Search Documents

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,' who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C'. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By J. J. Taber, W. K. Meyer

Experiments on consolidated sandstones have shown that a variety of conditions are responsible for the wide range of behavior observed when oil and water are displaced simultaneously by a solvent which is miscible with both. The type of displacement is influenced most strongly by the relation between the plait point of the ternary phase diagram and the composition path followed by the system as it achieves mis-cibility. Neglecting viscosity, the displacement becomes less efficient as the distance between the composition path and plait point is increased in either direction so that a very wide spectrum of displacements is possible with different alcohol, oil and brine systems. It is possible by choosing various composition paths as miscibility is achieved to exercise some control over the actual displacement mechanism. Control over the composition path is exercised by adding oil or water in specific amounts to the alcohol prior to its injection into the porous medium. This technique apparently makes it possible to obtain piston-like displacements with systems which are usually characterized by the efficient displacement of only one of the two phases i.e., either oil or water, while the other phase lags behind. However, the simultaneous displacement of oil and water is not as efficient as other miscible displacements at a similar mobility ratio. The evidence indicates that both oil and water "leak" into the alcohol "piston" in compensating amounts. With oils of low viscosities the displacement is inefficient because the low oil saturation in the stabilized bank causes oil to be trapped by water before miscibility is attained. INTRODUCTION The simultaneous displacement of oil and water by solvents such as alcohol has been investigated in the laboratory and in the field. The laboratorv workers investigating all-liquid miscible systems have recognized the great importance that the nature of the traingular phase diagram exerts on the efficiency of the miscible displacement. Gatlin and Slobod pointed out that displacement efficiency will be improved if miscibility can be retained for long periods and that this behavior tends to be followed if the applicable phase diagrams have very low binodal curves. In their unconsolidated sand tests the alcohol was considered an ideal miscible piston displacing both oil and water phases. Later workers have pointed out that an important feature of the phase diagram as far as oil recovery is concerned is the location of the plait point. This is particularly true in the case of consolidated Sandstone.3 Since the original discussion of this effect, the importance of plait-point location has been confirmed and discussed by other author The early workers394 recognized that the position of the plait point could be altered by changing the oil or the alcohol used in an experiment. In addition, recent work has demonstrated that the plait point can be shifted by altering the nature and concentration of dissolved salts in the aqueous phase. However, the entire scope of the relationship between displacement and plait point has not been discussed previously and a technique for changing the composition path as miscibility is achieved in a particular ternary system, i.e., oil, water and solvent, has not been demonstrated. * The importance of oil viscosity on the efficiency of oil displacement by alcohol has not previously been observed, probably because the range of viscosities used in earlier experiments was too restricted. It is the object of this paper to describe the relationships between the ternary phase diagram, fluid properties and the displacement achieved. A technique for controlling the nature of the displacement is also presented. THEORY AND DEFINITIONS PISTON-LIKE THEORY The theory of alcohol flooding has been discussed in some detail.2-4 The concept was advanced that

Jan 1, 1965

By J. E. Smith, P. B. Crawford, B. L. Laudrum

A method is presented by which the displacement efficiency of a steam-injection process may be determined. The method consists of a determination of the position of the steam front at a particular time and the application of the Buckley-Leverett theory to the hot and cold regions of the reservoir with the appropriate hot or cold fluid properties. A uniform, linear flow system is assumed for this study. The method is applied to a number of reservoir conditions. The primary properties which affect the results of a steam-injection process are the oil viscosities at steam and reservoir temperatures, injection rate, pay thickness and oil saturation. The efficiency of steam injection is compared with that of water injection for a 10-acre, linearly flooded reservoir. In reservoirs where the oil viscosity is about 35 times the water viscosity, the steam process yields recoveries about 20 per cent higher than the water flood. Where the oil viscosity is near 500 cp, the steam process may recover from three to four times as much oil as a water flood. INTRODUCTION In a previous paper,' a method was suggested for evaluating a steam-injection process. Emphasis was placed upon the determination of the steam-front position in the reservoir at various times. In the present paper, the displacement process is studied in more detail. The approach is essentially that employed by Jordan, Rayne and Marshall3 in their study of hot-water injection. The steam-injection process is quite complex, and an exact description of the process has not been found; however, a qualitative description can be made. When a quantity of steam is injected into a relatively cold reservoir, the leading edge of the steam front continaally flows into cool sand, and some steam condenses. As more and more steam condenses, a bank of condensed water will form which is augmented by displaced connate water. The reservoir may be divided in three regions—(1) a region containing displaced fluids at reservoir temperatures, (2) a region contain- ing water at reservoir temperature and (3) a region occupied by steam. The reasons for the lack of a region of hot water or oil of any appreciable size have been discussed.' A method has been presented by which the location of the steam front can be determined even when heat losses to the regions surrounding the reservoir are sizable compared with the amount of heat injected. It remains to show the effectiveness of steam injection in increasing the ultimate oil recovery. To illustrate the technique for determining the increase in displacement efficiency and, hence, the increase in ultimate production, two sets of hypothetical reservoir conditions will be studied in detail.

