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By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

By C. O. Fairchild

ONE of the fundamental principles of efficiency is the use of adequate and permanent records. The rapid increase in the manufacture and use of recording pryometers is a proof of the appreciation of efficiency principles on the part of the manufacturers engaged in the various technical industries. Where recording pyrometers are not employed in an industry in which temperature measurements are necessary, one will generally find that a printed form is used upon which is written, periodically, the temperatures measured by an indicating instrument. It is no serious condemnation of the workman to state that such records are often "doctored," but it is rather a reflection upon the executive who puts such temptation in the way of a workman. One of the well-known "tricks of the trade" is to "force." a furnace so that it will be at the proper temperature during the periodic trips of the foreman or other official. Indicating instruments and recorders may be used together to great advantage. The recorder furnishes .a printed record and a check upon the operator of the furnace, and a record of value in correlating properties of the finished product with the heat treatment. The indicator should be of assistance to the operator in controlling the furnace or oven. Modern practice requires a temperature-recording instrument that is as simple as possible, rugged, reliable, and sufficiently accurate. Of these qualifications reliability is paramount, particularly in cases where the recorder is used for controlling the temperature automatically. By a reliable instrument is meant one that will run continuously with little attention and with a consistent degree of accuracy. That is, if it is in error by 5 per cent. one day, it must be in error by a like amount on any other clay, and not by 2 per cent. or 10 per cent. The earlier forms of recorders were complex and delicate, or mechanically unsatisfactory and inaccurate, and required considerable attention to keep them in operation. Within the past few years, however, the development in the manufacture of temperature recording devices has been highly satisfactory and many excellent instruments are now available. .

Jan 9, 1919

By K. M. Kolobova, E. Z. Kurmayev, A. Z. Menshikov, S. A. Nemnonov, V. A. Trapeznikov

The present work represents a review of our intestigations into the X-ray spectra of solids, which have been carried out by us along two lines of upproach: 1) St@ of the electronic structure of high -rnelting compounds of transition metals; 2) stzddy of the interatomic binding forces by the fine structure of absorption spectra under varying temperature and concentration conditions. With this in mind, int>estigations hare been made into the emission and absorption spectra of the K-series of atoms of transition elements in alloys and compounds. In the problem concerned with the electronic structure of high-melting compounds of transition metals, considerable importance is attached to the question of ascertaining the role played by 3d4sp electrons of metal and 2p electrons of metalloid in the formation of chemical bonds and of giving, on the strength of this data, an explanation of the properties which seem to be contradictory at first sight: good conductivity inherent in metals and high brittleness and high-melting characteristics typical of covalent compounds. Over the last few decades this question has attracted the attention of many investigators whose studies were devoted to this type of compound. Many works, both of theoretical1-3 and experimental4- l5 nature , have contributed much to the elucidation of the physical character of the phenomenon referred to. Alongside the investigations in the field of electric resistance, Hall effect, paramagnetic susceptibility, electronic heat capacity, and the temperature of transformation into a superconducting state, we should particularly emphasize the studies on X-ray spectra, which have played a significant role in the development of the zonal theory for high-melting compounds. This fact has become highly evident after the theoretical calculation of the energy spectrum has been made and the density of states curve in Tic, TiN, and Ti0 has been plotted by Ern and Switendick3 who used the method of augmented plane waves. Correlation of the results of the theoretical calculation of the band structure in the compounds listed above with the data obtained by X-ray spectroscopy studies showed that X-ray spectra can be a source of valuable information on the electronic structure of high-melting compounds within a wide range of ener- gies. It is well known that X-ray emission spectra basically give a direct picture of the occupied excited states above the Fermi level of a solid (valence band, conduction band) and that the absorption spectra (region of initial absorption) give a similar picture of states corresponding to the unoccupied levels near the Fermi surface. Full information on the density distribution of electronic states by energies can be obtained by combining the emission and absorption spectra. Such an opportunity arises from investigation

Jan 1, 1970

By H. I. Aaronson, C. Laird

The kinetics of thickening and of lengthening of ?' plates in an Al-3.93 pct Cu alloy in the temperature range 203" to 300" C were determined by means of transmission electron microscopy. The rate of thickening was found to be less than that allowed by volume diffusion control at all temperatures, by amounts which increased with decreasing temperature, in agreement with the predictions of a general theory of precipitate morphology.1 Thickening was treated on the basis of the ledge mechanism. Ledges were deduced to spread across the broad faces of ?' plates at volume dzjrfusion-controlled rates, as anticipated from the disordered structure of their edges. Lengthening of 8' plates, on the other hand, took Place more rapidly than allowed by volume dzjrfusion. This occurred despite clear morPhological evidence of a bmrier to growth at the edges of these plates. It was concluded that the misfit dislocation structure comprising the barrier requires that lengthening take place by a jog mechanism. The tnisfit dislocations, however, also serve as diffusion short circuits, and allow high overall lengthening rates to be achieved. In Part I' it was shown that, within the range of aging temperatures and times studied, the broad faces of 8' plates formed in Al-4 pct Cu are fully coherent with the a, matrix. Virtually .all of the dislocations present in these faces were found to have developed as a result of plastic deformation in the a phase. Such dislocations are thus "intruders", rather than the more usual misfit-compensating variety. The edges of 8' plates were confirmed, by extension of the earlier studies of Mat-suura and Koda,3 to be made up of edge-type misfit dislocations, in sessile orientation with respect to lengthening of the plates. These interfacial structures should cause 8' plates to thicken and to lengthen at rates less than those allowed under the condition of volume diffusion control, such as would be expected if the interphase boundaries had disordered structures.' The narrow width of 8' plates, the reproducible crystallography of their broad faces, and the appearance of these plates in cross section as octagons rather than as circular discs2 provide qualitative support for these deductions. The present study of the rate of thickening and the rate of lengthening of 8' plates was undertaken in order to examine them on a quantitative basis. I) THICKENING KINETICS OF THE BROAD FACES OF?' PLATES A) Literature Review. The measurements now available on the thickening kinetics of single-phase precipitate plates consist of one plot of the thickening of a proeutectoid ferrite plate in an Fe-C alloy,' showing (as predicted) thickening rates less than those allowed by volume diffusion control. B) Experimental Procedure. Details of the preparation of the 4-3.93 pct Cu alloy used in this study have been previously reported.4 As in Part 1,' transmission electron microscopy was the observational tool employed. A general description of the apparatus and procedures of the electron microscopy studies is given in Section I of Part I. In thin foils, 0' plates tend to form at and parallel to the foil surface.' A direct investigation of the thickening process by means of hot-stage transmission electron microscopy was therefore not feasible. It was thus necessary to use the conventional method of aging individual bulk specimens for a wide range of different times at the various temperatures studied. In each specimen, the thicknesses of a number of plates were measured. Since thin foils prepared from "bulk-aged" material contain a large proportion of grains with orientations near (001) , it was relatively easy to find, near the edges of the foils, the characteristic multifold patterns of intersecting extinction contours which indicate regions where the foil is exactly at an (001) orientation. The thicknesses of large numbers of plates were measured along the (200) branches of the "stars" so that the 8' plates were precisely parallel to the optical axis of the microscope. Wherever possible, intersecting extinction contours were adjusted with the parameter s > 0 to improve the visibility of the plates in bright-field illumination. These precautions, in combination with taking the measurements at the thinnest parts of the foils, minimized the errors in the measurement of the thickness of the plates resulting from inexact parallelism to the electron beam. Since the plates were very thin, it was not easy to measure their thickness on the photographs. The techniques of enlargement and of microdensitometry were employed to minimize errors from this part of the measurement. A further source of possible error, that the plates can appear thicker because of contrast associated with mismatch normal to the plane of the plate, was also considered. The images of the plates were usually thinner than those of dislocations, however, and no anomalous changes in apparent plate thickness were observed when regions of foil containing plates were tilted through various diffracting conditions. Any error from this cause must therefore be small. Other sources contributing errors were: a) the microdensitometer traces per se and the subjective estimates of their peak limits, and b) slight fluctuations in magnification associated with small changes in the current of the objective lens of the electron microscope. The overall error probably amounted to no more than 5 to 10 pct. In order to obtain readily interpretable data on thickening kinetics, it is essential that the diffusion fields of adjacent ?' plates not be allowed to overlap. Calculations'-' showed that this condition is definitely not ful-

