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By M. H. Forester, John D. Cooner

ALTHOUGH the unmined anthracite will last for approximately 150 years, most of the thicker and cleaner coal beds have been almost entirely first-mined and pretty well robbed, leaving much of the present and future production to come from thin and dirtier beds. Herewith is a section of one of the dirty beds being mined in the Wyoming region [ ] This section shows that 45.8 per cent of the bed is made up of impurities and that the 45 in. of coal in the bed is in five benches, the thickest of which is 19 in. In some localities of the anthracite region there are 14 beds of minable coal. Orderly and proper mining of the coal makes it necessary to rob or second-mine--almost all beds have already been first-mined-in sequence from the top downward. Therefore the robbing of the few remaining portions of the thicker and cleaner beds is in many instances being held up by the mining of the overlying thin and dirtier coal beds. Impurities Impurities consist of fire clay, slate, rock, and bone. The latter, which is black, contains 40 to 60 per cent carbon and often resembles good coal. In some beds there are also bands of "blue" coal, which, as the name implies,

Jan 1, 1950

By Jouko O. Kallioinen

The control of zinc flotation at Outokumpu Oy's Pyhasalmi and Vihanti mines is described. At Pyhäsalmi the zinc flotation circuit is partially open. Zinc and other metal assays of pulp flows are measured and direct assay control of concentrates in various flotation steps is adopted. Assay control is carried out by adjusting flotation air and pulp levels. Optimization with copper sulphate ensures high Zn- recovery and minimum copper sulphate consumption. A froth depth monitor is used to measure froth quality. At Vihanti the zinc flotation takes place in closed circuit. The most important control loop is the Zn-assay control of rougher concentrate by adjusting flotation air. The quality of froth is measured indirectly and thus copper sulphate consumption is altered. The circulating load is controlled also by flotation air in the three cleaning steps. The comparison of the control strategies shows that a more sophisticated control is adopted at Pyhäsalmi because the selective flotation of this massive sulphide ore is considered to be difficult. The control strategy includes numerous tests performed by the computer and control algorithms developed for the case. The control targets of the two zinc flotations described are also different: At Pyhäsalmi Zn-assay control of final concentrate including copper sulphate optimizing, at Vihanti the control of circulating load and Zn-assay of rougher concentrate.

Jan 1, 1984

By J. J. Calaman, D. H. Fleming

DURING 1950 the jet-piercing process was used commercially in the piercing of primary blast-holes in magnetic taconite at the preliminary taconite plant of .the Erie Mining Co., Aurora, Minn. The Erie Mining Co. purchased a jet-piercing machine and associated equipment in 1949, and the machine has been in operation since its installation in the summer of that year. An overall view of the pit with the JPM-1 jet-piercing machine in operation is shown in Fig. 1. During three months of 1949 and continuously since February 1950, production piercing took place under all pit conditions. By the end of October 1950, a total of 15,000 linear ft of hole had been pierced in an open pit handling an average of 1200 to 1800 tons of crude a day in one 8-hr shift. While it is recognized that this output does not approach the millions of tons a year planned for the developing Minnesota taconite projects, the machine as a unit has been operating under conditions probably more adverse than those that eventually will be encountered in the large operations. This pilot operation has permitted evaluation of the piercing problem in the full-scale taconite plant. This paper describes jet-piercing process funda- mentals, important features of the latest jet-piercing burners and machine, actual piercing results obtained, and new developments that give promise of materially increasing overall process efficiency. To produce the blasthole, jet-piercing utilizes thermal energy, as contrasted with the application of mechanical energy in churn drills and jackham-mers. The heart of the process may be termed a tailored flame produced by a rocket-type burner, thermodynamically similar in every respect to that of the giant rockets being developed for military purposes. The heat release in the combustion chamber of the burner is about 50x10' Btu per cu ft per hr as compared with 5x10' for most modern steam generators.* Combustion of liquid petroleum fuels (kerosine, diesel oil, or No. 2 fuel oil) with gaseous oxygen in the burner chamber at pressures of 100 to 200 psi results in temperatures of about 4300°F. Expansion of the hot combustion gases through divergent nozzles produces high-temperature supersonic jets having measured velocities of about 6000 fps. Impinging the flame jets on rock causes a thin surface layer to expand and break away from the base as a result of the thermally induced stresses. This spalling action is aided further in chert and quartzite by the 0.82 pct volume change resulting from the 6 to p quartz inversion at 1066"F.t The dynamic action of the jets whisks the spalled rock

Jan 1, 1952

By Bennett R. Bates

Nowhere in the world has cone classification in closed-circuit grinding with tube mills reached as high a state of development as on the Wit-watersrand. In the development of the Far East section the necessity of fine grinding to obtain satisfactory residues gave rise to a situation with which the cone could cope only at a great sacrifice in efficiency of tube-mill grinding. H. A. White1 recognized the limitation of the cone in his study of the theory of tube milling as early as 1915, but it was not until Ewing, Davis and Willey2 carried out their tests at Springs Mines during 1920 that the advantages of mechanical classifiers were demonstrated. During the fall of 1924 the writer supervised a series of tests with Dorr classifiers undertaken by Mr. White, Consulting Metallurgist, at the mill of the Geduld Proprietary Mines, Ltd., Dersley, Transvaal (Far East Rand). The importance of classification to obtain efficient tube-mill grinding was thoroughly demonstrated. The installation of classifiers of the above type that followed the test confirmed the results of the experimental work. Tests with Cones, Straight Type and Bowl Classifiers The test at the Geduld mill was made to determine the relative grinding efficiency of a tube mill when grinding in closed circuit with cones, straight type Dorr classifier and Dorr bowl classifier. The efficiency of a tube mill, as expressed in this article, is based on the tons of minus 200-mesh material produced by the mill. The efficiency is also expressed in terms of tons of minus 90-mesh material produced by the mills to correspond to the standard practice on the Witwatersrand. The results given for the performance of the tube mills grinding in closed circuit with cones (Fig. 1) were taken from previous tests carried