By Walter Knox, J. D. Doherty

IN 1939, at the request of The Koppers Coal Co., the Koppers Company Research Department established a Stoker Coal Research Laboratory for the purpose of investigating the performance characteristics of stoker coals in typical domestic stoker installations. Fig. I is a photograph of part of the laboratory. The material in this paper deals with the performance of one coal in a single installation. Presented are details of this installation, mechanical characteristics of the stoker, and the results of a series of burning tests in which adjustments were systematically varied. SUMMARY OF RESULTS Mechanical Features I. A large percentage of the total power consumed by a domestic stoker is used to operate the gear case and motor (Fig. 3). 2. The power consumption per ton goes down with an increase in rate of coal feed (Fig. 4). 3. The automatic air control in this stoker showed advantages over manual control (Fig. 5). 4. The air velocities through the retort tuyeres were uniform around the retort, but varied between the rows of tuyere rings (Fig. 6). 5. The crushing of coal with this stoker increased the minus 1/8-in. from 1 1.6 per cent to 19.2 per cent. There was a noticeable segregation of coal as it came from the retort and distribution was not uniform (Fig. 7). 6. Measurement of air entering over the fire showed that with some not uncommon adjustments this air may he a high percentage of the total air supply (Fig. 8 and Table I). Operating Performance I. The removal of clinker was shown to give a period of poor performance characterized by a high fuel-bed resistance and a high percentage of carbon monoxide in the flue gases (Fig. 10). 2. The fuel-bed resistance was found to decrease as the fuel bed built up in a normal response to heat demand after a prolonged hold-fire (Fig. II). 3. With intermittent operation the burning rate was almost always less than the feeding rate. The wide variations were found to be greatly dependent upon the length of the On period and the length of the intervals between On periods (Fig. 12). 4. The maintenance of a low furnace draft led to less fly ash, better clinker formation, and higher efficiencies (Fig. I3). 5. The maintenance of a minimum of excess air also resulted in less fly ash, better clinker formation, and higher efficiencies (Fig. 14). GUIDING PRINCIPLES In planning the investigations, the following principles were adopted: Selection of Healing Equipment.-Use only standard models of stokers and furnaces representative of those widely used.

Jan 1, 1942

By M. B. Standing, R. I. Parsons, E. N. Lindblad

The recovery of the heavier components from a gas cap or retrograde pool is shown to be the greatest when the sand is cycled with a dry gas at a low pressure. This conclusion is in direct opposition to the belief that the most efficient production program is pressure maintenance and cycling at or near the dew point. The results are calculated from: (I) constant volume, variable composition pressure-volume-temperature tests on a mixture of trap gas and liquid from a producing well; (2) published equilibrium constant data and the measured composition of the dew-point material; and (3) the fact that in a sand section of homogeneous permeability, injected gas displaces reservoir gas nearly, quantitatively. The results are based on the simplifying assumption that variable permeability systems may be defined by the ratio of two statistical parameters, and that gas injected into an actual sand will behave as though the sand were composed of many layers, each of constant permeability. Introduction Pressure decline in gas-condensate type reservoirs is accompanied by the formation of a liquid phase throughout the reservoir. Over the past ten years the processing of the material from these types of reservoirs for the heavier hydrocarbon components and the return of the light fractions to the reservoir ("cycling") has become increasingly popular. It has often been stated that the purpose of such a program is to prevent the loss of the retrograde liquid phase formed in the reservoir. The purpose of this paper is to present the results of laboratory tests and computations concerned with several possible methods of producing a gas cap or condensate type of reservoir. The results show that the recovery of heavier hydrocarbons for this type of reservoir is not a maximum under conditions of cycling at or near the dew-point pressure. Instead, variations in permeability and the ability of the dry injected gas to revaporize condensate, point to cycling at a considerably reduced pressure as the optimum production-method. In addition the paper suggests a way of evaluating sands for their permeability variation. The calculations presented in the following sections of the paper are in terms of the production of the butanes and heavier fraction from the gas cap of a field which had an original pressure of approximately 3000 psi. Specifically, the calculations show: 1. To what extent the condensate formed in the reservoir after pressure decline can be recovered by the cycling of a dry absorber-plant gas through the sands. 2. Whether there would be greater recovery of hydrocarbons if cycling were instigated at the original reservoir pressure.

