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By R. Schuhmann

Distribution of material in the fine sizes of a comminution product generally is well represented by the empirical equation' y = 100 (x/k)a [1] in which y — cumulative percent finer, x = particle size, a -= distribution modulus, and k = size modulus. Charles3 found that the energy consumption in comminution is usefully expressed by another empirical relation, E = Ak(1-D) [2] in which E = energy input per unit volume of material, A = a constant, k = size modulus based on Eq. 1, and n = a constant; (1-n) is the slope of a plot of log E vs log k. Holmes3 has presented energy equations similar to Eq. 2. The constants a and n in Eqs. 1 and 2 have been shown to depend both on the nature of the material and on the comminuting device. Moreover, Charles showed that within experimental error a and n are a — n+1 = 0 [3] Combining Eqs. 2 and 3, E = A k-a [4] In the first sections of this article it is shown that the energy equation, Eq. 4, can be derived directly from the size distribution equation for the fine sizes, Eq. 1. The derivations are made without assuming any of the specific relationships between energy and particle size which have been common in previous literature. For comminution processes in which Eqs. 1 and 4 adequately represent the experimental data, the constant A in Eq. 4 is found to be a simple and useful inverse measure of grindability. That is, A is the energy consumption per unit volume of comminution product finer than unit size as determined from the straight line portion of the log-log plot of the size distribution. These considerations all lead to a unifying hypothesis of comminution mechanism from which both Eq. 1 and Eq. 4 can be derived. Finally, it is pointed out that this hypothesis raises serious questions as to the significance of the Rittinger hypothesis, the Kick hypothesis, and other theories in which energy numbers are systematically assigned to various size fractions of comminution products in order to calculate theoretical energy consumptions. Derivation of the Energy Equation from the Size Distribution Equation: For simplicity, consider the comminution of 100 volumes of a feed material of relatively uniform particle size. The comminution process may be considered as the summation of many individual and independent comminution events. The extent of comminution is most easily expressed as the number of comminution events, z. In the first derivation, the key assumption is that the characteristics of the comminution events in a given crushing or grinding process are substantially constant and do not vary with the progress of the comminution process. Accordingly the characteristics of an average comminution event may be defined. In one such event, a quantity of energy $E is applied to a single particle of size f and volume $v. The crushing of this particle produces fine particles with a size distribution similar to that given by Eq. 1: yw=100(x/ka)a0 [51 In this equation yo, a0, and k0 are used to characterize the product of an individual comminution event rather than the product of the comminution process as a whole. In using Eq. 5, we will not be concerned with values of x close to the feed size f and will therefore assume only that the equation is applicable to the finest sizes of the material. In 100 volumes of total product, the actual volume of product finer than x from a single comminution event, or dy, is given by The total volume of material below size x, resulting from z events, is then given by y = z(dy) =z(dv) (x/ka)a0 =" Eq. 7 reduces to Eq. 1 when we let a, = a and [8a] z =100/dv (ka/k )1 or k = ka (zdv/100)-1/a [8b] Eq. 8a shows that the distribution modulus of the comminution product is the same as for the product of an individual comminution event. Eq. 8b shows how the size modulus of the comminution product k varies with the extent of comminution as measured by the number of events, z, or as measured by the fraction of the feed actually subjected to com- minution1 zdv/100. The energy input to 100 volumes of total feed, or 100E, is the sum of the energy inputs for all the comminution events: 100E =z (dE) [9]

Jan 1, 1961

By J. E. Gosline

In any theory of a hydrodynamic nature dealing with the vertical flow of gas-liquid mixtures in pipes, the two factors that present the greatest difficulty are the relative motion between the phases and the energy loss resulting from turbulence work. The former has generally been referred to in the literature as "slippage" and the latter as "friction." A third factor of importance is the nature of admixture between liquid and gas for both the relative motion between the phases as well as the turbulence work are functions of the type of mixture. Although much work of a general nature has been performed on the vertical flow problem, there have been very few attempts made to study experimentally the factors involved in the phenomenon individually. Of these, perhaps the most notable is the work of Moore and Wilde1 on slippage. Some writers on the subject have assumed that over a wide range of operating conditions the controlling type of mixture is one in which gas bubbles of uniform size are distributed throughout the liquid, and that the data obtained from experiments on the motion of single bubbles through various liquids may be used in evaluating the slippage. Ver-sluys2 has further assumed another controlling type of mixture in which the liquid occurs as a dispersed phase within the gas and applies data on the fall of drops of water in air to calculating the relative velocity. It was for the purpose of studying the applicability of data on single bubble motion to the slippage factor and to further observe the nature of mixtures that a research program was conducted at the University of California during 1932 and 1933. These experiments formed a basis for

