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By B. Post, F. W. Glaser

Three borides of zirconium have been reported: ZrB,l ZrB2,2,3 and ZrB12, 4 The phase relationships, ranges of stability, and some physical properties of these compounds are described. THE zirconium borides differ considerably from one another, particularly with respect to their relative stabilities at high temperatures in the presence of carbon.4,5 ZrB2 is extremelv stable at all temperatures (to the melting point) in contact with carbon. Both ZrB and ZrB12 tend to decompose at elevated temperatures when carbon is present in excess of about 0.5 pct. ZrB forms ZrB2 and ZrC, and ZrB12 decomposes to form ZrB2 and a boron-carbide phase. In the ZrB12 preparation, boron present in excess of that needed to form ZrB2 reacts with carbon, if present, to form carbides, in preference to forming the higher boride. Similar instability of borides, other than diborides of the transition metals of the 4th and 5th groups of the periodic table, has been reported.5,6 special precautions had, therefore, to be taken to minimize carbon contamination in the preparation of ZrB and ZrB12. Reactions below 1400°C were carried out by heating powdered mixtures of zirconium hydride and boron in quartz tubes in a hydrogen atmosphere. For temperatures above 1400°C, reactions were carried out in graphite molds. Carbon contamination from the molds was minimized by employing extremely rapid heating rates to reduce carbon diffusion into the body of the specimen, and by subsequent "shaving" of sample surfaces that had been in contact with the graphite dies. A heating rate of about 2000°C per min was obtained by heating the dies (by direct conduction), using a current of 40,000 amp. Although this type of heating cycle apparently allowed little time for "homogenization," close approximations to equilibrium conditions were usually obtained as a result of the very strongly exothermic reactions between zirconium hydride and boron at elevated temperatures. Reproducibility of results in repeated runs under varying conditions was taken as a reasonable indication that equilibrium conditions had been effectively achieved. Quenching was accomplished by rapidly immersing the entire die, containing the reaction products, in water. Specimens could also be cooled at controlled rates by adjustment of the rate of flow of water through the water-cooled copper electrodes in contact with the graphite dies.

Jan 1, 1954

By R. S. Olson

An analysis of the wash thickener-two stage filtration circuit was undertaken to quantitatively describe the circuit performance. On the basis of information developed in this study, the factors of major importance in reducing soluble loss are: filter wash, wash zone size, filter capacity, filter feed pulp dilution, blow back, filter cloth, water to repulp, water to primary wash, water to feed pulp and thickener underflow. The wash thickener-two stage filtration circuit has been used in many hydrometallurgical plants to separate solute from leach solids. As many as 20 to 30 plant operating variables determine the performance of the wash circuit and hence the soluble loss. The complex relationships of these variables, with each other and with soluble loss, make the evaluation of their effect on mill performance difficult. An analysis of this type of circuit was undertaken to quantitatively describe the circuit performance. THE CIRCUIT The diagram in Fig. 1 represents the operation of the wash thickener-two stage filter circuit. This circuit provides for counter current, cross current or for a combination of countercurrent-cross current operation. The feed pulp stream, J, is intended to include any solution or water, other than primary and secondary filtrate, which enters the wash thickener. Except for filter washing, the operations in the circuit are simple mixing operations which can be described by material balance. The concentration of solute in the filtrate and cake solution after application of wash liquor cannot be described by simple material balance. The displacement washing equation, derived by Rhodes1 and extended by Choundhury and Dahlstrom,2 appears to best describe this case of miscible displacement in porous media. In a useful form, it is

Jan 1, 1963

By I. H. Pratt

The results of a study on the preparation of thin-film capacitor structures are discussed. The dietectric source material was quartz which was sputtered and deposited onto aluminum electrodes and counter-electroded to complete the metal-oxide-metal structures. This configuration was utilized to evaluate the dielectric, the device characteristics, and related process parameters. The effect of gas sputtering pressure, magnetic field strength, source-to-substrate distance, and power density on the rate of deposition is shown. Increased film thickness uniformity over a 3 by 3 in. area by optimum substrate positioning is indicated. Dielectric constant, dissipation factor, dielectric breakdown strength, insulation resistance, heat treatment, capacitance, and dissipation over the range 400 Hz to 5 MHz are reported. In the fabrication of silicon-integrated circuits, silicon dioxide has found use as a material suitable as a diffusion mask, for surface passivation of the silicon, and for protection of conductive films used for interconnections. Its use as a dielectric for thin-film capacitors in film hybrid circuits has been limited, to a degree, for lack of a compatible processing technique and because of its relatively low dielectric constant. With the recent advent of practical metal-oxide-semiconductor (MOS) field effect devices, the material is now being used to insulate the gate electrode from the conducting channel in the silicon. In this latter application, more stringent requirements have been imposed on .the oxide. A comprehensive resume of the use of silicon dioxide in integrated silicon device technology has been compiled including oxide film and bulk properties, method of oxide formations, and their applications.' A relatively new process to deposit SiO, and other dieIectrics is by rf sputtering, and the purpose of this paper is to describe the behavior of capacitors fabricated with a dielectric which has been sputtered from a quartz target and to indicate the relative effect of several of the process parameters on the film deposition. Work on rf sputtering of SiO2 and other dielectrics has been reported utilizing a triode type of sputtering system as described herein or a diode self-sustained glow discharge system. 2-8 SPUTTERING The process occurs during an electrical discharge in a gas plasma which provides the ions for acceleration to the target to produce the desired sputtering. The necessary plasma can be generated by a dc glow discharge through application of a high potential between two electrodes at approximately 2 to 10 x 10-2