Jan 1, 1948

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,' who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C'. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By S. W. Kennedy, M. Cohen, L. D. Calvert

A high-temperature X-ray diffraction method has been used to study the composition and the kinetics of formation of oxide scales at 800 °C on iron and pure iron-nickel alloys containing 25.6, 75, and 84 pct Ni. This technique has been combined with chemical analysis, and metallographic examination, and determination of weight-gain time curves. The 75 and 84 pct Ni alloys form a three-layer scale consisting of porous NiO next to the metal, a spinel layer, and a -Fe203 on the outside. The 25 pct Ni alloy produces a scale of spinel and Fe,O,, in which, however, traces of FeO and NiO are observed near to the metal. On all the nickel alloys the Fe20, is orieqted with the (107) plane parallel to the surfaces. The exposed surface of the Fe20, is in the form of needles whose axis is perpendicular to the specimen surface. Although the alloys show nonuniform oxidation rates as determined from weight-gain measurements, the X-ray data indicate that the total scale and individml scale layers grow uniformly and parabolically. Deep subscale formation is observed in the 25 pct Ni alloy only. This appeared to be associated with cracking of the scale and penetration of the oxygen along the grain boundaries. ALTHOUGH film formation has been investigated by high-temperature electron-diffraction techniques, for example by Gulbransenl and Hickman,' there have apparently been no investigations of scaling by methods permitting study of the scale during formation at the reaction temperature. Methods involving quenching of scales are based on the working assumption that no significant changes take place on cooling. In general, however, compounds may disproportionate, and the different thermal expansions of constituents may cause disruption of the scale on cooling. In particular, some scales cannot be quenched without spalling. These difficulties are avoided by X-ray diffraction examination at the temperature of formation. High-temperature diffraction procedures also provide a method of determining the kinetics of formation of each phase separately in a multicom-ponent scale. The scaling of binary iron-nickel alloys Containing up to 30 pct Ni at a temperature of 800°C has been studied by Benard and Moreau using cooled specimen~,~ whilst Foley, Druck, and Fryxel14 made an electron-diffraction study of cooled oxide films formed on an iron 42 pci Ni alloy. In the present work the scaling of three iron-nickel alloys containing 25.6, 75, and 84 pct by weight of nickel, at 800°C in oxygen at atmospheric pressure was investigated by X-ray diffraction techniques using a Norelco Geiger-counter diffrac-tometer. The oxidation of iron was investigated for comparison. In addition normal metallographic examinations and chemical and X-ray analyses were made, and weight-gain time curves obtained. EXPERIMENTAL Materials Used—The analyses of the alloys were as follows: Percent by Weight Nickel 25.6 pct 75.4 pct 83.2 pct Aluminum 0.004 None found 0.002 Cobalt — 0.05 0.05 Chromium — — — Silicon — 0.01 None found Carbon All less than 0.05 pct The chemical analysis of the iron was: Al— 0.002 i 0.001 pct, C—0.007 pct, Cr less than 0.001 pct, Cu—0.002 ± 0.001 pct, Mn—0.003 ± 0.001 pct, N—0.0002 pct, 0-0.013 pct, P—less than 0.0002 pct, Pb—not detected, S—0.0017 pct, Si—0.0095 pct, Sn—none detected. This iron was the same as that used to make the alloys and was obtained from the same source-Vacuum Metals Corp. One specimen of pure iron from The British Iron and Steel Research Association was used for preliminary investigation. Specimens were machined to shape from cast rod, polished (the final polish being with 600 Sic paper), degreased in trichlorethylene, washed, and etched. The etching and neutralizing procedure adopted by

