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By Orville R. Lyons

THE Russellton preparation plant of Republic Steel Corp., located north of Pittsburgh, Pa., prepares 395x0-in. Thick-Freeport coal by means of a 13-ft 6-in. diam Chance cone and 16 No. 7 Deister tables. The plant feed ranges between 370 and 410 tons per hr, of which approximately 31 pct is 1/4xO-in. size, and the plant reject ranges between 14 and 16 pct of the feed.

Jan 6, 1953

By L. F. Stutzman, George Thodos

The friction factor plot presented by Cornell and Katz4 and developed for the flow of fluids through consolidated formations has been directly adapted for handling fluid flow problems involvitrg both linear and radial flow. In this adaptation the friction factor plot is used directly for the solution of problems and thereby eliminates the use of conventional equations which are specific to laminar (Darcy) or turbutent flow. This upproach overcomes the disadvantages inherent in the use of these conventional equations. It eliminates the necessity of checking the type of flow occurring in order to identify the specific equation which must be used. In radial flow problems, because of the increasing mass velocity of the fluids as they approach the wellbore. the type of flow may no longer remain laminar. Consequently, it is necessary to use more than one equation in a problem and to identify the range over which each equation should be applied. Finally, in practice it has been found that much of the flow of gases through consolidated media occurs in a range that is neither laminar or turbulent. For this transitional region, no convenient equations are available. The method and presented friction factor plot are appficahle to both liquids and gases. INTRODUCTION The flow of fluids through unconsolidated media in packed beds has been treated extensively by a number of investigatorsl,2,3,5,7,8 Most of these studies present friction factors as a function of modified Reynolds number similar to those developed for conventional fluid flow through pipes. These friction factor plots are presented for linear flow; however, Elenbaas and Katz have extended these concepts to apply to radial flow. All of these studies on unconsolidated materials require a knowledge of packing properties such as sphericity. porosity, and particle diameter. Sphericity and particle diameter cannot be defined at the present time for consolidated formations such as those commonly found in gas or oil reservoirs. As a result many investigators have not utilized friction factors and Reynolds number in the study of fluid flow through consolidated media. However, Cornell and Katz4 present a plot (Fig. 1) for the flow of fluids through consolidated porous media, in which the friction factor defined as: The turbulence coefficient, P, is related to the formation permeability, K, as presented in Fig. 2. Three different types of flow may exist in the flow ot

Jan 1, 1957

By Joseph E. Pogue, F. G. Coqueron

Prior to 1934, published information covering expenditures by oil companies for properties, plant, and equipment and the residual investments in the various segments of the petroleum industry was not readily available. This paper presents an analysis of the funds invested by a selected group of oil companies during the years 1934 through 1942, based on an extensive study of the individual records of 30 oil companies. The sources, disposition, and characteristics of the capital employed by this group of companies are traced through a series of combined statements and appropriate charts, covering financial and operating data. The analysis of these statements not only constitutes a record useful for comparative purposes but also serves as a basis for a number of broad conclusions, as follows: 1. The petroleum industry generates the capital needed for its expansion almost entirely from its own operations and is therefore a singularly self-contained economic unit. 2. The long-term debt contained in the financial structure of the industry is small relative to the total capital employed, is less than the net working capital, and has increased but slightly during the period under review. 3. The capital expenditures of the group of 30 oil companies for 9 years amounted to 6.1 billion dollars, 58.3 per cent of which went into crude-oil producing facilities. The trend of this segment of expenditures has been downward since 1937. In 1942, expenditures for refining facilities increased sharply and for marketing facilities declined drastically. 4. The net working capital of the group increased 380 million dollars over the period, and the industry is in a favorable position of liquidity. The ratio of combined current assets to current liabilities was 3.21 at the close of the period. 5. The net income of the group displayed an upward trend for the period but with rather sharp cyclical fluctuations. 6. In 1942, Government funds entered the industry for the first time in substantial amounts and were utilized for the provision of war facilities needed for emergency use. 7. The group has paid out a relatively low percentage of net income in the form of dividends. For the period the average was 55 per cent of net income. 8. The rate of return on invested capital for the group averaged 6.4 per cent for the

Jan 1, 1944

By Joseph E. Pogue, F. G. Coqueron

Prior to 1934, published information covering expenditures by oil companies for properties, plant, and equipment and the residual investments in the various segments of the petroleum industry was not readily available. This paper presents an analysis of the funds invested by a selected group of oil companies during the years 1934 through 1942, based on an extensive study of the individual records of 30 oil companies. The sources, disposition, and characteristics of the capital employed by this group of companies are traced through a series of combined statements and appropriate charts, covering financial and operating data. The analysis of these statements not only constitutes a record useful for comparative purposes but also serves as a basis for a number of broad conclusions, as follows: 1. The petroleum industry generates the capital needed for its expansion almost entirely from its own operations and is therefore a singularly self-contained economic unit. 2. The long-term debt contained in the financial structure of the industry is small relative to the total capital employed, is less than the net working capital, and has increased but slightly during the period under review. 3. The capital expenditures of the group of 30 oil companies for 9 years amounted to 6.1 billion dollars, 58.3 per cent of which went into crude-oil producing facilities. The trend of this segment of expenditures has been downward since 1937. In 1942, expenditures for refining facilities increased sharply and for marketing facilities declined drastically. 4. The net working capital of the group increased 380 million dollars over the period, and the industry is in a favorable position of liquidity. The ratio of combined current assets to current liabilities was 3.21 at the close of the period. 5. The net income of the group displayed an upward trend for the period but with rather sharp cyclical fluctuations. 6. In 1942, Government funds entered the industry for the first time in substantial amounts and were utilized for the provision of war facilities needed for emergency use. 7. The group has paid out a relatively low percentage of net income in the form of dividends. For the period the average was 55 per cent of net income. 8. The rate of return on invested capital for the group averaged 6.4 per cent for the

