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By Ralph L. Erickson

The discovery of a Carlin-type gold deposit at Cortez, Nevada, in 1966 can be attributed directly to the use of geochemical exploration techniques. Most mineral deposits owe their discovery to geologic concepts, geologic analysis, and luck, but at Cortez, geochemistry as an exploration tool played the clearly dominant role in discovery. Of course, the economic significance of the discovery had to be determined by exploration and development drilling. The story of the discovery began in 1959 when field work was initiated on a new project, "Geochemical Halos Utah and Nevada," by R.L. Erickson and A. P. Marranzino for the US Geological Survey. The Cortez district was selected for geochemical work because it was an area with good geologic control where we could address the problem of how to prospect in barren outcrops for concealed ore deposits in potentially favorable structures (buried thrust zones) or favorable host rocks in the subsurface. Geologic mapping of the Cortez 15-min quadrangle, just being completed by Gilluly and Masursky (1965), showed that the quadrangle contained excellent exposures of both the upper and lower plates of the Roberts Mountains thrust fault, a major structural feature of north-central Nevada. Roberts (1960) had noted that a number of mining districts were associated with windows in the thrust. In 1959, Erickson and Marranzino did some reconnaissance rock sampling and spring-water sampling in the siliceous clastic rocks of the upper plate of the thrust. Results of this reconnaissance prompted a full-scale sampling program in 1960 in the upper plate rocks on the west flank of the Cortez window. Results of the investigation showed that anomalously high concentrations of metals occur in the upper plate rocks, and further, that the distribution of metals is fault controlled and shows a pronounced zoning pattern (central copper zone; intermediate zinc, copper, and lead zone; and outer arsenic zone). The anomalies were interpreted as primary leakage halos that originated from metal occurrences in the thrust zone or in carbonate rocks below the thrust and moved upward along normal faults that cut both upper and lower plate rocks. Erickson gave a talk about these anomalies in the summer of 1961 to the local AIME Section in Reno, Nevada; two short reports were published that year-" Geochemical Anomalies in the Upper Plate of the Roberts Thrust Near Cortez, Nevada" (Erickson et al., 1961) and "Hydrogeochemical Anomalies in Four Mile Canyon Near Cortez, Nevada" (Erickson and Marranzino, 1961). These releases prompted blanket staking in the area by several small companies. In 1963, geologic and geochemical mapping were started by the USGS in the lower plate carbonate rocks of the Cortez window west of the quartz monzonite stock at Mount Tenabo and north of the old townsite of Cortez. The results of the work showed anomalously high concentrations of arsenic, antimony, and tungsten in jasperoid, fracture filling, and shear zones in Silurian and Devonian carbonate rocks. The anomalous area was about 1.6 km (I mile) long and 300 m (1000 ft) wide. A brief report, "Geochemical Anomalies in the Lower Plate of the Roberts Thrust Near Cortez, Nevada" (Erickson et al., 1964a), was published in 1964. During this same time period, 1959-1964, several exploration or mining companies were active in the general area (chiefly mapping geology and acquiring property). In 1964, American Exploration and Mining Company (Amex) concluded that the entire Cortez district was worthy of an extensive exploration effort involving drilling as well as geologic, geophysical, and geochemical studies. To carry out the program, Amex formed a joint venture group with the Bunker Hill Company, Vernon Taylor, Jr., and Webb Resources. Their early efforts were directed to the upper plate rocks and to the lower levels of the old Cortez silver mine. The group also drilled some shallow rotary assessment holes adjacent to the area of the arsenic, antimony, tungsten anomaly in lower plate carbonate rocks described in Erickson et al. (1964a). Assay results from these holes offered little or no encouragement to the joint venture group. Splits of these drill samples were made available to the USGS. In order to enhance any metal content present in these rocks and to determine the mineral residence of any metals detected, heavy-mineral concentrates of each 3-m (10-ft) sam-

