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By R. I. Jaffee, J. W. Roberts, D. N. Williams

DISPERSION hardening as an alloying process has aroused increasing interest in the past few years. This alloying procedure, in which an insoluble phase is dispersed randomly through a metal or alloy, is believed to be especially suited for the attainment of creep strength at elevated temperatures since the dispersed phase is metallurgically stable. Another advantage is that the physical properties of the matrix phase, such as electrical conductivity, remain relatively unaffected by alloying. These two characteristics resulted in interest in the applicability of dispersion hardening to copper and copper alloys. A study of copper alloys prepared by powder metallurgy methods has shown some strengthening from oxide dispersions.' However, powder metallurgy processing would not be economical for large scale production of dispersion hardened copper-base alloys. Therefore, the research described in this article was initiated to examine methods of forming dispersion alloys which would not require powder metallurgy processing. If powder metallurgy processing is to be avoided, a method must be found by which the dispersion material can be introduced into and dispersed through the melt before casting. When the dispersed phase is an oxide or similar nonmetallic, it is extremely difficult to form a satisfactory liquid: solid dispersion since successful mixing requires that the melt wet the dispersed phase. It is almost impossible to force a nonwetted particle beneath the melt surface. This difficulty can be avoided, however, if the oxide particles are produced in molten copper by reaction within the melt. The problem would then reduce to maintaining randomness until solidification. Four procedures were considered for producing an oxide particle within molten copper by reaction. In all cases, the intent was to react oxygen (0) with a reactive metal (X) to form an oxide (XO) within the copper melt. These reactions were as follows: 1) (Cu-X), + (O)g (Cu)1 + (XO)S [1] 2) (Cu-X)1 + (Cu2O)s (Cu)x + (XO)S [2] 3) (Cu-OK)1 + (Cu-X)1 (Cu)1+(XO)9 [3] 4) (Cu-OK)1 +(X)s (Cu)1 +(XO)s [4] The reactions were carried out in an 8-lb melt of 99.98 pct Cu maintained in the vicinity of 2200oF by induction heating. Where possible the amount of the reactants was controlled to give 1 to 5 vol pct oxide. Mechanical stirring during the reaction period was used to minimize agglomeration of the reaction product. The presence of a reaction product was determined metallographically by study of an ingot cast from the melt at the end of the reaction period. Reaction [I] was studied by dissolving aluminum in the melt followed by forcing oxygen through the melt. The melts became quite sluggish during the reaction period suggesting that A12O3 was formed. However, the reaction product rose out of the melt rapidly, possibly due to the flushing action of the oxygen stream, and little dispersed phase was formed. Reaction [2] was examined by dissolving aluminum, silicon, or nickel i; the melt and then adding Cu20 (melting point 2250F). This procedure was unsuccessful. Although Cu2O was easily stirred into cop-

Jan 1, 1961

By C. E. Sims, C. A. Zapffe

AN investigation of the behavior of inclusions in steel several years ago1 led to the conclusion that some of the commonly occurring inclusions in steel have appreciable solubilities, particularly in liquid steel. In the belief that further study and clarification of this matter was warranted, a laboratory study of oxides in liquid steel was started. These oxides are generally the result of deoxidation treatment, and the basis of an understanding of their behavior must be, therefore, the behavior of the deoxidizer in liquid iron. The Fe-Si-O system was selected for the first study, and the apparatus used and experiments conducted are described herein. APPARATUS The apparatus is shown in Fig. I and the system is shown by diagram in Fig. 2. Furnace Atmosphere Commercial hydrogen (1) passes through an orifice (2) into a manometric system that measures the tankside pressure (3) and the back pressure (4) in the system. A water trap (5) guards against excess tankside pressure. A by-pass with stopcocks (6 and 7) is provided, so that the hydrogen can be routed directly from the tank to the furnace if desired. When stopcock 7 is closed and stopcock 6 is open, the gas proceeds through the conditioning train, of which the first unit is a furnace (8) that contains platinized asbestos at 350°C. The temperature is measured by a thermocouple and potentiometer (9) and is controlled by a slidewire resistance (10). In [ ] this furnace free oxygen is converted to water vapor. The exiting gas passes over a water bath (11) kept slightly below boiling temperature by an auxiliary heating unit (12). This unit also heats a surrounding copper coil (13) containing water, and the heated water rises through a collar (14)