Jan 1, 1944

By O. F. Walker, W. C. Hahn, V. A. Johnson, J. D. Wood

The diffusion coefficients of zinc in single-crystal zinc and carbon in single-crystal and poly crystalline nickel were measured by means of radioactive tracer techniques both with and without the application of ultrasonic vibrations under conditions such that the temperature of the sample was closely controlled. The results of this investigation indicate no enhancement of diffusion in any of the samples. It is suggested that previously reported enhancement may have been due either solely to temperature increases caused by ultrasonic vibrations or in combination with changes in the boundary conditions. A number of observations have been reported in the literature in which it has been implied or inferred that the application of ultrasonics enhances diffusion (see, for example, Refs. 1-5). The present study was undertaken in an attempt to observe this effect under carefully controlled conditions, particularly with regard to measurement and control of the temperature of the sample. Two different types of systems were studied; these were the self-diffusion of zinc and the diffusion of carbon in nickel. EXPERIMENTAL For diffusion with ultrasonic energy applied, the samples were included as part of a resonant ultrasonic system operating at 58.5 kcps. The ultrasonic generators used were rated at 100 and 250 w and could be tuned over a frequency from 10 to 100 kc. A PZT (lead titanate/lead zirconate) ceramic transducer provided the driving vibration. This system requires no metallurgical joining of the specimen to the acoustical transmission line since the ultrasonic driver and the follow-up section clamp the specimen in position by means of a constant pressure of 50 lb developed by an air cylinder. The ultrasonic driver and follow-up section, both made of titanium, were 4 in. in length from clamping point to the end in contact with the specimen. Using the relationship given by Mason,6 A = V/f, the resonant wavelength, A, in titanium is calculated to be 3.3 in. at a frequency, f, of 58.5 kc, taking the velocity of sound in titanium, V, as 1.95 X 105 in. per sec. The 4-in. driver and follow-up section, therefore, are each 4.0/3.3 =1.21 times the resonant wavelength. Clamping pressure must be applied at stress nodes of the transmission line in order to preserve resonance. Therefore, a specimen length of 0.58 times the wavelength in the specimen was required to place the clamping pressure application points at stress nodes exactly three wavelengths apart. A stress antinode was contained in the center 3 in. of the specimen. A small PZT ceramic disc attached to the follow-up section provided an output voltage proportional to the intensity of the standing wave. This output voltage was monitored on an oscilloscope and the ultrasonic system was tuned to resonance by varying the frequency until the output signal was a maximum amplitude. The amplitude of the output signal was maintained constant throughout the diffusion anneal. A split cylindrical stainless-steel chamber, which was purged with argon prior to and during the runs, was placed around the specimen. The chamber in turn was surrounded by a movable furnace whose temperature could be controlled to 7C. Heat exchangers were used to cool the driver, follow-up section, and ultrasonic transducer. Great care was taken to obtain the true specimen temperature in all cases. Several different methods were tried; the most successful was that in which the thermocouple was held in contact with the midlength of the specimen by means of an asbestos insulating pad and wire straps. In the case of zinc, single-crystal specimens of 99.999 pct purity were used. The samples were 0.25 by 0.25 in. square and of the proper length for resonance, that is 1.1 in. long with the c axis parallel to the long dimension of the specimen for the case of diffusion perpendicular to the c axis and ultrasonic motion parallel to the c axis, and 1.9 in. long with the c axis perpendicular to the long dimension of the specimen for the case of diffusion parallel to the c axis and ultrasonic motion perpendicular to the c axis. In each case, one of the rectangular faces was electroplated with a thin film of zinc containing Zn The constant pressure used to clamp the specimen in place in the ultrasonic system caused some deformation in some of the samples. For these samples the deformation was concentrated in either end of the specimen; thus, for all samples (both zinc and nickel) the center in. was cut from the specimen after the diffusion anneal to be used for sectioning and counting. The nickel single-crystal samples, of 99.999 pct purity, were used in the form of rods 0.25 by 0.187 by 2.07 in. long with the (100) direction parallel to the rod axis. The polycrystalline nickel samples of 99.97 pct purity had an average grain diameter of 0.007 in. and were used in the form of rods 0.25 by 0.125 by 1.87 in. long. The direction of ultrasonic motion was parallel to (100) direction (bar axis) for the single-cqstal samples and parallel to the bar axis for the polycrystalline specimens. A thin film of c14 suspended in methanol was applied to the diffusing face of the specimen. Two specimens were butted together lengthwise for each diffusion anneal to minimize oxidation. After diffusion, a precision lapping device similar to the one described by Goldstein7 and a radiation detector were used to obtain a plot of specific activity vs penetration distance for each specimen. (A scintil-

Jan 1, 1969

Executive JVW REYNOLDS, Chairman SYDNEY H BALL E DEGOLYER WILLIAM H BASSETT SAMUEL A TAYLOR Finance GEORGE D BARRON, Chairman H A GUESS GEORGE OTIS SMITH Membership ] H CALLOW, Chairman GEORGE D BARRON WILBER JUDSON JOHN A CHURCH, JR H N SPICER Alternates LEWIS W FRANCIS LOUIS D HUNTOON F T RUBIDGE