Jan 1, 1985

By E. C. Hopkinson, A. H. Youmans, R. A. Bergan, H. I. Oshry

A new log has been developed for quantitative formation evaluation which is based on a measurement of the length of time slow neutrons survive before they are captured in the rocks and fluids. The logging instrument employs a cyclically pulsed neutron generator and a gated scintillation counter which is synchronized with the source. The source emits short, intense bursts of 14 mev neutrons once every 1,000 microsec and is quiescent between bursts. During the period the source is quiescent, the detector is electronically actuated for two independent preselected intervals. A comparison of the counting rates during these two intervals gives a measure of the rate of decay of the slow neutrons and of the associated gamma radiation. The average neutron lifetime in most earth formations is in the range from 50 to 500 microsec. It can be measured during a continuous logging operation at conventional logging speeds. The design of the logging instrument is described and the results of tests are compared with theoretical predictiom. Formulas are developed which give the relationship between log response and formation properties. It is shown that the method is particularly sensitive to formation fluid salinity, and that salt water saturation can be measured accurately in either cased or open hole. The measurement can be made independent of borehole size, fluid type, casing and tool position in the hole by properly selecting the intervals during which the measurements are made. The results of tests with a prototype logging tool are given. INTRODUCTION A new nuclear logging system has been developed which employs the Accelatron,* an accelerator-type neutron source, and accurately measures formation brine saturation in an entirely new way. It has produced a type of formation log with better sensitivity, greater sampling depth and simpler quantitative interpretation than any other nuclear log thus far suggested. The new Neutron Lifetime Log* employs a pulsed electromechanical neutron source and a synchronously gated radiation detector. A prototype instrument has been field tested during recent months to demonstrate the operability of the apparatus and the feasibility of the method. Tests in wells and simulated boreholes have confirmed theoretical predictions and have shown that formation param ters can be measured independent of casing and other borehole parameters. Preliminary results of field tests have indicated that the log may have important and widespread applications. BASIC PRINCIPLE OF NEUTRON LIFETIME LOG The Neutron Lifetime Log is based on the fact that neutrons emitted by a source in a well are rapidly but not instantly captured by the material around the source. Their capture is a matter of statistical probability; the greater the number of capturing nuclei and the greater the "capture cross section", the greater is the probability that a neutron will be captured quickly. The average life of a thermal neutron in vacuum is about 13 minutes, but in common earth materials, the average neutron life ranges between extremes of about 5 rnicrosec for rock salt and perhaps 900 microsec for quartzite. The Neutron Lifetime Log responds to variations in this average neutron life. The theoretical basis for a log of this general type has been well understood by nuclear logging experts in many laboratories both in America and in Russia, and develop mental work along these lines has been in progress for many years. The Russian literature has reported both theoretical and experimental work1,2 but in this country there have been no published reports of progress toward a practical logging instrument. The logging instrument is designed to measure radiation produced by slow neutrons during selected intervals when no neutrons are being emitted by the source. The source is arranged to emit neutrons in bursts or pulses. During the quiescent interval between the pulses, it is possible to observe the exponential "decay" of the neutrons and the neutron-induced radiation as the individual neutrons progressively disappear due to capture by atoms in the formation or the borehole. When a short pulse of 14 mev neutrons is emitted by a source in a borehole, the individual neutrons are slowed to thermal energy within a few microsec. Thus, a cloud of "slow" neutrons is formed around the source within 10 to 50 microsec after the pulse. This cloud is most dense within a few inches of the source, and is progressively less dense out to a radius of about 3 ft, where radiation from the source is practically undetectable.