Jan 1, 1960

By W. V. Swarzenski

In its effort to combat waterlogging and soil salinity, the Water and Soils Investigation Division of WAPDA (West Pakistan's Water and Power Development Authority) has carried out an extensive program of test drilling andwater sampling since 1954. Data collected during the past ten years have permitted the delineation of fresh and saline groundwater zones in the Punjab Plain. Fresh groundwater containing generally less than 500 ppm of total dissolved solids is found in wide belts paralleling the major rivers and in other areas of fresh-water recharge. Locally, fresh groundwater extends to depths of 1500 ft and more. Saline groundwater occurs down gradient from sources of recharge, particularly in the lower central parts of the interfluvial areas, and presumably underlies most of the Punjab Plain. The groundwaters of the Punjab are characterized by their evolution from calcium, magnesium bicarbonate waters near sources of recharge to waters containing a dominant proportion of sodium. The highly mineralized waters of the Punjab are generally of the sodium chloride type, whereas in the Dera Ismail Khan District, sodium sulfate waters predominate. The pattern of distribution of saline groundwater zones and the observed gradual increase in mineral content, down gradient from sources of recharge, can be explained best by a hypothesis stressing the process of evaporation from the water table and solution of minerals within the alluvial aquifer. In 1954, detailed groundwater surveys in the Punjab Plain were initiated by WASID, the Water and Soils Investigation Division of West Pakistan's Water and Power Development Authority. The investigations, undertaken under a cooperative agreement between the governments of Pakistan and the United States, were aimed at the formulation of reclamation measures to improve waterlogged and saline soils, and to assess the groundwater potential of the Punjab and other areas of West Pakistan. The nature and urgency of WASID's primary task limited the exploration of the alluvial aquifer generally to its uppermost part. About 1030 test holes drilled in 47,000 sq miles of the Punjab defined the nature of the alluvium to depths of about 600 ft and yielded data on water quality to 400 or 500 ft. A report on the hydrology of the Punjab, based on the results of these investigations was published by WASID in 1963.' The present report incorporates data obtained by WASID since 1962 in a program of deep test drilling in the Punjab and the adjacent areas of Bahawalpur and Dera Ismail Khan District, permitting the definition of fresh and saline groundwater zones to depths of 1500 ft in some areas. Groundwater in the Punjab Plain is contained in alluvial deposits, predominantly sand and silt, which extend almost everywhere to depths of 1000 ft and more. The alluvium has been deposited by the Indus River and its tributaries since late Tertiary time and is contiguous with similar deposits in India. The Indo-Gangetic Plain extends from the foothills of the Himalayas to the ancient rocks of the Peninsular Shield in central India and to the ocean. Gradients are generally very low and range from about 1% ft per mile in the upper part of the plain to less than 1 ft per mile in the south and southwest. The monotony of the alluvial plain is broken by scattered bedrock outcrops in two of the interfluvial areas, Chaj Doab and Rechna Doab. The bedrock hills are projections of the northwest-trending Delhi-Shahpur Ridge that is largely buried by alluvium. The rocks of the buried ridge, presumably of Precambrian age, are essentially impermeable and define the lower limit of the alluvial aquifer in parts of Chaj, Rechna, and Bari doabs. Elsewhere in the Punjab, there are no outcrops of other consolidated rocks and their presence below the alluvium is conjectural. The principal areas of bedrock outcrops, near Kirana and Sangla, are shown diagrammatically in Fig. 1. The movement of groundwater through the alluvial aquifer of the Punjab has been described by Green-man and others.' In most of the area, the pre-irriga-tion water table sloped from the rivers downstream and toward the central axes of the doabs, indicating that the rivers were sources of groundwater recharge. As a result of seepage from irrigation canals, water levels have risen as much as 90 ft. In 1960 they were within 5 to 15 ft of the land surface and above the

Jan 1, 1970

By D. S. Flett, A. W. Fletcher

Equilibrium studies on the extraction of nickel and cobalt with kerosine solutions of naphthenic acid have shown that an exchange extraction reaction occurs at pH 5.5. The nickel/cobalt separation factor is constant at 1.8 for constant total metal molarity and varying nickel/cobalt ratios. The separation factor decreases with increasing total metal molarity in the organic phase beyond 0.2 M and also decreases with increasing temperature. From the equilibrium data, it has been possible to derive a mathematical model for the separation of nickel from cobalt by exchange extraction in multistage systems. Experimental data from a continuously operated multistage mixer/settler apparatus has shown a reasonable correspondence with computer-calculated data. The effective separation of nickel and cobalt in sulfate solution remains a problem in hydrometallurgy and the hope that this would be solved by solvent extraction has not yet been fulfilled. With chloride solutions, advantage may be taken of the ability of cobalt to form anionic complexes with the chloride ion. It can then be readily separated from nickel, which does not form stable chloro complexes, by extraction with a suitable long chain amine. However, in hydro metallurgical operations, sulfate solutions are generally obtained in which no extractable anionic species are present. Thus, the possibility of using cationic extractants must be considered, and in this paper attention is directed to the use of carboxylic acids. The method of separation studied has been termed exchange extraction, which involves replacement of a metal in the organic phase with a more acidic metal in the aqueous phase. Thus, (BR2).+ (Az+)aqt=(AR,).+ (B2+)aq (I) where metal A is more acidic than metal B, R represents the acidic radical derived from the acid RH, and the subscripts e and aq refer to the organic and aqueous phases, respectively. Ashbrook and Ritcey' have used this method for the separation of cobalt from nickel using the sodium salt of di-2 ethyl hexyl phosphoric acid, which preferentially extracts cobalt. Some nickel is coextracted, and this is removed by exchange with cobalt ions in the feed solution by suitable countercurrent operation in a pulsed column. Much work has been carried out by a number of workers in Russia on the general use of exchange extraction for the separation of metal ions using car-boxylic acids. Gindin et aL a have demonstrated that this technique could be applied to the separation of nickel from cobalt using a C--C. carboxylic acid and have applied the technique to the production of high purity cobalt solutions for electrolysis. Further worka was concerned with the development of a process for the separation of nickel from cobalt in a pulsed column. This system permitted the separation of iron and copper from nickel and cobalt in one system. The procedure involved center feeding with acid backwashing at the top and alkali addition lower down the column. Thus the system operated under a pH gradient and the metals were distributed in the column in the order of their basicities. A similar application was studied by Gel'perin et al,4,5 for the removal of copper and iron impurities from a nickel anolyte by means of a C10-C,12 fatty acid fraction. Ginden et al,' and Fletcher and Wilson' have studied the effect of pH on the extraction of a number of metals with carboxylic acids. These studies showed that metals such as iron, copper, lead, zinc, nickel cobalt, and manganese are extracted at pH values close to the pH of hydroxide precipitation. Nickel is extracted at a slightly lower pH than cobalt and thus the nickel/cobalt separation factor has a value not much greater than 1. More basic work on complex identification has been reported by Fletcher and Flett: by Tanaka; and Jay-cock and Jones." These studies have suggested that at low loadings in the organic phase, the nickel and cobalt carboxylates appear to be dimeric and solvated by free carboxylic acid molecules. As the concentration of metal in the organic phase increases, the complex changes and larger polymeric species are formed. In order to permit assessment of the potential of carboxylic acids as extraction reagents for separation of