Jan 1, 1942

By J. J. Stokes

Literature on the electrolysis of aluminum from cryolite melts and on the structure of these melts is surveyed critically. Data on density, freezing point, and other properties are reviewed. Theories of the electrolysis are examined in the light of these data. Two theories are presented which account equally well for the observations. ALTHOUGH the production of aluminum is a large-scale industrial process, consuming approximately 3 pet of all of the electric current generated in this country, the mechanism of the Hall Process remains a 70-year-old mystery. It is a remarkable fact that the aluminum industry, which was established largely through research and owes much of its growth to research, still employs as its basic process the one developed by Charles Martin Hall while he was still a young man working in a woodshed. There are, of course, modifications in detail and a tremendous expansion of the size of the units used, but basically the process employs carbon anodes and a carbon-lined iron vessel as a cathode for the electrolysis of alumina dissolved in molten salt. Of the almost infinite variety of salts available, the relatively minor Greenland mineral, cryolite, 3NaF.A1F3, is still the only one which gives good performance in the electrolysis. In the early days, the process was thought of as a simple one. The dissolved alumina dissociated and, during the electrolysis, the aluminum was carried to the cathode where it was discharged and collected in a pool of metal. The oxygen was carried to the carbon anode where it reacted to form primarily carbon dioxide together with some carbon monoxide. About the only virtue that can be claimed for this hypothesis is that of simplicity. The actual mechanisms must be tremendously more complex. This paper is devoted to a rather narrow part of the whole subject, namely, what ions are present in the bath, and by what mechanism the current is carried. The complexity of the literature on this system is demonstrated in Table I, which shows the ions postulated as being present during the process. This system is not easy to investigate. Cryolite melts at about 1000°C, so that all the investigations are at relatively high temperatures. Molten cryolite fumes in air, particularly if excess aluminum fluoride is present. The cryolite changes composition on heating at 1000°C, principally by reaction with moisture in the air, but apparently also by reaction with oxygen. Cryolite reacts with most of the customary materials of construction, and those that are not attacked by cryolite seem inevitably to react with molten aluminum. Graphite is the only common material that is inert to the electrolytic bath. Pure cryolite can be held in platinum. There is hope that some of the newer refractories will stand up in bath, and their development for this purpose would be a major advance in the field. The techniques to be discussed, then, are not the most advanced ones. Rather, they are examples of old standardized methods applied under difficult conditions. The principal methods that shed real light on the mechanism are density, electrical conductivity, freezing-point lowering, transport number, viscosity measurements, and reactivity of bath with carbon dioxide. The first measurement to be discussed is density. This procedure is relatively straightforward. A hollow platinum bob is suspended by fine platinum wire from an analytical balance into the melt being investigated. Density1-4 of the system sodium fluoride-aluminum fluoride is shown in Fig. 1. There is a maximum in the density near the cryolite composition, but actually the maximum is on the NaF-rich side of cryolite, close to the composition NaF - Na3AlF8. Density measurements are also useful in giving a clue to the nature of cryolite-alumina melts.1, 4 On the first addition of alumina, density decreases, Fig. 2, although the density of alumina, either solid or liquid, is higher than that of cryolite. These density results indicate that the systems are not simple. A great deal of effort has been spent in measuring the electrical conductivity of molten cryolite and of cryolite with various additives. Conductivity measurements are quite easy for fused salts that can be measured in a dip cell, but no successful dip cell has been made available yet for cryolite. Recourse is had