Jan 1, 1926

By N. F. Foster

The use of piezoelectric semiconducting materials for the fahrication of ultrasonic transducers has raised the upper fundamental frequency limit for transducers from about 200 mc to above 10 kmc, Several types of semiconductor transducer configurations have been proposed and examined experimentally. Depletion-layer transducers have been made and operated at frequencies below 1 kmc hut they appear to he better suited for operation at considerably higher frequencies around 10 knzc. Diffusion-layer transducers have been made and operated in the range 50 to 1000 mc and have exhihited considerably improved conversion losses and bandwidths compared with other transducers available in the frequency range. A variety of novel structures are possible using these new types of transducers, some of which could lead to substantial advances both in research and in the fabrication of ultrasonic delay lines and memory elements. THE field of ultrasonics today spans some five decades of the frequency spectrum from the audible to the kmc range and finds applications ranging from fundamental research into the atomic structure of matter to the degreasing of machine parts. To cover this wide range it has been necessary to develop a great many types of ultrasonic trandsucers utilizing a variety of materials and physical phenomena. The first ultrasonic transducers were made during World War I for a submarine-detection system. They consisted of plates of single-crystal quartz bonded between metal plates and were one of the first applications of the phenomenon of piezoelectricity discovered nearly 30 years previously. Despite the many advances which have been made in transducer technology, piezoelectric transducers using single-crystal quartz are still used almost exclusively for application above about 30 mc. Transducers at these frequencies are normally made in the form of thin quartz plates which are then bonded onto the medium in which the ultrasonic wave is to be propagated. The crystallographic orientation and geometry of these plates determines the type of wave generated and the way in which the efficiency of the electromechanical conversion varies with frequency. Analysis of the design parameters shows1 that the frequency of maximum efficiency (the fundamental or resonant frequency) is that frequency at which the transducer is approximately half the wavelength of the ultrasonic wave in the material. As the frequency increases, the ultrasonic wavelength, and therefore the optimum transducer thickness, decreases and in practice the fabrication of quartz transducers with fundamental freauencies above 100 mc becomes extremely difficult due to the extreme thinness required. For frequencies above 100 mc quartz transducers can be used in overtone-mode operation, and for very high frequencies (500 to 24,000 me) a technique using a quartz rod inserted in a high-Q microwave cavity4 is available. These techniques, however, exhibit comparatively low fractional bandwidths and rather poor conversion efficiencies. The present trend in ultrasonics is towards high frequencies and greater bandwidth to allow the use of shorter pulses which can give increased discrimination in radar-system delay lines and greater storage capacity in computer applications. The increasing demand for more efficient transducers with greater bandwidth

Jan 1, 1964

By H. F. Moore

DURING the last six years, there have been many extensive investigations of the fatigue of metals. The major work of 'these investigations has been the determination of constants for fatigue strength of wrought ferrous metals; but during the past year or two there have become available considerable test data on the fatigue strength of certain nonrferrous metals, including copper, brass, bronze, nickel, copper-nickel alloys, aluminum and aluminum alloys, magnesium and magnesium alloys. It is not proposed to give here extensive quantitative tables of test results; for such tables, reference is made to the published data of various laboratories. The following general conclusions, however, seem to be fairly well established: 1. The phenomenon known as "fatigue" of metal really a progressive fracture of metals. A minute (probably submicroscopic) crack is formed in the metal, the internat stress, is intensified at the ends' of the crack, and under successive applications of load the crack spreads like a minute hacksaw cut until there is not enough sound metal left in the cross-section of the piece to stand the load. applied, and then failure occurs suddenly. 2. For wrought ferrous metals, there is .a limiting intensity of stress (as computed by the ordinary formulas of mechanics of materials) below which, a metal is able to withstand an indefinitely large number of repetitions of stress without failure. This limiting stress is known as the "endurance limit or the fatigue limit.? For reversed flexure, the endurance limit for. wrought ferrous metals is usually not far from 50 per cent. of the ultimate tensile strength.