Jan 1, 1969

By J. H. Yang, K. E. Gray

Results of single-blow bit-tooth impact tests on saturated rocks under elevated confining pressures and zero pore pressure were reported in a previous publication.1 This paper presents an extension of the earlier work to include a study of crater formation during tooth impact on both gas- and liquid-saturated Berea and Bandera sandstones at elevated confining and pore pressures. The basic data obtained were force-time, displacement-time, velocity-time and force-displacement curves during crater formation. Crater volume was also measured and the mode of crater formation determined. Bit tooth geometry, depth of penetration and velocity of impact were held constant. Results indicate that, with pore fluid present in the rock, failure trends from brittle to ductile as pore pressure is increased at constant confining pressure (pore pressure and borehole pressure were equal) For a given rock type, the mode of crater formation was dependent not only upon the nominal effective stress, but also upon the fluid which saturated the rock pore space. When confining pressure and pore pressure were equal (zero nominal effective stress), bit-tooth impact resulted in brittle failure for nitrogen-saturated Berea, and brittle to transitional failure for nitrogen-saturated Bandera; when saturated with liquid both rocks failed in a ductile manner at zero nominal effective stress. INTRODUCTION Dynamic wedge penetration tests have been conducted by investigators in several fields, but the failure mechanism of rock under dynamic stresses is not understood completely. The complex action of drilling bits, even considering the action of a single tooth, may be considered as a combination of drag bit and rolling cutter action. Thus, as a first step in understanding rock breakage in oil well drilling, single chisel impact and rock planing are of fundamental importance. For example, Gray 2 and Crisp3 studied drag bit cutting action at brittle stress states. Simon4 and Hartman5 studied the reaction of rocks to vertical impact by means of drop tests. The depth of penetration, crater volume and force-vs-time curves during crater formation were observed. The significance of indexing single-bit impacts has been noted.4,6-8 Gamer et al,9 reported impact tests on impermeable Leuders limestone at atmospheric and elevated confining pressures. In all cases the tests were accomplished on dry rock and pore pressure was considered to be zero. The importance of both confining pressure and pore pressure on the failure characteristics of rock was described. 10-12 It was found that the yield strength and ductility of porous rock depend on the state of stress under which the sample is tested. The importance of pore pressure on drilling rate in microbit experiments was noted by Cumingham and Eenink. l3 Robinson 12 also pointed out that in drilling the most important parameter in rock failure is the effective stress, where effective suess is defined as confining pressure pc minus pore pressure pp. The effect of pore pressure and confining pressure on rock strength was also noted by Serdengecti and Boozer 14 in strain rate tests, and by Gardner, Wyllie and Droschackl5 in elastic wave studies. Until recently all reported wedge impact studies under simulated wellbore stress states have been conducted on dry rock. Maurer 16 reported impact tests on samples saturated with deaerated water. Borehole and formation fluid pressures were equal in these tests except when mud was used in the borehole. With mud in the borehole and a high borehole-to-formation fluid pressure differential. Maurer observed "pseudoplastic" crater formation. Podio and Grayl reported impact tests on Berea and Bandera sandstone saturated with pore fluids having wide ranges in viscosities. In Podio and Gray's tests, confining pressure was elevated, but pore pressure and borehole pressure were held fixed at atmospheric pressure. The presence of

By M. L. Brashears

IN the last 15 years industrial use of ground water has more than doubled, and in 1951 amounted to 5 billion gallons per day. A similar sharp increase in the utilization of ground water for irrigation and public-water supply occurred in the same period. In many areas rapid increase in withdrawal from wells has taken place almost entirely unhampered by regulatory control and with little or no integration of effort. As might be expected, the chief interest in many regions has been maximum production rather than sustained perennial yield. As a result, widespread depletion of underground reservoirs and deterioration of the quality of the water stored in them has taken place in many areas, even though total pumpage in the United States is far below ultimate potential. Of even more concern is the fact that excessive withdrawal has drawn salt water into the reservoirs beneath many heavily populated centers along the Atlantic, Gulf, and Pacific coasts, causing costly abandonment of pumping plants.' Many hydrologists expect that consumption of water will rise rapidly in the near future, and some predict that industrial requirements will more than double in the next decade.2,3 Thus it appears likely that the draft on many already heavily pumped underground reservoirs will be greatly increased and the search for additional sources of usable ground water intensified in years to come. In view of this, industry as a whole will be forced more and more to recognize the potentialities and limitations of ground-water reservoirs and to utilize them more effectively to prevent costly water shortages and disruption of production. Through painful experience, some industries are already well aware of the need for effective water utilization, and have managed individually or through joint effort to check trends threatening to deplete underground reservoirs completely or to impair the quality of the water. Various remedial measures have been used to bring about successful management of local or regional ground-water resources. Of these, replen-ishment of aquifers by recharge wells or basins has played an important role in overcoming some ground water problems. Artificial recharge of underground reservoirs by water spreading has been practiced successfully in the United States for many years. In the West it has become an important method of salvaging flood run-off for irrigation of crops and maintenance of public water-supply reserves, and it is used to some extent in parts of the East. Artificial recharge by means of wells, on the other hand, is a relatively new development. Until recently it was employed in only a few areas, principally along the East coast. For the last few years, in the ever increasing search for additional water supplies, industry has had greater recourse to this method. Utilization of recharge wells to control the temperature and quality of underground water supplies is also being considered seriously. Operation of recharge wells, like water spreading, is governed largely by local conditions. It requires water relatively low in turbidity, whereas in some areas water spreading has been used successfully with water of high turbidity and silt content. However, water spreading must be employed in large areas and can be carried on effectively only where aquifers crop out at the surface. Recharge wells can be used in limited space. Recharge wells are similar to production wells except that the water flows in the opposite direction. Thus any water-bearing bed that will yield water to wells may be recharged by wells. Often, however, the water available for recharge is of a different character and temperature from that existing in the ground-water reservoir and if transmitted directly underground from a recharge well to a production well might require expensive or difficult treatment before it could be used. Fortunately the physical characteristics of reservoir beds, which control the movement and behavior of ground water, are generally not homogeneous. Moreover, the movement of ground water is very slow because of the frictional resistance of the reservoir beds. By taking full advantage of hydrologic and geologic conditions, it is therefore possible in many instances to bring about favorable changes of temperature and dilution as the water moves from the recharge wells underground to the production wells. Furthermore, if the natural quality or temperature of ground water is unfavorable for industrial purposes, recharge wells may be used to introduce water of more favorable quality or temperature into the ground-water reservoir. When water is discharged into a recharge well, the head in the well is increased. Because of this, a cone of elevation is produced on the water table or the artesian pressure surface in the area surrounding the well. The cone of elevation is similar to the cone of depression produced around a pumping well except that the apex of the cone is above the water table or artesian pressure surface. Thus if a recharge well and a production well tapping the same water-bearing bed are close together, as would be the case at many industrial plants, some of the water discharged from the recharge well would be drawn into the production well within a short time. Under such conditions it is apparent that water of unfavorable temperature and chemical characteristics should not be used for recharging. The more important ground-water reservoirs in the United States often consist of alternating layers of impermeable beds and porous material that will yield water readily to wells. Physical characteristics of individual beds in a ground-water reservoir may not persist over great distances, the impermeable layers grading into beds that will yield large quantities of water. Thus the water-yielding material in underground reservoirs, whether large or small,

