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By C. D. Stahl, S. M. Farouq Ali, W. E. Culham

One- and two-dimensional mathematical models have been developed that simulate transient, two-phase flow of hydrocarbon mixtures in porous media in a manner that accounts for interphase mass transfer. Numerical simulations of one-dimensional depletion-drive experiments using a two-component hydrucarbon fluid were used to establish the validity of the mathematical models. In addition, the experimental and numerical data were used to demonstrate that production rate had a relatively insignificant effect on the recovery of individual hydrocarbon components from the experimental system, and that attainment of equilibrium between phases is possible for a wide range of liquid and vapor velocities in reservoirs containing light hydrocarbon fluids. Results of some two-dimensional numerical simulations are also presented. INTRODUCTION This study was undertaken to develop a mathematical model that would simulate transient, two-phase flow of hydrocarbon mixtures in porous media under conditions that result in interphase mass transfer and to test the validity of the assumptions used to set up the model. In addition, the study was designed to determine if production rate influences the recovery of individual hydrocarbon components from reservoirs producing by depletion drive. Two-phase flow in porous media, with interchange of components between the two phases, is important in many petroleum recovery processes. Studiesl-5 conducted within the last 3 years have outlined methods of solving multiphase flow problems incorporating mass transfer. Some of these studies have also indicated the importance of accounting for mass transfer under various producing conditions. An earlier work6 first demonstrated the importance of combining relative permeability data with equilibrium ratios in compositional balance methods. The mathematical model presented in this paper is formulated so that a phase behavior package, as described in previous papers,5,17 is not required as an integral part of the routine employed to solve for the primary dependent variables. The finite difference formulation is designed so that all the primary variables can be solved for simultaneously. This is accomplished by utilizing one basic set of equations. These innovations, which are in contrast to other models2,3,5 but are similar in some respects to the approach used by Taylor,l render the total problem computationally simpler than any of the previously referenced formulations. The mathematical model was developed by combining Darcy's law with a continuity equation for each hydrocarbon component. The principal assumptions invoked in the formulation were (1) that capillary forces and diffusional effects are negligible, and (2) that thermodynamic equilibrium exists in the reservoir at all times. No assumption as to the type of vaporization process was made in formulating this model. Experimental data were required to complete this study. These were generated by conducting several depletion drive experiments. The experimental apparatus consisted of a sandstone core enclosed in a pressurized casing. The apparatus was designed in such a manner that the core could be charged with a liquid hydrocarbon mixture and depleted at different production rates. The experimental tests were designed to determine the effect of production rate on component recovery. In addition, direct comparison of experimental and mathematically predicted

Jan 1, 1970

By Robert E. Campbell

Mining geophysics in 1969 marked a year of growth and consolidation in the application of ground and airborne geophysical methods and techniques with a 20% rise in expenditures for world-wide exploration. Growth was determined by questionnaire survey of industry, geophysical contractors, universities and government agencies conducted by the Society of Exploration Geophysicists. Relative position of metlhods is shown in the accompanying table on page 87. Methods and Techniques Electromagnetic airborne and ground methods showed the largest gains in the utilization of VLF-EM instrumentation. The VLF-EM instrument is a directional radio receiver which is tuned to distant radio transmitters in the 15 to 25 kilohertz band range. It measures vertical real and imaginary components of the magnetic field vector, and is used in geological mapping and surveying for various types of conductors in the ground. Ground VLF-EM instruments, Ronka EM-16 and Radem, are manufactured by Geonics, Ltd., Toronto, Ont., and Crone Geophysics. Ltd., Port Credit. Ont.