Jan 1, 1925

By Y. Kondo, S. Yamazaki, Z. Asaki

Thermal deco7nposition of Pyrite particles in a fluidized bed with inert gas stream was studied. Assuming that heat transfer from the surroundings to the fluidized particles controls the overall decomposition rate, rate equations for the batch process and for the continuous process were derived. In the batch experiment, a linear rate equation satisfies the experimental results and the overall heat transfer coefficient calculated from the rate constant agrees fairly well with that obtained by Leva.l1 For the continuous process, two rate equations were derived, one on the assumption of complete mixing of particles and another on the upward piston flow of particles in a fluidized bed. The former holds for a bed containing a higher fraction of decomposed pyrite realized at lower feeding rates. The latter can be applied for a bed at higher feeding rates. Thus, segregation of particles in the fluidized bed was indicated at higher feeding rates. Bed temperatures also correspond to these conditions. ThERMAL decomposition of pyrite may be represented by Eq. [I]. The pressure of diatomic sulfur gas reaches 1 atm at about 690°C. The thermodynamics,' kinetics,2'3 composition, and properties3-5 of decomposed products of such a reaction have been studied. Pyrite is a very common sul-fide mineral and is often accompanied with other sul-fides. It is of basic interest in nonferrous metallurgy to clarify the behavior of pyrite in the pyrometallur-gical processes of sulfide minerals of metals such as copper, lead, zinc, nickel, and so forth. Interest in this reaction increased recently because of possible elimination of arsenic from pyrite in processing highly purified iron oxide pellets. Producing elemental sulfur from pyrite, instead of sulfuric acid, also aroused interest in this reaction. It is indicated that the thermal decomposition of solid particles, such as calcium carbonate, proceeds through three major sequential steps: heat transfer, interfacial chemical reaction, and mass transfer.637 It is known that the decomposed product of pyrite is very porous2, 3 and the diatomic sulfur gas evolved can easily escape through this layer of decomposed product. It depends upon the circumstances, therefore, whether the heat transfer to the interface within particles or the chemical reaction at the interface determines the overall decomposition rate. The enthalpy change in the decomposition of pyrite is about 33 kcal per mole FeS2 which is comparable to that of calcium carbonate. The decomposition of calcium car- bonate becomes more and more dependent on the rate of transport of heat when reaction temperature increases, such as occurs in a fluidized bed.6'7 It is reasonable to presume, therefore, that the thermal decomposition of pyrite, an endothermic process, carried out in a fluidized bed may be analyzed according to the heat transfer controlling model. This work intends, first, to propose a mathematical model that determines the overall rate in a fluidized bed for the decomposition process and, second, to investigate a few characteristics of the fluidized bed based upon the experimental results obtained. KINETICS OF THERMAL DECOMPOSITION IN A FLUIDIZED BED It is intended in this section to obtain rate equations for thermal decomposition of pyrite in a fluidized bed by assuming that the overall rate is determined by heat transfer from the surroundings to the particles. Both batch and continuous processes are considered. 1) Batch Process. To obtain the rate equation in the batch process, the following two additional assumptions are made. First, the temperature of preheated inert gas, tg, blown into the fluidized bed is assumed to be the same as the temperature of the fluidized bed, tf. Thus, no heat exchange occurs between the gas and particles in the bed and only the heat transfer from the reactor wall kept at tw to the particles is to be considered. Second, the decomposition is assumed to start at the outer surface of the particles and to proceed toward the center. At any given time during decomposition, undecomposed pyrite remains in the tori at a temperature: td. The decomposed shell is composed of FeS1+x whose outer surface is at tp Diatomic sulfur gas evolving at the interface is heated to tf during its escape through the decomposed shell. This is illustrated in Fig. 1. With the above-mentioned assumptions of heat transfer, we have:

Jan 1, 1969

By R. S. McFarland

OKLAHOMA, in 1924, recorded the largest single increase of any state; the total oil production for the year being 176,206,397 bbl. (Oil & Gas Jnl.), which gives an increase over 1923 of about 9 per cent. Oklahoma ranked second in total amount, California being first, and produced almost 25 per cent. of the total production of the United States. This gain in production is accounted for entirely by the rapid development, deeper drilling, and efficient management of productive areas known at the beginning of the year, for, due to the small number of wells drilled, few new pools were discovered and developed up to any important stage during the year. Three major pools, Burbank, Tonkawa and Cromwell, furnished 37 per cent. of the total production. Burbank led by a wide margin, having the largest production of any single pool; there was a steady increase in production until September. The close. development of the pools in Okfuskee, Seminole, and Hughes Counties, together with the new deep-sand production at Tonkawa and increased drilling operations in Osage County, accounted for the big increase shown during the year. In January, 1924, the shutdown movement and curtailment of production in Hewitt and Tonkawa, which had been effective during the year of 1923, were stopped. The shutdown movement and curtailment of operations in 1923 does not give a fair comparison with 1924, as undoubtedly a great deal more oil would have been produced in 1923 had it not been for these measures. The sensational developments during the year, which were certainly beyond the prediction of the oil industry, were the Cromwell field, which started the year with 10,478 bbl. for January and increased rapidly to 1,267,032 bbl. for. December, and the discovery of the Wilcox productions below 4000 ft. in the Tonkawa field in May, which by the end of the year had produced 11,650,000 bbl. In this connection, it can be safely said that 1924 was a banner year for the Wilcox sand series; it has been estimated that between 40,000,000 and 50,000,000 bbl. of the production for the year came from this sand. Although numerous Wilcox pools were opened throughout the state, the big Wilcox production came from. the Tonkawa and Stroud pools. Oklahoma's deepest well, the Kingwood Oil Co. No. 1 Barnett in the northwest corner of the northeast quarter of the southeast quarter of Sec. 7 T. 7 N. R. 10 E., Hughes County, was abandoned in January, at 5281 ft. with numerous good shows recorded, which have stimulated-further drilling in the locality.