Jan 1, 1923

Buffalo Society of Natural Sciences, Buffalo Museum of Science, Humboldt Park, Buffalo, N Y. Of the many scientific bulletins issued by the Society only one of those now available is of particular interest in this directory. Vol 7 (1901), Bulletin 1, Guide to the geology and paleontology of Niagara Falls and vicinity, by A. W. Grabau, $1 unbound or $2 bound. The bulletins are distributed through the Research Librarian at the above address

Jan 1, 1933

By Eugene R. Rice

(Canal Zone Meeting, November, 1910.) THERE are many methods for determining the meridian, but all of those in common use involve at least two separate observations, one for latitude and one for azimuth. Such observations made upon a south star at any hour are open to the objection of possible inaccuracy due to ignorance of the absolute refraction, and also to slow change in the altitude of the star when near the meridian. The method of observing a circumpolar star at elongation, besides requiring a separate observation for latitude, is open to the serious objection that clouds may obscure the star at the critical moment. Moreover, a tedious wait for the star to come to elongation is sometimes necessary. Many of us can recall long, cold, weary vigils, waiting for Polaris to reach elongation. For observing a circumpolar star at any hour, not only the latitude, but also the true time, must be known. This it is practically impossible to obtain, except in regions reached by the telegraph, and usually then one has to know the longitude also, in order to reduce "standard time" to "local time." The results obtained by this method, when the star is at culmination, are not very good, unless the true local time is absolutely known. The methods of obtaining the meridian from the sun, by means of a solar attachment, or by direct observation, while good, are not absolute, by reason of refraction, change in declination of the sun, and small change in vertical angle, when the sun is near the meridian. For these two methods, latitude, time, and approximate longitude have to be known. In the method here described, only one observation is needed, and from it azimuth, latitude, and sidereal time are computed. In other words, one can observe a circumpolar star-Polaris

Nov 1, 1910

By Henry J. Sandri

The use of economic models for forecasting purposes is an inexact yet necessary tool for mineral decision making. One method not commonly used is cyclical analysis because of its "non-scientific approach". However, under certain circumstances a modified cyclical approach can provide useful insight to mining companies. The current paper discusses mineral modeling, the type of economic models and the use of cyclical forecasting for mining firms (not speculators) involved in precious metals.

Jan 1, 1984

By J. J. Arps

This paper is a study of the effect of temperature on the electrical resistivity of sodium chloride solutions based on the published resistivity and density data in the International Critical Tables. This temperature effect is of considerable importance in quantitative interpretation of electric logs, where it is frequently necessary to correct mud resistivities measured under surface conditions to temperatures existing at the bottom of the bore hole. An empirical approximation formula was developed for this conversion which has proved to be very useful and seems to provide results well within the range of accuracy of the data involved. This approximation formula states: sistivities of sodium chloride solutions at temperatures of t and t degrees Fahrenheit, respectively. INTRODUCTION Research by various investigators during the past 20 years has clarified the physical principles of the phenomena which cause the natural or spontaneous electric potential in rotary drilled bore holes. The basic relationship which is most commonly used reads: in which the SP deflection, as measured from the shale base line, is expressed in millivolts. K is a constant, which appears to vary between 50 and 110; the low value applying to shaly sands, whereas the higher values are more common in carbonate rocks. A good average value for K = 70. for which value there is considerable theoretical justification." In order to calculate the resistivity of the connate water R and to estimate its "equivalent salinity" (as NaCl) from an electric log by means of this SP relationship from a knowledge of the static self potential and of the resistiv- ity of the mud filtrate R it is necessary to first correct the resistivity of the mud filtrate measured under surface conditions to the resistivity of this same mud filtrate in the well bore at a different temperature. In order to make this temperature conversion for the mud filtrate the variation of the electrical resistivity of sodium chloride solutions with temperature is commonly used. Since some discrepancies were found in the charts ordinarily used for this purpose, it was felt desirable to make a new study of this relationship based on the published measurement data. Because of the fundamental nature of these relationships and as an aid to other workers in this field, an attempt has been made in this study to show every step in the calculations. CONDUCTIVITY VS MOL CONCENTRATION The most complete published reference on the temperature relationship of sodium chloride solutions of different concentrations is provided in the International Critical Tables.' The basic measurement data on the electrical conductivity of aqueous sodium chloride solutions, at different temperatures, as given in these tables, are reproduced in Table 1. The electrical conductivity values in this Table 1 are expressed as 10' times the specific conductivity k in ohm-'cm'l per unit of concentration in milligram mols per liter of solution C, or: RESISTIVITY VS MOL CONCENTRATION These conductivity values from Table 1 were first converted to the corresponding electrical resistivity values (R) , expressed in ohm-meters, as is conven-

Jan 1, 1953

The paper describes a cyclic method for processing manganese ores using sodium sulphate as the basic reagent. Sodium sulphate is electrolyzed in a diaphragm cell to give an anolyte sodium sulphate acid and a catholyte containing caustic soda, a part of which is carbonated in a cyclic manner to Form ash. and reduced ore is leached with the anolyte to dissolve the manganese and the impurities are precipitated by addition of catholyte. Manganese in the pregnant solution is precipitated as synthetic rhodochrosite with a carbonated catholyte, and sodium sulphate is regenerated. Calcining the manganese carbonate site a high-grade product and the carbon dioxide is returned to the carbonation step. the results of laboratory tests using cells equipped with synthetic fiber diaphragms and permselective membranes which permit transfer of using or cations during electrolysis are described. The article from which the above abstract is reprinted appears in Trans. AIME (1955) 203, p. 51; Journal op Metals (January 1955).