Jan 1, 1971

By P. A. Robbins

FAR NORTH, on the bare Arctic tundra, 11 mi. above the mouth of the Keewalik River where the latter discharges into Kotzebue Sound. several ., Eskimos garbed in parkies and muck lucks mingle with a small group of similarly clad white men. All of them shield their eyes from the white glare of the arc as a gasoline-driven arc-welding set rains molecules of metal on the break in a bull wheel, the large gear wheel which swings the boom and cab of a dragline shovel.

Jan 1, 1937

By F.S. Norcross

Manganese has long been considered one of the United States' most important strategic raw materials. Its indispensabil-ity in steel manufacture makes it vital to the nation's industrial life. Coupled with this indispensability is the fact that domestic producers have not been able as yet to supply more than a small part of the nation's manganese needs; consequently the United States has had to depend upon such distant foreign sources as the U.S.S.R., British India, the African Gold Coast and Brazil for the major portion of its ore. The great bulk of the mineral is consumed in the form of ferromanganese, an alloy that averages 80 per cent manganese and 20 per cent mainly iron and carbon. Manganese is used as a deoxidizer and desulphurizer in steel manufacture. By combination with the residual oxygen and sulphur of the bath, it helps to produce a clean, sound metal. Approximately 14 lb. of manganese, it is estimated, is used in making one ton of steel. For standard-grade ferromanganese, the ore should have a minimum of about 48 per cent Mn and preferably more. Beneficiation methods have not yet been developed for making the immense low-grade deposits in the United States salable at prevailing prices. Dependence upon foreign sources thrust the United States into serious difficulties during the World War. At the start of hostilities in 1914, the nation was obtaining about four-fifths of its ore from the Eastern Hemisphere. Domestic production had been negligible, amounting to only 3000 to 7000 tons a year. As the war continued, shipments from the East, endangered by sea attack and blockade, dwindled rapidly. Imports from Brazil mounted. In this grave emergency, the United States, starting almost from scratch and under the stimulus of high prices, succeeded by 1918 in producing a peak of 3II,000 tons, about 35 per cent of its consumption that year. Since the war, the United States has depended upon foreign sources for more than nine-tenths of its high-grade ore. During 1936, 1937 and 1938, imports for consumption averaged 736,000 tons a year. During the same period, domestic shipments averaged 21,000 tons a year. Of the imports, the U.S.S.R. accounted for an annual average of 280,000 tons, the Gold Coast 208,000 tons, India 74,000 tons, and Brazil 72,500 tons. But India and Brazil, which in 1936 ranked third and fourth in the list of importers, were displaced in 1937 and 1938 by a new and much nearer source—Cuba. From less than I per cent of United States imports in 1931, the island republic increased its shipments to more than 27 per cent in 1938. Cuba's average for this three-year period was 97,000 tons, and its total for 1938 was 131,000 tons. History The story of the economic development of manganese in Cuba dates back to the Spanish-American War days. John Green-way, then one of Theodore Roosevelt's

Jan 1, 1943

By B. H. Sage, W. N. Lacey

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By C. S. Barrett, C. T. Haller

Twinning in magnesium is known to occur profusely under certain conditions, and when it occurs in polycrystalline materials it brings about a partial or even a complete change in the preferred orientation. The amount of research on this subject, however, has not been in proportion to its importance as a mechanism of deformation and reorientation. Much of the research has been limited to twinning in single crystals. The present study1 concerns polycrystalline sheet, and is an investigation of the twinning produced by plastic deformation as a function of the following variables: 1. Direction and type of deformation. 2. Amount of deformation. 3. Speed of deformation. 4. Temperature of deformation 5. Composition and temper of the sheet. 6. Twins previously produced. 7. Twins previously produced, then annealed. By proper control of these variables it is shown that, on a laboratory scale, samples can be produced that are free from preferred orientations. The materials used were samples of commercial magnesium-alloy sheets with nominal compositions given in Table I. X-ray diffraction was used in most of this work to detect the twins and to estimate the amount of twinning. Since twinning on (102) planes causes a re-orientation of the crystal lattice by 86", it is very easy to study with X-ray diffraction patterns, particularly if one notices the diffraction ring from the basal plane— the 002 reflection. By properly directing the X-ray beam, it is possible to produce 002 reflections from twinned material at, say, the 6 and 12 o'clock positions on the 002 ring, with the untwinned material reflecting to 3 and 9 o'clock positions; and by judging the relative intensity of the arcs on the diffraction ring at these positions, it is possible to judge the amount of twinned material relative to the untwinned. This X-ray method of estimating the amount of twinning is generally superior to metallo-graphic observation, for it was found