Jan 3, 1925

PHILIP L. GILL, New York, N. Y. (written discussion*).There is one feature of the fire-refining of electrolytic copper which I believe should be mentioned when the relation of oxygen content to the "pitch" or "set" of refined copper is under discussion; that is, the segregation of impurities. Variation of "pitch" or "set" is frequently noted in castings of different shapes, cast at the same time from the same furnace, though the oxygen content remains identical. For instance, it is possible to cast two wire-bars in the same shaped molds from the same ladleful of copper, the one 2 in. thick showing a good level set, the other, 4 in. thick, being overpoled. Also, when two bars are cast of the same weight and at the same time from the same furnace, one bar in a copper mold at the proper temperature, the other in a mold that has been allowed to get overheated, the bar in the hot mold will show

Jan 8, 1918

By D. E. Wolfson, H. J. Gluskoter, M. R. Geer, John A. Harrison, H. F. Yancey, I. S. Latimer

When this chapter was prepared for the kst edition in 1942, continuous mining machines virtually were unknown, and hand loading in underground mines, which gave an opportunity to discard impurities, accounted for 55 percent of the production of bituminous coal and lignite as compared with the 1965 figure of 11 percent. Only 24 percent of the total production was cleaned mechanically, compared with the present (1965) figure of 65 percent. The amount of refuse discarded during preparation for the same period increased from 13 to 21 percent. Changes in the equipment used in the cleaning process were as follows: [ ] Unclassified nearly 8 percent. Data on the amount cleaned by flotation was not collected until 1960 when 1.8 million net tons was so treated. In 1965 this figure increased to 6.9 million tons. Although the great increase in mechanization and full seam mining has resulted in substantial increases in the impurity content of the raw coal as well as in a finer size consist, some phases of face preparation are still important, particularly the variability of the distribution and thickness of the interbedded impurities and the changes in the character of the roof and floor from place to place in the mine. Knowledge of these factors in relation to all phases of the mining operation, particularly selective mining, are still of importance to the treatment of raw coal in the preparation plant. The major characteristics of coal and impurities from the standpoint of mechanical cleaning are particle size composition, generally called size consist, density differences, the relative friability of the coal and of its associated impurities, hardness, and strength. Some of the other factors related to preparation are petrographic composition and rank. COAL PROPERTIES Rank Perhaps 95 percent or more of the coal cleaned mechanically is of bituminous rank. Only a very small tonnage is subbituminous and prac-

Jan 1, 1968

By C. E. Lesher

Low-TEMPERATURE carbonization needs no introduction to the literature on coal. This paper will attempt no review of that literature; it tells the story of the commercial development of one of the processes for carbonizing coal at so-called low temperatures, dealing with the technology and economics of the process rather than with the design of equipment. The process used is that covered by the patents of C. B. Wisner, with improvements and changes made by the Pittsburgh Coal Carbonization Co. The important and novel feature of the process is the phenomenon of making the product in ball form (Fig. 1). Melting coal dust into smokeless solid fuel in an apparatus as simple as a revolving cylinder of ordinary mild steel has been proved to be practical. Furthermore, it has been found that the process has a wide application, for by applying a knowledge of why and how this balling action is accomplished, the apparatus can be designed and adapted to treat any coal that has a certain minimum agglutinating property. The operating plant is 20 miles west of Pittsburgh, adjacent to the Champion preparation plant of the Pittsburgh Coal Co. The coal used is cleaned minus 3/8 -in- or finer sizes. The products are low-tem-perature coke, tar and tar products. Present capacity is 7000 tons per month of low-temperature coke and 140,000 gal, of tar. There is no surplus gas for sale, and none of the light oils are stripped from the gas. The coke is marketed in two sizes, 1 to 2 in. and 1 to 6 in., through retail coal dealers for domestic con-sumption in hand-fired furnaces, and for fireplace fuel. The smaller size is bagged by dealers. Crude tar and many distillates and road tars are sold.