Jan 1, 1969

The pressure of the gas in equilibrium with sphalerite has been determined in the temperature range of 680' to 825°C, using the Knudsen orifice method. A comparison of these experimental pressures with those calculated from thermal data and from other equilibrium measurements shows that the vapor above sphalerite is predominantly dissociated ZnS. Equations have been given for correctly calculating dissociation pressures using the Knudsen orifice method. It has been shown that the experimentally determined pressure is the same, whether the zinc sulphide is sphalerite or not, or a mixture of wurtzite and sphalerite. CONFLICTING points of view appear in the literature on the constitution of the vapor in equilibrium with solid zinc sulphide in the vicinity of 800°C. By comparing the dissociation pressure calculated from thermodynamic data and the vapor-pressure determination of ZnS by Veselovski,1 Lumsden2 has concluded that the vapor consists largely of dissociated ZnS. Sen Gupta,' however, concludes from his spectroscopic determinations that the vapor is largely ZnS molecules. In view of the fact that the thermodynamically calculated' dissociation pressure is higher than that experimentally measured by Veselovski, it seemed in order to repeat Veselovski's measurements. Experimental Procedure The method used for the determination of the pressures in this papel- is the Knudsen effusion cell. The apparatus and procedure were described in a previous paper- from this laboratory on the determination of the vapor pressure of silver. The only difference is that the Knudsen cell in this work is made from platinum and there is no external cover around the cell. The cell is an ordinary platinum crucible of 2.2 cm top diameter with a capsule cover. It was thought that platinum might stand up at these temperatures to the solid and gaseous ZnS, since it was found that the weight of the platinum cell itself did not change appreciably on heating ZnS in it at the working temperatures. To insure that reaction of the zinc sulphide with the cell was not giving' a false value, a stabilized zirconia cell was employed for check runs. Fig. 1 shows the comparison, which is satisfactory. Veselovski previously had measured the vapor pressure of ZnS using a silica Knudsen effusion cell. On repeating his experiment in this laboratory, it was found that ZnS at-tacked the silica cell, giving it a marked frosty appearance. This led to the belief that Veselovski's result:; may be in error. Also, he was operating at pressures above the range ordinarily considered safe for the Knudsen method. The effusion rate was measured by weighing the cell before and after each run. The weight loss during heating to temperature and cooling down was measured and subtracted from the weight loss during the actual run. The zinc sulphide used in this investigation was from two sources: Fisher cp grade, and a sample of pure sphalerite supplied by Mr. E. A. Anderson of the New Jersey Zinc Co. Before and after the series of runs with Fisher ZnS, X-ray analysis showed that both wurtzite and sphalerite were present. However, the ratio of sphalerite to wurtzite increased. All measurements were made below the transition temperature which has been reported" to be 1020°C. The data obtained in this investigation are tabulated in Table I. The pressure was calculated by the usual Knudsen formula" on the assumption that ZnS molecules were effusing. From these data, using pure sphalerite in the platinum Knudsen cell, the vapor pressure of ZnS, in mm of Hg, as a function of temperature is given by the solid line in Fig. 1. The best straight line, as determined by the method of least squares, is given by 14405 logpzns =-14405/T +11.032. A comparison of these results with Veselovski's shows that his results are about 50 pct lower. Discussion The vapor in equilibrium with solid zinc sulphide in the temperature range of this study will consist of Zn, S2, and ZnS mol, since other species of zinc and sulphur' are relatively unstable. The question to be settled is whether or not ZnS is largely dissociated. The derivation8 which follows gives the method of calculating the pressure of zinc and sulphur over solid ZnS, assuming complete dissociation, from Knudsen cell data. The free energy of the reaction 2 ZnS(solid) ? 2 Zn(gas) + S2(gas) is given by ?F?° = -RT In K = —RT In p12p2 where p1 is the zinc pressure and p is the sulphur pressure. If dissociation occurs in a closed system,

Jan 1, 1955

By T. F. Witherbee

Discussion of Mr. Baker's paper, read at the Lake Superior Meeting, September, 1904. MR. T. F. WITHERBEE, Durango, Mexico (communication to the Secretary*) : Mr. Baker's paper is very instructive in that it shows how furnace-derangements sometimes originate from apparently slight causes. In 1896 a similar burning through of the lining occurred at the Mayville furnace of the Northwestern Iron Co., Mayville, Wis., in exactly 38 days from the time the furnace was blown in. At that time I attributed it to the fact that the bell was carried several inches to the front side of the furnace, the length of the versed side of the arc described by the lever, thus dumping a little more of the charge on the back side, which made the front side of the furnace-charge more open and consequently increased the circulation of the furnace gases through it. After reading Mr. Baker's description, I believe that possibly a little more ore was charged on the back side of the hopper, due to the fact that it was nearest to the elevator. This unequal charging, however, was unconsciously done, as the fillers were both honest and faithful. The illustration of the burned lining of Furnace No. 1, given in Fig. - of Mr. Baker's paper answers very well for the Mayville furnace. It shows that in both cases the destruction of the lining was largely due to faulty construction, in that there were no cooling-plates in the angle of the bosh and in one or two courses of brick above it, where I believe they are-more in demand than anywhere else in the furnace. The presence of these cooling-plates at the angle of the bosh would have obliged the current of the hot gases to turn the corner and would have prevented them from following the angle of the bosh com¬pletely through the lining and shell.