Jan 1, 1970

By Akinobu Kasami, Keiji Maeda, Makoto Naito, Masaharu Toyama

Gap electroluminescent diodes have been prepared by the vapor phase diffusion of zinc into n-Gap crystals which were grown from a gallium solution (10 wt pct Gap) doped with tellurium and Ga203. A marked improvement in the efficiency of the red electrolumines -cence has been achieved by heat treatment after diffusion. External quantum efficiencies of diodes annealed under optimum conditions are 0.2 to 0.6 pct at room temperature, or about 200 times higher than the efficiencies of diodes quenched after diffusion. The optimum dopant concentrations in the gallium melt from which the crystals were grown are 3to6 x at. pct Te and 4 to 8 x 10-2 mol pct Ga203. The efficient diodes are characterized by linearly graded junctions with an i-layer 0.1 to 0.2u thick. Annealing increases the emission intensity by a factor of 20 to 50 and decreases the current density to 1/3 to 1/8 that of quenched diodes at a given bias. The decrease in current is attributed to an annihilation of deep recombination centers in the depletion layer. The increase in emission intensity is interpreted in terms of an increase in lifetime of minority carriers and an increase in the relative intensity of red-to-infrared emission. The dependence of these quantities on the tellurium and oxygen doping levels is also discussed. A number of studies have been made of the red light emission from for ward-biased Gap diodes.' At room temperature this emission band is centered at 7OOO? with a spectral width of nearly 1000?. Low-tempera-ture photoluminescence indicates that this emission is due to either the radiative annihilation of an exciton bound to a pair of zinc and oxygen atoms substituting on nearest neighbor lattice sites2,3 or the radiative recombination of an electron bound to this Zn-O pair with a hole bound to an isolated zinc shallow acceptor.3 An emission band is also observed with a spectral peak at 9800?. This infrared emission has been shown to be due to the recombination of an electron trapped at an isolated oxygen deep donor with a hole trapped at an isolated zinc acceptor.4 The red emission from Gap diodes is fairly efficient at room temperature because the nearest neighbor Zn-0 pair forms a deep electron trap at 0.3 to 0.4 ev below the edge of the conduction band.2'4 In diodes grown by liquid epitaxy an external quantum efficiency of 2.1 x 10-2 (photon/electron) has been attained by heat treatment at relatively low temperatures.5 This heat treatment was found to increase the efficiency by a factor of 3 to 6. However, no detailed studies have-been reported on the effects of heat treatment. We can only cite Onton and Lorenz's work6 on the change ; in the relative intensity of red-to-infrared emission. Heat treatment has also been tried on junctions built in during growth, but contrary to expectations the efficiency decreased. In-diffusion is a simple and controllable method of fabricating p-n junctions. For Gap, zinc is generally used to form a p-type layer on n-type crystals. The emission efficiencies of in-diffused diodes are, however, extremely low in comparison with liquid epitaxial diodes.' Although efficiencies as high as 2 x 1O-3 have been reported, values from 10-6 to 10-4 are generally obtained by typical diffusion techniques. Out-diffused diodes are known to be a little more efficient than in-diffused diodes. Nevertheless, the quantum efficiency is at most 7 x 10- 3 and ordinarily of the order of 10-4.8 NO results have been reported on heat treatment of either in-diffused or out-diffused diodes. This paper reports a marked improvement in the efficiency of the red emission observed for in-dif-fused diodes as a result of heat treatment after diffusion. The method described reproducibly yields diodes with external quantum efficiencies of 2 to 6 x 10-3. The observed dependence of efficiency on annealing time and on doping level will be discussed in terms of the lifetime of minority carriers and the formation of Zn-O complex pairs. EXPERIMENTAL A) Diode Fabrication. The n-Gap crystals used in this study were grown from a saturated gallium solution by a slow cooling method.8 The Gap content in the gallium melt was fixed to 10 wt pct corresponding to a growth temperature of about 1100 Tellurium was chosen as the n-type dopant and added to the melt in concentrations ranging from 0.001 to 0.06 at. pct. Oxygen was added in the form of Ga2O3, whose concentration was varied from 0.004 to 0.2 mol pct. The resulting crystals were platelets with well-developed (111) surfaces. Typical electrical properties were Hall mobilities of 130 to 30 sq cm per v-sec and carrier concentrations of 1016 to 10" cm-3 at room temperature. Diodes prepared from crystals with relatively low doping levels, in which u = 130 to 100 sq cm per v-sec and n = 0.6 to 6 x 1017 Cm-3, were examined in detail. The p-n junctions were produced in these n-Gap crystals by the diffusion of zinc from the vapor phase by the following procedure. The platelets were carefully lapped on both sides to a thickness of 150 to 200 u while maintaining the (111) orientation. After being etched in hot aqua regia, the crystals together with the zinc were sealed in an evacuated 12 mm ID quartz ampoule 20 cm long. The crystals and the zinc were then separated from each other at opposite ends

Jan 1, 1970

By Reinhard Fischer

The consumption of lead for batteries in some western countries and Japan amounts to 870,000 T. annually. Battery life is 2-3 years. Therefore after a short time a considerable quantity of lead flows back to smelters. The production of lead from scrap batteries is discussed from the following points of view: 1. Separation of the acid contained in the batteries. 2. Separation of the components which are free of lead from the components containing lead, e.g. cases, separators. 3. Separation of metallic lead from lead compounds. 4. Avoidance of manual-work. A process has been developed and perfected at a plant, which began operation in 1965. The procedure consists essentially of the following steps: 1. Breaking the cases and removing the acid. 2. Crushing the batteries in an impact mill. 3. Screening off separators. 4. Separation of slurry. 5. Gravity separation of metal and organic material. The plant has a one-shift capacity of -24,000 T. batteries/year.

Jan 1, 1970

By Bruce A. Kennedy

SME hopes to publish its first separate volume of Mining Exploration Transactions later this year. The reason for this separate publication was stated in "Rock in the BOX," December 1969 [ ], p. 14, as follows: "Because of the great upsurge in mineral exploration (during) the last few years and the fragmentation and narrow specialization of the earth sciences into a great many fields not directly related to exploration, many explorationists feel that a need for a special journal devoted to mineral exploration now exists." To summarize the history behind this change in publication policy of the Mining and Exploration Division, we go back to 1968 when a small group of M&E Division members advocated the establishment of an entirely separate journal devoted specifically to exploration. S. Parker Gay Jr. was appointed chairman of an ad hoc committee to investigate the feelings of the other Division members toward such a journal. Approximately one thousand questionnaires were sent out and the returns showed an extremely favorable reaction. Gay reported the results of his survey to the M&E Division Executive Committee Meeting in Salt Lake City in September 1969. These results were also published in the December 1969 issue of [ ].