Jan 1, 1940

By B. E. Terkelsen, B. J. Piearcey

A study has been made of the effect of unidirectional solidification on the creep behavior, stress-rupture properties, and thermal shock resistance of four nickel-base superalloys. The alloys Mar-MZOO, B-1900, IN 100, and TRW 1900 show improved rupture ductility and thermal shock resistance when tested with the columnar grains parallel to the major stress axis during test. The relative improvement in creep-rupture properties depends on the intrinsic strength of the alloy, a property which depends on composition, heat-treatnient, and crystallographic orientation. The data clarifies some of the factors affecting the properlies of the cast nickel-base superalloy. COMPONENTS designed for high-temperature use have, in recent years, been fabricated by precision casting techniques using nickel-base alloys developed specifically for use in the conventionally cast condition. This development was a result of both the increasing complexity of the component and the recognition that high-temperature strength was incompatible with workability. The use of castings can be economically favorable, but, more important, the recent complex designs of air-cooled gas turbine blades and vanes in alloys which possess the necessary high-temperature strength cannot be forged. Common modes of failure of high-temperature components are excessive creep, creep rupture, and thermal fatigue. If rupture occurs then the mechanism is usually by inter crystalline cracking along those grain boundaries oriented transverse to the major stress axis. In the stronger alloys, rapid propagation of intercrystalline cracks result in apparent premature failure demonstrated by the absence of third stage creep in a creep-rupture test and low rupture ductility. Tensile ductility shows a similar trend, that is, decreasing ductility with increase in strength. It is not surprising, therefore, that increases in creep strength have only been obtained with a loss in resistance to thermal shock, a property which shows a dependence on tensile ductility. VerSnyder and ~uard' showed that the application of unidirectional solidification to a brittle Ni-Cr-A1 alloy both improved the rupture life of the alloy and increased rupture ductility. Since this casting method results in columnar grains, it appeared that the solution to the lack of ductility in nickel-base alloy components was the elimination of the source of failure, namely the transverse grain boundaries. This concept was recently developed2 to produce cast-to-size gas-turbine blades and vanes consisting entirely of columnar grains oriented parallel to the major stress axis of the component. Not only did the process impart increased rupture life and ductility to the components, but it also increased their resistance to thermal shock. During this development, the effect of unidirectional solidification on the properties of several alloys was investigated. The resulting data allows certain conclusions to be drawn regarding the factors affecting the creep and stress-rupture properties of the cast nickel-base superalloy and also its resistance to thermal shock. Detailed information was obtained on the alloys Mar-MZOO, B-1900, In 100, and TRW 1900. The composition of the alloys studied are shown in Table I. MATERIAL PREPARATION AND TESTING The conventionally cast alloys are cast as +-in.-diam bars in innoculated shell molds under conditions designed to maintain control of grain size. Unidirec-tionally solidified casting were produced in the form of 3-in.-diam ingots. Specimens from the latter were machined such that the axes of the columnar grains were parallel with the axis of the test bar, except in certain cases where the transverse properties of the material were being evaluated. The specimens were tested in an axial loading creep machine.' Temperatures were measured with thermocouples, attached just outside each end of the gage length, to assure uniform temperature along the entire specimen. Chromel/alumel thermocouples were used up to 1800"F and Pt/Pt-10 pct Rh thermocouples above 1800"F. The specimen temperature was recorded and maintained within i2"F throughout the test. Creep extensions were measured automatically with extenso-meters attached to ridges on the specimen and recorded continuously using linear variable differential transformers and multipoint recording equipment. MICROSTRUCTURE The microstructures of transverse sections of the four alloys studied are shown in Figs. 1 and 2. Fig. 1 shows optical micrographs of the alloys, both in the conventionally cast and unidirectionally solidified conditions. Each alloy displays a cored dendritic structure, a distribution of MC carbide, and the presence of the y — y' eutectic constituent.~ In the case of IN 100 and B-1900, Fig. 1 indicates that in these specimens the eutectic is degenerate. That is, it consists only of y' pools indicating that the y constituent has been solutioned during the cooling period after solidification. The major effect of unidirectional solidification on the microstructures of the alloys is a tendency to promote a more dendritic form of MC carbide and an increase in dendrite arm spacing, both effects being a result of the slower solidification rate in the unidirectional solidification technique. V, lec tron micrographs of transverse sections of the four alloys in the two cast conditions are shown in

Jan 1, 1968

By D. J. Salley, M. Burke, G. L. Simard

A PREVIOUS paper1 described experiments on the interaction of dithiophosphate with galena and suggested that the process had characteristics of both chemisorption and surface chemical reaction. In order to add to this knowledge, a study has been made of the competition of a second ion with the dithiophosphate for a galena surface. Use again was made of radiotracer methods. Since radiophosphate was readily available, it was chosen as the competing ion. It is a feature of the tracer method that, in spite of similarity in the chemical behavior of the ions, the measurement of one ion in the presence of another can be made as simply as if only one ion species were present. In order to study the competition effectively, it naturally was necessary to examine the interaction of phosphate with galena alone as well as in the presence of dithiophosphate; consequently, this report consists of two parts. The first is devoted to a study of the rates, the isotherms, the desorption, and the exchange in the phosphate-galena system in the same manner as was done for the dithio-phosphate-galena system. The second portion is concerned with the studies on the competition. Flotation experiments on the three-component sys- tem are also outlined and the relationships involved are discussed briefly. The experimental method was that of the previous paper. The preparation of the galena, the radioactive and the nonradioactive dithiophosphate, and the procedures for radioactive counting, for sorp-tion, and for flotation measurements were identical to those previously employed. The radiophosphate* was used in the form of disodium phosphate solution. In the competition experiments the effect of the phosphate ion in depressing dithiophosphate uptake was followed by holding the initial concentration of nonradioactive phosphate constant while varying the initial concentration of the radioactive dithiophosphate. Counterfashion, the depression of phosphate by dithiophosphate was obtained by keeping the initial nonradioactive dithiophosphate ion concentration constant and altering the initial concentration of the radioactive phosphate ion. All solutions were buffered at a pH of 7.8 a0.1 by 20x10-' mol per cc of sodium carbonate. Measurements with radiocarbonate indicated that little or no carbonate could be sorbed in the presence of