Mar 1, 1905

By J. E. House, J. L. Drobnick, R. R. Swanson, D. W. Agers

The paper describes an improved process for the recovery, purification, and concentration of copper values from acidic dump leach liquors. The process employs a new liquid ion exchange material (LIX® 64 reagent) capable of separating copper values from iron and other impurities common to dump leach liquors in the typical pH range of 1.4-3.0. Properties and performance of the reagent are discussed. Design scale-up information for both pilot plants and commercial installations, including preliminary economics, are presented. Economic considerations include the production of electrolytic copper from the purified copper aqueous concentrate. INTRODUCTION Since the commercial acceptance of the liquid ion exchange process in the mineral processing industry, it has been predicted that a wide selection of chemical reagents to efficiently and economically separate many metals in solution under a wide range of conditions would be commercially available. Several years ago, General Mills began a basic research and development program to determine if it were possible to develop a reagent to extract economically metallic ion from existing process streams. Progress toward reaching this objective was reported in late 1963, when development of quantities of LIX -63 reagent, a highly selective reagent for the extraction of copper, was introduced. The properties of this reagent are described in a previous paper.' The development work with this reagent indicated that perhaps the largest potential application for a copper extractant, the treatment of acidic dump leach liquors, would not be economically possible with LIX-63 because of limitations of the reagent to extract copper below a pH of 3.0. The relatively small pH adjustment required with LIX-63 would result in a significant processing cost and the undesirable precipitation of ferric hydroxide from the liquor. This pointed to the need for another copper extractant which would extract copper from dump leach liquors without pH adjustment. General Mills was successful in synthesizing a molecule which does not have the pH limitation of the LIX-63, yet possesses the selectivity-solubility properties required of a metallic extractant. The resulting LIX-64 reagent broadens the pH range from which copper can be effectively extracted and separated from other metallic impurities. Of special significance is the fact that the reagent, LIX-64 was developed by combining the technical requirements of a specific problem in hydro-metallurgy with theoretical organic and physical chemical principles.

Jan 1, 1967

By Truman Aldrich

THE Clinton group of the Silurian holds the red or fossiliferous ore; its outcrops have been mapped by the State or U. S. Geological Survey. This group is from 100 to 500 ft. thick in Alabama. There are places where it is entirely missing (doubtless islands in the Silurian Sea). In Etowah County, in part of Greasy Cove and vicinity, the upper seam is a coral reef impregnated with the red ore; in this same county, step, faults bring up the ore in three or four separate ridges practically parallel. In Blount County and on Raccoon Mountain, the ore runs under the carboniferous rocks and outcrops in the valleys. In examining some bore holes made in drilling for oil, the writer found the Clinton group continuing under the Warrior coal field wherever the drill has gone deep enough. It demonstrates the possibility of a source for red ore not seriously thought of until lately. The following bore holes made principally for oil, given in Bulletin No. 22, Geological Survey of Alabama, show the presence of either ore or red rock, and suggest vast resources yet to be outlined and developed for ore in the future. The locations are given by number on the map. Hole No. 1 was drilled 6 miles southeast of Russellville, Franklin County, by the Woodward Oil & Gas Co. It passed through 160 ft. of Clinton, but only a small show of red ore was found at 1280-1400 feet. A test well, No. 2, drilled near Atwood, Franklin County, in section 26, township 8, range 14, penetrated the Clinton at 1608 ft. and found 38 ft. of limy red rock, also 8 ft. of some blood red ending at 1820 ft., making 46 ft. of red rock in all. It is reported that some good ore was cut through but this work was done by a churn drill. The hole was continued by diamond drill from here. At least 400 ft. of the formation was classified as Clinton.