Jan 1, 1954

By W. F. Stowasser

downdraft traveling grate process to agglomerate pelletized iron ore concentrates has been successfully demonstrated in a pilot plant at Carrollville, Wis. Work there followed several years of development in the Allis-Chalmers Mfg. Co. laboratories, and the pilot plant phase was carried out in cooperation with Arthur G. McKee & Co., consultants and engineers to the iron and steel industry. End result of the process is conversion of iron ore concentrates into a form which can easily be transported and smelted in the blast furnace. Process Description The first of two process steps incorporates the art of balling and prepares the concentrates for burning. The second step consists of burning the green balls on the grate machine to the hardness required for shipping and handling purposes and for reduction in blast furnaces, see Fig. 1. Facilities are provided at the pilot plant to receive carload quantities of concentrate. The concentrates are loaded into a 50-ton bin direct from railroad cars. Because of the variable moisture content of the concentrates after shipment in an open railroad car it is necessary to repulp and refilter the concentrates to maintain a uniform and proper moisture content for the balling operation. Concentrates are conveyed to slurry tanks, and the slurry, at 50 to 60 pct solids, is pumped to a 4x4-ft drum filter. The filter provides feed of uniform moisture to the plant. Magnetite concentrates are normally filtered to produce a cake containing about 10 pct moisture, a necessary requirement for the following balling operation. The filtered concentrate is conveyed to a rotary bin table feeder which acts as a surge bin for the filter cake and delivers a steady flow of concentrates to the balling drum. It is often desirable to make additions to the concentrates as they are fed to the balling drum. These additives, such as bentonite, increase the strength of the finished green pellet and improve ballability of the concentrate. A vibrating feeder supplies additive to the feed belt, and the additive is mixed with the concentrate in the balling drum. The balling drum, shown in Fig. 3, is 8x3-ft diam. An oscillating cutting bar maintains the lining in the drum by trimming off the buildup of excess concentrate as it forms. The drum is operated in closed circuit with a lx4-ft rod-deck vibrating screen. Undersize pellets or seed pellets from the screen are returned to the balling drum until they grow to the desired size. Size of pellets is controlled by the opening in the screen deck. The formation of pellets in the balling drum is affected by many variables. Some of these are: the size distribution of the feed, the particle shape of the concentrate, the feed rate to the drum, the moisture in the concentrate, the speed of rotation of the drum, the slope of the drum, and the type of trimming obtained with the cutting bar. In this process, attempts are made to control the pellet size within the limits of % to 5/8 in. diam. The screened oversize pellets are conveyed under a coal feeder where sufficient powdered coal is added to the belt to produce desired results in the burning process. The top size of the coal successfully used has been 20 mesh, and anthracite was used in the test program. Fig. 4 illustrates the vibrating screen and the coal feeder. The pellets and free coal are conveyed together to the 5x3-ft diam- reroll drum that rolls the coal onto the surface of the pellets. This drum is also equipped with a cutting bar. The prepared pellets, containing bentonite, water, and surface coal, are elevated to the traveling grate, which consists of a continuous strand of 37 pallets. Each pallet, with a grate bar area 2 ft wide by 1 1/2 ft long, has 14-in. high side plates, Fig. 5. Feeding and distribution of the green balls to the grate is handled by a short conveyor which oscillates back and forth across the 2-ft width of the grate. An adjustable vertical plate located several inches in front of the head pulley of the oscillating conveyor controls the height of the bed and levels the moving bed of pellets. This method of feeding prevents segregation of various size pellets as well as fines and produces a uniform, permeable bed. The pallet train moves under the furnace and across four windboxes, located beneath the pallet frames, see Fig. 2. As the green pellets are deposited on the grate, partial drying of the pellets begins over a 2-ft long updraft windbox. The low temperature air reduces the moisture in the pellets in the lower level of the bed and this operation is essential to prevent sagging of the bed during later stages of the Process. The air used for this drying is recuperated from cooling the pellets on the grate, and supplemental heat, required for starting the Process, is obtained from an auxiliary burner. The pellets are then moved by the grate into the furnace and over an 8-ft windbox, designated as the downdraft waste windbox. Products of combustion are exhausted from this windbox to atmosphere. The furnace, shown in Fig. 6, is constructed with three chambers to provide downdraft drying, preheating, and ignition, respectively, to the pellet bed as it passes through. Overall length of the furnace is 5.57 ft; however, the exterior wall ends may be moved to reduce the length and also adjusted to Obtain the bed height desired, The drying, preheating, and ignition sections of the furnace are supplied with medium temperature