Jan 1, 1947

By R. Priestner, R. F. Krause

Solid, cylindrical crystals of a iron have been fractured at 10°K by the simultaneous application of tension and torsion stresses. Thus, a complex distribution of normal (sN) and shear (ss) stresses existed in a cleavage plane at fracture. In every crystal the clearage-plane normal was inclined to the specimen axis, so that a unique point, M*, in the operative cleavage plane was defined where the quantities sn and s2 N + s2 S) were maximized. It is shown that the maxirrzum resolved normal stress on the cleavage plane at fracture decreased as the resolved shear stress in the cleavage plane at M* increased. Thus, a normal stress la?*! for fracture was not satisfied. A fracture law which takes shear stress into account. and which predicts that (s2 N +s2S) should be constant, is to be preferred. However, the data is best represented by a linear dependence of sN on sS, sS which 110 physical significance can be attached. It is suggested that the fracture-nucleating -mechanism is a short-range one. A critical stress law has not yet been unequivocally established for the propagation of cracks in metals. Measurements of the tensile fracture stresses of variously oriented zinc single crystals1 failed to establish the normal stress law expressed by In Eq. [1], sN is the fracture stress, P, resolved normal to the fracture plane, and 0 is the angle between the fracture -plane normal and the stress axis. Similarly, a comprehensive investigation failed to verify the normal stress law for the tensile fracture of a-iron single crystals.' However, a subsequent investigation,3 using iron from the same ingot, presented fracture data which obeyed the normal stress law. It has been shown previously4,5 that the Griffith criterion for fracture6 does not predict such a normal stress law. This result is of particular significance in considering the fracture of metals, such as zinc and iron, which may fail by cleavage. In these metals fracture propagates in a well-defined "cleavage" plane, whether or not an applied stress is normal to it. When the cleavage-plane normal deviates from the direction of application of a uniaxial stress, for example, the crack propagates under the combined action of normal (sN) and shear (ss) stresses. When the presence of a resolved shear stress in the crack plane is taken into account, the Griffith criterion is expressed by4

Jan 1, 1967

By H. H. Rachford

This work presents a first-order analysis of the instability underlying viscous fingering in adverse viscosity-ratio water floods. It extends previous analyses of frontal instabilities, which were carried out with equations for parallel plate models, by including effects of the saturation transition zone observed behind the front in water floods in water wet systems. This zone tends to insulate incipient fingers from the high-mobility watet;. thus conditions for the onset of fingering differ from those in the parallel plate theory. Finite-difference solutions of the two-dimensional equations of displacement in porous media exhibited the predicted stability characteristics in six hypothetical field- and laboratory-scale floods in rectangular reservoirs. In contrast to results with parallel plate systems, this paper concludes that for waterwet reservoirs, laboratory models scaled by the usual criteria are also correctly scaled for frontal instability. Further, fingering in the systems studied can occur in any saturation range behind the front, and may occur at an intermediate saturation even though stability obtains both at the saturation corresponding to the Buckley-Leverett front and near residual oil saturation. Other points of contrast are that the likelihood of occurrence of fingering may not increase as flow rate or viscosity difference increases, but my be sensitive to changes in he relative permealdlity and capillary pressure functions. INTRODUCTION The recovery of oil by water flooding frequently involves displacing the oil by water of a lower viscosity. Displacement of a fluid by a less viscous one may lead to gross channeling or fingering like that observed in solvent floods, in which it severely lowers recovery efficiency.1 In addition to adverse effects on recovery, it has been suggested that the unstable move- ment causing fingering may interfere with interpretation of scaled model studies of proposed water floods, since the instability in the model might not be faithfully scaled to that in the reservoir prototype. In view of the serious implications of this possible breakdown of widely used scaled model techniques4-6 it is the purpose of this paper to examine the question further. Instabilities in the solutions of systems of differential equations imply a loss of smooth dependence on initial and boundary conditions. Thus, the possibility exists that in using models whose scaling is based on the differential system there may arise size- and rate-dependent factors which are not properly scaled. This possibility was examined in detail by Chouke et al., who analyzed the instability of frontal advance in a related problem, water-oil displacement in parallel plate models,2 in which a moving interface separates two regions of constant, unequal mobilities. First-order perturbation theory predicts the existence of a critical wave length for the growth of perturbations: and a wave length of maximum instability of A, = The interpretation is that wave lengths in a perturbation which are longer than A, will grow. Thus, if the width of a two-dimensional channel is greater than A,, fingers will grow, and the spacing of the fingers which grow at the maximum rate will be approximately It is important that the higher the velocity and/or the difference in flow resistance, the lower is A,, and thus the greater the number of fingers that can grow in a given model. In applying these conclusions to porous media, a pseudo-interfacial tension, , was assumed for the invasion front. Since this would not necessarily be equal to the liquid-liquid interfacial tension, an unknown constant was substituted for the foregoing expression for A, This was determined