Jan 1, 1970

By Amitava Gangulee

A recent investigation has shown that solid solution hardening is almost absent in the quasibinary system SnTe-pbTe.1 The lack of solid solution hardening was attributed to the small difference of only about 3 pct between the atomic sizes of lead and tin, and to the fact that the formation of these solid solutions involved changes only in the sublattice occupied by the lead and tin atoms. The investigation reported here is concerned with the quasibinary system PbSe-PbTe which, similar to the SnTe-PbTe system, forms a continuous series of solid solutions2 and has the same NaC1-type (Bl) structure. The size difference between the selenium and tellurium atoms, however, is slightly larger than 7 pct. No indication of any ordering of the lead and tin atoms at. selected compositions had been found in the system SnTe-PbTe, which had been explained by the weak second-nearest-neighbor interactions between lead and tin atoms.' The possible occurrence of an ordering transition in the system PbSe-PbTe was also investigated in the present work. Polycrystalline specinlens of PbSel-1-xTex (x = 0, 0.20, 0.25, 0.33, 0.50, 0.67, 0.75, 0.80, and 1.0) were prepared by melting appropriate amounts of 99.999 pct pure Pb, Se, and Te j.n evacuated and sealed Vycor capsules. The capsules were quenched in water. The solidified ingots were homogenized at 800°C for 14 days. Chemical analysis of the homogenized ingots showed that the deviations from the stoichiometric compositions were less than 0.1 at. pct for each component. Part of each ingot was ground to pass through a 75 g sieve and pressed into 25.4 mm by 12.7 by 2 mm briquettes. Duplicate sets of specimens, each containing at least one briquette and part of the ingot of each composition, were sealed in evacuated Vycor capsules. Both sets were annealed at 500°C for 7 days; one set was quenced in ice-water and the other was cooled to room temperature over a period of 14 days.

Jan 1, 1970

By A. Paul Bond

Two series of 17pct Cr iron-base alloys with small, controlled amounts of carbon and nitrogen were vacuum-melted in an effort to detertmine the meclz-uniswls of inter granulur corrosion in ferritic stain-less steels. An alloy containing 0.0095 pct N aid 0.002 pct C was very resistant to intergranular corrosion, even after sensitizing heat treatments at 1700" to 2100o F. However, alloys containing more than 0.022 pct Ni and more than 0.012 pct C were quite susceptible to intergranular corrosion after sensitizing heat treatments at temperatures higher than 1700°F. This corrosion was observed after the usual exposure tests and after potentiostatic polarization tests. Electronmicroscopic examination of the alloys susceptible to intergranular corvosion revealed a small grain boundary precipitate; this precipitate was absent in the alloys not susceptible to such corrosion. Thc electronmicrographs indicate that intergranu1ar corrosion of ferritic stainless steels is caused by the depletion of chromium in areas adjacent to precipi-tates of chromium carbide or chromium nitride. It also seems likely that the precipitates themselves are attacked at highly oxidizing potentials. Confirma-tion of the proposed mechanisms was obtained in tests on air-melted ferritic stainless steels containing titanium. The titanium additions greatly reduced susceptibility to intergranular corrosion at moderately oxidizing potentials but had no beneficial effect at highly oxidizing potentials. A major obstacle to the use of ferritic stainless steel has been their susceptibility to intergranular corrosion after welding or improper heat treatment. It appears that sensitization of ferritic stainless steel occurs under a wider range of conditions than for austenitic steels. In addition, a greater number of environments lead to damaging intergranular corrosion of sensitized ferritic stainless steels than to sensitized austenitic steels. The chromium depletion theory of intergranular corrosion is widely accepted for austenitic stainless steels'" although there: are some objections.3 On the other hand, several alternative mechanisms proposed for ferritic stainless steels include precipitation of easily corroded iron carbides at grain boundaries,' grain boundary precipitates that strain the metal lat-tice,5 and the formation of austenite at the grain bound-arie.6 The application of the chromium depletion theory to ferritic stainless steels has been discussed extensively by Baumel.7 The present investigation was undertaken to determine which of the proposed mechanisms can be sub- A PAUL BOND IS Research Group Leader, Climax Molybdenum Co of Michigan, Ann Arbor, Mich. stantiated with experimental data obtained on ferritic stainless steels. High-purity 17 pct Cr alloys containing small controlled additions of carbon or nitrogen were therefore prepared, and then examined electro-chemically and metallographically. EXPERIMENTAL PROCEDURES Materials. Two series of experimental alloys were prepared from electrolytic iron and low-carbon ferro-chromium using the split-heat technique. In this technique, the base composition is melted, and part of the melt is poured off to produce an ingot. To the balance of the melt, the required addition is made and the next ingot cast. This process is repeated until a series of the desired compositions is cast. By this procedure the impurity levels are essentially constant within each series. All the alloys in the carbon-containing series were melted and cast in vacuum. The base composition in the nitrogen series was melted and cast in vacuum; subsequent ingots in the series were melted with additions of high-nitrogen ferrochromium, and cast under argon at a pressure of 0.5 atmosphere. Two additional alloys were produced starting with normal purity materials. They were induction-melted while protected by an argon blanket and cast in air. Table I gives the composition of the alloys. The 2-in.-diam ingots produced were hot-forged and hot-rolled to a thickness of 0.3 in. and then cold-rolled to 0.15 in. All specimens were annealed at 1450°F for 1 hr. The indicated sensitizing heat treat-s s ments were performed on annealed material. All heat treatments were followed by a water quench. Specimen Preparation. For the 65 pct nitric acid test, 1 by 2 by 0.14-in. specimens were wet-surface ground to remove surface irregularities and polished through 3/0 dry metallographic paper. For the modified Strauss test, $ by 3 by 0.14-in. specinlens were similarly prepared. Immediately prior to testing, the Table I. Compositions of the Alloys Composition, pct Alloy Cr hio C N 270A 16.76 0.0021 0.0095 270B 16.74 0.0025 0.022 270C 16.87 0.0031 0.032 270D 16.71 0.0044 0.057 271A 16.81 0.012 0.0089 27 IB 16.76 0.018 0.0089 271C 16.69 0.027 0.0085 271D 16.81 0.061 0.0O71 4073' 18.45 1.97 0.034 0.045 4075† 18.5 2.0 0.03 0.03

