applications made here will not pertain directly to any actual field situation. However, they should serve to illustrate what could be done with fundamental laboratory data if they were extended to cover the field of consolidated sands. From this point of view, it is hoped it will serve to encourage further laboratory research on this problem. The particular application to be treated here relates to the calculation of the productivity factors for oil-gas-water systems in the steady state. This specific problem seems especially appropriate for discussion in view of the recent publication by Johnston1 of the results of produc-

Jan 1, 1942

By M. Muskat, H. H. Evinger

A methoD of calculating productivity factors for oil, gas, and water systems in the steady state is presented as an illustration of the quantitative application of the fundamental data on the flow properties of heterogeneous fluid systems. While the numerical results of the calculations cannot be applied directly to field conditions, because they are based on permea-bility data for unconsolidated sands and involve specific assumptions regarding the nature of the reservoir fluids, the methods of analysis and interpretation should havc significance in considering certain specific field situations when the necessary field and laboratory data become available. Moreover, it is felt that even under the idealized conditions to which the numerical calculations refer they should serve to give at least the orders of magnitude of the effects of gas-oil ratio and connate water on observed productivity factors. Within the indicated limitations, the computations imply that the foregoing factors can explain only a part of the apparent discrepancy between the homogeneous fluid productivity factors and those obtained recently in field measurements on the West Coast. IntroductioN Sufficient laboratory research has been carried out in the last several years on the fundamental features of the flow of heterogeneous fluids through porous media to call for consideration of what can be done with this type of information. It has, of course, already led to a, much clearer general understanding of the mechanics of oil production. However, examples of the quantitative application of the results of such laboratory studies are few in the literature. part of the explanation for this fact lies undoubtedly in the lack of sufficient laboratory data relating to practical fluids and sand systems such as would occur ill actual oil reservoirs. However, unless it can be shown that if such data were obtained quantitative applications could be made, serious doubt may be cast upon the desirability of carrying on further extensive experimental research work on fluid flow. The purpose of this paper is to present one approach to the problem of quantitative application of laboratory data to practical field problems. Because the published results on the basic experiments with three-phase fluid systems in porous media are limited entirely to uncon-solidated sands, the numerical applications made here will not pertain directly to any actual field situation. However, they should serve to illustrate what could be done with fundamental laboratory data if they were extended to cover the field of consolidated sands. From this point of view, it is hoped it will serve to encourage further laboratory research on this problem. The particular application to be treated here relates to the calculation of the productivity factors for oil-gas-water systems in the steady state. This specific problem seems especially appropriate for discussion in view of the recent publication by Johnston1 of the results of produc-

Jan 1, 1942

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

HE high vapor pressures of metals such as lead, calcium, lithium, bismuth, and magnesium at steel-making temperatures present experimental problems which have thus far rendered it almost impossible to obtain really reliable data for their solubilities in liquid iron. Many investigators have attempted to equilibrate liquid iron in the same crucible with the undissolved liquid phase of such volatile metals. The published results,l-6 although useful, are often questionable on the grounds of not being obtained under true equilibrium conditions. Such information is not always of practical value in any case since the equilibrium vapor pressure is often several atmospheres and steel is not currently made at these pressures. Solubility measurements at lower partial pressures (< 1 atm) appeared to be more practical and easier to make. These data could be used to calculate solubilities at other pressures where Henry&apos;s Law is obeyed, and to estimate solubilities under other conditions of temperature and pressure with useful accuracy. This note outlines the development of a general technique for the measurement of solubilities in systems of this kind. The method involves equilibration of the high-boiling metal at known temperatures with the vapors of a low-boiling metal at known partial pressures. Analyses of quenched samples provide vapor pressure-solubility data and make calculations of alloy thermodynamics possible. The principle involved is similar to the closed-system diffusion-transport method which is difficult to apply with most high-melting liquid metals like iron, due to closure problems. A two-zone horizontal (molybdenum wire element) tube furnace, Fig. 1, provides two constant-temperature zones in a reaction tuve (3/4 in. ID by 1 in. OD by 36 in.). A high-boiling metal sample, 9, introduced in the higher-temperature zone, is maintained at temperature T1, and a volatile metal sample, 7, in the lower-temperature zone, is held at T2. A stream of argon with 10 pct hydrogen is passed via flowmeters, 1, and mixing-drying towers, 2 and 3. through the reaction tube at a favorable flowrate and acts as a carrier gas which entrains vapor from the volatile liquid metal at a specific constant partial pressure. The gas mixture passes through a system of constrictions, 6 and 8, to the higher-temperature zone, establishes intimate contact with the high-boiling liquid sample, 9, and exits through a small condenser tube. The entire system is at (nearly) atmospheric pressure and the volume of carrier gas passed is measured with a wet gas meter. When the high-boiling sample attains equilibrium with the vapor phase, both samples are removed and quenched. Analysis of the high-boiling sample for solute content reveals its solubility for the low-boiling metal at a vapor pressure calculated from carrier-gas volume and either a) weight loss of volatile metal or 6) weight gain of high-boiling sample plus condenser (which collects the undissolved vapors). To test the capabilities of the method, liquid silver at 1403&apos;C was equilibrated with lead vapor at various partial pressures. The relatively simple Pb-Ag system was particularly suitable for uncovering experimental problems and providing the first step toward investigations with more volatile metals and more difficult combinations.