Jan 1, 1956

By Fred H. Kan

The production of petroleum in Venezuela during 1931 was approximately 118,767,000 bbl., a decrease of 18,904,000 bbl., or 13.7 per cent, compared with the previous year. This is the first break in production, which has risen steadily since 1920, and is attributable to restriction of output and drilling operations, in harmony with lessened demand, rather than to any real decline in potential production. Venezuela ranked third among the world's producers, having lost second place to Russia. The Bolivar coastal fields, which were extended approximately 14 miles southward during the year, continued to supply most of the oil. La Concepcion, Los Manueles and Quiriquire all showed marked increases. A new field of light oil was discovered on the north coast near Puerto Cumarebo, State of Falcon. Exports declined 15.7 per cent, from 137,377,000 bbl. in 1930 to about 115,800,000 bbl. in 1931. Crude oil in storage at the end of the year amounted to 7,450,000 bbl., a decrease of 2,150,000 as compared with 1930. Tankage utilized is about 40 per cent of the available space. A drastic decline in drilling activity reduced the number of wells completed in producing areas from 401 in 1930 to 116 in 1931. Only three wells were drilled in the Lagunillas field proper, but, the amount of closed-in production and proven acreage gave assurance of a satisfactory potential output. Of the 1580 wells drilled to the close of 1931 in the producing areas of the Bolivar Coast, 631 were active and 853 were closed in; 96 had been abandoned. The status of the active wells at the end of 1931 was as follows: flowing, 331; pumping, 99; gas-air lift, 201. Producing wells closed in numbered 452; workovers, 8; totally inactive, 393. Lago Petroleum Corp. and Venezuela Gulf Oil Co. placed in operation the first units of their electric power plants, the former at Punta Gorda and the latter at Las Morochas, and are replacing steam power in their operations as rapidly as possible. Compressor stations were also installed for use in connection with air-gas lift operations. A considerable volume of gas was treated in gasoline extraction plants, the tail gas being recom-pressed and utilized together with natural high-pressure gas, for stimulation of production.

Jan 1, 1932

By E. M. Kalar, I. Iwasaki, J. D. Zetterstrom

Several methods of removing fatty acid coatings from iron ore flotation concentrates were tested both on a Mesabi oxidized iron ore and on a magnetic taconite concentrate, and their effects on the duplex flotation process and on pelletizing were compared. Either acid or alkali alone could not remove the coatings, but a combination of such reagents as lime and quebracho, calcium chloride and pyrophosphate, or sulfuric acid and an organic acid (oxalic, malonic, or citric acid) was quite effective. The use of activated carbon was found to be particularly promising. The removal of fatty acid coatings from iron ores is of much practical interest when a pelletizing process is being considered for a concentrate floated with a fatty acid collector or when a duplex flotation process is being considered for upgrading an oxidized iron ore. A duplex flotation process is a fatty acid flotation of iron minerals followed by an amine flotation of the siliceous gangue from the rougher iron concentrate. Such a process is being used in the Florida phosphate fields.' Although in northern Michigan mills fatty acid flotation concentrates have been pelletized successfully, at other locations fatty acid coatings on iron flotation concentrates have proved so undesirable in the agglomeration operation that other methods of concentration had to be sought.' Since fatty acid coatings cannot be removed as readily with a simple acid or alkali treatment from iron oxide surfaces as from Florida phosphates, a combination of reagents, such as lime and quebracho,3 lime and alkali phosphate,4 or sulfuric acid and oxalic acid,' has been proposed. It was also thought that activated carbon might be effective in removing fatty acid coatings due to its high adsorptive capacity. Activated carbon, with its enormous surface per unit of volume, is well known for its exceptional efficiency in removing organic pollutants from industrial effluents. This article presents the practical aspects of the above methods when they are applied to the duplex flotation process and to the pelletizing of iron flotation concentrates. The article also includes a preliminary investigation of the common parameters involved in the depressant activity of the reagents. EXPERIMENTAL WORK Initially, the experimental work was directed towards the optimization of each method for the removal of hydrophobic coatings from iron oxide surfaces floated with fatty acids. Subsequently, the methods thus optimized were tested in the duplex flotation process with an oxidized iron ore and in the pelletizing process with a magnetic taconite concentrate. Preliminary Flotation Tests: Although the three types of chemical treatment reported in the literature were briefly investigated for the purpose of comparison, major emphasis was placed during the preliminary flotation tests on the use of activated carbon because it was thought to have certain advantages over the chemical methods. LIME AND QUEBRACHO - To obtain a flotation concentrate for optimizing the lime and quebracho method of fatty acid removal, the magnetic taconite concentrate was used. The concentrate had a size consist of 90% passing 325 mesh and analyzed 64.5% iron. After a few preliminary tests the fatty acid flotation procedure with the magnetic taconite concentrate was standardized as follows. A 1200-g sample of the magnetic concentrate was pulped in a Fagergren laboratoy flotation cell to 40% solids, conditioned with 0.5 lb of soda ash per ton for 2 min, and then further conditioned with 1.0 lb of Acintol FA-2 per ton for 2 min. After 5 min of flotation, recovery was nearly complete, averaging 98.6% of the weight and 98.7% of the iron. The cell product, which amounted to 1.4% by weight and analyzed 63.2% iron, consisted mainly of relatively coarse middling particles. Since the repro-ducibility of the flotation concentrates produced by this procedure was vey high, the same procedure was used to prepare fatty acid concentrates for each of the six tests of the lime and quebracho method. To test the removal of the fatty acid from the magnetite surfaces by the lime and quebracho method, a fatty acid froth product was returned to the flotation cell, repulped by 30 sec of agitation, and then con-