Jan 1, 1970

By C. J. Delisio

The basic concept of tunnel boring has not changed since the late 1800's. R. Stanley of Great Britain obtained a Canadian patent as early as December 1891. Mr. Stanley's machine was a device that consisted of a rotating wheel equipped with drag-type teeth; it had a means of thrusting the cutterhead against the face or heading; it had a means of clamping or gripping the machine in its bore; it had a means of collecting and depositing the cuttings into a screw-type conveyor located near the invert of the tunnel. It even had a means of varying the speed of the forward motion of the machine to suit different hardnesses of rock encountered. This description essentially fits the latest tunnel-boring machines being built today. In short, there has been no significant advance in the basic concept in 70 to 80 years. It may well be that no significant change can be expected for some time into the future. Today's machines, while still basic in concept, offer many advances aimed at faster tunneling. Among these are 1 ) improved cutters, 2) guidance and steering devices, 3) dust-control devices, and 4) mechanisms to aid in installing tunnel supports. CUTTERS The most important part of a hard-rock tunnel borer is the cutter. If the cutter can cut the rock, it is a boring machine. If the cutter cannot cut the rock, no other part of the machine can. When Jarva, Inc. decided to build a machine, the first problem was to find a good cutter. In our search, we looked at most of the cutters on the market. We selected Reed Drilling Tools' cutter because the design of their cutter was aimed at hard-rock tunneling. We feel that they build the best cutter available and provide the best possible service to their customers. As tunnel-boring machine design advanced, the transition from drag bits to roller bits was natural because harder formations required a roller bit, and it is the goal of all mole users to bore harder formations. Roller bits

Jan 1, 1970

By W. C. Schafer

In tunneling or mining where hydraulic shields, moles, or rock boring equipment is used lasers such as those shown guide the production machine by providing a continuous and visible line and grade reference. In this application the laser may be mounted in the heading, preferably somewhere above spring line. If we view the circular heading as a compass in the vertical plane with 0º referencing at the crown of the heading and 180º on the invert, then it might be said that the laser may be mounted anywhere from 270º through 0º to 90º. The laser is generally mounted 2 to 3 ft off the wall or the crown of the heading by means of a bracket that may be attached directly to the liner plate. In cases where no liner plate is used, then brackets may be bolted directly into the ribs, or grouted directly into the rock. Once the laser is in position the beam is projected to the face. Two points must be surveyed upstream between the laser and the face which define line and grade. Targets may be suspended beneath each of these points approximately 2 to 3 ft. These targets may be circular or rectangular with a surface area which approximates 16 sq in. Each of these two targets should have a ½ to ¾ in. hole drilled directly in their center. When the laser is adjusted so that the beam passes through the holes in each of the two targets, the laser beam itself will parallel the center line of the tunnel and become a visible line and grade reference over the total beam projection.

Jan 1, 1970

By Jack Fox

Although this is going to appear in the December Issue of &E, it is being written long before the end of the year. December, of course, is the time for a summing up of the year's activities. Perhaps, the best way to begin is to report on what went on at the SME Board of Directors Meeting in St. Louis on October 20. This won't be a chronological report, and I shall take time to comment on some of the items we cover as we go along. You should be encouraged to know that your Directors take their duties seriously. Of the 21 current Directors, 19 were present, and three of the new 1971 Directors came to observe what goes on at an SME Board Meeting.