Jan 1, 1959

By John P. Hager, Igor A. Wilkomirsky

The thermodynamic properties of the Pb-Ag system have been determined between 775° and 950°C by the cell: Electrotransport measurements on silica-saturated PbO-SiO2 melts established that the conduction was entirely ionic and that lead is present only in the divalent state. The activities of lead and silver exhibit Positive deviations from ideal behavior. In dilute solutions the activities of lead and silver follow Henry's law. The values obtained for yhb and yig at 1200°K are 1.49 and 1.69, respectively. Determination of a portion of the liquidus curve agrees well with the established phase diagram. provides an accurate means for the thermodynamic study of liquid alloy systems. However, Wagner and wernerl have shown that cells of type I are limited to alloy systems for which the reaction at the alloy-electrolyte interface will be extremely small. The traditional electrolyte for cells of type I has been a low melting point mixture of group IA chlorides, to which a small amount of the compound ACIZa has been added. However, the choice of a chloride electrolyte may not always be practical, in that the Gibbs free energies of formation of the compounds ACIZ, and BCIZb may not be sufficiently different to minimize Reaction [I]. On the other hand, the Gibbs free energies of formation of the oxides of metals A and B may be sufficiently different to minimize Reaction [I]. In this case, the use of molten oxide electrolyte would be clearly advantageous. In the present study, the thermodynamic properties of the Pb-Ag system have been investigated using the cell: Previous galvanic cell studies on the Pb-Ag system2'= are not reliable due to the displacement reaction between the alloys and the chloride electrolyte. Wagner and ~erner,' using Laitinen and Liu's' value at 450°C for the standard electrode potential of Reaction 111, have estimated the percent error in the activity of lead bPb) when using a chloride electrolyte. At 1000°C the error for xpb = 0.10 is 12 pct. Taking the Gibbs free energies of formation for PbClz and Ag cI,' and the equations of Wagner and Werner,' the error in apb at 1000°C and Xpb =0.10 was calculated to be 140 pct. However, using the Gibbs free energies of formation for Pb O' and an estimated value for Ag 20, the error in apb when using a molten oxide electrolyte at 1000°C was estimated to be less than 1 pct for The virtual reaction of cell I1 for the passage of n Faradays of positive electricity from left to right in the cell is: where 5 is the Faraday equivalent (23,063 cal per v equivalent), E is the electromotive force of the cell in volts, and n is the number of Faradays of electricity required for the transfer of 1 g-atom of lead through the cell. The value of n should be equal to 2 since lead is generally divalent in oxide melts. However, the presence of either tetravalent lead ions or electronic conductivity through the molten oxide electrolyte will result in a value of n greater than 2. Bockris, Kitchener, and Davies' have determined the amount of ionic conductance in a liquid PbO-SiO2 mixture (xPbO= 0.50) at 920°C by measurement of the volumes of CO and C& evolved at a carbon anode during electrolysis. From their data a value of 2.13 * 0.16 was calculated for n. Although their measurements indicate the possible presence of multivalent lead ions and/or electronic conductivity, their measurements were not at silica saturation and no definite conclusions can be drawn. However, as a result of the electrotransport measurements described in the next section the ;due of n can be taken as equal to 2.

Jan 1, 1969

By Stuart S. Forbes

Changes and additions made to the Canadian Copper Refiners Ltd. electrolytic refinery between 1949 and 1955 are reviewed. The effect of high current density on current efficiency and section work is discussed. OPERATING and physical changes which have been made to the electrolytic tank house of Canadian Copper Refiners Ltd. suggest a review of present conditions. Previous papers1 a have described the general arrangement. Since then, expansion, closer anode spacing, and higher current densities have increased annual cathode capacity from 112,000 to 182,000 tons. A recent extension to the tank house, begun in the spring of 1954 and completed in August 1955, was undertaken to handle the monthly production of about 3,000 tons of anodes from Gasp6 Copper Mines. The anticipation of these additional receipts and large stocks of unrefined copper caused by the increase in custom smelting at Noranda made it necessary to increase production without immediately available additional cell capacity. Accordingly, from December 1954 through March 1955, the tank house was operated successfully at a current density of 24.0 amp per sq ft. Again, as of September 1955, one of the two tank house circuits is being operated at this high density. Although other refineries may operate at current densities higher than 24 amp per sq ft, none is doing so with anodes which contain silver and gold content as high as those being refined at Canadian Copper Refiners Ltd. General Arrangement The original building consisted of two parallel bays, each 660 ft long and 60 ft wide, with a 24 ft pump bay extending along the west side of the building. A previous expansion, completed in 1939, was to the west of the original building and consisted of two 60 ft parallel bays 240 ft long. The length of these two bays was extended in 1954 to 540 ft, adding one stripper and 12 commercial sections to No. 2 electrical circuit. Space is still available for an additional six commercial sections and one stripper section. Construction on these seven sections started in September 1955, and will be completed early in 1956. The tank house capacity will then be 206,000 tons of cathodes per year. In the two tank houses there is a total of 900 cells distributed as follows—commercial, 468; stripper, 36; total, 504 in the No. 1 tank house (No. 1 circuit): commercial, 360; stripper, 36; total, 396 in the No. 2 tank house (No. 2 circuit). Section arrangement consists of nine cells to a tier and two tiers or 18 cells to a section. Anodes, weighing 620 lb each, are cast with a Baltimore groove and are refined by the multiple system. Solution enters each cell through a bottom inlet at one end and overflows at the top of the opposite end. Rate of solution flow through the cells is controlled by valves at each section to 4.5 gpm. Electrical power to the tank house is now provided by nine 675 kw motor generator sets. Each set consists of a 135-12 v 5000 amp dc generator, driven by a 980 hp 2300 v synchronous motor. When No. 1 circuit is operated at 22,000 amp, five sets, at 4400 amp each, are connected in parallel. As the maximum allowable current on No. 2 electrical circuit has recently been set at 18,000 amp, only four sets are connected in parallel on No. 2 circuit. A tenth set, now being installed, will be reserved as a spare, for use in either circuit as required. Recent Changes In 1949, the annual capacity of the tank house was increased from 112,000 to 132,000 tons by closing the