Jan 1, 1956

By H. L. Stone, A. O. Garder

A numerical method of solving the partial differential equations which describe the one-dimensional displacement of oil by gas has been presented. Possible extension of the method to treat multidimensional flow is discussed, and the limitations of this extension are indicated. Using this method, it is possible to allow for the existence of a gas cap, the presence of any number of gas-injection or oil-production wells and the evolution of dissolved gas from the oil. It is also possible to allow for variation in the cross-sectional area, elevation, porosity and permeability of the reservoir. The influence of relative permeability and the force of gravity in the direction of flow upon the displacement is considered. The influence of capillary pressure upon the flow and the effect of gravity in the direction perpendicular to flow are neglected. The physical properties 01 the fluids are considered to be Junctions of pressure only, and equilibrium between contiguous phases is assumed. The numerical calculations can be readily carried out by the use of a digital computer. Several example analyses have been performed using the IBM 704 computer, and about one-third of an hour of computing time was required per case. Reservoir behavior predicted by use of this numerical method was compared to data obtained by other methods for three cases — complete pressure maintenance, dissolved-gas drive and gas-cap drive. The independent solutions to these problems were obtained by analytical solution, laboratory experiment and field data, respectively. Agreement of the numerical solution with data from these sources was good; this agreement establishes the convergence and accuracy of the numerical method. INTRODUCTION Most petroleum reservoirs can be produced by any one of several alternative programs. When a reservoir is produced by primary methods, production economics can be influenced by controlling the number and location of wells and the flow rate of each well. An even greater influence may be achieved by augmenting the recovery of oil obtainable by primary methods. This can be accomplished by injection of fluids such as water, natural or enriched gas or a bank of light liquid hydrocarbons. Selection of the most desirable operation requires a means of predicting the reservoir behavior which will result from each of the several alternative programs. The purpose of this paper is to present a mathematical method for predicting the behavior of reservoirs produced by gas-cap drive, dissolved-gas drive or pressure maintenance by gas injection. The method described herein takes cognizance of phase changes caused by a decline or an increase (due to gas injection) in reservoir pressure, of the presence of a gas cap and of the effect of gravity on the flow of gas and oil. Relative permeability relationships are used to define the flow properties of the rock. Allowance is made for variation in cross-sectional area, elevation, permeability and porosity of the reservoir. Both the influence of capillary pressure upon the flow and pressure gradients in the gas cap are neglected. Whenever a liquid phase and a gas phase are in contact, they are assumed to be in equilibrium. The physical properties of the fluids are considered to be functions of pressure only. Therefore, if the method is to be used to predict the effects of a gas-injection program, mixtures of the injected gas and formation crude should-have the same physical properties as mixtures of formation gas and crude. The equations to be presented in this paper apply only to a one-dimensional case; therefore, they neglect the influence of gravity in the direction transverse to the flow. As is well known, this gravitational influence may lead to overriding of oil by gas. Consequently, this procedure as presented is most applicable to long, thin reservoirs for which gravity overriding is not important. On the other hand, the equations presented can be generalized to treat multidimensional flow and, hence, to consider gravity overriding, if desired. A word of caution on two points is advisable here, however. First, the authors have not demonstrated the accuracy of the numerical technique for multidimensional flow. Second, and more important, capillary pressure will often be of importance in multidimensional problems. Obviously, in such cases a generalization of the

By D. J. Carney, C. W. Boquist, E. C. Rudolphy

Effect of variations in sinter feed composition on sinter strength, bulk density, re-ducibility, chemical composition, and microstructure were determined by sintering experimental samples on a production sintering machine. Increasing amounts of roll scale, ore fines, return fines, and blast furnace slag were most beneficial to feed permeability, sinter bulk density, and strength. Burnt lime additions improved feed permeability but were not beneficial to sinter strength or bulk density. Sinter reducibility was adversely affected by all additives. DEVELOPMENT of methods for evaluating sinter quality, which would in some way predict the behavior of the sinter during charging and smelting in the blast furnace, has been given considerable attention in recent years. In a previous investigation at South Works of the United States Steel Corp., standard sinter sampling and testing procedures were developed.1,2 By modifying the sinter sampling device, a method of sintering experimental mix sinter samples upon a production Dwight-Lloyd sintering machine was also developed. This technique afforded a rapid and controlled method of investigating the effects of the various raw materials and additives on sinter quality and was used in this present investigation. Since the beginning of the present study in 1953, the results of numerous sinter investigations have been published, most of which were concerned with production tests of iron ore sinter, both here and abroad. Three groups of investigators reported results of experimental sinter studies that were related to this investigation. Voice et al.3 studied the effects of controlled variables on sinter quality by producing and testing experimental Northants iron ore sinter using an experimental sintering unit. Mor-rissey and Powers' determined the relationship between iron ore sinter quality and the moisture and coke content using a small laboratory sintering system. Burlingame et al.5 studied the effects of "additives" upon iron ore sinter using a laboratory sintering apparatus and laboratory grade raw materials. At South Works, it was considered desirable to study the effects of sinter mix composition and additives upon the quality of a flue dust-base sinter produced on a production sintering unit. Extrapolation of controlled laboratory test data to sintering plant operation lacking such precise control is not altogether satisfactory. Therefore, the present study was conducted in a manner which approximated production conditions as closely as possible. The raw materials used were those commonly encoun- tered in the production of flue dust and flue dust ore-type sinters and these were varied within extremes encountered in this type of sinter production. Experimental Procedure The experimental sinters were produced from 100 lb mixtures of sinter feed. The principal raw materials and additives used, their particle size, and approximate chemical composition are listed in Table I. The mixing of the raw materials was accomplished by means of a miniature single shaft pug mill shown in Fig, 1. The use of the pug mill as a mixer was decidea upon after encountering difficulty in reproducing the mixing and chopping effect of the sinter plant pug mill with other types of available small mixers. The miniature pug mill was constructed, consisting of 31/2x2x1/4 in, blades spaced 3 in. apart along a 3 ft shaft. Preliminary tests were run with this small mixer to establish the proper rotation speed and the required number of passes through the pug mill to thoroughly mix and distribute all the raw materials in a manner approximating the production Pug mill- Although the effects of varying the mosture content were determined in one particular series of tests, the amount of moisture added was changed as the composition of the experimental mix was varied. The aim in making water additions was to achieve a permeability as high as possible for each particular

Jan 1, 1956

By G. Pizzi, G. M. Ciucci, G. L. Chierici

The use of the material balance equation to estimate the volume of hydrocarbons originally present in a reservoir, whose producing mechanism is partly due to water drive, has been discussed in the literature by several authors. There is no general agreement upon the possibility of obtaining reliable results by this method. Gas reservoirs in contact with an active aquifer are considered in this paper. Theoretical considerations based on the cybernetic principle of uncertainty (which states that the internal structure of a system cannot be uniquely determined from its observed external behavior) lead to the conclusion that the volume of gas originally present in a reservoir of this type cannot be uniquely determined from its past history. The range of values which encompasses the actual value of the reserves varies from case to case and must be determined by either numerical or analogical methods. Results obtained for six gas fields are reported. All these fields were produced with small fluctuations in their production rates, as is common practice for gas reservoirs; no gas storage fields were considered. Results obtained show that reserves values in a range of 1 to 2, associated with appropriate aquifers, allow the matching of the reservoir past history with mean-square deviations less than the experimental errors involved in pressure and produclion measurements. Similar results have been found in several other partial water drive gas reservoirs. From these results it is concluded that gas reserves cannot be uniquely determined from the past performance of partial water drive reservoirs, at least in cases where the reservoir has been submitted to small fluctuations in the production rates, and pressure data of normal accuracy are available. INTRODUCTION A number of authors have analyzed the problem of estimating the reserves originally present in a partial water drive reservoir from its past pressure-production performance. Literature which deals with this subject can be grouped, according to their conclusions, as follows. 1. A reliable value for the reserves can be obtained even if reservoir data (pressure and cumulative production) are affected by errors within the normal range.'-' 2. A reliable value for the reserves can be obtained only if reservoir data are very accurate'- or if past production performance has been subjected to abrupt variations in the production rate."' 3. No unique value for the reserves can be obtained from reservoir past production performance. This conclusion has been based upon theoretical considerations" and verified in several field cases. The purpose of this paper, which deals only with partial water drive gas reservoirs, is to test the above conclusions against actual field cases. Some theoretical considerations on this problem are also presented. THEORETICAL CONSIDERATIONS As the behavior of a gas reservoir communicating with an aquifer depends on both the aquifer and the reservoir characteristics, the physical system to be studied is the combined gas reservoir plus aquifer. The information which is available for studying the performance of such a system is the well production rates and bottom-hole pressures, all given as functions of time. The external behavior of the reservoir-aquifer system is therefore described by 2n input variables (Gp, Wp,) and n output variables (p,), n being the number of wells in the reservoir. In reservoir engineering it is common practice to consider the reservoir as a whole, disregarding the internal distribution of pressures and of producing wells. This practice is equivalent to substituting the above multi-variable system with a single-variable system, where the average reservoir pressure is the only output variable and the cumulative production G,(t) and W,(t) are the input variables. The internal structure of such a system, defined by initial gas reserves G, aquifer shape and dimensions, boundary conditions and petrophysical parameters distribution throughout the aquifer, is unknown. Therefore, from a cybernetic point of view the system is a "black-box It has been demonstrated" that for a blackbox the indetermination principle holds. Accordingly, the number of different internal structures (or set of parameters) which can account for the observed external behavior is infinite. As a consequence, the initial reserves cannot be uniquely determined from the reservoir past performance. When W,(t) is known, the determination of G from