Jan 1, 1970

By E. T. Turkdogan, Klaus Schwerdtfeger, P. Grieveson

The rate of growth of "Fe4N" on a iron was measured by nitriding purified iron strips in flowing am -monia -hydrogen gas mixtures at 504" and 554°C. It is shown that a dense nitride layer is formed when a zone -refined iron is used in the experiments. With less pure iron, the nitride layer is found to be porous. Through theoretical treatment, the self-diffusivity of nitrogen is evaluated porn the parabolic rate constant, and found to be essentially independent of nitrogen actirlity, e.g., D* = 3.2 x l0-12 and 7.9x l0-12 sq cm per sec at 504" and 554?C. Some consideration is given to the mechanism of diffusion in the nitride phase. THERE is a great deal of background knowledge on the solubility and diffusivity of nitrogen in iron, and on the thermodynamics and crystallography of several phases in the Fe-N system. Although case-nitrided steels have many applications in practice, no work seems to have been done on the diffusivity of nitrogen in the iron nitride, ?', phase. The only work reported on the related subject of which the authors are aware is an investigation by Prenosil,1 who measured the growth rate of the e phase on iron by nitriding in ammonia-hydrogen gas mixtures. EXPERIMENTS Purified iron plates of approximate dimensions 1 by 0.5 by 0.03 cm were nitrided in flowing mixtures of ammonia and hydrogen, in a vertical furnace fitted with a gas-tight recrystallized alumina tube. After a specified time of reaction, the sample was cooled to room temperature by withdrawal to the water cooled top of the reaction tube. The furnace temperature was controlled electronically in the usual manner within *l°C; the temperature was measured using a calibrated Pt/Pt-10 pct Rh thermocouple. For each experiment the iron strip sample was cleaned with fine emery cloth and degreased with tri-chloroethylene prior to the experiment. The ammonia-hydrogen gas mixtures were prepared from anhydrous ammonia and purified hydrogen using constant pressure-head capillary flowmeters. The gas mixture flowed upward in the furnace with flow rate of 400 cc per min at stp. The composition of the gas mixture was checked by chemical analysis at regular intervals. In most cases, the compositions of the exit gas and metered input gas agreed within about 0.3 pct, indicating that cracking of ammonia did not pose a problem at the temperatures employed. Two series of experiments were carried out using two different types of purified iron samples. In the first series of experiments at 550°C, vacuum carbon deoxidized "Plastiron" was used. The main impurities present in this iron were, in ppm: 4043, 50-Cr, 20-Zr, 40-Mn, 20-P, 20-S, 20-C, 50-0, and 10-N. In these experiments the rate data were obtained by measuring the change in weight of the iron specimen suspended in the hot zone of the furnace by a platinum wire from a silica spring balance. The nitride layer formed in these experiments was found to be porous, particularly near the outer surface. In other experiments, high purity zone-refined iron (prepared in this laboratory) was used. The total impurity content of this iron was 30 ppm of which 20 ppm was Co + Ni, 4 ppm 0, other metallic impurities were less than 1 ppm. The zone-refined iron bar, -2.5 cm diam, was cold rolled to a thickness of about 0.03 cm and the specimens were prepared for the experiment as described earlier. After the nitriding experiment, the sample was copper plated electro-lytically and mounted in plastic for metallographic polishing. After polishing, the thickness of the ?' layer was measured using a metallographic microscope. The nitride layer formed on the zone-refined iron was essentially free of pores. RESULTS The different morphology of the nitride layers grown on "Plastiron" and zone-refined iron is shown in Fig. 1. Both samples were nitrided side by side for 55 hr. The holes in the less pure iron, Fig. l(a), are confined to a region about one half thickness from the outer surface. The dense layer grown on zone-refined iron, Fig. l(b), is thinner than the porous layer on the "Plastiron". The impurities in the iron are believed to be responsible for the formation of a porous nitride layer. The pore formation may be due to the high nitrogen pressures existing within the nitride layer, e.g., the equilibrium nitrogen pressure is 1.2 x l05 atm in the 38.6 pct NH3-61.4 pct H2 and 6.6 x l03 atm at the Fe-Fe4N interface at 554°C and 0.96 atm. It is possible that the oxide inclusions present in the electrolytic iron may facilitate the nuclea-tion of nitrogen gas bubbles within the nitride layer. Support for this reasoning is the fact that pores are only encountered in the outer range of the layer where nitrogen pressures are largest. The photomicrographs in Fig. 2 show the effect of reaction time on the thickness of the dense nitride layer formed on zone-refined iron. These sections are from samples nitrided in a stream of 29 pct NH3-71 pct H2 mixture at 554°C for 22, 70, and 255 hr. In all the sections examined the nitride-iron interface was noted to be rugged. These irregularities are be-

Jan 1, 1970

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By C. W. Volek, J. E. Chappelear

The injection of a hot liquid into initially cool porous media, saturated with the same liquid and surrounded by two impermeable but heat conducting media (cap and base rock), has been studied both experimentally and theoretically. The temperature dependence of the viscosity was included in the theoretical model, but it was assumed that the specilic heats and densities of the various materials were independent of the temperature. Solutions to the theoretical model were approximated by numerical methods. Both theoretical and experimental results indicate that center-line temperatures are significantly higher than boundary temperatures. Comparison of experimental and theoretical results with a cold/hot viscosity ratio 01 19:1 were in reasonable agreement. Theoretical calculations show that the effect of the temperature dependence of viscosity was very significant at ratios of 100:l to 1000:1, which are typical of those that occur when injecting hot water to flood heavy oil reservoirs. INTRODUCTION We consider the problem of prediction of fluid flow and temperature distribution in an initially cold-fluid-filled reservoir on the injection of the same hot liquid by the use of mathematical and physical models. The results reported are for a two-dimensional rectangular section of the reservoir, as shown in Fig. 1. The injection and withdrawal faces are assumed to be equipotentials for fluid flow. The ultimate purpose of such models would be to predict hot-water injection performance. However, we note that in the work presented here, one of the most significant aspects of the problem — the instabilities resulting from two-phase, water and oil flow — is not included. We will not give a historical review, but refer instead to the paper of Spillette and Nielsen,1 which contains a rather complete bibliography and critical discussion. The physical problem is exactly the same as Spillette and Nielsen, except for certain simplifications in our assumptions. The mathematical details are somewhat different, and we will present the details of our method here. The mass flow equation, which is elliptic in character, is handled by successive overrelaxation. The heat flow equation, which is parabolic in character, is handled by a straightforward explicit approximation. Some difficulty arose in the over-all heat balance due to small errors in the solution of the mass flow equation, and we feel that a different formulation of the heat flow equation would be desirable for future work. In addition to the mathematical solutions for the temperature distributions in a porous medium due to the injection of hot liquids, experimental data are presented to check the validity of these solutions. A schematic diagram of the model is shown in Fig. 2. Certain qualitative physical conclusions were obtained from our numerical and experimental results. These are: 1. Assuming high (infinite) conductivity normal to the bedding plane in the reservoir is a poor approximation, and may lead to overestimates of the total heat losses (to cap and base rock) of as much as 50 percent. 2. More heat is retained in the reservoir (per unit of heat injected) for higher viscosity changes. 3. Any particular temperature isotherm moves more rapidly along the center line for higher viscosity changes. Consequently, the approximation of temperature independent viscosity is not suitable for obtaining quantitatively correct results. MATHEMATICAL MODEL Our mathematical model is that of a reservoir of thickness 2h. The problem is idealized from that of a linear hot-water drive, and we imagine that the input face is sufficiently far away from the injection wells that the stream lines enter it normally. Similarly the production wells are far enough from the outflow face that the flow lines leave it normally. The reservoir and surrounding cap and base rock