Jan 1, 1965

By Winston A. Wong, John J. Jonas

Commercial purity aluminum was deformed by extrusion over the temperature range 320° to 616°C and the strain rate range 0.1 to 10 per sec. Flow stresses and strain rates were calculated from the experimenLa1 ram pressures and speeds. The stress-strain rate-lemperature relationship in extrusion was found to be similar to that in creep. Extrusion, torsion, compression, and creep data extending over ten orders of magnitude of strain rate and over two orders of magnitude of stress were correlated by a single creep equation. It was concluded that hot-working is a thermally activated process, in which the rate-controlling mechanism is either the climb of edge dislocations or [he motion of jogged screw dislocations. The microstructural changes observed during extrusion were consistent with the proposed deformation mechanisms. ALTHOUGH great progress has been made in understanding the technology of extrusion, very little is known about the actual deformation mechanisms operating during flow. Previous accounts describing extrusion have indicated that the relationship between ram speed (V), pressure (P), and temperature (T) can be given as follows:1 V = apb and P = A' exp(-AT). In these equations, a and b are constants which depend on temperature, A' is a constant which depends on ram speed, and A is a "coefficient" with a different value for each metal. Although these equations have fairly wide application, they do not contribute much to a fundamental understanding of the deformation. Furthermore, extrusion has not hitherto been considered as a thermally activated rate process. This lacuna is surprising because hot-working is similar to high-temperature creep in several respects. There is, in fact, a fair body of experimental evidence suggesting that the material response under hot-working conditions is similar to that occurring under creep conditions, in spite of the many orders of magnitude difference in strain rate.2"4 Since creep has been extensively analyzed in terms of dislocation mechanisms, the comparison of hot-working to creep is useful, for it can suggest the possible deformation mechanisms operating during hot-working. In this paper, the hot extrusion of aluminum will be examined from the point of view of thermally activated deformation mechanisms, such as operate during creep. EXPERIMENTAL PROCEDURE The experimental procedure consisted of extruding commercial purity aluminum* over a range of ram velocities and temperatures at constant die reduction by the direct method. Details of the experimental equipment have been published elsewhere.5 Extrusion was carried out at each of the following billet temperatures: 320°, 376°, 445°, 490°, 555°, and 616°C at the following constant ram speeds: 0.002, 0.008, 0.02, 0.1, and 0.2 in. per sec.* All results were obtained using a square-shouldered die with an extrusion ratio of 40:1, giving a reduction in area of 97.5 pct. The ram force was the dependent variable, and was measured by means of strain gages on the ram and was plotted as a function of ram travel. The sequence of events before making an extrusion was duplicated before each run so as to minimize as much as possible variations in experimental conditions. For example, after the equipment had been assembled, the billet was allowed to heat up to temperature inside the insulated container. Once the container attained the desired temperature, a period of 1/2 hr was allowed to elapse before the extrusion was made. This time was found to be required to allow the billet to reach a steady-state temperature, as determined from previous tests. When all was ready, extrusion was carried out without interruption; that is, the billet was upset and extruded in one operation. EXPERIMENTAL RESULTS AND DISCUSSION The two usual experimental approaches for investigating high-temperature deformation exhibit an important common feature. In the first approach, which corresponds to creep, a constant stress (or load) is applied to the material at constant temperature and the resultant strain is recorded against time. After an initial transient stage, a state of constant strain rate exists (secondary creep), in which a steady-state condition is established which is sensitive to variation in either applied stress or temperature. In the second approach, a constant strain rate is applied and the resultant flow stress is recorded. This corresponds to the situation in hot torsion or hot compression, where it is observed that, for a constant test temperature, there is an initial rise in stress to a steady value which is maintained up to very high strains. In tests of this type, a steady-state region is also established in which the stress is sensitive to variation in either the strain rate or the temperature.3,4,6-16 In both types of tests, therefore, a steady-state region is established after an initial transient. In the case of hot-working this region may be called steady-state hot-working, and it is analogous to steady-state creep with which it has many common features. Stress Dependence of the strain Rate in Extrusion. In order to assess the stress dependence of the strain rate under extrusion conditions, and to compare it to that of creep, as well as of hot torsion and hot compression, the extrusion data were analyzed according to power, exponential and hyperbolic sine creep equations.