Jan 1, 1957

By H. T. Kennedy, J. E. Little

An empirical equation for the prediction of the viscosity of several pure paraffin hydrocarbons and nitrogen is presented. It involves temperature, pressure and six constants of the material, and it applies reliably to both liquids and gases. The equation is similar in form to van der Waal's equation of state. For the paraffin hydrocarbons methane through r-hexane and nitrogen, an average absolute deviation of 1.9 percent was obtained on 1,006 data points described in the literature by 14 authors. When this equation is extended to complex, liquid hydrocarbon mixtures, a correlation was obtained with an average absolute deviation of 9.9 percent. INTRODUCTION Equations describing the flow of gas and liquid through porous media contain the viscosity coefficient of the fluid. If other pertinent variables remain constant, the volume rate of flow is inversely proportional to this coefficient. In dealing with condensate fluids and volatile oils, however, the compositional effects resulting from changing pressure materially affect the viscosity. The effect of compositional changes also may be significant in certain secondary recovery or pressure maintenance processes, notably miscible displacement or gas injection. Early attempts to describe the performance of reservoirs utilized a volumetric material balance method wherein gas and liquid in the reservoir were identified as produced gas and liquid at the surface. This method of analysis proved adequate for reservoirs at moderate temperature and pressure that contained gas with moderately low amounts of condensable materials. The volumetric material balance procedures for "black oil" reservoirs leave much to be desired when applied to condensate and volatile oil reservoirs because phase behavior and compositional changes are relatively more important in these cases. The alternative is a compositional material balance, which in turn, requires a correlation of properties of the reservoir fluid with composition. This paper supplies this correlation in regard to viscosity, for reservoir crude oils. REVIEW OF LITERATURE The literature contains many empirical equations describing the effects of composition, temperature and pressure on the viscosities of pure liquids and binary liquid mixtures. However, the applicability of a majority of these equations is limited to very low pressures and to a small number of systems. Most of them, when applied to complex hydrocarbon systems, are of little value. The lack of utility of the majority of equations results from the fact that they were developed to show the separate effect of temperature, pressure or composition on viscosity, but not to predict the viscosity as a function of all three variables. And with the few exceptions noted below, they were developed to apply to much simpler systems than hydrocarbon mixtures. Eakin1 developed an equation for the viscosity of pure light hydrocarbons applicable in the gas, liquid and dense fluid regions, and in its most general form is written as µ - µo =A(ebP - e-cpk) The pure component viscosity at atmospheric pressure and temperature T, µo, was calculated using the Sutherland equation: µo = BT3/2/T + S The constants in Eakin's equation permitted the term e-CPk to become quite small at high densities (above 0.215 gm/cc), and the general equation would simplify to