Jan 1, 1968

By S. Arthur Krom

(New York Meeting, February, 1912.) THE James diagonal-plane slimer is specially adapted to handle the finest slimes, but it will also handle sands as coarse as 40-mesh. The saving efficiency of this machine is due to the original construction of the deck, and to the rapid reciprocating movement imparted to it by the head-motion. The deck consists of a plurality of connected planes, having a certain fixed ratio of inclination one to another. These planes intersect each other diagonally to the stroke-line of the table and are arranged so as to give the pulp on the table a double treatment. This double concentration performed by the diagonal-plane deck produces cleaner concentrates and tailings than those obtained by the operation of two separate machines. The action of the diagonal planes settles, combines, and holds all the concentrates in one compact mass, sharply defined from the gangue, and easily cut away without loss. Many slime-concentrating machines distribute the feed-pulp for a distance of 4 or 5 ft. only, and upon a very limited settling-surface. This results in a thick, heavy deposit, from which it is impossible to stratify the values and wash, away the gangue, the resulting products being dirty concentrates, and tailings carrying high values. The diagonal-plane slimer distributes the feed-pulp for a distance of 10 ft., and upon a settling-surface having an area of 40 sq. ft.; in other words, it spreads the pulp thinly on the table, which allows the metallic values to settle through the gangue quickly, forming a bottom stratum from which the thinly-distributed overlying stratum. of gangue is easily brushed away by the feed-water without disturbing the underlying concentrates. Referring to Fig. 1, plane A is the main settling-section, of the table. The feed pulp flows gently down this plane and is

Jun 1, 1912

By B. A. Eaton, R. H. Jacoby

This paper presents the depletion-performance correlations developed using data from PVT studies and well-completion tests of 27 rich gas-condensate and volatile-oil reservoir fluids. The PVT behavior for each fluid war determined experimentally in the laboratory, and the depletion performance of each fluid was then calculated. Well-completion test data consisting of reservoir pressure and temperature, initial total gas-oil ratio, and stock-tank oil gravity were used with the depletion-performance data to develop general performance correlations. Three correlations are presented. The first equation shows the empirical relation of gas in place per barrel of hydrocarbon pore space with reservoir pressure and temperature, and initial total gas-oil ratio. The second equation is the correlation of stock-tank oil in place per barrel of hydrocarbon pore space. The third equation relates stock-tank oil production (to 500-psia depletion pressure) with pressure, temperature and oil gravity. All three correlations are also presented in convenient graphical form. Gas production to 500-psia depletion pressure is approximately 92.6 per cent of the gas in place for each fluid, so no correlation was developed for gas production. INTRODUCTION The rate of discovery of shallow, low-pressure and low-temperature oil reservoirs in the United States has been declining in recent years. For this reason, the search for oil has gone to greater depths where high pressures and temperatures are encountered. A high-pressure and high-temperature reservoir is the environment in which many rich gas condensates and highly volatile oils are found. Because of this trend, the performance prediction of such reservoirs has become an important task of the reservoir engineer. The need and usefulness of a performance correlation based on field data that are available from the usual well-completion tests have previously been established. These earlier attempts have shown that the phase behavior of rich gas-condensate systems and volatile-oil systems can be correlated with fluid properties, pressure and temperature. However, very little information on gas-condensate depletion performance5 was available at the time of these earlier attempts. The availability of more recent data has made possible the development of an improved correlation. The data, as listed in Tables I and 2, are for 25 gas-condensate and two volatile-oil systems that were studied. The problem was to correlate the data for in-place fluids and the production data with the initial total gas-oil ratio, initial reservoir pressure and temperature, and stock-tank oil gravity. These correlations were obtained by multiple regression analysis, whereby the data were fitted to an equation by the method of least squared error. BASIS OF THE CORRELATIONS 1. The data used in the development of these correlations were obtained from depletion-performance calculations6 and well-test or production measurements. 2. All of the independent variables used in the correlations are available from the usual well-test completion data. 3. The reservoir volume considered is 1 bbl of hydrocarbon pore space (HCPS). 4. The gas-oil ratio used is the total standard cubic feet of gas (at 14.7 psia, 60F) coming off the entire separator train per barrel of stock-tank oil. This minimizes the effect of separator conditions which might vary from system to system. 5. The correlated pressures are the actual reservoir pressures which might or might not be the saturation pressure of the reservoir fluid.