Jan 1, 1965

By Joseph E. Pogue

FOR a number of years the petroleum department of The Chase National Bank has been making a continuing study of the financial aspects of thirty oil companies. (See Pogue and Coqueron, "Financial Analysis of Thirty Oil Companies," pamphlet, The Chase National Bank, November 1945, for data covering eleven years, 1934-1944, and the list of the companies making up the group. See also "Capital Employed in the Petroleum Industry," by the same authors, M&M, November 1944.1 This group represents a large sample of theAmerican petroleum industry, covering about two thirds of the business. Certain aspects of this study concern the capital employed in crude oil production, the main features of which arc presented in this paper.

Jan 1, 1946

IF you do not make the disc at the same time as the core and as part of it, it is necessary to make it by itself. This is done by spreading on a board or other flat surface a layer of clay as thick and wide as [88] the disc that you made at the feeding head of the first pattern of the gun. When it is dry, mark it exactly with compasses and then, cutting with a chisel or rasp, make it fit exactly into the empty space at the head. Likewise, make a hole just as wide as the thickness of the core exactly in the middle of this clay disc. When you have put the disc in its place in the mould and then pass the core through this hole, it passes exactly through the center of the mould in such a way that it meets the iron ring that you put at the foot of the mould for this purpose. As I said above, if&apos; you do not make it as part of the core, it is necessary to proceed in the aforesaid way. But if&apos; you wish to make it attached to the core (which I like better because it can be done more accurately) make a

Jan 1, 1942

By M. Weinstein, J. F. Elliott

IN conjunction with a study on the solubility of hydrogen in liquid pure iron and iron alloys, new and

Jan 1, 1963

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-&apos;, and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.&apos; This phenomenon suggests comparison with effects being observed with magnesium,&apos; indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.&apos; Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,&apos; or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.&apos;-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,&apos;lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By Oscar Aguilar, Jin-ichi Nakamura, Kazuo Nakamura

Michiquillay deposit is porphyry copper type with over 500 million tons of 0.70% Cu ore. In order to reflect the true nature of the orebody as to shape and value distribution and to compensate for insufficient data in the outer perimeter and lower portion, "Triangular Interpolation Method" is used in the computation, wherein block grades are determined by "Plane Regression". The results thus obtained are compared with the data from additional investigation and are found to match well with each other. Aside of total Cu, assays of Fe, S, MoS2 and geological data such as alterations, rock types, faults, mineralogical compositions are also stored in the computer. By this system, their distribution and relation to alteration become clear and classification of ore into types affecting recovery become possible. The outputs of this system make clear the characteristics of the orebody and furnish valuable geological data on the orebody.