Jan 1, 1969

Jan 1, 1923

By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

Jan 1, 1923

By J. C. Todd

The volume of air needed to move the combustion wave through each acre-foot of the reservoir is a very important quantity for engineering economic analyses. A new method, which involves backflowing the injection well, has been developed for determining the air requirement .for the forward combustion thermal pilot in the Delaware-Childers field. The method depends on measurement of the total volume of air injected and measurement of the pore volume in the zone swept out by the combustion front. The basic premise of the method is that the pore volume of the swept zone contains air, while the formation around this zone contains flue gas, oil and water. The pore volume of the swept zone is determined by blowing down the pilot section of the formation through the injection well after the pilot is shut down. Oxygen balance is used to differentiate between air from the swept zone and flue gas from the surrounding formation. Data indicate that air'is produced from the swept zone by relatively efficient miscible displacement by the flue gas. The pore volume occupied by the air in the swept zone is determined by simple PVT relationships. The average temperature of the swept zone is calculated by heat balance from the total amount of heat generated during the pilot and losses to the surrounding formation. The new method was applied successfully at the conclusion of the pilot in the Delaware-Childers field; the air required for the reservoir conditions involved was calculated to be 19.2 MMscf/acre-ft of reservoir swept. INTRODUCTION One of the most important pieces of information to be found from a forward combustion pilot is the air requirement; that is, the volume of air needed to move the combustion wave through each acre-foot of the reservoir. Compression costs per barrel of oil recovered, which are a direct function of the air requirement, are a large portion of the expenses incurred in the thermal recovery process. Thus, the profitability of thermal recovery depends largely on the air requirement, which is a measure of the amount of fuel deposited and burned in the thermal recovery process. Several attempts have been made to correlate crude oil properties with fuel deposition and, hence, air requirement.l*2 Other attempts have been made by our laboratory to find the air requirement by material balance, gravity survey, pressure transient analysis,3 magnetic survey and the poten-tiometric model. Better methods are needed to predict more accurately the economics of fieldwide application of the process. Another method of finding the air requirement consists of operating a pilot thermal project for several years. This is followed by an extensive coring program to define the volume swept by the combustion wave. The air requirement is found from the total injected air divided by the volume of the swept region found from the coring operation. This method is costly; an adequate coring program usually costs several hundred thousand dollars. A thermal pilot was operated in a watered-out portion of the Delaware-Childers field, Bartlesville sand, from Nov., 1960, until May 3, 1965. One of the primary purposes of this pilot operation was to determine the air requirement for economic calculations which determine the advisability of expanding the project to the entire 128,000 acre-ft field. Barnes4 has described the result of this pilot operation,, including calculation of the air requirement from limited coring data. The value obtained, as calculated, was 15.8 MMscf/acre-ft. One purpose of this report is to describe a new method of finding the air requirement from a thermal pilot operation. A second purpose is to describe the application of this method to the Delaware-Childers thermal pilot. THEORY AND DESCRIPTION OF THE METHOD The combustion zone in the forward combustion process is propagated from injection w producing