Jan 1, 1936

By L. Dudley Stamp

On April 1, 1937, Burma, formerly a province of the Indian Empire, was formally separated from India and became an independent unit of the British Commonwealth. In future, therefore, statistics of oil production in India will exclude Burma and those for Burma will be separately published. The last few years have been marked by noteworthy, almost spectacular, developments in the oil fields of Burma and the Punjab. In Burma these developments have been the proving of unexpected extensions of the existing fields and not the discovery of entirely new fields. The new extensions are important not only to Burma in giving a new lease of life to her fields, but also in general as stressing some interesting geological aspects hitherto neglected. Production The production of crude oil in Imperial gallons has been: Burma India 1934 254,760,070 67,265,210 1935 251,338,974 . 71,323,362 1936 265,656,393 69,241,504 1937 (eat.) 270,000,000 70,000,000 The Chindwin Fields.—The small field at Indaw continues to produce steadily about 3,000,000 gal. a year, but no really deep test has yet been successfully carried out and resources are thus not yet fully known. The remote location of the field, inaccessible except by river and situated 22 miles from the Chindwin 270 miles up that river from its junction with the Irrawaddy, has not encouraged active exploitation. The field is worked exclusively by the Indo-Burma Petroleum Co., Ltd. (I.B.P.), using now an automatic gas-lift system, and the company formerly refined the oil at a small refinery at Pantha on the river near by. The chief market was for kerosene in upper Burma. The refinery has now been closed. The oil is stored on the field during the low-water season

Jan 1, 1938

By J. E. Gosline

In any theory of a hydrodynamic nature dealing with the vertical flow of gas-liquid mixtures in pipes, the two factors that present the greatest difficulty are the relative motion between the phases and the energy loss resulting from turbulence work. The former has generally been referred to in the literature as "slippage" and the latter as "friction." A third factor of importance is the nature of admixture between liquid and gas for both the relative motion between the phases as well as the turbulence work are functions of the type of mixture. Although much work of a general nature has been performed on the vertical flow problem, there have been very few attempts made to study experimentally the factors involved in the phenomenon individually. Of these, perhaps the most notable is the work of Moore and Wilde1 on slippage. Some writers on the subject have assumed that over a wide range of operating conditions the controlling type of mixture is one in which gas bubbles of uniform size are distributed throughout the liquid, and that the data obtained from experiments on the motion of single bubbles through various liquids may be used in evaluating the slippage. Ver-sluys2 has further assumed another controlling type of mixture in which the liquid occurs as a dispersed phase within the gas and applies data on the fall of drops of water in air to calculating the relative velocity. It was for the purpose of studying the applicability of data on single bubble motion to the slippage factor and to further observe the nature of mixtures that a research program was conducted at the University of California during 1932 and 1933. These experiments formed a basis for

Jan 1, 1936

By Samuel Wyer

THE art of natural-gas compressing is now over 25 years old, and has grown at practically the same rate as the increase in domestic natural-gas consumers. There are now over 200 natural-gas compressing stations in North America, aggregating more than 320,000 hp. of compressor capacity and representing a property value of more than $22,000,000, and compressing more than 85 per cent. of all the gas used. The age and magnitude of the art make it evident that the use of gas compressors is a recognized integral part and universal custom of the natural-gas business. The public also is not without its rights and vital interests in this problem. Approximately 1,700,000 domestic natural-gas consumers in North America are dependent upon gas compressors for their natural-gas service. That is, if the use of compressors were to be prohibited, the majority of these consumers would be unable to secure adequate natural-gas service. Each consumer represents between four and five persons, and it therefore follows that the comfort and well-being-as far as natural-gas service is concerned-of at least 8,000,000 persons would be affected if the use of natural-gas compressors should be prohibited. These 1,700,000 consumers have invested, in services, house piping, fixtures, and appliances, an average of about $90 each, or an aggregate of $153,000,000, which is much more than the companies' investment in gas compressors. Furthermore, in all cases where the rate paid by the consumers is fair to the gas company-considering the value of the service rendered by the gas company-the consumers are entitled to continued service and protection of the investment they have made on the faith that the gas service would be continued in the future.