Jan 1, 1970

By J. D. Livingston, H. E. Cline

The lamellar-dendritic transition in Sn-Pb alloys near the eutectic composition has been studied at high growth rates. Lamellar structures were found over a substantial range of tin-rich compositions, and this range extended to increasingly tin-rich concentrations as growth rate increased. These results are discussed in terms of stability and competitive-growth arguments. Various experimental and structural limitations to the rate of directional solidification are discussed. The rate of heat removal at the heat sink is the major experimental limitation. ReCENT interet1,2 in the use of fine composite structures produced by directional solidification of eutectic alloys makes it important to determine the range of composition and growth conditions that yield such microstructures. Because increasing growth velocities produce increasingly finer microstructures, it is particularly significant to determine the factors limiting the rate of solidification. Mollard and Flemings3 have shown that composite structures, free of primary dendrites, can be obtained in Sn-Pb alloys of off-eutectic composition. The composition range of composite structures was found to increase with increasing values of G/V, where G is the temperature gradient and V is the growth velocity. These results are in good quantitative agreement with an analysis of the stability of a planar eutectic interface.4 This analysis specifically predicts that over a small range of compositions stable lamellar structures will be obtained even for G/V = 0, hence, even at very high growth rates. The lamellar-dendritic transition in Sn-Pb alloys has also been analyzed with a model based on competitive growth between dendrites and the composite structure.576 This treatment, based on earlier work on organic eutetics,7 predicts that the composition range yielding composite structures in Sn-Pb will increase rapidly at high growth rates. An increase in the composition range of composite structures at high growth rates was recently observed in Cu-Pb alloys near the monotectic composition.8 In view of these results, and the predictions of the stability and competitivegrowth analyses, it was decided to study the lamellar-dendritic transition in Sn-Pb alloys at high growth rates. EXPERIMENTAL Using 99.999 pct pure materials, a series of Sn-Pb alloys were prepared containing 16.8 at. pct to 27.6 at. pct lead. (Eutectic composition is 26.1 at. pct Pb.) Ingots were extruded to 0.175 in. rod, and some rod was drawn to 0.070-in. wire. Directional solidification was accomplished in two different ways, Fig. 1. For growth rates up to 2 x 10-1 cm per sec, a 0.175 in. diam sample was placed in a graphite crucible 5 in. long with 0.250 in. OD and 0.035 in. walls. Samples were melted under flowing argon in a vertical, platinum-wound furnace, and solidified by driving the crucible downwards through a \ in. hole in a water-cooled copper toroid, Fig. l(a). An insulated chromel-alumel thermocouple was imbedded in the center of a representative sample, and moved with the sample during solidification. The local temperature is plotted against the distance travelled by the sample in Fig. 2. As the growth rate increased, the solid-liquid interface moved closer to the water-cooled toroid and the temperature gradient increased. At growth rates above 10-1' cm per sec, heat was not removed fast enough and the sample moved into the toroid in the liquid state. The curve for V = 2 x 10-1 cm per sec shows a plateau caused by incomplete removal of latent heat from the interface, a problem which will be discussed later. To improve the heat removal, the toroid was cooled by nitrogen gas precooled in liquid nitrogen. This allowed successful solidification at rates up to 2 x 10-1cm per sec. Higher solidification rates required still more effective heat removal. Samples 0.070 in. in diam were placed in graphite tubes 0.125 in. in diam with 0.020 in. walls. Instead of cooling by sliding contact with a cooled toroid, these thinner samples were sprayed or directly immersed into water, Fig. l(b). After solidification, samples were stored in liquid nitrogen until they could be examined metallographic-ally. The surface was prepared with a diamond-knife microtome, followed by a light etch. The presence or absence of tin dendrites, Fig. 3, or lead dendrites, Fig. 4, was noted by optical microscopy, usually of a transverse section near the center of the sample. Replicas of the surface were prepared and examined in an electron microscope to resolve the fine lamellar structures, Fig. 5. The structures observed at various compositions and growth rates are summarized in Fig. 6. Composite structures were observed at increasingly cin-rich compositions as growth rate increased. This transition from dendritic to composite structure with increasing growth rate was also demonstrated by solidifying half a sample at a slow rate and then suddenly increasing the growth rate by lifting the furnace and quenching the sample with a water spray. A longitudinal section of this sample, Fig. 7, shows that the tin dendrites, which extended ahead of the slow-moving composite interface, were bypassed by the composite when the growth rate was increased. The range of composite structures at high growth rates was limited by the appearance of primary lead dendrites on the tin-rich side of the eutectic composition. Observation of representative longitudinal

Jan 1, 1970

By G. C. Hancock

The operating plant of The Broken Hill Associated Smelters Pty. Ltd. is situated at Port Pirie in South Australia and it treats to finality the whole output of lead concentrates from the mines of The Zinc Corporation Ltd., North Broken Hill Ltd., and aroken Hill South Ltd. at Broken Hill, New South Wales. Lead bearing ores from other sources are also purchased for treatment and lead scrap and residues are treated on a toll charge basis. The present output of the plant is approximately 200000 tonnes of refined lead per annum and there is a substantial production of by-products including refined silver, gold, cadmium, antimonial lead alloys, copper matte and sulphuric acid. Recently the Company commenced the production of zinc by slag fuming and electrolysis from a six million ton dump of lead blast furnace slag, which has been accumulating at Port Pirie for over fifty years. The slag fuming plant contains two furnaces of conventional design, but features a high degree of pre-heat for the blast air and this is obtained by the use of all-metal recuperators. The raw zinc oxide fume produced by the plant is roasted in a rotary kiln prior to treatment in the leaching and electrolysis sections, which follow conventional practice for nigh current density plants. Present output is approximately 36000 tonnes of electrolytic zinc per annum.