Jan 10, 1924

By H. B. Bell, P. C. Lidster

A study has been made of the use of ThO2-Y2O3 solid electrolytes to determine activity of chromium in Fe-Cr and Ni-Cr alloys in the temperature range 1300° to 1700°K. This method has been shown to give results which agree with the best vapor pressure measurements. SEVERAL investigations1"5 have been made of chromium activities in Fe-Cr alloys. Most of these have been made by vapor pressure measurements using knudsen cell techniques while one has been made using gas equilibration with H2/H2O gas mixtures. In the present investigation electromotive force measurements have been made on this system using a thoria yttria solid electrolyte. This system was -chosen to establish the technique of measurement at low oxygen potentials, before extending it to Fe-Ni-Cr alloys. The cell used was Pt Cr • Cr2O3 ilThO2 • Y2O3 llalloy • Cr2O3 IPt Since the oxygen pressure of the chromium-chromic oxide mixture lay in the range 10"19 to 1027 atm in the temperature range investigated, thoria yttria electrolytes were used. It was soon found during the investigation that considerable care was required to prepare satisfactory electrolytes and a study was made to find the best method of preparing pellets of TI1O2-Y2O3 solid solution of as near theoretical density as possible. Various compositions in the range 2 to 15 mole pct Y2O3 were studied but the experimental measurements were made with electrolytes containing 4 to 5 pct Y2O3. The method of preparation finally adopted was to use thorium oxalate and yttria as raw materials. The thorium oxalate was decomposed at 900°C for 6 hr to give a reactive powder. This powder was then mixed with the appropriate amount of yttria and ground in an agate mortar for about 4 hr. The powder was moistened with absolute alcohol as a lubricant and pressed in a metal die at a pressure of 7 tons per sq in. The pellets were then heated at 1100°C for 24 hr followed by 24 hr at 1250°C. After this firing cycle the material was reground and repelleted and again fired at 1100° and 1250°C followed by heating for 7 days at 1600°C. It was found in later experiments that a further firing of 4 hr at 2000°C improved the density further and gave pellets of only 2 pct porosity. After firing, the pellets were polished on emery paper and finally with the 2 µ diamond paste. The polishing was followed by a final firing of 24 hr at 1500°C. Investigation showed that this final treatment minimized reaction between the electrolytes and chromium oxide. It was believed that this was because of a lowering of the surface energy of the electrolyte surface. Two types of investigation were carried out to check that the pellets were satisfactory oxygen ion elec-

Jan 1, 1970

By Earl Oliver

Dean Roscoe Pound, of Harvard Law School, in addressing the A.I.M.E. Petroleum Division on Feb. 22, 1934, said, "When you are able to work out a program that is mechanically feasible, that is economicaIly advisable, and which seems in your judgment, which is just as good as that of anyone, to be politically wise, you will not have very much trouble in the end in inducing the courts of today to find that it is legally sound." The purpose of this paper is to show: first, legal conditions necessary to promote conservation and stabilization; and second, to suggest operating procedure when those legal conditions are established. The proposal is mechanically feasible and economically advisable. A growing public understanding should make it politically wise. The disappointing progress in the development of conservation and stabilization can be attributed to the lack of two legal concepts as integral parts of oil and gas law; i.e., (1) a practical substitute for the capture rule, (2) collective ownership control for the individual oil and gas pool. When these two concepts are established on an equitable basis, conservation and stabilization procedure will become a comparatively simple process, more or less automatic in its adaptation and operation. Establishing these concepts is the function of the law-making agencies and might well be left to them for discussion except that the mechanical processes that give them form and substance must first be developed by the engineer. A Substitute for the Capture Rule Much has been written on these subjects, but the most concrete statement that has come to the attention of this writer is the following from an article by Charles G. Haglund in the Kentucky Law Journal of May, 1934: The Oxford1 case is not only authority for the proposition that it is competent for the legislature to modify the old property law of capture with respect to oil and gas but that it may also delegate such authority to a subordinate body.

Jan 1, 1935

By Arnulf Muan, R. E. Johnson

Equilibrium CO2 /CO ratios of a gas phase coexisting with selected oxide phase assemblages of the system CaO-"Fe0"-SiOz and vnetallic iron have been determined at 1080°C. The data obtained are used to calculate activity-conzposition relations for metasili-cute, orthosilicate, and CaO- "FeO" solid solutions, and to determine a new value for the free energy of formation of C&S&0,. The metasilicate solution is practically ideal, whereas large deviations from ideality exist in the othe,r two solid solutions. BECAUSE of the geochemical and metallurgical importance of the oxides CaO, "FeO", and SiOz, the system CaO-"FeO"-SiO2 has been the subject of several experimental studies during the past 30 years. Following the delineation of phase relations at liquidus temperatures by a group of investigators at the Geophysical Laboratory of the Carnegie Institution of Washington in 1933,1 Chipman and associates in the early forties2,3 determined activities of FeO in liquids of this system. Since that time, many attempts have been made to interpret the data of Chipman et al. in terms of the constitution of the silicate liquids and the interaction parameters among the various constituents of the system (see for instance papers by Richardson4 and by Flood and coworkers5). One of the assumptions made in some of these interpretations4 is that the binary silicate systems CaSiO3-FeSiO3 and CazSi04-Fe2SiO4 mix ideally in the solid state. The objective of the present study is to provide experimental data on activity-com position relations in solid solutions of the system CaO-"FeO"-SiO2. Such data will contribute toward an understanding of the thermodynamics of silicate solid-solution phases in general, and will serve specifically to confirm or refute some of the assumptions made in interpreting liquid slag behavior. PREVIOUS WORK Phase relations in the system CaO-"FeO"-SiO2 in contact with metallic iron were determined by Bowen, Schairer, and Posnjak,1 and additional phase-equilibrium data for this system have been presented by Allen and snow.' A reproduction of the most up-to-date phase diagram for this system is shown in Fig. 1.7'8 Of particular interest in the present investigation are the relations among the various crystalline phases slightly below the lowest solidus temperature in the system, as shown in Fig. 2. The present work will be concerned primarily with some of the composition