Jan 2, 1916

By Wilbur Nelson

THE year 1923 has been a dull period in oil development in Kentucky and Tennessee, with the exception of the Kettle Creek area along the Tennessee-Kentucky line, in Clinton and Cumberland Counties, Kentucky, and Clay County, Tennessee. The price of oil during the year has been so low that wildcatters have shown little interest in drilling. At the beginning of the year, light oil sold for $2.31 per barrel and medium oil for $2.06 per barrel. Prices increased to the highest point for the year in February, when light oil brought $2.86 per barrel and medium oil, $2.61. In April, prices had declined 35 c. while in May an additional decline of 25 c. went into effect. During June, prices declined 20 c. per barrel; during July, 45 c. per barrel; remained stationary during August and September, and dropped during November and December to the low price of $1.36 per barrel for light and $1.21 for medium oil. At present, an increase of 29 c. has brought the price of light oil up to $1.55, and indications are that the price will continue to increase during the coming months. It can readily be seen that during 1923 the price of oil was such as to prevent any drilling except that necessary to hold leases and to maintain production enough to take care of overhead expenses.

Jan 3, 1924

By L. O. Howard

MUCH work has been done recently on the lead-antimony system1 in connection with lead-rich alloys of commercial importance containing less than 20 per cent. antimony. Dean, Zickrick and Nix have called attention to the perpetuation in the literature of several erroneous data, such as a eutectic temperature of 228° C. at 12.5 per cent. antimony, instead of 247° at 13 per cent. The series is given as a classic example of a straight eutectiferous series in such late books as those of Heyn and Grossmann,2 Jeffries and Archer,3 Guillet and Portevin4 Pulsifer,5 Rosenhain,6 and Liddell,7 as well as the somewhat earlier works of Hofman (1918), Wang (1909) and Williams (1920). The work of Dean has definitely showed a solid solution of antimony in lead at about 2.5 per cent. antimony. While lecturing to a class in general metallurgy at the University of Idaho, the writer had the students prepare a series of lead-antimony alloys for the purpose of illustrating methods of thermal analysis. Proper proportions of powdered antimony (sold as C.P.) and test lead were mixed and melted in graphite crucibles under a reducing cover. Cooling

Jan 1, 1928

By L. O. Howard

Much work has been done recently on the lead-antimony system1 in connection with lead-rich alloys of commercial importance containing less than 20 per cent. antimony. Dean, Zickrick and Nix have called attention to the perpetuation in the literature of several erroneous data, such as a eutectic temperature of 228° C. at 12.5 per cent. antimony, instead of 247° at 13 per cent. The series is given as a classic example of a straight eutectiferous series in such late books as those of Heyn and Grossmann, 2 Jeffries and Archer,3 Guillet and Portevin,4 Pulsifer,5 Rosenhain,6 and Liddell,' as well as the somewhat earlier works of Hof-man (1918), Wang (1909), and Williams (1920). The work of Dean has definitely shown a solid solution of antimony in lead at about 2.5 per cent. antimony. While lecturing to a class in general metallurgy at the University of Idaho, the writer had the students prepare a series of lead-antimony alloys for the purpose of illustrating methods of thermal analysis. Proper proportions of powdered antimony (sold as C.P.) and test lead were mixed and melted in graphite crucibles under a reducing cover. Cooling

By C. D. King

THIS year the American Institute of Mining and Metallurgical Engineers celebrates its seventy-fifth anniversary as well as the same anniversary of iron and steel in this country as we now know it. The society's span of life comprehends the very beginning and gradual development of the present-day iron and steel industry and its TRANSACTIONS are rich with the trials and achievements of the pioneers in this field. It is difficult to believe that in the first year of the Institute's existence there was produced in this country only 84,000 net tons of ingots, of which only 2000 tons was made by the open-hearth process; that the bessemer process was just barely beginning; that charcoal and anthracite were virtually the only blast-furnace fuels; that Mesabi ores had not been used in blast furnaces, and such pig iron as was then made was produced at a number of small units, each adjacent to its ore and fuel supply. The growth from 84,000 net tons production of steel ingots to 95,500,000 tons in 1945 eloquently tells the story of America's industrial growth.