Jan 1, 1952

By G. F. Dillion, A. F. Armington

THE present method for the ultrapurification of boron involves the formation, distillation, and decomposition of boron tribromide.' However, the boron tribromide prepared contains several impurities in the ppm range, even after distillation. Some of these impurities, notably carbon, can be reduced after decomposition by zone refining. In this study, a comparison of the purity of boron tribromide at various formation temperatures is presented. The apparatus employed consisted of a bromine flask connected to a 22 mm ID horizontal quartz reaction tube packed with amorphous boron powder, which was in turn connected to a receiving flask cooled with an ice bath. Argon was used as a carrier gas. The approximate rate of passage of bromine to the reaction tube was 25 g per hr. The reaction was first investigated at several temperatures in order to determine the lowest temperature necessary to produce a colorless product which was assumed to be an indication of complete reaction of the bromine. The lowest temperature found in this study was 420oC. The amount of impurities found in the boron tribromide at various formation temperatures is shown in Table I. The data presented are emission spectroscopic results of boric oxide produced by the hydrolysis of 2 to 3 g of boron tribromide in 10 ml of distilled water. After hydrolysis, the samples were dried several hours on a hot plate. Assuming equilibrium conditions in the reactor, one can make approximate thermodynamic calculations estimatling the completeness of reaction of bromine with boron and its impurities at various temperatures. Data for these calculations were taken from Rossini,3 and must be taken as approximations since the T?S factor was not included in the calculations. The results of such calculations indicate that, with the exception of carbon bromina-tion, all impurities would react almost to completeness (> 99 pet) at all temperatures between 400" and 900oC. In the case of carbon, which cannot be accurately analyzed spectroscopically, it is estimated that only about one sixth as much carbon tetrabromide would be formed at 400" than at 900°C. Since some marked reductions in impurity content were observed at the lower reaction temperature which would not be predicted by thermo-

Jan 1, 1962

By Theron Wasson

Michigan produced 16,637,000 bbl. in 1937. This makes it a record year in the history of Michigan's oil industry. During the year 953 wells were completed; 779 within the limits of established fields and 174 wildcats; 616 new oil wells, 68 gas wells and 269 dry holes. Table 1 has been arranged in alphabetical order of field names. Production figures for 1936 have been corrected because December figures were estimated. In this year's summary, December production is based on actual reports. The Leaton and Mt. Pleasant fields have been re-defined. Mt. Pleasant production north of the south line of Denver township, Isabella County, has been included with Leaton in accordance with usual practice in Michigan. The locations of fields discovered since the last map was published1 are shown in Fig. 1. Activity during 1937 Buckeye Field.—The Buckeye field of Gladwin County was the center of greatest activity during the year and was responsible for the increase of 4,700,000 bbl. over the state total for 1936. Buckeye produced 6,428,-000 bbl. in 1937. In this field 328 producing wells were completed during the year—over one-half the oil producers drilled in the state. Buckeye was subject to voluntary and cooperative proration from April 1 to the end of the year. Other pools of the state were not prorated. The new production at Buckeye is from porous Dundee limestone of Devonian age, similar to the older fields. Other New Fields.—The Sherman field was second in importance as a source of new production, with a total of 1,532,000 bbl. Salem township, Allegan County, on the southwest side of the Michigan Basin, was developed during the year. Production at Salem is from the Traverse limestone at a depth of 1600 ft., and 52 producing wells have been drilled in this pool. Other active pools were Clayton and Adams townships, Arenac County. The Bentley pool, discovered in October 1937 southeast of

Jan 1, 1938

By H. D. Outmans

In steady vertical flow, the interface of an immiscible liquid-liquid displacement is horizontal for any flow rate below the critical. In nonvertical flow, however, the shape of the interface in the steady state does depend on the flow rate, and the purpose of this paper is to calculate the unsteady interfaces during the transition of one steady state of flow to another. A knowledge of these transient interfaces is of considerable importance in reservoir engineering where the calculation of breakthrough recovery depends on the instant the interface reaches the producing wells and on the shape of the interface at that time. Although the emphasis is put on transient interlaces, which eventually approach stable equilibrium, it is shown that if the displacement exceeds a critical rate no equilibrium is possible. The interface is then unstable and viscous fingers are formed during the displacement. The critical rate and the shape of the transient and equilibrium interfaces are affected by the effective interfacial tension; but since this effective interfacial tension appears in the calculations only in combination with the inverse square of the thickness of the medium, its effect in the reservoir would appear to be negligible compared to its significance in model experiments. INTRODUCTION Stability criteria and the early growth of interfacial disturbances in a plane parallel to the boundaries of a dipping formation in which oil is displaced by an incompressible fluid were described in a previous paper.l This type of instability is significant in thin reservoirs. However, if the reservoir has appreciable thickness, then interfacial stability in vertical planes, normal to the upper and lower boundaries, also becomes important (the displacement is supposed to be parallel to these vertical planes). The difference between the two stability problems is that, in the first case, the intersections of the interface with planes parallel to the boundaries are normal to the direction of the displacement; in the second case, the intersections, this time with vertical planes, are not normal to the displacement. Instead, they are tilted at an angle which depends on the displacement rate. The tilt of steady interfaces was calculated by Dietz2 who also determined the critical rate of displacement for stability in the vertical plane by assuming that this rate would coincide with an interfacial tilt equal to the dip of the formation. The critical rate thus calculated is the same as has been found for thin reservoirs (see Eq. 1.1 of Ref. 1 and of the present paper). Dietz's calculation of the stable tilt was verified by laboratory experiments and the agreement was found to be fairly good.3 It is doubtful, however, that stable tilts actually exist in the reservoir because a change in production rate is not followed by an instantaneous adjustment of the interface to the new rate but, rather, by a transition period during which the interface changes from one equilibrium tilt to the other. The principal objective of this paper has been to describe these transient interfaces without putting any restrictions on the flow conditions or the shape of the interface, as had been done previously. The second objective was to compute the critical velocity, taking into account capillary effects, and the third was to evaluate, at least qualitatively, the shape of the front at rates above the critical, again without making the simplifying assumptions introduced by previous investigators.2,3 In the following sections two examples are given of the calculation of interfacial motion. The first describes this motion for an initially horizontal interface in a dipping layer, and the second for a vertical interface in a horizontal layer. The mathematical formulation of the problem is nonlinear in the boundary conditions, and this prohibits its solution in closed form. Instead, the solution is obtained in the form of higher-order approximations. 1 Before proceeding to a description of the mathematical model, however, we define two quantities