Jan 1, 1966

By C. H. Lee, R. Maddin

The diffusion rates of Ag110 in cylindrical single crystals of 99.99 pct pure silver, which were twisted to a total surface strain of 0.91 during the diffusion anneal at temperatures of 700°, 750°, and 800°C, were measured by sectioning and counting as a function of the strain rates. The ratio of the diffusivities while strain ing occurred (Ds) to those of the unstrained specimens varies linearly with the rate of twisting and attains values of near 100 for some of the rates used. The enhancement of diffusion by straining is inversely proportional to the temperature at which diffusion occurs. The activation energy for diffusion determined from the data plotted as a function of the rate of twisting decreases from 44,090 cal per mole for zero strain, to an asymptotic value of 21,000 cal per mole for the strain rates of 22 x it)"5 see-l. Qualitative explanation for the observations based on the generation of nonequilibrium number of defects by plastic deformation will be discussed. The initial research of Buffington and cohen1 on self-diffusion in a iron under compressive stresses contributed the first quantitative information concerning the effect of applied stresses on diffusion. These results were obtained from radioactive Fe55 plated on one of the horizontal surfaces and compressing the large-grained specimens while the diffusion-anneal was occurring. Enhancement of diffusion of a maximum of seventeen times was observed provided the strain was in the tertiary stage of creep and the rates of straining were at least as fast as rates used in the normal creep test. On the other hand, Darby, Tomizuka, and Balluffi,2 extending silver single crystals up to 30 pct elongation at rates of straining about equal to those used by Buffington and Cohen observed no effect. For the past two and a half years at the University of Pennsylvania, we have been investigating the effect or torsional strains on self-diffusion in silver single crystals. If enhancement is observed as has been reported1 a possible explanation may be based upon the generation of fairly large numbers of point defects and their role in the diffusion process. Hence, since torsion should produce an abundance3 of point defects, an increase in the diffusivity while the crystal is being twisted should easily be measured. EXPERIMENTAL PROCEDURE Our research uses single crystals of silver prepared from 99.99 Ag by the Bridgman method in a dynamic vacuum of less than 25 µ. As grown, they are about 25 cm long by 1.3 cm in diam. The crystals are cut into 7.5 cm lengths with a jeweler's saw and machined to the shape shown in Fig. 1. The test length of the crystal is machined to a 0.6 cm diam after which the ends are masked and the test section etched heavily in HNO3, and KCN:(NH4),S2Os , solution to remove the effects of machining. The specimen is then annealed in vacuum for 8 to 12 hr at 800°C to remove any residual stresses and also to recrystallize the end sections. The recrystallized ends are necessary since experiments showed that single-crystalline end sections are too soft to transmit the desired torque. Occasionally, recrystalliza-

Jan 1, 1960

By John C. Bilello

The brittle fracture behavior of cold-worked sintered tungsten was studied over the temperature range 4.2° to 298°K using a high-sensitivity strain measuring system and electronfractography. Similar observations were made on a swaged electron beam zone-refined monocrystal. In sintered tungsten irreversible plastic deformation was observed during cyclic load-unload tests at stress levels well below the fracture stress for all temperatures, but general microyielding could be detected only down to 202°K. For the zone-refined samples macroyielding occurred at all test temperatures with evidence for twinning below -202°K. The fracture stress of the sintered tmgsten was virtually independent of temperature, while the zone-refined crystal showed a 2.3 times increase over the same temperature range. Electronfractography confirmed the presence of numerous rod-shaped and spherical submicroscopic voids which ranged in diameter from 1400 to 4300A in the sintered tungsten; no voids could be found in the zone-refined tungsten. Contrast effects observed on the replicas in the vicinity of certain voids indicated that plastic deformation could be induced by the local stress concentration. It has been suggested that the presence of these voids may be responsible for the low-temperature brittle failure of sintered tungsten. Based m this suggestim und on the evidence obtained here, a dislocatim model is presented to account for the brittle behavior of sintered tungsten. In this model slip, which is induced by the local high stress concentration in the region at the edge of a favorably oriented void, could cause the void to grow to a microcrack of critical size. STUDIES of brittle fracture in bcc metals have led to the well-known experimental relationships between grain size, yield stress, fracture stress, and temperature which have formed the basis for the various dislocation pile-up1-3 or interaction4'= models for slip-induced microcrack nucleation. While microcracks can be nucleated by deformation twins,6,7 there has been no direct evidence furnished by transmission electron microscopy to support conclusively either the Zener pile-up or Cottrell dislocation reaction models for producing micro-cracks in all "brittle" materials. In addition to the "inverse" grain size relationship for yield and fracture stresses the cottrel14 theory predicts that the fracture stress below the transition temperature should behave in a fashion similar to that of the yield stress above this temperature. Such behavior has been verified for several bcc metals.8-10 With reference to both grain size effects and the tem- perature dependence of the fracture stress below the transition temperature, the behavior of sintered tungsten appears anomalous. Early work by Bechtold and Shewrnon 11 showed no apparent temperature dependence of the fracture stress below the ductile-brittle transition temperature (DBTT). They attributed this result to the intergranular nature of the fractures observed. More recent work by Wronski and Four-deux12'13 on considerably purer material did not show any systematic relationship between the fracture stress and temperature below DBTT. The dependence of flow and fracture stresses on grain size is also not clearly established for sintered tungsten. Koo, for example, has shown that the DBTT for sintered tungsten depended chiefly on the annealing temperature and was relatively insensitive to the actual grain size achieved. Using electrofractography and transmission electron microscopy, Wronski and Fourdeuxl3 showed that numerous spherical and rod-shaped submicroscopic voids could be found in sintered tungsten but not in melted tungsten of nominally the same purity. They suggested that these voids could be responsible for the temperature insensitivity of the fracture stress below the DBTT. In the present work the temperature dependence of the fracture stress for high-purity commercially sintered tungsten has been determined. The presence of submicroscopic voids in sintered materials was confirmed, and these were studied in detail to examine the role they could play in nucleating brittle fracture. A dislocation model is suggested which could cause an inherent spherical void to lengthen into a Griffith crack of critical size. EXPERIMENTAL PROCEDURE Commercially sintered tungsten rod was obtained in the as-swaged condition from Sylvania. A zone-refined crystal was obtained from the same source. This crystal was grown by giving three zone passes (at 25.4 cm per hr) to a sintered rod of high-purity tungsten. The rod axis prior to cold working was -15 deg from the [110] direction. Originally the zone-refined rod was -6 mm in diam; it was reduced to -3 mm by eight swaging passes, at high temperatures, with each step having about the same reduction of area. The final swaging step gave a 7.5 pct reduction of area at 1050°C. All swaging operations were performed in a hydrogen atmosphere. For the sintered rod a similar working schedule was employed. Metal-lographic examination of the sintered material revealed that the cold-worked structure had an apparent grain diameter of -25 u transverse to the swaging direction (obtained by the intercept method). In the longitudinal direction cold-worked grains were approximately 1.5 to 2 times their diameter. No distinct fiber structure could be observed optically for the zone-refined rod. The cold-worked structure in the