Jan 1, 1969

By Leroy A. Palmer

All the domestic production of magnesite during 1925 came from two states, California and Washington. Of a total of 120,660 tons of crude ore, 64,600 tons, or 54 per cent., were produced in California.' Of this quantity California produced about 99 per cent. of the caustic calcined, but only 10 per cent. of the dead-burned. The largest producer was C. S. Maltby, of San Francisco, who operated the Red Mountain mine, in Santa Clara County, and the Sampson mine, in San Benito County, under lease. These two mines have been studied by the author, and offer interesting comparisons as to mining and treatment methods and final products. Geology The general geology of the magnesite deposits of California has been described by Hess,2 Bain3 and others4 and although a detailed discussion is not necessary here, a brief summary will assist in understanding mining conditions. California magnesite, when comparatively pure, is usually a white, fine-grained rock, with a conchoidal fracture, occurring in veins and lense-like masses in serpentine. The veins vary considerably in width, and usually occur in a series of more or less parallel veins intersected by other series or systems of veins, probably following original or secondary fissures in the enclosing serpentine. The most generally accepted theory of origin is that the magnesite was formed by the action of surface waters charged with CO2 percolating downward through fissures and changing the magnesium silicates of the serpentine into magnesium carbonate.

Jan 1, 1927

By W. W. Vaughn, R. H. Barnett, E. E. Wilson

Soon after the search for uranium ores on the Colorado Plateau began in earnest, thousands of feet of drill core ranging from 1 1/8 to 2 1/8 in. diam became available for study. Although significant advances had been made in the technique of quantitative gamma-ray borehole logging, instrumentation was in the development stage, and complete reliance could not be placed on gamma-ray logs alone to interpret quantitatively the meaning of radioactivity in a drillhole. A method that would be faster than chemical analysis and still give reproducible and reliable results for various drill core sizes was desirable to provide additional information on the enormous footage of drill core being accumulated. A solid phosphor scintillation drill core scanner was designed and constructed. Basically the instrument was developed to measure radiation from a drill core which would not be clearly recorded by a gamma-ray logger using a Geiger tube as the sensitive element. Such data would be beneficial in constructing isorad maps to delineate ore-bearing zones. A calibration in the range 0.01 to 0.1 pct eU3O8 was provided; above 0.1 pct eU3O8 gamma-ray logs were available and were being used to calculate grade and tonnage of ore reserves. The core scanner, however, has been used to estimate equivalent uranium content of ore-grade materials containing as much as 2.2 pct eU308 with an accuracy of ±10 pct, the sample being in the form of a BX drill core. Actually, an apparent calibration of eU308 vs counts per unit time is a straight line with a slope that is a function of the sensitive element and the geometry of the counting assembly. A true calibration that will show the expected departure from a straight line is due principally to the random nature of the pulse from a radiation source and the nonlinearity of the electron circuitry.

Jan 6, 1959

By W. H. Meyer

Although an aerial photograph is not a map, most of the information that is necessary for compiling a map is recorded in the photograph provided some form of radial-line method is used to determine the true position of images. The slotted- templet method, which is based on the well-established radial-line principle, has made it possible to construct accurate mosaic maps at a cost comparable with that formerly charged for the average mosaic. It makes possible the securing of these results with far less ground control, which is always expensive. It has expanded widely the possible use of aerial photographs for mapping. ALTHOUGH a vertical or oblique aerial photograph is not a map, most of the information that is necessary for compiling a map is recorded in the photograph. Some ground controls or data are needed, the number and accuracy to be governed by the mapping method to be used and the scale and final accuracy desired in the finished map. RADIAL-LINE CONTROL It is essential that the principle of radial-line control in the use of vertical aerial photographs be understood and accepted before any confidence in the slotted-templet method can be gained. A simple sketch and some enlargements showing the Empire State Building will serve to illustrate the cause of displacement of an image that is above the datum plane as recorded in the photograph. The top of the tower of the Empire State Building is directly above the base, and when the image of the top is shown almost two blocks away from the center of the base, it is evident that the image of the top of the tower is not the true location, and in this particular case we know where the true location is; namely, over the center of the base of the tower. If the top of the tower were the top of a hill 1250 ft. high, we would have no way of knowing by inspection the true position of the top of the hill, so it is very important to have a method whereby the true location of any such point can be determined, and thereby make it possible to convert the detail of an aerial photograph into accurate information for mapmaking.