Jan 1, 1968

By E. T. Turkdogan, B. B. Rice

Desulfurization of limestone during and subsequent to calcination has been investigated using U.S. Steel's Rogers City quarry-Michigan limestone cut to 25-30-mm diam spheroidal shapes. The experimental observations indicated that the sulfur present as iron pyrite in commercial limestone is oxidized partly to SO, during calcination and partly converted to sulfides (FeS, CaS) and CaSO4. If calcination is carried out under oxidizing conditions, most of the sulfur is converted to CaSO4, which can be removed from burnt lime readily in CO,-CO mixtures, the higher the CO content the faster is the rate of reaction. In the 30-mm-diam spheroids gas diffusion in the pores of limestone and burnt lime is fast relative to rates of the desulfurizing reactions. Over the temperature range investigated, e.g., 850° to 1200°C, there is internal desulfurization.

Jan 1, 1974

By I. R. Kramer

The delay time for single crystals of iron, zinc, and pre-strained aluminum was measured under conditions of high-speed deformation. The delay time of aluminum was found to be affected by the orientation of the crystal. Under the dynamic conditions employed, tile calculated "activated volume" term appears to be very small for the three metals studied. IN a previous paper,1 it was shown that under dynamic testing conditions at 78° K, there was a delayed yield in single crystals of aluminum and copper which had been cold-worked prior to testing. The experimental results also indicated that the delay-time effect was not due to the interaction of dislocations with impurity atoms or vacancies, but rather to a dislocation-dislocation interaction since aluminum which has not been prestrained shows no delay-time phenomenon. In this paper, some data are reported on the effects of orientation on the delay time of aluminum single crystals; the delay time of zinc single crystals saturated with nitrogen and the delay time of iron single crystals also were measured. EXPERIMENTAL PROCEDURE Aluminum (99.997 pct) and zinc (99.999 pct) crystals, 1/2 in. in diam and 8 in. long were grown by the Bridgman technique. The iron single crystal was supplied by Dr. R. Maddin. The zinc crystals containing nitrogen were prepared by melting high-purity zinc in a graphite crucible and the nitrogen was introduced by additions of ammonium chloride. The liquid zinc was then drawn up into glass tubes of 1/2 in. diam and allowed to solidify. The rods were cooled to room temperature before the transfer to the mold for conversion into single crystals. The orientation of all specimens was determined by the Laue' back-reflection technique, Fig. 2 and Table I. To prepare for the delay-time measurements, the crystals were cut with a fine jewelers saw and the ends carefully machined. The specimens then were electrolytic ally polished to remove the cold-worked metal, mounted in a special fixture and hand-lapped. As a final step, the crystals were annealed in evacuated tubes. Specimens of aluminum crystals, Nos. 24 and 26, were compressed 0.5 and 2 pct, respectively, in the direction of the later impact. The zinc specimens were aged at 50°C for 15 min, In the case of iron, only two specimens could be obtained. To obtain sufficient data, it was necessary to resort to a reaging treatment. After each delay-time test, the specimens were aged at 65° C for 100 min. This treatment, according to Clark,2 is sufficient to restore the original delay time. It is believed that although the specimens were plastically deformed approximately 10-4 pct, after each test the delay-time values are reliable. The delay-time measurements were made in an apparatus similar to that described previously.' Single crystals approximately 1 in. long and having a diameter of 1/2 in. were placed in a pendulum which consisted of a bar 1/2 in. in diam and 8 ft long, designed with a crystal holder to accommodate the specimen at low temperatures. The crystal was held at a position 2 ft from the front part of the pendulum. This portion of the apparatus was supported on a fine molybdenum wire. A projectile bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on

Jan 1, 1962

By F. X. Spiegel, D. Bardos, Paul A. Beck

Ti6NileSi7)G is known to be cubic, with 116 atoms in the unit cell. In the present work four new G sili-cides were found with other transition elements and five G germanides. The titanium-group elements are very efficient in forming G phases. The vanadium -group elements are somewhat less efficient, and the chromium-group elements do not form any. Cobalt can replace nickel in most cases, but it is somewhat less efficient. Iron was not found to form any G phases. Germanium is somewhat less efficient than silicon. The (TiNiSi)E phase has been previously identified by Westbrook. However, its crystal structure has not been determined. In the present work the E phase was found to have an orthorhombic unit cell with lattice parameters a. = 7.02, bo = 5.18, co = 11.11A. A large number of other E phases were found at the same stoicheometric ratio in ternary systems of silicon and germanium with transition elements. Lattice parameters similar to those for TiNiSi were measured. The number of atoms per unit cell is estimated at 30 to 36. The vanadium-group elements are somewhat more efficient in forming the E phase than the titanium-group elements. Chromium-group elements were not found to form any E phases. Cobalt is somewhat less efficient than nickel, and iron is less efficient than cobalt. Germanium is not as efficient as silicon. ThE ternary silicide designated as G-phase was first identified by Beattie and versnyder1 and by Beattie and Hagel2 at the approximate composition TiNi2Si. Westbrook et al.' gave the composition as Ti2Ni7Sis. This phase was found to be fcc with a. = 11.201A and 116 atoms per unit cell. Beattie4 and more recently independently Hladishevskii, Kripyakevich, Kuzma, and Teslyuk5 were able to show that this structure is isotypic with MgeSi7CuLe and Th6Mn23. The latter structures had been determined by Florio, Rundle, and snow,' Nagorsen and Witte,7 and Bergman and Waugh.8 According to the crystal structure, Ti8Ni6Si7 may be considered as the ideal composition. The Russian investigators5 identified six additional ternary phases isotypic with Ti6Ni6Si7, in which titanium is replaced by Mn, V, Nb, Ta, Zr, and Hf, and one, namely MneNil6Ge7, in which germanium replaces silicon. They also found that Cr6Ni6Si7, which does not occur as a ternary phase, can be stabilized by replacing 1 at. pct of the Cr by V, Mn, or Ta. Another ternary silicide was found by Westbrook et al.3 at the composition TiNiSi, and it was designated by them as the E phase. The crystal structure of this phase has not been deter-