Jan 1, 1976

By C. L. Meyers, A. V. Levy, G. Y. Onoda, R. J. Kotfila

This paper presents the hypothesis that solid-solution hardening of regions in the order of tens of angstroms thick along grain boundaries is the most important mechanism controlling the ductile -brittle transition behavior of poly crystalline bcc refractory metals. Further, a physical model is developed and a general equation is derived to describe the dependence of the solute concentration at grain boundaries on temperature, nominal impurity concentration, thermal treatments, vain size, and prior plastic deformation. Analytical curves of the solute concentration at grain boundaries us temperature, calculated by means of the derived equation, are found to have the same general form as curves of ductility us temperature plotted from experimental data. Senziquantitative relationships between the transition temperature and metallurgical variables can he determined by using the physical model. The room-temperature brittleness of the poly-crystalline refractory metals (tungsten, molybdenum, and chromium) is a result of their high ductile-brittle transition temperatures. Recently studies on single crystals have revealed that, when sufficiently pure, these crystals have much lower transition temperatures than polycrystalline specimens of similar purity.&apos;-3 For example, the transition temperature (measured by reduction in area in tensile tests) for very high-purity tungsten crystals has been reported to be as low as -50°F whereas polycrystalline specimens of similar purity had a transition temperature near 400" ~.&apos; These results suggest that the ductile-brittle transition behavior of these polycrystalline metals can be attributed principally to the influence of grain boundaries on plastic flow and fracture. This paper contains a discussion of the manner in which grain boundaries influence the ductility of the poly-.crystalline bcc refractory metals and proposes that the segregation of impurities to grain boundaries is the most important mechanism for controlling the ductile-brittle transition behavior of these metals. Further, this paper contains an analysis of the effect of the compositional and structural variables on the grain boundary-ductility relationship, and introduces a semiquantitative model that can provide a foundation for more theoretical treatment to describe the influence of these variables on ductile-brittle transition behavior. PHYSICAL MODEL FOR PREDICTING DUCTILE-BRITTLE TRANSITION BEHAVIOR Grain Boundary Segregation of Impurities. Based on their own observations and on theoretical grounds, numerous investigators have suggested that impurities segregate to the grain boundaries. Such segregation would be expected because regions exist where both large and small foreign atoms fit with less strain than within the undistorted crystal structure. Therefore, the concentration of impurities should be higher at boundaries than within the grain body. TO estimate the degree (i.e., the ratio of grain boundary to nominal bulk concentration) to which an interstitial solute tends to segregate at boundaries within a solvent metal, the solubility rather than the size misfit could be used as a guide because solubility expresses the joint effect of both elastic and electronic factors.5 The solubilities of interstitial elements such as carbon, hydrogen, nitrogen, and oxygen are low in the group V-A metals and very low in the group VI-A metals.6 These low solubilities suggest that segregation to grain boundaries should occur for each of these solutes in both refractory metal groups. The difference between the ductility of single-crystal and polycrystalline bcc refractory metals can be described in terms of two distinct effects.4 The first of these is the general observation that grain boundaries hinder slip within grains and slip transfer between grains, and the second is that deformation is more complex in each grain of a polycrystalline specimen than it is in a single crystal. Mc Lean has pointed out, furthermore, that strong slip-hindrance effects at grain boundaries should occur in metals having strong segregation of impurities to grain boundaries. Therefore, the effect of grain boundaries on the hindrance of slip is expected to be the dominating influence on the ductile-brittle transition behavior of these polycrystalline refractory metals. cahn5 has suggested that temperature and solute mobility should influence solute equilibrium segregation at grain boundaries, and Fig. 1 illustrates

Jan 1, 1965

By Gareth Thomas

The analysis of Kikuchi pattersns of exct ovientalions from single cryslals and paired Kikuchi lines from single and overlapping crystals is shown to be useful and quanlitalve and is applied to Phase transfovnzcitions including ordering, spinodals, mavten-silic, and nuclealion and growth pyocesses. 112 pinciple, the analysis of exacl orientations enables the crystal system and the Bravais lattice of a crystal to he determined. The advantages of the davk-field imaging technigure for detecting vevy small precipitates are also described. ALTHOUGH Kikuchi electron-diffraction patterns were first observed nearly 40 years ago,&apos; little systematic application seems to have been made of them, until fairly recently during electron microscopy, when their usefulness in contrast experimen and for determining exact orientations8&apos;9 has been pointed out. With the availability of gonio-metric specimen tilting stages it has now become possible to make much wider use of diffraction patterns, particularly the Kikuchi pattern, which is the main subject of this paper. The treatment presented here is not exhaustive but it is hoped that it will stimulate more use of Kikuchi patterns during electron-microscopy investigations. The Kikuchi pattern is formed as a result of Bragg diffraction of the inelastically scattered electrons produced during the interaction of the beam and thick specimens, The important feature of these patterns is that they give an accurate representation of the symmetry of the crystal being investigated, so that it is possible to identify crystal systems and even the Bravais lattice. This means that new structures, e.g., formed in phase transformations, may be identified during normal electron microscopy, so that Kikuchi-pattern analyses considerably extend the uses of the electron microscope. Recent work has also shown that dark-field images are more informative than bright-field images, particularly, for observing small precipitates. The second part of this paper discusses some applications and advantages of dark-field imaging in studies of two-phase systems. 1) DIFFRACTION PATTERNS 1.1) Spot Patterns. Electron-diffraction spot patterns have their limitations because of the importance of the form factor on the intensities and shape of the reciprocal lattice points. Because of the extension of these points into relrods, reflections are possible over a large angular range (+5 deg) and the patterns from thin regions can be complicated because second-layer relrods intersect the reflecting sphere. Spot patterns can thus give only an approximate idea of the crystallography unless the foil is tilted into exact orientation. In this case the spot pattern is symmetrical, with equal numbers of spots on the positive and negative zone directions about the origin. Such cases are necessary for structural analyses and have been used recently to determine the crystal structure of the ordered Ta64C phase." Exact orientation means that the plane of the reciprocal lattice lies exactly normal to the incident beam as shown in Fig. 1(b). It should be noted that in exact orientations the angle of reflection is less than the exact Bragg angle 9 so that the reciprocal lattice points lie to the outside of the sphere, Fig. 1(b). This deviation is denoted by the parameter s and in the usual convention4 s is negative for exact orientations and, of course, zero at the exact reflecting position shown in Fig. l(a). In order to avoid secondary reflections from thickness relrods it is advantageous to work in thicker regions of foils. Diffraction from thick regions may also produce Kikuchi patterns and as dis-

Jan 1, 1965