By F. E. Buch

The smelter is designed for a production capacity of 10,000 short tons of blister copper per month, when operating on the present concentrate grade. The :smelter lay-out is shown in Fig I. The major units of equipment comprise two reverberatory furnaces, three 13 by 30 ft Peirce-Smith converters, two straight line casting machines, one being served by a 13 by 30 ft holding furnace and the other by a ladle tilting quadrant, two converter aisle cranes and two converter blowers. The plant is compact and the general arrangement of standard gauge railway tracks and conveyor belts provides for a smooth flow of incoming materials and metallurgical products. Concentrate is received by conveyor belts and fluxes in standard railway trucks. The local track system is covered by an electric trolley locomotive. The Smelter treats a wet (10 pet moisture) flotation concentrate containing approximately 53 pct total copper and 0.9 pet oxide copper. The predominating minerals are chalco-cite, chalcopyrite and bornite accompanied by small quantities of malachite and cuprite. The gangue is highly siliceous and requires limerock as a flux. Metallurgy would be straightforward were it not for the necessity for eliminating bismuth which occurs as an impurity in the ore along with the copper. Directly or indirectly most of the Smelter problems can be traced to the necessity for bismuth removal. Copper recovery, based on new copper treated, averages 97.5 pct. General Description Flotation concentrate, containing 10 Pet moisture, is conveyed from the filter plant to the smelter storage bins by conveyor belts, the material being weighed in transit by a revolving drum type of weigh-hopper manufactured by Samuel Denison and Son, Ltd. The weigher consists of a steel drum with dished ends carried on a horizontal shaft and rotated by an 8 hp squirrel-cage motor through a worm and Spur reduction gear. A feed mouth in the drum permits of filling and discharging. The whole unit is supported on a framework resting on weighing levers, which in turn connect to transfer levers, thence to an indicator of the steelyard type situated 16 ft from the centre line of the drum. The indicator is of the "Denison" patent equilibrium controlled ticket stamping type, insuring mistake-proof records by a combination of electrical and mechanical movements which Prevent the operator from printing until the cover enclosing the steelyard is closed and until the poise-weights have been Set correctly to the weight of the hopper and contents. The machine is capable of weighing 30 short tons at a time but the usual load is 28 tons. After obtaining the gross weight the drum is rotated and discharged into a receiving bin situated below it. The empty drum is weighed and the net weight re-

Jan 1, 1949

By D. E. Menzie, D. L. Dauben

This paper discusses the physical parameters involved in the slow flow of high molecular weight polymer solutions in porous media. The interacting effects of polymer properties and porous media properties on flow performance are considered. Experiments were conducted with the polyethylene oxides, with molecular weights ranging from 200,000 to over 5,000,000. Frontal advance velocities ranged from I to 30 ft/day. The porous matrix consisted of a flow cell packed with glass beads. Polymer solutions were characterized by viscosity and normal stress measurements. Under certain conditions, unexpectedly high flow resistance was observed. This behavior was observed to be a function of flow rate, pore size, polymer molecular weight and concentration. The polymer solutions exhibit "dilatant" flow behavior in porour media in contrast with the pseudo-plastic behavior in simple flow systems. A theoretical ex-planation of such behavior is presented. INTRODUCTION The use of polymers in the injected water of a waterflood increases oil displacement efficiency by reducing the mobility (k,/pu) of the driving phase. A reduced driving phase mobility results in improvements in the areal sweep efficiency and in the vertical coverage in stratified reservoirs. This mobility reduction may be achieved by a permeability reduction, a viscosity increase or by a combination of the two. Early attempts at increasing the injected water viscosity were not successful because of the poor economics involved. The use of such materials as glycerin, sugar or glycols to increase water viscosity was not economically feasible. Attempts in using certain naturally occurring polymers were not too successful because of the high polymer losses to the rock. A high molecular weight, partially hydrolyzed polyacry-lamide was introduced 3 years ago as a waterflood additive.',' Initial work by Pye' indicated that the presence of these polymers in dilute concentrations decreases the water mobility 5 to 20 times more than would be expected from measurements of the solution viscosity. Such an effect would be of obvious economic value since only a small polymer concentration would be required to accomplish a large reduction in water mobility. This research was designed to study the basic flow mech anisms of polymer solutions in porous media. The interacting effects of polymer properties and porous media properties on flow performance are considered. This study indicates some of the conditions under which these interactions can lead to significant mobility effects. is valid only for Newtonian fluids. For polymer solutions and other non-Newtonian fluids the equation must be modified to consider that viscosity is a variable quantity. Modification of the Darcy equation to include non-Newtonian effects has been the subject of several recent investigations."" The modifications generally adopt a rheological model. such as an Ellis or Dower law model. to Dorous media by defining some characteristic channel radius. Most of these studies showed the porous media flow behavior to be predictable from viscometric data. Investigations involving the flow of high molecular weight polyacrylamide solutions through cores have generally encountered the high flow resistances reported previously by Pye. This high flow resistance has generally been attributed to an in-depth permeability reduction, as evidenced by a reduced permeability to water which has displaced polymer solution from the porous media. Marshall and Metzner" report high flow resistances, which they attribute to viscoelastic effects. In this paper, the effects of polymer molecular weight, pore size, flow rate and concentration are considered. The polymers used are the polyethylene oxides known as Poly-ox. This class of polymers was used because of its availability in a wide range of molecular weights and because of its known ability to propagate well through porous media. THEORY PHYSICAL PROPERTIES OF POLYMER SOLUTIONS The polymer molecule dissolves in water by means of hydrogen bonding, but retains some of its own structural identity while in solution. Nonionic polymers, such as polyethylene oxide, are generally considered to have a random coiling configration. This type of molecule has the ability to "sequester" or hold a large volume of solvent within its coils in a manner similar to that of a sponge. The random coil is easily deformed and under an applied stress