Jan 1, 1963

Albin, B. R. Billings, Mont. '28 Amster, Nathan L 25 Broad St., New York, N. Y. '28 Bache, Jules S 42 Broadway, New York, N. Y. '28 Barrett, C. P 5338 Harper Ave., Chicago, Ill. '28 Baum, Frank G., Cons. Hydro-Electric Engr Cassel, Shasta Co., Cal. '28 Bayless, William S Russ Bldg., San Francisco, Cal. '28 Bean, Louis H., V.P., Dwight P Robinson & Co., Inc. 125 E. 46th St., New York, N. Y. '28 Beatty, Ross J 1105 First National Bank Bldg., Chicago, Ill. '28 Benwell, Oswald F 110 Gilpin St., Denver, Colo. '28 Beymer, Albert S., V P., Keystone National Bank Pittsburgh, Pa. '28 Blumenthal, Hugo 44 Pine St., New York, N. Y. '28 Boettcher, Charles Ideal Cement Bldg., Denver, Colo. '28 Bowlus, Thomas H Iola, Kans. '28 Brown, Colvin B. .. Chamber of Commerce, Washington, D. C. '28 Burt, Maxwell Struthers Southern Pines, N. C. '28

Jan 1, 1923

By R. J. Watson, A. H. Juch

About half a million sucker-rod pumps are installed in oil wells in the U. S. alone. In Venezuela, too, the system is widely used; some 5,000, or 90 percent, of Cia. Shell de Venezuela's wells produce a total of 400,000 BOPD by this method. Most of the crude pumped is viscous, gassy and contains relatively small amounts of free water. API gravities vary from 90 to 16O; dead oil viscosities vary from 10 to 10,000 cp at the pump; and GOR's range from 100 to 2,000 cu ft/bbl. Pumps are set at depths ranging from a few hundred to 6,000 ft; the average setting depth is about 2,500 ft. From the literature, it appears that although recent years have seen significant progress toward understanding the rod pumping system as a whole, relatively little attention has been paid to those key items, the sucker-rod pump and the subsurface gas separator or gas anchor. Perhaps because of proration in the U. S., pump manufacturers have seemingly concerned themselves more with the durability of their product, achieved mainly through robust design and metallurgical know-how, than with its working efficiency. In 1963, CSV commenced a major rehabilitation and expansion of its heavy oil fields along the Bolivar Coast. The advent of the more efficient gravel-packed completion and of large-scale thermal recovery (mainly steam soak) operations resulted in well potentials *Now with B. I. P. M., The Hague, The Netherlands. greater than pump capacities. Hence, an urgent need arose to improve over-all pump efficiencies and to attack those special problems related to the production of both the extremely viscous and the hot, steam-laden crudes that formed an increasing proportion of the total stream. There followed a detailed investigation and testing program, carried out in close cooperation with a major pump manufacturer. This culminated in the introduction to the oil industry of a new line of sucker-rod pumps. Early Investigations and Experiments Field Tests Extensive field tests were carried out in three primary Bolivar Coast wells with an in-situ dead oil viscosity ranging from 400 to 6,000 cp. In these installations provision was made to (1) monitor bottom-hole pressures below, in and above the pump by means of pressure transducers, and record casing- and tubing-head pressures continuously; (2) measure accurately the annulus gas, as well as measure the tubing gas and liquid production from the well; (3) take special PVT samples of the well fluid; (4) measure power consumption of the prime mover; and (5) measure the rod loads at the polished rod. A typical test installation is illustrated in Fig. 1. It was established from the pressure transducers that with viscous oils, there is considerable flow resistance across the pump and gas anchor assembly. Pressure surges were observed over each pump cycle,