Jan 1, 1970

By Morris Muskat

A theory is presented for calculating the performance history of complete water-drive systems producing from idealized stratified formations. The general equations are applied to systems where the permeability stratification is either of the exponential or linear type. Calculations were carried through for different degrees of permeability stratification, but with special emphasis on the effect of the mobility ratio between the produced oil and the invading water on the resultant performance. These results are also expressed graphically as curves for the initial water breakthrough recovery, for the different degrees of stratification, as a function of the mobility ratio, and of the composition of the produced fluid stream as a function of the cumulative oil recovery. For several typical cases the latter has also been plotted as a function of the cumulative oil and water throughflow. The general result is that when the mobility of the oil is lower than that of the invading water the channelling tendency resulting from the permeability stratification becomes aggravated as the higher permeability zones become flooded out. Situations of this type would obtain when producing low gravity or highly viscous oils. Conversely, if the mobility of the oil is high compared to that of the invading water, the flooding of the high permeability zones will lead to a retarding and choking effect, and the gross bypassing phenomena will be partially suppressed. These conditions would correspond to those of flooding high gravity or low viscosity oils. A discussion is given of the various basic assumptions made in the analysis, including that of ignoring the stripping phase of the production history as implied by relative permeability concepts. INTRODUCTION The physical ultimate recoveries from oil reservoirs are basically determined and limited by the physical oil displacement processes associated with the reservoir producing mechanism. In practice, however, the economic ultimate recoveries are further limited by the mobility of the reservoir fluids and the uniformity and continuity of the producing formation. In fact, it is the differential depletion between the component parts of the composite reservoir which ultimately determines the total recovery at the time of field abandonment. While this observation applies to both the solution gas drive and gravity drainage mechanisms, in which use is made only of the energy contained within the original oil-bearing reservoir, it is of even more paramount importance under operations wherein the energy associated with extraneous fluids provides the ultimate oil expulsion mechanism. Whether the invading fluid is the water from an edgewater drive, water injected for pressure maintenance, gas injected for pressure maintenance, or gas returned to the formation in a cycling program, it is often the continuity and uniformity of the producing section which will control the economic efficiency of the operations. The importance of the problem of reservoir non-uniformity does not, of course, lessen its complexity or the difficulties of its solution. In fact, these are inherently such that the concept of a "general" solution is virtually meaningless. About all that can be reasonably hoped for is the analysis of specific and well-defined types of non-uniformity which may give some degree of approximation to actual reservoir conditions. Since variations in the nature of the reservoir which depend only on the position along the streamlines will not lead directly to major differential depletion development within the reservoir, the types of non-uniformity considered thus far have involved stratification assumptions. That is, the producing section has been replaced by a multi-layer "sandwich," each uniform areally, and differing from the others only in its basic physical constants as to thickness, porosity and permeability. The fluid motion in the composite system is thus approximated by a parallel superposition of the independent fluid movements in the individual strata. For the specific application to cycling operations the theory of the effect of permeability stratification has been developed for both discontinuous' and continuous types of permeability stratification. Among the latter, treatments have been given of systems in which permeability distributions are governed by exponential, linear' or probability3 functions. In all these studies complete dynamical equivalence was assumed between the injected dry gas and the displaced wet gas. The overall effective permeability of each stratum was therefore considered as constant and independent of the degree of invasion of the injected fluid. In the case of the displacement of oil by water, the assumption of dynamical equivalence between the water and oil will be strictly valid only by accident. Even if the oil viscosity should be the same as that of the water, the effective permeability to the oil in the presence of the connate water will in general be quite different from that of the water behind the water-oil interface flowing past the trapped residual oil. As a result the effective permeability for the stratum as a whole and rate of water invasion will change with time as the intrusion continues. The differential fluid motion in the individual strata will thus also vary with time. Qualitatively, it is easy to predict the resultant effects. If the permeability to viscosity ratio of the invading fluid exceeds that of the fluid displaced, the stratification and bypassing effect of the perme-