By Joel H. Watkins

The terms kaolin, china clay, ball clay, and paper clay are more or less loosely and interchangeably applied to a large class of white-burning clays. These clays are made up chiefly of hydrous amorphous (colloidal) aluminum silicates with variable amounts of free silica and other impurities in small quantities. Occasionally also the term kaolinite is wrongly applied to a white-burning clay, for kaolinite is a mineral of definite chemical composition and definite crystalline form which occurs but sparingly in nature. It is not the purpose of this paper, however, to define or classify clays, or to enter into a discussion of the chemistry of clays. It is rather a general description of the occurrence and methods of mining of a kindred group of clays, and a discussion of their future economic aspect. In the Southern Appalachian States, the mining of white-burning clays has in recent years become an important industry. Although these clays are of several distinct types, which occur in as many localities under different geologic conditions, they are for the most part primarily of the same origin. They are essentially the same in elementary constituents, and are largely consumed in the game industrial arts. From the standpoint of a mining engineer, therefore, and for convenience in comparison and correlation, it should be interesting to discuss them under one heading. Kinds of Clay The most important types of clay which are now being actively mined in the Southern Appalachian States and with which this paper is particularly concerned are the North Carolina, Virginia, and Georgia kaolins or china clays (residual); the South Carolina and Georgia kaolins or paper clays (sedimentary); and the Florida and Tennessee plastic kaolins or ball clays (sedimentary). Other varieties which are interesting but which are as yet of little importance are the pocket deposits of white clay in Augusta County, Virginia, the bauxitic kaolins of Tennessee,

Jan 1, 1915

By M. Sheffield

This paper presents a technique lor predicting the flow of oil, gas and water through a petroleum reservoir. Gravitational, viscous arid capillary lorces are considered, and all fluids are considered to be slightly compressible. Some theoretical work concerning the fluid flow in one-, two- and three-space dimensions is given along with example performance predictions in one- and two-space dimensions. INTRODUCTION Since the introduction of high speed computing equipment, one of the goals of reservoir engineering research has been to develop more accurate methods of describing fluid movement through underground reservoirs. Various mathematical methods have been developed or used by reservoir engineers to predict reservoir performance, 193-5,7,8 The work reported in this paper extends previously published work on three-phase fluid flow (1) by including a rigorous treatment of capillary forces and (2) by showing certain theoretical mathematical results proving that these equations can be approximated by certain numerical techniques and that a unique solution exists. DISCUSSION The method of predicting three-phase compressible fluid flow. in a reservoir can be summarized briefly by the following steps. 1. The reservoir, or a section of a reservoir, is characterized by a series of mesh points with varying rock and fluid properties simulated at each mesh point. 2. Three partial differential equations are written to describe the movement at any point in the reservoir of each of the three compressible fluids. All forces influencing movement are considered in the equations. 3. At each mesh point, the partial differential equations are replaced by a system of analogous difference equations. 4. A numerical technique is used to solve the resulting system of difference equations. Capillary forces have been included in two-phase flow calculations.1,4,8 The literature, however, does not contain examples of prediction techniques for three-phase flow that include capillary forces. Where capillary forces are considered, each of the three partial differential equations previously discussed has a different dependent variable, namely pressure in one of the three fluid phases. Therefore, three difference equations must be solved at each point in the reservoir. Where large systems of equations must be solved simultaneously, an engineer might question whether a unique solution to this system of equations actually exists and, if so, what numerical techniques may be used to obtain a good approximation to the solution. It is shown in the Appendix that a unique solution to the three-phase flow problem, as formulated, always exists. It is also shown that several methods may be used to obtain a good approximation to the solution. The partial differential equations and differenceequations used are shown in the Appendix. Matrix notation has been used in developing the mathematical results. Two sample problems were solved on a CDC 1604. They illustrate the type of problems that can be solved using a three-phase prediction technique. SAMPLE ONE-DIMENSIONAL RESERVOIR PERFORMANCE PREDICTION A hypothetical reservoir was studied to provide an example of a one-dimensional problem that can be solved. Of the several techniques available, the direct method of solution as shown in the Appendix was used. The reservoir section studied was a truncated, wedge-shaped section, 2,400 ft long, with a 6' dip. (A schematic is shown in Fig. 1.) This section was represented by 49 mesh points, uniformly spaced at 50-ft intervals. The upper end of the wedge was 2 ft wide, and the lower end was 6 ft wide. The section

Jan 1, 1970

By A. J. Ardell, O. D. Sherby

The elevated-temperature steady-state creep behavior of polycrystalline a Zr was studied in vacuo under constant tensile stress. The experiments were conducted from 660° to 845°C over the stress range 870 to 5400 psi. The steady-state creep rate, is, of a Zr was found to be related to the applied stress, a, and temperature, T, by the equation where C is a constant. Two interpretations of the data are considered, each requiring different values of the parameters ß, Q, and . It is shown that this formula can be derived using Gilman's phenomeno logical equation relating dislocation velocity to the shear stress for the case where dislocation mobility is limited by the nucleation of kink motion. From the fundamental dependence of strain rate on dislocation velocity and the density of mobile dislocations, the factor exp(ßo) can be related to the stress dependence of the dislocation density, and Q to the energy of kink formation. The two interpretations considered are as follows: Case I—the parameters are adjusted so that the equation above describes the data over the entire range of stress and temperature, implying that creep is controlled exclusively by dislocation glide; Case IIthe parameters are adjusted to allow for the possibility that creep is diffusion-controlled at high stresses but glide-controlled at low stresses. For both cases the values of the parameters are within the spread permitted by the data. Factors favorable to the observation of the unusual stress -dependence of i, for a Zr are discussed and it is shown that the anomalously rapid rates of self-diffusion and the low modulus on the principal glide system are primarily responsible for the anomalous creep behavior. Metal-lograflhic observations are presented and discussed with reference to the overall creep behavior. PREVIOUS investigations of the creep behavior of a Zr have been conducted from room temperature to about 500C The results of these investigations are primarily of engineering significance because of the variety of conditions under which they were carried out, and the low testing temperatures employed. Little information is available concerning the fundamental nature of the elevated-temperature creep behavior of a Zr. This investigation of the creep behavior of a Zr above half the melting temperature (the melting temperature, T,, of a Zr is estimated to be about 1860"K was initiated because there are two significant anomalies of the physical properties of a Zr: a) the rate of self-diffusion in polycrystalline a Zr is anomalously rapid: b) both Young's modulus for polycrystalline a Zr and the shear modylus as-sociated with the prismatic slip system { 1010)( 1120) (the principal slip system in a Zr 7) have anomalously large temperature variations The importance of these quantities to the understanding of creep behavior has been demonstrated, and it was hoped that this investigation would provide a critical test of the predictions based upon the analysis of creep data for other pure metals. However, as the investigation progressed it became increasingly clear that the unusual creep behavior of a Zr could not be analyzed in a conventional manner. 1) EXPERIMENTAL EQUIPMENT AND PROCEDURES Two grades of zirconium, designated A and B, were used in this investigation. The analyses, as supplied by the vendors, are presented in Table I. Material A, with a nominal purity of 99.84 pct, was supplied by the Wah Chang Corp. in the form of cold-rolled sheet from which specimens were machined without further fabrication. Material B, with a nominal purity of 99.95 pct, was purchased from the Nuclear Materials and Equipment Corp. in the form of iodide crystal bar.