Jan 1, 1965

By F. S. Norcross

Manganese has long been considered one of the United States' most important strategic raw materials. Its indispensabil-ity in steel manufacture makes it vital to the nation's industrial life. Coupled with this indispensability is the fact that domestic producers have not been able as yet to supply more than a small part of the nation's manganese needs; consequently the United States has had to depend upon such distant foreign sources as the U.S.S.R., British India, the African Gold Coast and Brazil for the major portion of its ore. The great bulk of the mineral is consumed in the form of ferromanganese, an alloy that averages 80 per cent manganese and 20 per cent mainly iron and carbon. Manganese is used as a deoxidizer and desulphurizer in steel manufacture. By combination with the residual oxygen and sulphur of the bath, it helps to produce a clean, sound metal. Approximately 14 lb. of manganese, it is estimated, is used in making one ton of steel. For standard-grade ferromanganese, the ore should have a minimum of about 48 per cent Mn and preferably more. Beneficiation methods have not yet been developed for making the immense low-grade deposits in the United States salable at prevailing prices. Dependence upon foreign sources thrust the United States into serious difficulties during the World War. At the start of hostilities in 1914, the nation was obtaining about four-fifths of its ore from the Eastern Hemisphere. Domestic production had been negligible, amounting to only 3000 to 7000 tons a year. As the war continued, shipments from the East, endangered by sea attack and blockade, dwindled rapidly. Imports from Brazil mounted. In this grave emergency, the United States, starting almost from scratch and under the stimulus of high prices, succeeded by 1918 in producing a peak of 3II,000 tons, about 35 per cent of its consumption that year. Since the war, the United States has depended upon foreign sources for more than nine-tenths of its high-grade ore. During 1936, 1937 and 1938, imports for consumption averaged 736,000 tons a year. During the same period, domestic shipments averaged 21,000 tons a year. Of the imports, the U.S.S.R. accounted for an annual average of 280,000 tons, the Gold Coast 208,000 tons, India 74,000 tons, and Brazil 72,500 tons. But India and Brazil, which in 1936 ranked third and fourth in the list of importers, were displaced in 1937 and 1938 by a new and much nearer source—Cuba. From less than I per cent of United States imports in 1931, the island republic increased its shipments to more than 27 per cent in 1938. Cuba's average for this three-year period was 97,000 tons, and its total for 1938 was 131,000 tons. History The story of the economic development of manganese in Cuba dates back to the Spanish-American War days. John Green-way, then one of Theodore Roosevelt's

Jan 1, 1943

By Dennis H. Laubscher

INTRODUCTION The selection of mass mining methods is the situation facing not only planners of new operations, but also those involved with cur- rent operations, including the eventual change from open-pit to underground. Increasing ground control problems on many mines, plus a better understanding of dilution and ore loss problems have meant a review of current mining methods and support techniques. Experiments are only successful if conducted in the right mining environment and on the right scale. Mining personnel have been known for their conservatism and will tend to persevere with an established method rather than change; often, hidden costs will obscure the correct economic assessment. An established mining sequence is not necessarily correct in the long term. However, recommendations to change are usually met with opposition because of inconvenience, temporary production problems and the desire for a trouble-free guarantee. In any planning exercise, care must be taken that time and money are not wasted in trying to achieve the unattainable. During the decision-making period, production personnel must be involved, and, if possible, they should visit similar omrations to that proposed. Co-operative production personnel will help ensure success. Descriptions of mining methods are available in technical papers and books, and it is not intended to discuss this aspect, but, rather, the various factors which must be recognised before arriving at a final selection. In another paper presented at this Conference (Heslop and Laubscher, 1981) factors affecting ore recovery and dilution are discussed in greater detail for various cave mining methods. PRELIMINARY CONSIDERATIONS Comprehensive Geological Data. Geological information is available during the exploration stage, but, often, core from exploration drilling is not analysed with the selection of a mining method in mind. Drilling costs are high, therefore the maximum benefits must be derived from this operation. Holes which have not intersected ore may provide data on possible shaft sites, and 35 mm colour slides of core, sound logging and geomechanics classification, will provide a record which can be used with confidence at a later date. Intersections of the various rock types should be kept for future study; for example, is weathering likely to be a problem, bearing in mind that this can be accelerated in the warm, humid atmosphere of an underground mine. The accumulation of data required to select a mining method starts with initial geological work in the target area, whether this be surface mapping or a diamond drill hole. Publications. As technical papers, reports and books are used in the selection of mining methods, an appeal is made to authors to describe the geological environment so that readers can relate to their own conditions. Not enough emphasis is given to the problems experienced and the techniques employed to overcome them. Follow-up papers are seldom written and we should be prepared to discuss our failures. Diagrams are often misleading, as the ideal and not actual situations are depicted. The caved ore/waste interface is not a straight line, and whereas this may not be significant in a diagram of a 200-117 draw height, it certainly is in sub-level caving with draw zones only 1 - 2 m width but up to 20 m high. SUMMARY OF FACTORS AFFECTING THE SELECTION OF UNDERGROUND MASS MINING METHODS (a) Regional rock stresses and mining geometry. (b) The geomechanics rock mass classification of the orebody and surrounding rock mass. (c) Ratio of the surface area of the ore/unpay interface to the contained ore which determines ore losses and dilution. (d) The cavability and fragmentation data of the ore and hangingwall. (e) The mineral distribution in the orebody and its dilution zone.