Jan 1, 1950

By A. D. Zunkel, A. H. Larson

Equilibrium arsenic contents of Pb-As alloys in contact with PbO-As2O3 slags containing less than 30 mol pct As2O3, were determined at 650°, 700: and 750 C in an inert at?rzosphere. In this temperature range, the arsenic content of the alloy increased with increasing temperature in the single-phase liquid slag region and decreased with increasing temperature in the two-phase slag region and the single-phase solid-solution slag region. The PbO-As2O3 phase diagram below 22 mol pct As2O3 was determined by thertrzal analysis and by application of a log ?As2O3/?PbO vS log XAs2o3 /x3pbO plot determined from the equilibrium actiuity data. The resulting phase diagram was not well-defined since the eutectic temperature was not detected in the thermal analysis experiments, although a region of terminal solid solubility of As2O3 was found. Results from the phase diagram determination are compared with an existing diagram in the literature. THIS experimental investigation is an extension of a study by the authors1 on the slag-metal equilibria in the systems concerned with commercial lead refining processes such as softening and dross fuming. The first part of this investigation was a study of the slag-metal equilibria in the Pb-PbO-Sb2O3 system. The only experimental work previously done on the Pb-PbO-As2O3 system was by Pelzel2,3 in which the phase diagram for the PbO-As2O3 system was determined below 50 wt pct As2O3 and the equilibrium constant for the reaction 3Pb + As2O3 + 3PbO + 2As was determined as a function of temperature. No slag-metal equilibrium data have been determined. It is due to the scarcity of information regarding the Pb-PbO-As203 system that this work was undertaken. This paper describes the determination of the slag-metal equilibria in the Pb-PbO-As203 system by equilibrating Pb-As alloys with PbO-As2O3 slags in an inert atmosphere, the effect of 1 wt pct additions of bismuth and copper on the slag-metal equilibria, and the PbO-As2O3 phase diagram both by thermal analysis and the use of the slag-metal equilibria data. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade and assayed as follows: 1) 99.8 pct PbO (0.014 pct insoluble in CHJCOOH, 0.02 pct not precipitated by H2S, 0.1 pct CaO, and 0.08 pct SiO2); 2) 99.95 pct As2O3; 3) 99.99 pct Pb; 4) 99.0 pct As; 5) 99.99 pct Cu; and 6) 99.97 pct Bi. Room-temperature X-ray patterns revealed no detectable impurities in any of these materials. Apparatus for Equilibrium and Thermal-Analysis Determinations. The resistance-heated crucible furnace used in this investigation employed nichrome elements and was mounted so that it could be raised to surround the reaction tube during each experiment and, subsequently, lowered. A schematic diagram of the apparatus is shown in Fig. 1. Each charge was heated in a 3+-in.-OD by 31/2-in.-high 416 stainless-steel crucible placed in a 41/4-in.-1D by 18-in.-long fused-silica reaction tube which was closed at one end. On a shoulder around the crucible was placed a 3: -in.-OD by 12-in.-long open-end fused-silica condenser tube. The open end of the reaction tube was covered by a water-cooled brass cap with ports for 1) admitting an inert atmosphere to the system through a stopcock, 2) introducing a stainless-steel, motor-driven, paddle stirrer into the crucible, 3) evacuating the system with a mechanical vacuum pump, and 4) sampling the melt with Vycor sampling tubes. The brass cap was fitted to the open end of the reaction tube with a silicone gasket and collar clamp. The furnace temperature was controlled by a Barber-Coleman Capacitrol controller and a chromel-alumel thermocouple. Due to the corrosiveness of the melt, the controlling thermocouple also served as the measuring thermocouple. The temperature of the melt was calibrated against the controller temperature and was checked periodically during each test with a Vycor-enclosed calibrated chromel-alumel thermocouple. The temperature measurement and control can be considered accurate to ±3°C. Procedure. The charge placed in the crucible for each experiment consisted of 1000 g of Pb-As alloy and 300 g of PbO-As2O3 slag. The crucible was then placed in the reaction tube, the condenser tube was placed on the shoulder of the crucible, the silicone gasket and brass cap were fitted on the open end of the reaction tube, and the entire system was evacuated and filled with argon ten times. After the last flushing, a positive argon pressure of 1 psig was impressed on the system. The furnace was then raised to sur-