Jan 1, 1968

By N. Brown, R. Kossowsky

Plain carbon steels with 0.48 and 0.95 pct C were quenched and tempered at 705°C to produce carbide dispersions with spacings on the order of 1 p. The morphology of the structure consisted of a carbide-dislocation network. The strengthening due to the dispersion was found to vary linearly with M-½ where M is the mean free-ferrite path determined by the entire network. No preyield microstrain preceded the upper yield point. After prestraining, the lowest stress at which dislocation movement could be detected was 104 psi; this frictional stress was independent of the dispersion and prestrains up to 6.5 pct. The Cottrell-Petch equation for grain-size strengthening was used to discuss the dispersion strengthening in this investigation. The results support an impurity mechanism for the upper yield point rather than one based on the Johns ton- Gilman theory. IT was pointed out by Gensamerl that the mean free path in the matrix is the important variable which controls the degree of dispersion strengthening. Gensamer's data on steels showed a linear relationship between the yield point and the logarithm of the mean free-ferrite path. The first theory was by Orowan,2 who suggested the mechanism of dislocations bowing between particles, with the resulting relationship that where a is the yield point, P is the distance between particles, and G is the shear modulus. The Orowan equation applies to that range of dispersion where P is large compared to the particle size and the particles are not coherent, so that the matrix is essentially free of internal stresses. As was pointed out by Orowan, there are different degrees of dispersion which, in turn, will influence the strength-controlling mechanism. However, in this investigation, we wish to confine ourselves to the region of coarse dispersion, where the Orowan mechanism should, intuitively, be applicable. It was soon evident that the data, which existed at about the time that the Orowan theory was proposed, did not agree with the Orowan equation in that the actual strengthening was always greater than the theoretical predictions. Thus, Fisher, Hart, and pry3 modified the Orowan theory by suggesting that the Orowan process took place in the microstrain region preceding macroscopic yielding and the subsequent, rapid work hardening in the form of residual dislocation loops around the particles largely determined the observed macroscopic yield point. The F-H-P theory stated that the increment of strengthening due to the work-hardening mechanism was proportional to f3/2 where f is the volume fraction of the precipitate. F-H-P used data by Shaw, Shepard, Starr, and Dorn4 on A1 3-5 pct Cu to support their theory. Roberts, Carruthers, and Averbach5 were the first to make a microstrain study of dispersion strengthening, and they found that for steel the Gensamer relationship was obeyed. Hayman and Nutting6 suggested that in the case of tempered steel 1) the ferrite grain boundary was the primary obstacle and 2) the carbide particles simply formed part of the grain boundary obstacles. They found that the strength varied as G"" where G is the ferrite grain size. Turkalo and LOW' determined the structure of quenched and tempered plain carbon steel using a replica technique; they concluded that the carbide particles did not necessarily lie in the ferrite grain boundaries. When they defined the mean free-ferrite path as being determined by both particles and the ferrite path boundaries, their data obeyed the Gensamer relationship. Meiklejohn and skoda8 showed that the strengthening from iron particles in mercury was a function of the particle size and the distance between particles. Dew-Hughes9 explained the Meiklejohn and Skoda results by the following theory: 1) grown-in dislocations which surrounded the particles were produced by the thermal stresses during the time the material was cooled to the testing temperature, and 2) the observed strengthening was associated with the cutting of the grown-in dislocations by the glide dislocations. Ansell and Lenel10 proposed a theory in which the glide dislocations pile-up or surround the particle until the number of dislocations in the pile-up is sufficient to yield or fracture the particle. The resulting theory says that the yield point varies as p-1/2, where P is the distance between particles. The Ansell-Lenel theory is almost identical to the

Jan 1, 1965

By Wilbur T. Stuart

TO assist the mining industry in attacking problems of water control, the U. S. Geological Survey has begun a program of research in mining hydrology. In certain fundamental respects water control is similar to development of water supplies from wells or to the drainage of agricultural lands, as many of the tools developed in recent years for quantitative ground-water problems are applicable, with modification, to mine-water problems. In 1952 a 30-day pumping test conducted jointly by the Eureka Corp. Ltd. and the Defense Minerals Exploration Agency provided an opportunity to gain knowledge concerning water movements around a flooded mine shaft. The methods of analyzing the data may be used as a guide for the evaluation of similar problems elsewhere. The Fad shaft of the Eureka Corp. is on Ruby Hill, 1 1/2 miles west of Eureka, Nev. The shaft was completed at a depth of 2465 ft in November 1947 at a site adjacent to the downfaulted block in which the ore was found. As the drift on the 2250 level progressed toward the ore zone, a large flow of water was encountered after the Martin fault was intersected. This flow exceeded the installed pump capacity, and an unsuccessful attempt to recover the shaft and the 2250 level was made in 1948.1, 2 Geology and Hydrology: The complex structure of Ruby Hill is that of an anticline broken first by thrust faulting and later by normal faults. The present orebody comprises several mineralized zones within a block of the Eldorado limestone of middle Cambrian age which was downfaulted 1400 to 1600 ft, and it may be related to a similar body mined at a higher level south of the Ruby Hill fault. At the depth of the largest zone of ore the block is roughly rectangular in shape, about 1000 ft wide and 1500 ft long, and dips about 30" NE, see Fig. 1. It is apparently bounded on the south by the Ruby Hill fault, on the east by the Jackson fault, on the north by the Martin fault, and the west by the Bowman fault. Within the block, but between the Ruby Hill and the Martin faults, are the Office and Adams Hills faults; west of the block and the Bowman fault are the Albion and Spring Valley faults. There are many conflicting reports concerning the water-yielding characteristics of the Eldorado limestone and the condition of the fault zones, that is, whether they are open or tight. However, the diamond-drill records indicate that open spaces as much as 2 or 3 ft across were encountered, and considerable cementing and lining of holes was necessary to maintain circulation of drilling fluid. There is also evidence that the Eldorado limestone was cavernous where it was mined in the early days south of the Ruby Hill fault. At the site of the Fad shaft the formations encountered from the surface down included the Pogonip limestone, Dunderberg shale, Hamburg limestone, and Secret Canyon shale. These formations did not yield large quantities of water to the shaft. The Pogonip limestone, which appears to be permeable and might yield water elsewhere, is above the water table in the vicinity of the shaft. The Secret Canyon shale, immediately overlying the Eldorado in some places but in most places separated from it by the Geddes limestone,3 is apparently tight and does not transmit water. During the 30-day test period the shale briefly confined the water in the underlying formations so that artesian conditions were observed in drillholes E and F, which are cased into the Eldorado limestone, whereas unconfined conditions were observed in drillholes B, C, and D, which were open to the shale. The Geddes limestone, which normally lies between the Secret Canyon shale and the Eldorado limestone, was not encountered in the Fad shaft. The Geddes, a flaggy, fractured limestone, is reported capable of yielding large volumes of water. Water stored in the interstices of this thin-bedded limestone within the Ruby Hill fault zone on the 1200 level of the Locan shaft drowned the pumps in 1923 when the Richmond-Eureka Mining Co. attempted to explore the area along the fault. Eldorado limestone was not encountered in the Fad shaft. In the ore-block area the Eldorado limestone was not entirely offset from other water-yielding formations by movement along the Bowman fault; therefore it may be hydraulically connected with the other formations. Adjacent to the Ruby Hill, Jackson, and Martin faults, the Eldorado lies in contact with other possible water-yielding formations. One of these, the Prospect Mountain quartzite, is separated from the Eldorado by thin, sheared, and broken beds of the Geddes within the Ruby Hill fault zone. A limited examination by the author of the Prospect Mountain quartzite in the Richmond mine at a higher level and south of the Ruby Hill fault indicates that the quartzite is poorly permeable. The monzonite mass south of the quartzite would be a further barrier to the flow of water. The poor permeability of this area is substantiated by records of levels at which water was encountered south of the Ruby Hill fault. In view of the normally low rate of ground-water recharge, if this desert area had been permeable, water levels could not have been maintained at altitudes of many hundred feet above the present water table west and north of Ruby Hill. Thus the ore-bearing block of Eldorado limestone is in contact with possible water-yielding rocks on at least two sides, and if the fault zones are possible conduits for water circulation the geologic and hydrologic conditions are suitable for the infinite-aquifer type of analysis as used and modified here. History of Pumping: During sinking of the Fad shaft a maximum pumping rate of 1500 gpm kept the shaft dewatered sufficiently, but in March 1948, after the 2250 level drift passed through the Martin fault into the Eldorado limestone, the pumps and shaft were flooded. Subsequently additional pump-