By P. M. Robinson, M. B. Bever

THE heats of formation at 273°K of the compounds InBi, In2Bi, and TIBi2 have been determined by metal solution calorimetry with bismuth as solvent. The published information on the thermody-namic properties of these compounds is limited. The structure of the compound InBi (mp, 383°K) is tetragonal of the PbO (B10) type.1 The compounds In2Bi (mp, 362°K) and TIBi2 (mp of highest-melting composition, 486°K) are now believed to have structures of the NizIn (B8) type273 and not the A1B2 (C32) structures reported earlier.4, 5 The compounds In2Bi and TIBi2 have limited homogeneity ranges at room temperature, while the compound InBi has no detectable homogeneity range.' Samples of the compounds were prepared from 99.99 pet Bi (Mallinckrodt Chemical Works), 99.999 pet in (American Smelting and Refining Co.), and 99.99 pet Tl (Amend Drug and Chemical Co.) by melting the components in sealed, evacuated Vycor tubes. The compounds InBi and in2Bi were of the stoichiometric compositions. The compound TIBi2 contained 40 pet T1; this composition was chosen because at room temperature the alloy of stoichiometric composition does not lie within the homogeneity range.' The melts were held approximately 50°C above the liquidus for 8 hr and then quenched into iced brine. The samples were homogenized for 48 hr at temperatures 20°C below the temperature of complete solidification. Metallographic examination of sections taken from the center and the ends of the ingots did not reveal second phases or segregation . The heats of formation were determined as the difference in the heat effects on solution of a compound and of a mechanical mixture of its components added from the reference temperature of 273°K to liquid bismuth at 623°K. The details of the calori-metric procedure and method of calculation have been described elsewhere? The calorimeter was calibrated by adding bismuth at 273°K to the bismuth bath at 623°K. The calculated values of the heats of formation of the compounds, listed in Table I, are based on a value of 4.96 keal per g-atom for the difference between the heat contents of bismuth at 273" and 623oK7 No published values are available for the heats of formation of the compounds InBi and In2Bi. Hultgren et a1.7 have calculated a value of -0.50 i 0.10 keal per g-atom for the heat of formation at 423°K of the compound TIBi2 containing 40 at. pet T1 from heat-content measurements in the range from 398" to 700°K and the heats of formation of the liquid alloy. The difference between this value and the value of -0.66 * 0.01 keal per g-atom at 273°K is too large to be attributed to a difference between the heat capacities of the compound and the components over the temperature range 273o to 423oK7 However, the direct determination of the heat of formation by a calorimetric method should give a more accurate value. The heats of formation at 273°K of the compounds InBi and In2Bi lie on a straight line when plotted as a function of composition, Fig. 1. The compound In2Bi, therefore, appears to be barely stable with respect to its neighboring phases. In order for the free energy vs composition curve to be concave towards the composition axis, the entropy change on formation of In2Bi must be more positive than that on formation of InBi. As the compounds are ordered,2, 3, 8 there is no configurational entropy change on formation. The difference between the entropy changes on formation of the two compounds, therefore, is probably associated with the vibrational entropies. In view of the low heats of formation, the changes in vibrational entropy, due to changes in bond strength on formation of the two compounds, are likely to be small. Owing to the volume contractions on formation of the two compounds,5 the vibrational entropies probably decrease slightly but the decrease of the vibrational entropy of InBi is expected to be larger than that of In2Bi.

Jan 1, 1965

By John Finch

IN AUGUST, 1927, the writer examined certain copper deposits in New Mexico, which occur in beds of sandstones and shale, and in connection therewith reviewed the literature upon deposits of this type. Such deposits are known and have been reported upon at various points in Texas, Oklahoma, Arizona, Colorado, Wyoming and Utah, but in New Mexico they have been given more development than elsewhere and apparently occur there more conspicuously than in the other states. Some 25 years ago the writer examined deposits of similar origin in northern Arizona and more recently other deposits in western and southwestern Colorado, and these examinations have led him to realize how widely scattered are the deposits and how generally non-commercial they are. On superficial development, to one without a comprehension of their geologic nature, they are alluring on account of occasional small amounts of high-grade ore and much misplaced capital has been expended upon them. This paper, therefore, aims to present briefly certain theories of genesis, some details of which may possibly be new, and to lead up to practical conclusions which may be useful to other geologists and engineers. A bibliography of the more important literature upon such deposits is given below.2 Coffin's Bulletin upon the Radium, Uranium and Vanadium Deposits of Colorado, published in 1921, is a particularly clear discussion. The most comprehensive recent statement is Butler's. He describes a large number of occurrences in Utah and connects them up genetically with deposits in other states.