Jan 1, 1968

By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

By J. B. Conway

Stress-vuptuve data for several of- the refractory metals are frequently found to yield a linear relationship between the Larson-Miller parameter and the logarithm of the applied stress. In such cases linear stress-rupture isotherms result with slopes bearing a definite relationship to the temperature. It also follows that the stress to produce rupture in a certain period of time will be linear in temperature. Data for several refractory metals have been reviewed and excellent linearity is shown in this type of isochronal plot. In addition, the af ore - mentioned lineavity leads to a linear relation between the log of the stress to produce rupture in a certain time and the homologous temperature. This has been illustrated for the Group VI-A metals, tungsten and molybdenum. EXTENSIVE use has been made of the Larson-Miller' parameter in the interpolation and extrapolation of stress-rupture and creep data. In those cases where this particular parametric approach is applicable a convenient and fairly straightforward procedure is made available for the correlation of experimental stress-rupture data. It is quite common to employ this parameter in the form of a master rupture plot in which the parameter, T(C + log tr), is expressed as a function of log stress. In many cases this functional relationship in log stress is linear within acceptable accuracy and hence the following relation results: where P is the parameter, C is the Larson-Miller constant, T is the absolute temperature, t~ is the rupture time, a is the stress, and a and b are constants. Examples of such a relationship are contained in the work of Green, Smith, and 01son2 dealing with high-temperature rupture behavior of molybdenum and in the work of Green' dealing with the high-temperature behavior of tungsten. In addition, pugh4 has shown a similar linearity for some fairly low-temperature data for molybdenum. It can be shown that when the relationship in Eq. [I] is exhibited certain generalizations can be made concerning the form of the stress-rupture isotherms. For example, rearranging yields: For a given material (constant C) at a given temperature the first term on the right-hand side of Eq. [2] is a constant and hence this equation defines a straight line when log stress is plotted as a function of log-rupture time. This is recognized as the standard form usually employed in this type of data presentation. Such linearity then suggests the linear form of the Larson-Miller parameter. Or, in other words, the linear parametric relationship in Eq. [2] results only when the stress-rupture data are linear on a log-log plot of stress vs rupture time. Another interesting observation can be made in regard to Eq. [2]. It can be noted that the slope of the stress-rupture isotherms is given by - T/b and hence a direct calculation of the constant b is available. It also follows that since the value of b is the same for all temperatures the slopes of the various isotherms on the log-log stress-rupture plot cannot be the same. Indeed, the existence of the relationship in Eq. [2] precludes a system of parallel lines on this common stress-rupture plot. As a matter of fact it further specifies that in addition to being nonparallel the slope of these isotherms must decrease (i.e., become more negative) with increasing temperature. Such a condition is indeed found to exist in the case of the stress-rupture data reported for molybdenum.' As a corollary to the above, it may be stated that stress-rupture data which do not lead to a linear log-log stress-rupture plot or whose isotherms do not exhibit a decrease in slope as the temperature increases will not yield the linear relationship of Eq. [I]. Applying Eq. [2] to two different temperatures and solving for C yields: Eq. [3] affords a simple and rapid method for calculating the Larson-Miller constant from the log-log stress-rupture plot. The slope of a given linear isotherm is measured and the value of "b" calculated based on Eq. [2] as: slope = - -Tb Then at an abscissa value of 1.0 hr (making log tr in Eq. [3] equal to zero) read the stress corresponding to rupture for two different temperatures. Substitution in [3] yields: A value of the Larson-Miller constant can thus be calculated from a few simple mathematical procedures employing data read directly from the log-log plot of the stress-rupture data. Of course, it is not to be overlooked that the above reasoning has been based on the linear relationship of Eq. [I] being applicable. However, if as mentioned above the log-log plot is

Jan 1, 1967

Jan 1, 1892

Jan 1, 1914

By M. K. McCarter

Jan 1, 1985

By R. N. Kust, J. C. Agarwal, H. E. Barner, N. Beecher, D. S. Davies

Kennecott Copper Corp. has developed a new hydro-metallurgical process for extracting nickel, copper, cobalt and molybdenum from manganese nodules. This process (KCC Cuprion Process) utilizes a reduction leach operating at atmospheric pressure in the temperature range of 45 OC to 50°C and has been successfully demonstrated in a continuous pilot plant processing 350 kg/d of nodule ore. The chemistry, basic flowsheet and operating characteristics are presented and discussed.

Jan 1, 1980

Jan 1, 1963

BRANCH COUNCILS Mining Branch E R Price, Chairman (Coal) Howard A Meyerhoff (Industrial Minerals) J V Beall, Secretary Richard M Foose (Industrial Minerals) Carroll F Hardy (Coal) Frank A Hardlaw (Mining, Geology, and Geophysics) S J Swainson (Minerals Beneficiation) Philip J Shenon (Mining, Geology, and Geophysics) Grover J Holt (Minerals Beneficiation) A C Callen (Mineral Industry Education) C H. Behre, Jr. (Mineral Economics)

Jan 1, 1952

By John B. Pearse

The works heretofore used in carrying out the Bessemer process have been constructed substantially as follows: The whole works or plant has been divided into three parts. 1. The division in which the metals for conversion are melted. 2. The division in which the metals are converted into steel and cast into ingots, or the converting department. 3. The engine and boiler department which supplies the hydraulic power required to move the machinery, and which furnishes the blast used for converting the crude metal into steel.

By Jacob Reeese

I HAVE discovered a new method by which steel and other metals may be burnished by the automatic action of the burnishing machine, and by which the cost is greatly diminished, and more perfect work produced. And in addition to the polishing and burnishing action of

Jan 1, 1881

By William G. Fricke

MaCROSEGREGATION, as distinct from microseg-regation, is often inverse in nature. That is, the eu-tectic solute elements, which are expected to be con-

Jan 1, 1970