Jan 1, 1956

By John Wulff, J. H. Hollomon

Service failures in brass condenser tubes are often due to corrosion. One of the commonest types of corrosion reveals a surface structure of redeposited copper.' The study of the effect of alloy addition agents in preventing this kind of corrosion has received impetus from the extensive publication of Bengough and May.2 The mechanism of such inhibition gauged from immersion corrosion,2 cell corrosion,3 and electrolytic potential4 measurements is controversial. This controversy may be attributed in part to a lack of definite knowledge5 of the actual nature of the initial films formed in corrosion experiments. In our own corrosion work on copper and 70-30 brass this lack became apparent and necessitated an examination of surface films by X-ray and electron diffraction methods. The present paper is but an introduction to the subject of inhibition and reports the structure of films formed in active corrodents. Experimental Procedure The arsenical coppers and brasses used in this investigation were made by one of the writers* in the plant of the Revere Copper and Brass Co. at Rome, N. Y. Standard commercial melting practice was followed. O.F.H.C. copper and electrolytic zinc were used and all arsenic additions were made by additions of a master copper alloy. The final analyses are given in Table I. Likewise, the extrusion, cold-rolling, and intermediate anneals employed followed standard usage. Final heat-treatments were given to all materials to produce a similar grain size (0.035 to 0.045 mm. for brass and 0.015 to 0.025 for copper) for the alloys containing various percentages of arsenic. Samples 1/2 by M by 1/4 in. were cut from sheet material resurfaced and finished with 0000 metal-lographic papers. The surfaces were all degreased in alcohol and benzine before immersion. After immersion in the corrodent, they were washed gently in tap water, dipped first in alcohol and then in pure benzine and allowed to dry in the diffraction apparatus. The reflection electron diffraction apparatus used has been described by Burwell and Wu1ff.6 Fig. I is typical of the photo-grams obtained. The X-ray apparatus was

Jan 1, 1941

By John J. Secretary Egan

The present list of problems relating to the physical chemistry of steelmaking has been prepared by the Committee on the Physical Chemistry of Steelmaking, from answers to a questionnaire submitted to a number of metallurgists engaged in both industrial and educational work throughout the United States. The purpose of the project is to make available to research laboratories a list of problems, all reduced to their simplest terms, the solution of which would aid in creating a better understanding of the steelmaking process. It is not intended to restrict the problems to practical steelmaking. The list also includes the study of the properties, and their correlation, as well as the physical and chemical reactions, of all substances that occur or that may be in any way associated with steelmaking operations, such as metallic substances, refractories, nonmetallic inclusions, and the constituents of slags. Many of the problems can be carried out in university or other research laboratories. Others may be most successfully attacked by cooperation of the research men with the operating personnel. It is the Committee's earnest wish that this cooperation be fostered. It is requested that investigators who are working on any of the problems listed and who anticipate future publication of their results, notify the Secretary of the Committee that such investigation is in progress. Suggested additions to the present list are also requested. The Committee is undertaking to act as a clearing house for information regarding the topics in this field that are being actually studied. Interested persons are invited to correspond with the Secretary. I. Data involved in the state of equilibrium for the various systems (laboratory work, almost entirely). A. Specific heats, heats of formation, entropies and free energies of various PURE ELEMENTS OR COMPOUNDS; ALSO CERTAIN TYPICAL SLAGS AND REFRACTORIES I. Determination of specific heats and entropies of oxides, sulphides, nitrides, etc, over a wide temperature range. 2. Determination of free energies of oxides, sulphides, nitrides, etc., over a wide temperature range. 3. Determination of the heats of formation of the oxides, sulphides, nitrides, etc. 4. Determination of the thermodynamic properties of the more important mineral-ogical constituents of the basic open-hearth slags such as calcium silicates, calcium phosphates, calcium ferrites, manganese silicates, FeO and Fe2O3. 5. Determination of the specific heats of open-hearth slags, including liquid silicates, if possible.

Jan 1, 1941

By G. E. Pellissier, C. W. Mason

Tin has long been cited as offering a classic example of polymorphism, second in repute only to the allotropy of sulphul.. The notorious "tin disease," which Cohenl has studied so exhaustively in terms of the enantiotropic transformation of tetragonal white P tin to cubic gray a tin, has apparently encouraged the expectation that one or more additional polymorphic modifications might exist. The search for confirnmntion of this idea has, as might be anticipated, led to the accumulation of a body of miscellaneous evidence, much of which would probably never have been sought, or taken seriously even by its discoverers, but fur previous assumptions. The ball apparently was started rolling iii 1880 by Trechmann,2 who reported a new modification of tin (7 tin), which was brittle and found in "hard head," a highly arsenical, slaggy material produced in a certain stage of tin smelting. A mixture of two kinds of crystals was obtained from a Cornish tin furnace, and those thought to be 7 tin were studied crystallographically. The results indicated that these crystals were rhombic and of different density from the tetragonal tin prepared electrolytically by Miller. Their analysis was given as 98.7 per cent Sn, 1.3 per cent Fe, and traces of As, Sb, Bi and S. In 1881 von Foullon4 obtained similar crystals from a Bohemian tin furnace. Headden5 examined crystals similar to those of Trechmann and von Foullon and reported them to be monoclinic, but of analysis corresponding to stannous sulphide. Later, Stevanovic,~ by goniometric measurements, proved that these crystals of SnS were really rhombic. Groth7 pictures and describes both "rhombic tin" (Fig. 9, vol. 1) ant1 stannous sulphide (Fig. 84, vol. 1); their faces and angles correspond within the accuracy of measurement. Spencers in 1921 examined the above evidence critically; lie lound similar crystals from Cornish tin furnaces, proved them to be SnS, and even was able to analyze some of Trechmann's original specimens, finding high sulphur content. (Apparently Trechmann's analysis had been based on :L second lot of crystals, not described crystallographically.)

Jan 1, 1939