Jan 1, 1981

By C. S. Barrett, C. T. Haller

Twinning in magnesium is known to occur profusely under certain conditions, and when it occurs in polycrystalline materials it brings about a partial or even a complete change in the preferred orientation. The amount of research on this subject, however, has not been in proportion to its importance as a mechanism of deformation and reorientation. Much of the research has been limited to twinning in single crystals. The present study1 concerns polycrystalline sheet, and is an investigation of the twinning produced by plastic deformation as a function of the following variables: 1. Direction and type of deformation. 2. Amount of deformation. 3. Speed of deformation. 4. Temperature of deformation 5. Composition and temper of the sheet. 6. Twins previously produced. 7. Twins previously produced, then annealed. By proper control of these variables it is shown that, on a laboratory scale, samples can be produced that are free from preferred orientations. The materials used were samples of commercial magnesium-alloy sheets with nominal compositions given in Table I. X-ray diffraction was used in most of this work to detect the twins and to estimate the amount of twinning. Since twinning on (102) planes causes a re-orientation of the crystal lattice by 86", it is very easy to study with X-ray diffraction patterns, particularly if one notices the diffraction ring from the basal plane— the 002 reflection. By properly directing the X-ray beam, it is possible to produce 002 reflections from twinned material at, say, the 6 and 12 o'clock positions on the 002 ring, with the untwinned material reflecting to 3 and 9 o'clock positions; and by judging the relative intensity of the arcs on the diffraction ring at these positions, it is possible to judge the amount of twinned material relative to the untwinned. This X-ray method of estimating the amount of twinning is generally superior to metallo-graphic observation, for it was found

Jan 1, 1947

By W. N. Lacey, B. H. Sage

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By A. G. Guy

Zinc vapor from a reservoir of liquid zinc maintained at lower temperatures was diffused into sets of copper-zinc alloys at 759° and 870° C and into sets of silver-zinc alloys at 650° and 700° C. Each set of ,four copper-zinc alloys consisted of pure copper and 90/10, 80/20, and 70/30 brass. Similarly the set of silver-base alloys consisted of specimens containing 0, 7, 15, and 20 pct Zn. Natural markers at the initial surfaces of the specimens ware "trapped" under a thin electroplate and their depth of burying was measured after diffusion. The ratio of diffusivities of the two components determined from these data and the chemical diffusion coefficient calculated by the Matano method agreed with previously reported results. The line of markers was irregular and was often discontinuous when a grain boundary was crossed. TECHNIQUES involving the vapor phase have been widely employed in studying diffusion phenomena in metals. Many investigators have evaporated the more volatile component from an alloy, but it is generally believed that the porosity created under these conditions interferes with adequate interpretation of the experimental results. The extensive work of Gertsriken6 has been criticized on this score. Accary1 found that the diffusion coefficient for de-zincification of brass is larger by a factor of five than that for zincification, although he attributed the difference to a higher vacancy concentration under conditions of dezincification. Balluffi and siegle2 thoroughly investigated the technique of adding a more volatile component to a less volatile base metal as a means for studying diffusion. They verified that no porosity forms in a brass under these conditions and that the diffusivities of the two components can be determined from observations of the motion of markers originally placed on the surface of the specimen. The mathematical analysis that they developed for treating the experimental data was modified in a later note, but essentially it involved using the graphical Boltzmann-Matano method that is customarily applied to solid-solid diffusion couples. The experimental method used in the present research was similar to that employed by Balluffi and Siegle except for two modifications. Balluffi and Siegle used alloy chips as the source of metal vapor. This procedure has the disadvantage that the concentration of solute at the surface of the specimen changes during the diffusion experiment as the alloy content of the chips is gradually decreased. This disadvantage was overcome by employing liquid zinc as the source of zinc vapor in a manner similar to that described by Herasymenko.9 There was then no limitation on the amount of solute usefully available, and several relatively large specimens could be diffused in a given experiment. The second modification was the use of natural markers on the surface of the specimen rather than larger, artificial markers, such as the alumina powder employed by Balluffi and Siegle. It was expected that the fine, natural markers would permit more precise measurement of the buried interface as in the case of ordinary sandwich specimens.10 EXPERIMENTAL The experiments were designed so that zinc from the vapor phase would maintain a constant zinc content at the surface of pure copper (or silver) and

Jan 1, 1960