Jan 1, 1970

By C. B. Manula, H. Gezik

In planning modem-day mining operations, management needs to pass from the area of subjective decision-making to an area of objective decision-makirlg. Planning procedures currently being practiced by many mine managers depend primarily on common sense and trial-and-error methods which oftentimes never reach optimum solutions. For this reason, an attempt is made to provide an understanding of linear programming to solve production planning problems. More specifically, a linear programming model is proposed to solve the production scheduling problem as it was found to exist in the crushed stone industry. Optimal production scheduling is of prime concern here, since the industry has to cope with seasonal demands for its products. The solution, as determined through the application of the model, provides management not only with an optimal production schedule but also with the following information regarding the improvement of existing facilities: (I) the location of bottlenecks which limit production and profit; (2) the directions in which the company i fixed equipment should be expanded or modified; and (3) the evaluation of unused resources. Future trends in stone production will quite likely parallel those in the construction industry. Continued record expenditures for structures such as dams, highways, and buildings are the reasons for this accelerated growth. Production forecasts for the next decade are predicted to be around one billion tons with an approximate 7% annual increase. The problem of increasing production from 570 million tons in 1966 to 1 billion tons by 1976 offers no small challenge. This situation is further compounded by other problems and economic factors. Population expansion, government regulation, labor agreement, and changes in technology wd cause managers and operators to be confronted by many more complexities than characterize present-day operations. Some of these. problems and economic factors are: (1) In some metropolitan and other urban areas, easily accessible sources of stone are almost depleted. Transportation costs will be a prime concern of the industry. (2) Population growth has forced residential expansion to a point where many quarry operators must conform to urban and suburban regulations. (3) Government regulation in regard to air and water pollution, noise, and reclamation as well as zoning developments necessitate that crushed stone producers keep abreast of changing conditions and requirements. (4) The crushed stone industry operates under pressure of a highly competitive situation. Every company's objective is to retain a favorable marketing position by exercising great attention to production and marketing costs. This is rather difficult, since the crushed stone industry is one segment of modern mining which has to cope with a seasonal demand for its products. Among the problems posed here, the one of exercising great attention to production and marketing costs is of current interest to management. Under seasonal demand conditions, this problem creates further difficulties for managers who need to plan and forecast. STATEMENT OF THE PROBLEM Various methods of Operations Research have been developed to handle a problem whose genesis is explained above. It is very seldom, however, that these quantitative means are used in practice by the mining industry. This paper describes the use of Operations Research methods to solve a production planning problem when demand is seasonal. The seasonal production planning problem is an important one because of the substantial costs associated with changing production, employment, and inventory levels to adjust to seasonal sales patterns. Most companies try to operate within reasonable levels of employment changes and hold inventories within storage capacities. In general, little or no attempts were made to develop minimum cosl schedules or to provide objective means to compare various production policies. When demand varies within a fixed time period, 11:-oduction requirements may be met by following one

Jan 1, 1970

By M. N. Shetty

LARGE copper whiskers were grown from cuprous iodide by reduction with hydrogen at about 500°C. Carefully selected single-crystal whiskers of [loo], [110], and [Ill] orientations were used and the whisker shapes and cross sections are shown in Fig. 1. Spec-trographic analysis of a typical batch of whiskers showed that the composition was better than 99.9 pct with iron and silicon as the major impurities. The test specimens varied from about 70 to 400 u in diam and they did not show a conspicuous yield drop as observed in very fine whiskers (diam <25 u), tested by Brenner.1 The characteristics of the stress-strain curves were similar to those of bulk single crystals, even though the maximum flow stresses reached in some orientations were comparable to the yield stresses observed in fine whiskers. Mechanical properties of whiskers of different materials and copper whiskers up to about 100 u in diam have been reviewed,&apos; and a mechanism of slip band propagation in fine whiskers has been recently suggested.3 Whiskers in this work were tested in a floor-model Instron testing machine using low strain rates. (Details of the testing procedure, diameter dependence of the yield stress, and the characteristics of the load elongation and stress-strain curves have appeared esewhere.4) Due to the extensive deformation, >50

Jan 1, 1970

By Freeman Bishop

The Interior Department has been in a state of disarray for many months. At first this was attributed to Interior Secretary Walter Hickel&apos;s inability to anticipate how his words would be interpreted by Press-Radio-TV. But then the already disquieted ernployees in the Department became aware that plans were afoot to take bits and pieces of the various antipollution programs from Interior; Health, Education and Welfare: the Atomic Energy Commission and other agencies and lump them together into a new Federal agency. Interior, many predicted, would be a shell of its former robust self. Hardly had this rumor started to add to employee uneasiness before the other big shoe hit the floor. The new rumor had it that the Bureau of Mines was being stripped of most of its research functions and that the Office of Coal Research and allied research groups would be abolished altogether.