Jan 1, 1969

By N. A. Gokcen, J. Chipman

Aluminum and oxygen dissolved in liquid iron were brought into equilibrium with pure alumina crucibles and atmospheres of known H2O and H2 contents to study the reactions: 1—Al2O3(s) = 2 Al + 3 0; 2—Al2o3(s) + 3H2(g) = 2Al+ 3H2o(g); and 3—H2(9) +O = H2O(g). Aluminum strongly reduces the activity coefficient of oxygen and similarly oxygen reduces that of aluminum. Values of the product [% All" • [% O]3 are much smaller than those found in previous experimental studies and are of the order of magnitude of the calculated values. ALUMINUM is the strongest deoxidizer commonly A used in steelmaking, but the extent to which it removes dissolved oxygen has been debatable. The relationship between aluminum and oxygen has not been determined reliably not only on account of the usual experimental difficulties at high temperatures but also because of uncertainties in the analyses of very small concentrations of oxygen and aluminum. The earliest experimental attempt of Herty and coworkers' was followed by a more systematic study of Wentrup and Hieber.' These authors added aluminum to liquid iron of high oxygen content in an induction furnace and considered that 10 min was sufficient to remove the deoxidation products from the melt. Parts of the melts thus obtained were poured into a copper mold and analyzed for total aluminum and oxygen (soluble plus insoluble forms), assuming that the insoluble parts were in solution at the temperatures from which samples were taken. It is conceivable that the furnace atmosphere in their experiments, consisting of mainly air at 20 mm Hg pressure, was a serious source of continuous oxidation and therefore that their oxygen concentrations were correspondingly high. Scattering of their data was explained to be well within the maximum inaccuracy of 10°C in the temperature measurements and errors of ±0.002 pct each in the oxygen and total aluminum analyses. Maximum and minimum deoxidation values, i.e., values of the product [% All' . [% O] differed by factors of 10 to 15; mean values of 9x10-11 and 7.5x10-9 ere reported at 1600" and 1700°C, respectively. Hilty and Craftsv determined the solubility of oxygen in liquid iron containing aluminum, using a rotating induction furnace. Pure alumina crucibles used in their experiments contained the liquid iron which in turn acted as a container for slags of varying compositions consisting mainly of Al2O3, Fe2O3, and FeO. The furnace was continuously flushed with argon, and additions of aluminum and Fe2O3 were made in the course of each experimental heat. The inner surfaces of their alumina crucibles were covered with a substance other than pure Al2O3, containing both iron oxide and alumina. Although frequent slag additions can change the composition of slag in the liquid iron cup formed by rotation, the inner surface of the crucible must depend upon the transfer of oxygen or aluminum through the liquid iron for any adjustment in composition. It is not clear that their metal was in equilibrium with the crucible wall, but it is clear that it was not in equilibrium with Al2O3. Their deoxidation product, [% A].]" • [% O]3, varied by a factor of more than 50; the average values of 2.8x10- and 1.0x10-7 were selected for temperatures of 1600" and 1700°C, respectively. Aside from the experimental determinations, attempts have been made to calculate the deoxidation constant for aluminum indirectly from thermody-namic data. Schenck4 combined the thermodynamic data for Al2O3 and dissolved oxygen in liquid iron by assuming an ideal solution. His calculated values are 2.0x10-15 and 3.2x10-13 at 1600" and 1700°C, respectively. Later, Chipman5 attempted to correct for the deviation from ideality and derived an expression which led to deoxidation values of 2.0x10-14 and 1.1x10-12 at 1600" and 1700°C, respectively. The errors in these treatments originate mainly from inaccuracies of thermal data and uncertainties regarding the activity coefficients of dissolved oxygen and aluminum. The purpose of this investigation was to study the equilibria represented in the following reactions in the presence of pure alumina: Al2O3(s) = 2Al + 3O K = aAl2.ao3 [1] Al2O3(s) + 3H2(g) = 2Al + 3H2O(g) H2O K2 = aAl2(H2O/H2 ) [2] H2(g) +O = H2O(g) K3 = 1/ao (H2) [3] The experimental method consisted of melting pure electrolytic iron, usually with an initial charge of aluminum, in pure dense alumina crucibles under a controlled atmosphere of H,O and H2 and holding