Jan 1, 1928

By R. O. Leach, O. W. Wagner

Because of unfavorable wetting conditions much residual oil is left when a porous material is Pushed by water. Methods suggested to change reservoir wetting to improve oil displncernrnt efficiency are generally expensitlr. The present 1aborator.y study was undertaken to gain an under.standinx of the factors which determine reservoir wettability, arid to find out if oil displacement efficiency might be improved by a wettahility change accomplished at low cost in on oil reservoir. Contact angle measurements were made on mineral surfaces using sevc.r~zl sets of reservoir oil and water samp1es. Results of the contact angle studies suggest that reservoir wetta-hility may he primarily determined by natural surface-active substances present in the reservoir fluids. The effect of changing sa1inity and pH of the water phase was studied. The re.suits suggest that gross changes in preferential wettability might be acc~o~npli.shed by injection of water containing simple chernicnls to alter pH or salinity in the reservoir. Such treatment could he much less expensive than injection of commercial surface-active agents. Waterflood tests have also been made using synthetic cores and oil and water having wening characteristics similar to those of reservoir fluids. Cores initially oil-wet were flooded in such a way that they were made prefermtial1y water-wct by the advancing flood water. This reversal in preferential wettability achieved greater oil displacement efficiency than when either oil-wet or water-wet conditions were maintained throughout the flood. For the systems studied, the higher the oil viscosity the greater the percentage improvement obtained over conventional waterflood recovery. This suggests that a flooding process making use of wettability-reversal may extend the oil viscosity range over which water flooding is attractive. Because a precise adjustment of reservoir wettability does not seem to be required, and because altering the pH or salinity in some reservoirs may be inexpensive, it appears that a waterflooding process employing wet-[ability-reversal could find .succesful field application. I NTRODUCTION The efficiency with which water will displace oil from a porous material is related to the nature of the capillary forces present. These in turn are controlled by the preferential wetting of the solid by the two fluids. Because of unfavorable wetting conditions, 30 per cent or more of the original oil in place may remain unrecovered in that portion of a reservoir flushed by water. This paper is concerned with the possibility of improving waterflood oil displacement efficiency by alterations in the wettability of the porous material. A laboratory study was made to gain a better understanding of the factors which control reservoir wettability, and to determine if the oil displacement efficiency could be improved by some inexpensive means of manipulating wettability of the porous medium. Contact angle measurements were made with several natural and synthetic oil, water and solid systems (1) to obtain a better understanding of how to duplicate reservoir wettability in the laboratory, and (2) to discover possible means for changing preferential wettability of natural reservoir systems. Flooding tests were also made in synthetic systems to determine if oil displacement efficiency could be improved by those wettability manipulations suggested by the contact angle measurements. Based on these studies a possible method for improving waterflood oil displacement efficiency is presented. This method involves causing an originally oil-wet porous material to become preferentially water-wet during the course of a water flood. The purpose of this paper is to present results of the laboratory studies. THEORY Rock surfaces in some oil reservoirs are believed to be covered with a firmly attached bituminous or other organic coating. Such surfaces would be preferentially oil-wet in the presence of both oil and water, regardless of composition of reservoir fluids. Other reservoirs are believed to contain rock surfaces not permanently coated with such materials, and which would be preferentially wet by water in the presence of water and oil free from surface-active substances. However, when the reservoir fluids do contain certain natural surface-active materials in sufficient quantity, rock surfaces acquire a degree of preferential oil wettability caused by adsorption of these natural surface-active materials on the solid. The equilibrium amount of these materials adsorbed per unit surface area is believed to depend upon their concentration in the bulk liquid phases.

By H. A. Wriedt

A method of calculating activities in binary systems having miscibility gaps is described. The method, which applies only to the phase in which the gap occurs, is exact when the function defined by the equation varies linearly with composition. Analytical and numerical solutions (as a function of the conjugate phase compositions) are presented for two coefficients A and B from which the thermodynamic activities can be calculated. Deviations from Henry's law, calculable by the method presented, are shown graphically for the particula~ case of the component i at the edge of the miscibility gap more remote .from pure component i. For symmetrical gaps, the deviation from Henry's law at this gap edge becomes smaller as the gap becomes wider, The interrelation of gap location, the direction of departures from Henry's law and the occurrence of maxima and minzma in these departures is discussed in some detail. Values for a and for activity calculated from phase diagrams show fair to excellent agreement with corresponding experimental values in the Al-Zn and CaO-SiO2 systems. WHEN structurally similar phases, B and 6, lie at the sides of a two-phase region in a constitution diagram, it can be assumed that, stably or metast-ably, they will become completely miscible at a higher temperature. The B and 6 phases are particular composition ranges of a single B6 phase region with a miscibility gap. Below, as above, the critical solution temperature, the free energy of formation of the 06 phase is a continuous function of composition through the range of the miscibility gap. It is the purpose of this paper to use this continuous free-energy function in order to develop a simple method for computing the thermodynamic activities in the B6 solution of a binary system. To make these calculations it is assumed that the function ai, familiar from Gibbs-Duhem integrations and defined by the equation

Jan 1, 1962