Jan 1, 1947

By E. Hornbogen

The deformation mechanisms of a iron-phosphorus alloys were compared at 20oand —196°C. Alloying with phosphorus increases the resistance to slip, but has little effect on the resistance to twinning. The stress for onset of twinning is nearly independent of temperature, but there is an increasing tendency for cleavage along (112) twin boundaries with decreasing temperature and increasing phosphorus content. FIVE iron-phosphorus alloys and one high-purity iron (0.004 pct C, 0.004 pct N, 0.05 pct O) were vacuum melted and cast, then homogenized for 6 hr at 1100oC and water-quenched. Single crystals were cleaved from the coarse grains produced in this manner. The hardness was measured* on polished (100) surfaces of the crystals at 20" and -196°C. Laue back-reflection patterns indicated a deviation of not more than 3 deg from coincidence of the {100} plane with the surface. The deformation mechanisms were studied by relief effects on the polished surfaces. Yield points in compression (0.5 pct offset) were measured with polycrystalline material. At 20°C the addition of phosphorus to a iron leads to a change from slip to twinning as the main deformation mechanism, Figs. 1(a), (b). Between 2 and 4 at. pct P slip and twinning occur simultaneously. In alloys with more than 4 at. pct P twinning is the main deformation mechanism and slip was observed only in the neighborhood of twin intersections. All cracks at 20oC were on (100) planes, some initiated by twins.' From measurements made at-196oC, hardness and yield points of all the alloys were nearly constant and the same as the hardness of high phosphorus alloys that deformed by twinning at 20°C, Figs. 2 and 3. In the high-purity iron, plastic deformation at -196°C occurred by both slip and twinning, but deformation in the iron-phosphorus alloys appeared to be entirely by twinning. In the high phosphorus alloys a large number of cracks formed along the (112) twin boundaries and at intersections of twins, in addition to the (100) cleavage, Fig. 1(c). DISCUSSION In , iron, plastic deformation can occur either by slip or by twinning, depending upon composition,

Jan 1, 1961

By F. A. Veer, W. G. Burgers, B. H. Kolster

Starting-- from Cu-Si diffusion couples a study of diffusion in the intermetallic compound Cu3Si of the Cu-Si system has been made. Mmker experiments showed copper to be the diffusing element. From the rate of growth of the Cu3Si phase diffusion coefficients were derived. The activation energy for diffusion is 18.6 kcal per mole. The couples show some interesting microscopic features, for which a tentative explanation is given. THE synthesis of dimethyldichlorosilane, (CH3)2SiC12, an important compound in the manufacture of methyl-silicones, takes place at the surface of a thin Cu3Si layer deposited on a mass of silicon particles."' By passing CH3C1 vapor at about 350°C, silicon atoms are consumed from Cu3Si in forming the volatile silane molecules, thus leaving copper atoms at the surface. It is well-known that copper acts as a poison for the above-mentioned reaction by catalyzing the dissociation of methylchloride.' However, no poisonous effect is observed, at least not before most of the silicon from the particles is converted into silane.3 This would be understandable, if either the copper atoms diffuse through the Cu3Si deposit to the underlying silicon or silicon atoms diffuse in the reverse direction to the copper, both processes resulting in the formation of new Cu3Si and so ensuring the proceeding of the reaction. In this paper experiments are described, demonstrating copper to be the diffusing element. Also a very low activation energy for the diffusion is observed. EXPERIMENTAL The silicon used contained 1 ppm Mg and 1 ppm Cu; the copper was spectroscopically pure (Fe: 2 ppm; Ag, Mg, Si: 1 ppm). The copper and silicon samples were prepared in the form of blocks of approximately 10 by 10 by 5 mm with two parallel sides by spark-machining. The blocks were ground on emery paper (grit 600), etched (copper with nitric acid, silicon with a 4:l nitric acid:hydrofluoric acid mixture), and cleaned with alcohol. As the brittleness of the silicon did not allow a welding procedure to prepare the diffusion couples, the copper and silicon blocks were pressed together in a steel clamp. The pressure exerted by the clamp brought about contact between the parts of the couple and so ensured proceeding of the diffusion. The couples were heated in a vacuum furnace (about 10"5 Torr). The temperature was stabilized within 1 pct. After a heat treatment a section parallel to the direction of diffusion was examined in the microscope and in the X-ray scanning microanalyzer. To determine whether copper or silicon is the diffusing element marker experiments were carried out using tungsten wires with a 20-p diam. EXPERIMENTAL RESULTS Figs. 1, 2, 3, and 4 give micrographs of diffusion zones of Cu/Si couples. Analysis by the electron mi-croprobe of the Cu/Si samples after a definite heat treatment revealed the existence of only one intermetallic phase as can be seen from the line scan shown in Fig. 5. From the X-ray diffraction pattern it could be deduced that this phase was CU 3 Si.4 Even when diffusion zones of considerable width (up to 600 p) were obtained, no other phases occurring in the Cu-Si system could be detected, neither by the electron microprobe nor by X-ray diffraction analysis. The optical anisotropy of the Cu3Si phase made it possible to observe the columnar shape of the crystal-