Jan 1, 1954

By W. L. Kerlie, J. H. Richards

The variation in hydrogen content of basic open-hearth steels during refining and the effect of changing from steam to air atomization were studied. The water content of the furnace atmosphere, the slag basicity, and the degree of oxidation of the slag-metal system largely control the hydrogen in the steel. SMALL amounts of hydrogen have an adverse effect on the ductility of steel and a wide range of hydrogen contents has an adverse effect on the internal soundness of both ferrous and nonferrous castings. This has been of major concern to the metal industry, both manufacturers and fabricators, for many years. As one of the results of continuing investigations of the hydrogen problem, much has been learned about methods of reducing the hydrogen content of liquid metals below the relatively high levels that are normally associated with such phenomena as rising ingots and excessive porosity in sand casting. However, it was not until a reliable and simple method for sampling and analyzing liquid metal was developed that much progress was possible in quantitatively evaluating the effect of steelmaking practice on hydrogen contents at levels below 6 to 8 ppm. Throughout all the work described in the following presentation the Geffner pintube technique was used to obtain samples of liquid metal1 * and the tin-fusion method, developed at Massachusetts Institute of Technology,2 was used to analyze the samples. Before attempting a systematic experimental program for minimizing the hydrogen content of open-hearth steels, it was necessary to determine the variation in hydrogen in the open-hearth bath during the normal processing of a heat. The logs of ten heats are illustrated in Figs. 1 through 7. The number at each point on the graphs refers to the number of pintube samples analyzed for hydrogen. An increase in the hydrogen content of the liquid metal during the early period of refining is apparent in all heats. There is evidence of a decrease in hydrogen later in the refining period, see Fig. 2, for example. Therefore, the existence of a maximum hydrogen content at some intermediate time during the refining period is anticipated. To test for the existence of a maximum, the data illustrated in Figs. 1 to 5 were grouped together so that they could be examined on a collectively comparable basis. The grouping was effected, as illustrated in Fig. 8, by superimposing Figs. 1 to 5 so that the apparent hydrogen maxima coincided at a fixed position, indicated by the zero on the time axis. Also, by vertical adjustment until the graphs appeared to the eye to be superimposed, the hydrogen scale was made to show the change in hydrogen content. That is, a standard amount was subtracted from the hydrogen values for each heat. Therefore, Fig. 8 represents a generalized presentation of the data and, for this reason, cannot be used to predict the actual hydrogen content of the bath during refining, but rather to show the probable rate of change in hydrogen during refining. Statistical examination of the grouped data in Fi.g. 8 shows that the apparent. increase and suhsequent decrease in hydrogen are real and confirms the existence of a maximum in general. The average increase In hydrogen during the early period of refining is between 0.8 and 1.3 ppm per hr, and the

Jan 1, 1958

By J. Chipman, N. J. Grant, R. Rocca

Desulphurization of liquid iron by reducing slags of the electric-furnace type was studied from 65 heats. Variations were made in basicity over a wide range and in FeO up to about 5 pct for their effects on desulphurization. The role of FeO in desulphurization from the blast furnace, to the electric furnace, to the oxidizing conditions of the open hearth is shown to fit a relatively simple pattern of behavior. THE mechanism which controls the desulphurization of molten iron by basic slags has been the object of several investigations. In particular, equilibrium determinations have been made both in the field of basic open-hearth slags, which have a high iron-oxide concentration, and in the field of blast-furnace slags which have a very low iron-oxide concentration. In both cases the desulphurization ratio has been found to increase with increasing basicity of the slags; however, the mechanism of desulphurization differs in the two cases. In basic open-hearth slags desulphurization occurs mainly as a partition of iron sulphide:&apos; FeS * (FeS) and the desulphurization ratio is approximately independent of iron-oxide concentration in the slag. In blast-furnace slags the concentration of iron oxide is very low as a result of the highly reducing conditions in which they are formed. The controlling reaction for desulphurization is then:2,3 FeS + (CaO) <=* (CaS) + (FeO) The slags of the reducing stage in the electric furnace have an iron-oxide concentration which is intermediate between blast-furnace and open-hearth slags. The study of the mechanism of desulphurization for these slags has been the object of this investigation. The importance of low (FeO) in the slag for desulphurization was first verified by Bardenheuer and Geller,& who found that high desulphurization ratios were obtained in highly reduced slags. It was recognized" hat iron oxide in the slag becomes a controlling factor in desulphurization only at FeO concentrations approximately under 5 pct. A recent investigation conducted by Buehl,7 upon the suggestion of one of the authors, confirmed this opinion from the results obtained from a heat conducted in a small arc furnace. In the present investigation, slags of very high basicity, such as often are encountered in the basic electric furnace, could not be studied, but equilibrium data have been obtained for slags in a wide basicity range. The iron-oxide concentration in these slags ranged from 0.08 to 15 pct and was controlled by the addition of silicon to the metal. Other constituents of the slags were mainly CaO, MgO, SiO2, A120,, and CaF,. The experimental technique was essentially the same as that of previous investigations.1 8-lo In an open magnesia-lined induction furnace, 65 lb of Armco ingot iron was melted. An atmosphere of hydrogen was maintained over the melt for 1 hr to bring the carbon content down to approximately 0.010 pct maximum. The bath then was exposed to air for 25 min to remove hydrogen. The electrodes were put in place, and the furnace was operated from this point on in an atmosphere of nitrogen. A synthetic slag was added to which additions of silicon and iron sulphide were made. A rate study conducted at the beginning of this investigation had

Jan 1, 1952