Jan 1, 1970

By Ashok K. Sinha

During the course of an in~*estigation into the occurrence of ordered AB3 structures, the following new phases have been found —CrRh3 (AuCu3 type), CrCo3 (MgCd3 type), HfCo4 (Ths Mn23 type), and WPt, MoPh type). The composition of the TiPt3-x phase (TiNi, type) is close to Ti23Pl77. The alloy chenzistry of transition rnetal AB3 structures is rezliewed in the light of electron concentration correlations of hex-agonality recently obtained for quasi-binary alloys. The relatizte colurne contraction in the AB3 structures increases with increasing difference in volume of the conzponents. A family of ordered close-packed layered structures is formed by stacking identical layers of composition AB, in various sequences, such that the coordination is twelvefold throughout and there are no A-A contacts. Previous work&apos; on quasi-binary AB3 alloys has led to the conclusion that the stacking sequence of the AB, structures changes with increasing radius ratio RA/RB from a purely cubic, through different mixtures of hexagonal and cubic stacking to a purely hexagonal stacking. However. for binary AB3 alloys, a correlation between the type of the crystal structure and the position of the components in the various volumns of the periodic table has been noted.2-5 It has been noted6 that this correlation appears to hold even though the radius ratio RA/RB may vary over a considerable range with the location of the components in the three long periods. Another study7" of several quasi-binary systems led to the conclusion that an increase in hexagonality of the stacking is associated with increase in the electron concentration e/a. as defined by the average per atom of the total number of electrons outside the inert gas shells. In apparent conflict with this conclusion, it is known that seven binary alloy structures isotypic with TiNi3 which is 50 pct hexagonal occur at a higher electron concentration (e/n = 8.5) than that (e/a = 8.25) for the 100 pct hexagonal MgCd3 type structure present in seven binary AB3 alloys. Table 111. In the present work, an investigation into the occurrence of binary AB3 structures in transition metal alloys was made, and a survey of binary AB3 structures is presented. EXPERIMENTAL The starting materials were pure metals of 99.9 wt pct purity. The alloys were arc-melted under partial pressure of argon and annealed in sealed silica capsules lined with molybdenum foil under argon at- mosphere. The total weight loss upon melting and subsequent annealing was always less than 1 pct and hence the alloys will be referred to by their intended (unanalyzed) compositions. Wherever the constitution permitted. the alloys were given a homogenizing treatment at 1200°C (3 days) prior to annealing. Unless otherwise stated all alloys were annealed at 900°C for 1 week and water-quenched. Sometimes the final annealing treatment was carried out on powders to accelerate the attainment of equilibrium. X-ray powder patterns were taken using a Guinier-de Wolff focusing camera (CuK, radiation) or an asymmetrical focusing camera (Co or CrK, radiation). For lattice parameter determination. internal silicon standards were employed. The intensity calculations were made using a Fortran IV program written by Jeitschko and parthe.9 RESULTS Twenty AB3 and three AB4 alloys were investigated. Table I lists the crystallographic data on some of the intermediate phases encountered in the present work. Table II contains the X-ray data for HfCo, (Th,,Mn,, type). The positional parameter, x. was assumed to be 0.378. the value for Th6Mnn2310 The X-ray pattern of ZrCo, was very similar to that of HfCo, and the previous structure determination of ZrCo, by Kuzma el al." was confirmed. Ordering in the alloy CrCo could be ascertained by the presence of only one weak super lattice line (101). the others being too weak presumably owing to the small difference in the scattering powers of chromium and cobalt. This line was observed in the X-ray pattern of powder from the massive sample annealed at 830°C (7 days) after the powder had been reannealed at 600°C (24 hr). The diffraction pattern of the powder similarly reannealed at 830°C (24 hr) contained only the lines due to a mixture of hcp and fcc Co(Crj solid solutions. Therefore, it appears reasonable to assume that O2 and/or N2 contamination which would be less likely to occur during the 600°C anneal was not responsible for the observed weak reflection. Also. this reflection cannot be identified with any of the strong lines of the neighboring s phase which is present in the Co-Cr system at higher chromium contents. The composition corresponding to the TiNi3 structure observed by Raman et al.12 in the two-phase alloy Ti,zt,, has been established in the present work as being between There was satisfactory agreement for the low-angle lines (up to d = 1.997A) between the observed diffraction pattern of TiCua and that calculated assuming the ZrAu, structure. as recently proposed by Pfeifer-et a1.I3 However. some of the superlattice lines. e.g., at d = 1.937 and 1.919A. predicted by the ZrAu, structure were not actually observed eve? though neighboring lines. at d = 1.947 and 1.986A. of comparable calculated intensity were present. The ZrAu

Jan 1, 1970

By Earl R. Hoskins, James E. Russell

The electrical resistivity of rocks has been studied quite extensively, in particular, the effects of temperature and confining pressure on resistivity. References 1 through 6 at the end of this chapter pertain to electrical resistivity of rock and contain further references on the same topic. The present study is motivated by an interest in determining the in-situ properties of rock as well as the stress state of the rock and how these quantities are changing with time. Most of the previous work on the electrical resistivity of rocks has been directed toward saturated rocks at relatively high confining pressures and temperatures. The present study was oriented towards air-dry surface rock that might occur in mine pillars. The mean stress and temperature under such conditions are comparatively low. It has been demonstrated that the resistivity of rock is highly dependent upon the porosity. In fact, for saturated rocks, a relationship referred to as Archie&apos;s law has been established between porosity and electrical resistivity. In the case of saturated rock, the property that is actually being measured is the resistivity of the solid/fluid system. Since the resistivity of the fluid alone is usually much lower than that of the dry rock, it is understandable that the resistivity of a saturated rock is in general several orders of magnitude lower than the resistivity of a relatively dry rocli. For dry rock, it seems reasonable that the electrical resistivity should increase as microcracks open within the material. Since microcracks open as material is stressed closer and closer to its failure point, it appears that there should be a correlation between electrical resistivity

Jan 1, 1970