Jan 1, 1970

By R. E. Old

Through the use of pressure and production records, formation properties and bottom-hole sample data, the performance of an oil reservoir may be studied analytically to define and evaluate the natural forces acting on and within the reservoir. Use is made of material-halance methods and the equations for natural water encroachment. to estimate reserves. Methods for calculation of pressures are given. A study of the Jones sand, Schuler field, Arkansas, has been made and is given here to illustrate the value of the methods discussed. Introduction With the decreasing rate of discovery of new oil reserves, attention is necessarily focused on the efficient development, evaluation, and production of existing reserves. From the nation's viewpoint, the necessity of conserving resources is obvious. From the operator's viewpoint, the problem is to lengthen the period of profitable operation, in an attempt to increase the return on his investment. To do this the operator must take advantage of the natural forces acting on and within the reservoir. Natural water encroachment, the nemesis of profitable operation in the past, can be and is being harnessed to produce a greater oil recovery during the stage of flowing production. Proper evaluation of water encroachment rates and a fuller under- standing of reservoir behavior dictate the appropriate production procedures. Complacency in hit and miss production is obsolete. Oil production must and will approach the efficiency of other businesses, such as manufacturing. A manufacturer will not place an article on the market until he has fully investigated the processes involved, additional investment in equipment, costs of production, and expected profits. These may be modified by actual experience at a later date, but at least he begins with an idea of expected return. It is just as logical that an oil operator should investigate these same factors during the development and the early period of production of an oil reserve. The complexity of the problems existing in oil reservoirs should not be underestimated. Conversely, they should not be regarded as insoluble. Many completely defy solution, but there are others that can be solved completely or attacked intelligently to yield approximate results. The petroleum engineer has many tools, both figuratively and literally, at his disposal. Physical data such as core analyses, electrical logs, bottom-hole sample analyses, and bottom-hole pressures are accumulated extensively. Advances in the analytics of fluid flow have kept pace with the advances in measurement of physical data. It is the purpose of this paper to show how some of these records may be analyzed to define certain phases of reservoir behavior.

Jan 1, 1943

By R. E. Old

Through the use of pressure and production records, formation properties and bottom-hole sample data, the performance of an oil reservoir may be studied analytically to define and evaluate the natural forces acting on and within the reservoir. Use is made of material-halance methods and the equations for natural water encroachment. to estimate reserves. Methods for calculation of pressures are given. A study of the Jones sand, Schuler field, Arkansas, has been made and is given here to illustrate the value of the methods discussed. Introduction With the decreasing rate of discovery of new oil reserves, attention is necessarily focused on the efficient development, evaluation, and production of existing reserves. From the nation's viewpoint, the necessity of conserving resources is obvious. From the operator's viewpoint, the problem is to lengthen the period of profitable operation, in an attempt to increase the return on his investment. To do this the operator must take advantage of the natural forces acting on and within the reservoir. Natural water encroachment, the nemesis of profitable operation in the past, can be and is being harnessed to produce a greater oil recovery during the stage of flowing production. Proper evaluation of water encroachment rates and a fuller under- standing of reservoir behavior dictate the appropriate production procedures. Complacency in hit and miss production is obsolete. Oil production must and will approach the efficiency of other businesses, such as manufacturing. A manufacturer will not place an article on the market until he has fully investigated the processes involved, additional investment in equipment, costs of production, and expected profits. These may be modified by actual experience at a later date, but at least he begins with an idea of expected return. It is just as logical that an oil operator should investigate these same factors during the development and the early period of production of an oil reserve. The complexity of the problems existing in oil reservoirs should not be underestimated. Conversely, they should not be regarded as insoluble. Many completely defy solution, but there are others that can be solved completely or attacked intelligently to yield approximate results. The petroleum engineer has many tools, both figuratively and literally, at his disposal. Physical data such as core analyses, electrical logs, bottom-hole sample analyses, and bottom-hole pressures are accumulated extensively. Advances in the analytics of fluid flow have kept pace with the advances in measurement of physical data. It is the purpose of this paper to show how some of these records may be analyzed to define certain phases of reservoir behavior.