Jan 1, 1969

By J. Kucera, J. Vreštál

DIFFERENT authors1 ' have been engaged in meas-uring the vapor pressure of pure cobalt. The results of their measurements satisfy the expected temperature dependence of vapor pressure and are in mutual agreement, with the exception of the results by De Dyk Man and ~esmejanov.~ The latter authors, by using the effusion method, have achieved considerably higher values than other workers. By using the isotope exchange method they obtained much lower values than other authors. The determination of thermodynamic functions of the binary Ni-Co system was carried out, as far as we know, only by De Dyk Man and Nesmejanov.4 This determination was based on extremely low values of vapor pressure over pure cobalt obtained by the isotope exchange method. Therefore we considered it useful to repeat these measurements. Furthermore, the reliable values of thermodynamic functions should complement the migration characteristics, the inner magnetic field data obtained by Miissbauer effect measurements, specific heat data, and the K effect and positron annihilation characteristics that have been achieved for the Ni-Co system in the Institute of Metallurgy of the Czechoslovak Academy of Sciences in Brno.5-9 The measurements in this paper were performed by the isotope exchange method. In this method, as has been shown by analysis,10-'3 the vaporization rate, w, can be calculated from the relation w = k/1oSw [1] i0Sw) [1] where L, is the activity per unit mass of the source, S is the area of evaporation, k is the tangent at the point t = 0 to the curve giving the radioactivity de-pendence of the target vs annealing time, t, and wis the probability for the tracer atom condensation on the target surface. The value for cc. can be obtained from the equation w = a + 2P(l-a) [2] where P is Clausing's coefficient and a is the condensation coefficient. In the present work the cylinder shaped containers for annealing the samples were used, characterized by the ratio 1:d = 1.06. Here 1 is the length and d the diameter of the container. For this ratio P = 0.514 and w =0.5, and w is independent of the condensation coefficient. The vaporization rate is related to the vapor pressure p by the relation where R is the gas constant, T is the absolute temperature, and M is the molecular weight of the component investigated. Measurements of the vapor pressure of the i component over the pure metal, p!, and the alloy, pi, at the given temperature and composition enable one to calculate the thermodynamic activity of this component from the equation ai=pi/pi [4] is and the activity coefficient ri=ai/xi [5] xi where xi is the molar fraction of the investigated alloy component. EXPERIMENTAL Evaporization rate measurements were carried out with pure cobalt and eight different Ni-Co alloys, which were kindly delivered by the Centre National de Recherches Me'tallurgiques Liege, Belgium. The composition of the alloys is given in Table I. The cobalt used in these alloys contained the following impurities: 0.016 wt pct Fe, 0.014 wt pct Cu, 0.01 wt pct Mn. Other elements were present in much lower concentrations. From the melts, samples in the form of small cylinders of 12 mm in diam were ma-chined. The thickness of the targets and sources was 2.5 and 1.2 mm, respectively. The lower thickness of the sources was chosen to make their over-all ac-tivity as low as possible. Sources were activated in

Jan 1, 1970

By B. M. Larsen, L. S. Darken

SOME years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2 by a high concentration of active (or "free") lime and of manganese oxide dis) solved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. DISTRIBUTION OF MANGANESE BETWEEN SLAG AND METAL AT EQUILIBRIUM On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction [FeO + Mn = MnO + Fe [A]slag metal slag metal] the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as [K" aMoO aFeI1 dFec) aMn] where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term [afe] may be combined with K" to give a new constant K'. Making these changes,

Jan 1, 1942

By Leonard A. Wood, A. G. Winslow

Subsidence has occurred in several areas of the upper Gulf Coast region of Texas, although in most cases this is not evident without precise instrumental leveling. As referred to in this report, the region com- prises about 7200 sq miles of the Gulf Coastal Plain and includes all or parts of the following counties: Harris, Fort Bend, Waller, Brazoria, Galveston, Liberty, Chambers, Orange, and Jefferson (Fig. 1 ). Topographic relief is low, ranging from sea level at the Gulf of Mexico to 300 ft or more in northwestern Harris County.