Jan 1, 1943

By O. M. McRae

The Courtland-Gleeson area is in Cochise County about 15 miles east of Tombstone in southeastern Arizona. Rocks exposed in the area range in age from Pre-cambrian to Quaternary. The Precambrian is repre-sented by the Pinal schist. Paleozoic rocks include the Cambrian Bolsa quartzite and Abrigo limestone, Mississippian Escabrosa limestone, and the Permo-Carboniferous Naco Group limestones. Rocks believed to be of Triassic and/or Jurassic age include the Copper Belle monzonite porphyry, Turquoise granite, and Gleeson quartz monzonite. The Cretaceous is represented by andesitic volcanics and various sedimentary rocks. Tertiary rocks include the intrusive and extrusive Sugarloaf quartz latite porphyry and numerous dikes of various rock types. Quaternary conglomerates cover the northern and eastern part of the area. The geologic structure is extremely complex. All rocks as old as early Tertiary have been involved in either tilting, normal faulting, high angle reverse faulting, imbricate thrusting or folding and overfold-ing. Major deformation was initiated during the first half of the Tertiary. Northeast-southwest compres-sional forces caused thrust plates containing lower Paleozoic rocks to override Cretaceous rocks. Subsequently, two large slide blocks of lower Paleozoic rocks, acting under the influence of gravity, moved eastward. The imbricate structure and the gravity slide blocks were then broken by late Tertiary normal faults. INTRODUCTION The Courtland-Gleeson area, or Turquoise Mining District, has long been recognized as an area of extreme structural complexity. Gilluly 2 referred to the entire district as a "gigantic thrust breccia". In 1962, Bear Creek Mining Company completed a two year program of detailed geologic mapping supported by exploration drilling. The purpose of this paper is to present some of the results of this investigation and to provide a structural interpretation based on these results. The geologic map that accompanies this report is generalized and shows only the major and significant features. The area was initially mapped on aerial photographs on a scale of 1 in. equals approximately 500 ft. These data were transferred to a planimetric base using a vertical sketch master. LOCATION The Courtland-Gleeson area is in central Cochise County, about fifteen miles east of Tombstone, and about twenty-two miles northeast of Bisbee in southeastern Arizona (Fig. 1). The area is readily accessible over graded gravel roads from both Tombstone and Elfrida. GENERAL GEOLOGY Rocks exposed in the area range in age from Pre-cambrian to Quaternary. wilson3 and Gilluly2 have published very detailed descriptions of the principal rock units exposed in the area. Only a summary description is provided in Table I. A great number of previously unmapped narrow Tertiary dikes and small irregular masses of hornblende andesite porphyry, lamprophyre, and aplite intrude the Gleeson quartz monzonite in the western part of the map area. The scale of the map prohibits showing them. The aplite dikes are related to, and bear the same structural relationships as, the Sugarloaf quartz latite dikes found in this area. For that reason, and because both the hornblende andesite porphyry and the lamprophyre are post-mineral and post-thrusting, their omission from the map is not considered significant. Because so many of the contacts in the district are fault contacts, because bedding faults appear to be prevalent but are difficult to recognize and map, and because igneous intrusions are so common throughout the sedimentary section, it is virtually impossible to measure an exact total thickness of any of the sedimentary rock units. Nevertheless, neither the field mapping program nor the diamond drilling provided any basis for suspecting that the thicknesses of the sedimentary units are significantly greater or less than what might be inferred from surrounding districts.

Jan 1, 1967

By F. L. Ruhlman, Max C. Eastman

The termination of the recent war marked a major changc in the oil-field operations at. Elk Hills. Production was greatly curtailed, various experimental production projects were started, and a long-range exploratory program was inaugurated. Production was reduced from the wartime peak of 65,000 bbl per day to the current rate of about 8ooo bbl per day in order to maintain an available source of crude that can be drawn upon during a national emergency. The existing production rate is deemed essential to carry on the experimental production projects. These projects are being conducted to determine the best methods and means of maintaining the Reserve, shut in, but in a state of readiness to produce the maximum quantity of oil in the most expeditious manner. Projects now being investigated include: (I) protection of surface equipmerit; (2) repair of wells that might damage the reservoir; (3) gas injection; (4) water eneroachment, (5) gravity drainage. An exploratory program is being carried on to determine the amount of recoverable oil in the unexplored portions of the Reserve. The Shallow-zone exploration is practically completed, but owing to the complexity of the Stevens structure and the magnitude of the oil discoveries in the Stevens, exploration will probably continue in that zone for another two years. Introduction Summary of Development History of Elk Hills Although a detailed history of Elk Hills oil field is presented in various publications,1,2 a summary of its unusual development and production history will be given in order that the present problems may be more readily understood. The first development that resulted in commercial production was in the central part of the Reserve. The first well, Hay No. I, in sec 36-R,* was completed in January I9I9, and was soon followed by 37 Others in the same general area. It is commonly referred to as the Hay-Carman area and was shut in in stages from 1925 to 1934 as a result of litigation regarding the title to the land. Not being highly producti,, only about 6½ million barrels of oil with a large volume of gas was produced from the area prior to the shutdown. Shortly after the start of the development of the Hay-Carman area, drilling was started 6 miles east in sec 36-S' Tupman NO. I came in for 5000 bbl per day early in I92o, It was followed by more than 200 others in the next few years, and the field became one of major importance. Produc-

Jan 1, 1949

By O. G. Lellep

Modern shaft kilns in Europe are fully mechanized and burn cement of acceptable quality at 700,000 Btu per bbl and lime at 3.2 million Btu per net ton. Rotary kilns for cement have increased in thermal efficiency by using exit gas heat for preheating incoming raw material and by recovering heat from outgoing clinker in air-quench coolers. The dry process Lepol or ACL kiln has the lowest fuel consumption, 580,000 to 630,000 Btu per bbl, and very low dust loss, about 1 pct weight of clinker. The Holdebank-Gygi system reaches 720,000 Btu per bbl. The calcinator kiln for the wet process consumes 1.1 million Btu per bbl. IN every country economic circumstances prescribe the method used to produce a commodity at lowest cost. In Pennsvlvania a man's wages for working 4 hr buys a ton of coal wholesale; in Germany a laborer must work 40 hr, or ten times as long. In western Europe, therefore, conservation of fuel is of primary importance, and recent practices of burning lime and cement differ from those employed in the United States. 'This Paper presents data collected during a trip through western Europe in 1953. Considered uneconomical, shaft kilns for burning

Jan 1, 1955