Jan 10, 1959

By R. P. Smith

The carbon content of a number of alloys ranging (before carburitation) from purified iron to purified cobalt was determined for fixed activities of carbon by equilibration with each of six CO-CO2 atmosphere at 1000°C. At fixed carbon activity, the carbon content decreases continuously with increasing cobalt content. For concentrations of 0 to 50 at. pct Co the results can be expressed by a linear interaction equation of the type In y2 = 7.76n2/(n1+n3)+ 2.30 n3/(n1+n3) where y2 is the activity coefficient of carbon (standard state such that y2— 1 as n2 — 0 in the Fe-C binary) and n1, n2, and n3 are the number of atoms of iron, carbon, and cobalt per unit weight of alloy. The results are also given in terms of the a functions. In the same concentration range, the results are in accord with the regular solution theory of Alcock and Richardson. THE carbon content of Fe-Si, Fe-Mn, and Fe-Ni alloys at fixed activities of carbon has been reported previously.'-, The present work extends R. P. SMITH, Member AIME, is Research Chemist, E. C. Bain Laboratory for Fundamental Research, United States Steel Corp., Research Center, Monroeville, Pa. these measurements to a series of Fe-Co alloys. These alloys, like the Fe-Ni alloys, are fcc ("aus-tenitic") over the entire range of composition at 1000°C. EXPERIMENTAL PROCEDURE The alloys were made from electrolytic cobalt and Plast-Iron in a small vacuum-melting furnace. A small amount of graphite was added to each melt to keep the oxygen content low. The ingots were analyzed for iron and carbon: the amount of cobalt was obtained by difference. Analysis of the top and bottom of the ingots indicated that they were uniform in alloy content. Except for the pure cobalt the ingots were hot-rolled to approximately 0.15 cm thickness, cleaned by sandblasting, then cold-rolled to about 0.045 cm. We were not successful in cold rolling the pure cobalt; therefore it was hot-rolled to the final thickness. The last traces of surface oxide were removed by acid pickel, then the samples were treated in a hydrogen-2 pct water vapor mixture at 1100°C to remove carbon and most of the oxygen. The carburizing procedure was similar to that previously described.1,2,4 The alloys in the form of strips about 1.7 cm wide, 7.5 cm long, and 0.04 cm thick, together with a similar specimen of purified iron, were equilibrated with each of six CO-CO2 mixtures of fixed composition, then quenched in the

Jan 1, 1965

By E. R. Atkins, G. H. Smith

Results of laboratory tests are presented to show that lire value of "m", in the Archie expression dernlined by the shapes of the particles in the system. Tile value of m "the shape factor", is constant for a system of particles of a given shape for a range of F - + values. Applying this concept, one can predict F - + relationships for mixtures of particles with different shapes, and these predicted relationships are useful in electric log interpretation. It is suggested that an equation of the form 1/F -10mcan be used to describe the properties of natural formations containing varying amounts of sand and clay. From this work and values of "a" and "m" reported in the literature, it appears that in many cases rocks in the same geological horizon have a common primary porosity but contain varying amounts of a particular clay. It is concluded that the equation can be applied to a rock-water system only when values of "a" and "m" have been established for the particular system. INTRODUCTION The petroleum literature contains many reports of the results obtained by determining formation resistivity factor F and porosity + of rock samples from oil fields all over the world. The usual practice is to use data from a large number of samples from a number of fields to find an average relationship between F and +. Several such average relationships have been advanced. In the absence of data on a particular formation or field, it has been the practice to use the average relationships to give a rough approximation of the F - + relationship. The purpose of this paper is to report on basic relationships that exist between F and + for naturally occurring particles in water solutions. Other workers' have found the same relationships apply to the diffusion of hydrogen through packed beds of dry particles. In the work discussed here, relationships for application to unconsolidated sands or shales containing mix- tures of particle shapes are derived. These relationships, developed for unconsolidated formations, may apply to consolidated formations. EXPERIMENTAL To evaluate F- relationships for unconsolidated rocks, the results of laboratory measurements on simple slurries of clay or sand will be used. Such laboratory studies are concerned with the electrical behavior of water-containing rocks. The wet rock constituents are electrically similar in slurries and in rocks. Archie2 defined formation resistivity factor as All resistance measurements were made using a 1,000-cycle impedance bridge with an oscilloscope as the null detector." The accuracy of this bridge was better than * 0.15 per cent. For the particular apparatus employed, no additional reactance was required to achieve balance for samples with resistances between

By B. M. Larsen, L. S. Darken

SOME years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general. our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2-by a high concentration of active (or "free") lime and of manganese oxide dis) solved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. DISTRIBUTION OF MANGANESE BETWEEN SLAG AND METAL AT EQUILIBRIUM On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction [FeO + Mn ;7± MnO + Fe [A] slag metal slag metal] the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as [K" aFPI OFeO ? aMn] where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term aFe may he combined with K" to give a new constant K'. Making these changes.

Jan 1, 1942

By F. R. Scauzillo

Equilibrium data which should be useful in the design and/or evaluation of glycol dehydration units were prepared from an analysis of various published data and the correlation of these data by the use of the thermo-dynamic equilibrium ratio. The equilibrium ratios of water are used to solve the glycol absorber problem; such solutions are necessary to define the number of trays and the glycol circulation rate needed to meet drying requirements. Activity coefficients were obtained which relate directly to the equilibrium ratios of water in the water-TEG-natural gas system. These activity coefficients have been used to calculate the equilibrium dew points for aqueous TEG concentrations of 60 to 99.9 weight per cent for the temperature range of 40° to 120° F. They also provide a means of calculating equilibrium ratios for water in the water-TEG-natural gas system; this applies to any desired TEG concentration and to the temperature range from 40° to 120°F. INTRODUCTION During the last several years, the drying of natural gas with aqueous triethylene-glycol (TEG) solutions has become very prominent. Most users of TEG as a drying agent have been satisfied with the performance of TEG solutions at the conditions used; however, there always has been some discussion of the drying ability of TEG solutions at conditions not commonly encountered such as temperatures below 50° or 60°F, but more particularly temperatures above 100°F, and pressures above 1,000 psia. Today, when higher wellhead temperatures such as 120°F are more commonly encountered many are skeptical of TEG's ability to dry sufficiently well to provide dew points around 32°F, which is generally the maximum tolerable when attempting to dry a gas to contract specifications of 7 Ib/MMscf. These views probably have evolved to some extent from the days when suppliers would not guarantee dew-point depressions in excess of 65° to 75 °OF. Also, the feelings about TEG drying may have arisen from the lack of information about the equilibrium relation of water in the drying operations. Porter and Reid' have reported equilibrium data for a 95 per cent TEG solution, while Townsend2 reported equilibrium data for 95, 98 and 100 per cent TEG solutions. Townsend also presented a calculational method which obtains activity coefficients in the liquid phase and, subsequently, the equilibrium water content of a saturated gas over glycol from published3 atmospheric dew points. Wise, Puck and Failey' presented activity data for the water-TEG system at atmospheric pressure. In the past, the equilibrium ratios published for water in a 95 per cent by weight aqueous TEG solution have been used indiscriminately by many for all concentrations of TEG encountered in gas drying operations. Since essentially all such gas operations require the use of more concentrated TEG solutions, a study was undertaken to correlate the existing equilibrium data for aqueous TEG and gas systems and to provide some means of calculating the equilibrium ratio of water in the natural gas-water-TEG system where TEG concentrations were other than 95 per cent. The data presented herein consider only the equilibrium drying ability of the TEG solutions and do not consider the effect of temperature and pressure on the tray eficiency of contactors. In other words, this paper is concerned primarily with the development of the equilibrium relationship between water in the dried natural gas and the water in the lean TEG entering the top tray of the absorber. BASIC EQUILIBRIUM RELATIONS A relationship which relates the K value of water in the natural gas-water-TEG system to the vapor pressure of water at the system temperature, the total pressure of the system and the activities of the liquid and gas phases has been evaluated. It is well known that, for any component of a mixture at equilibrium between a gas phase and a liquid phase,

By Ronald J. McGregor, Anton R. Hendriksz

INTRODUCTION The NIMCIX contactor was developed in the late sixties at the National Institute for Metallurgy in South Africa, for the main purpose of extracting uraniuy from relatively low-grade uranium solutions. ' The concept was sufficiently developed by 1974 to permit the operation of a 1500 litre per minute column to treat unclarified urgnium-bearing solution under industrial conditions. The plant operated so successfully that several large-scale units have subsequent18 teen constructed and are operating efficiently. ' Total resin consumption figures as210w as 3 per cent per annum have been reported, and the extraction efficiencies of the installations have been exceptionally good. All the solutions treated have been acidic in nature and in every case have been of such a nature as to significantly depress the maximum uranium loading on the resin beads. The chemical constituents of the leach solution fed to the loading column determines the ease with which the soluble uranium can be absorbed by an ion exchange resin. The concentration of competing ions and various resin foulants define the nature of the continuous ion exchange equipment required for efficient extraction performance. The basic NIMCIX concept is retained in these various alternate designs, but batch or continuous elution methods with fully automated or manual control systems may be selected for the different process solution conditions. BRIEF DESCRIPTION OF THE NIMCIX CONTACTOR The NIMCIX ion exchange column is a multi-stage fluidized bed contactor which is designed to permit a counter-current flow of solution and resin in order to maximize extraction efficiency. The flow o resin is periodic, based on the Cloete and Streat 5 principle of reverse flow. The basic operating cycle can be divided into five periods, as illustrated in Figure 1. For the purposes of describing the cycle, the loading column is considered; how- ever, a similar sequence may be applied to the operation of a NIMCIX continuous elution column. S'I'EP 1: During the forward flow period, Solution flows up through the column and fluidizes the resin contained in each stage. The uranium depleted solution overflows the upper flared-section of the column as the tail solution. Step 2: The flow of solution to the column is temporarily stopped and the resin is allowed to Settle onto the plates in the column. STEP 3: During the reverse flow period, a fixed volume of solution is drained from the column to the transfer vessel. This flow causes resin transfer to occur from stage to stage and also out of the bottom stage. At the end of this period, which expires when the low level switch (LS) is actuated, some of the resin is left in the conical section of the column and the pipe interconnecting the column and the vessel. STEP 4: The cone flush period ensures that all the resin left in the cone of the column and the pipe is transferred to the transfer vessel before forward flow commences. STEP 5: The loaded resin in the transfer vessel, which has been isolated from the column, can either be hydraulically transferred to the top of the elution column or eluted in the vessel before being transferred to the top of the loading column. The major advantages associated with the NIMCIX concept are: (i) Simple method of operation (ii) Contactor can readily be scaled up to large diameters. (iii) Because the resin does not pass through pumps or airlifts, and valves cannot be closed on resin beads at any time, the resin losses are exceptionally low. (iv) Operating costs are low. (v) Relatively few valves in the system. (vi) Stable operation is achieved over a wide range of feed rates and concentrations.

Jan 1, 1980

By C. D. Stahl, R. Sandrea

This investigation was made to evaluate the comparative effects of the viscosity and the phase behavior of the buffer fluid in the composite solvent displacement of Bradford crude from waterflooded sandstone cores. Buffer slugs of propane, naphtha and other refined hydrocarbons exbihiting increasingly favorable viscosity ratios and decreasing solubility relationships, respectively, with Bradford crude, were used in long Berea sandstone cores. The secondary slug was isopropyl alcohol. The results indicate that higher oil recoveries are obtained for increasingly favorable phase relationships even when these are accompanied by unfavorable viscosity ratios within the range studied. Moreover, when propane is used as a buffer slug with an adverse viscosity ratio of 36, it gives higher oil recoveries than at a similar size slug of an any1 alcohol having a viscosity ratio of 1.09. The investigation was extended to the study of the effect of flooding rate on oil recovery. Residual Bradford crude was displaced from a 6-ft Berea sandstone core at rates varying from 0.3 to 30 ft/ day. The results show that as flooding rates were increased above or decreased below a minimum range of 1 to 2 ft /day, displacement efficiency increased considerably. INTRODUCTION In recent years, the alcohol slug process as a means of tertiary recovery has been the subject of many investigations. Gatlin and Slobod showed the advantages of the combination solvent slugs over the previous single-slug process.1 The combination slugs require less total slug material to obtain similar oil recoveries. The basic combination process involves injecting a primary or buffer solvent which is preferentially oleophilic, followed in turn by a water-driven slug of isopropyl alcohol. This procedure ensures that the buffer slug, which is miscible only with the reservoir oil, displaces and replaces the oil and is in turn displaced, together with the water, by the isopropyl alcohol slug miscible with both fluids. Likewise, for those reservoir oils that show some degree of phase incompatibility with isopropyl alcohol, as does Bradford crude, a proper buffer solvent can artificially make the alcohol process technically feasible. From an economic standpoint, propane or LPG would be the most appropriate primary solvent to be used in the field; however, Taber, et a12 have indicated that the alcohol process becomes highly inefficient in the displacement of light hydrocarbons because of the entrapment of these hydrocarbons during the stabilized bank formation. Moreover, since materials such as propane have such low viscosities, adverse viscosity ratios with most reservoir oils would be penerated, thereby possibly further reducing the efficiency of the buffer solvent. This paper presents the results of an experimental study of the comparative effects of viscosity ratio and phase relationships on the displacement efficiency of Bradford crude by means of dual solvents. The work was extended to include the effect of flooding rate on oil recovery. Rates within the range of field and laboratory values were used. EXPERIMENTAL PROCEDURE APPARATUS The porous media used in this study consisted of two 10-ft and one 6-ft Berea sandstone cores, 3-in. in diameter. These were cast in galvanized steel pipe of 31/2-in. ID and the annulus was filled with Armstrong cement. The 10-ft cores were assembled by connecting two 5-ft units, which were joined together by 8-in. steel flanges fitted to the pipe. Intimate contact between the two sections was obtained by inserting a thin disk of the same sandstone between the core faces. The outlet and inlet ends of the cores were covered with threaded pipe caps. The injected fluid was gravity fed to two variable-rate positive-displacement pumps. The fluids were filtered before entering the core and the effluent was collected in an automatic fraction collector and

Jan 1, 1966