Jan 1, 1939

By W. H. Meyer

Although an aerial photograph is not a map, most of the information that is necessary for compiling a map is recorded in the photograph provided some form of radial-line method is used to determine the true position of images. The slotted-templet method, which is based on the well-established radial-line principle, has made it possible to construct accurate mosaic maps at a cost comparable with that formerly charged for the average mosaic. It makes possible the securing of these results with far less ground control, which is always expensive. It has expanded widely the possible use of aerial photographs for mapping. Although a vertical or oblique aerial photograph is not a map, most of the information that is necessary for compiling a map is recorded in the photograph. Some ground controls or data are needed, the number and accuracy to be governed by the mapping method to be used and the scale and final accuracy desired in the finished map. Radial-line Control It is essential that the principle of radial-line control in the use of vertical aerial photographs be understood and accepted before any confidence in the slotted-templet method can be gained. A simple sketch and some enlargements showing the Empire Stale Building will serve to illustrate the cause of displacement of an image that is above the datum plane as recorded in the photograph. The top of the tower of the Empire State Building is directly above the base, and when the image of the top is shown almost two blocks away from the center of the base, it is evident that the image of the top of the tower is not the true location, and in this particular case we know where the true location is; namely, over the center of the base of the tower. If the top of the tower were the top of a hill 1250 ft. high, we would have no way of knowing by inspection the true position of the top of the hill, so it is very important to have a method whereby the true location of any such point can be determined, and thereby make it possible to convert the detail of an aerial photograph into accurate information for mapmaking.

Jan 1, 1941

By W. H. Meyer

Although an aerial photograph is not a map, most of the information that is necessary for compiling a map is recorded in the photograph provided some form of radial-line method is used to determine the true position of images. The slotted-templet method, which is based on the well-established radial-line principle, has made it possible to construct accurate mosaic maps at a cost comparable with that formerly charged for the average mosaic. It makes possible the securing of these results with far less ground control, which is always expensive. It has expanded widely the possible use of aerial photographs for mapping. Although a vertical or oblique aerial photograph is not a map, most of the information that is necessary for compiling a map is recorded in the photograph. Some ground controls or data are needed, the number and accuracy to be governed by the mapping method to be used and the scale and final accuracy desired in the finished map. Radial-line Control It is essential that the principle of radial-line control in the use of vertical aerial photographs be understood and accepted before any confidence in the slotted-templet method can be gained. A simple sketch and some enlargements showing the Empire Stale Building will serve to illustrate the cause of displacement of an image that is above the datum plane as recorded in the photograph. The top of the tower of the Empire State Building is directly above the base, and when the image of the top is shown almost two blocks away from the center of the base, it is evident that the image of the top of the tower is not the true location, and in this particular case we know where the true location is; namely, over the center of the base of the tower. If the top of the tower were the top of a hill 1250 ft. high, we would have no way of knowing by inspection the true position of the top of the hill, so it is very important to have a method whereby the true location of any such point can be determined, and thereby make it possible to convert the detail of an aerial photograph into accurate information for mapmaking.

Jan 1, 1941

By G. St. J. Perrott

One of the important hazards in coal mining is the danger of ignition of explosive mixtures of methane and air or coal dust and air, or both, by the explosives used in blasting the coal. It has long been recognized that certain explosives are more dangerous than others in this respect. ' In America and abroad, government testing stations have been established for officially passing on the suitability of explosives for use in coal mines. In this country the Federal government is given no power to enforce the use of the approved explosives but merely publishes from time to time, through the Bureau of Mines, those explosives which have passed the tests necessary to place them on the list for use in coal mines. In spite of this lack of police power, the increase in the use of permissible .explosives since the promulgation of the fist list in 1909 has been rapid. In 1912, only 8 per cent. of the explosives used in coal mines were permissible; in 1925, this figure had increased to 25 per cent. While the past record of permissible explosives has been most gratifying, it is very desirable that we pave the way for further improvement in explosives and blasting methods by learning more about the mechanism of ignition of gas and coal dust by explosives. To this end a considerable amount of investigative work already has been carried out and a large amount yet remains to be done. It is the purpose of this paper to discuss briefly the effect of the characteristics of explosives and method of loading in the borehole on the liability of a blown-out shot to ignite explosive mixtures of gas or dust. For an account of the methods by which an explosive is tested for permissibility for use in coal mines, the reader is referred to Schedule 17-A of the U. S. Bureau of Mines. Safety Factor in Using Explosives The factors that affect the liability of an explosive to ignite gas or dust are already known in a qualitative way but quantitative data are

Jan 1, 1927

By P. B. Baxendell

The performance of a water-drive reservoir having a gas cap depends primarily on the movement of the gar-oil and oil-water contacts. The movement of the contacts during production depends in turn on fluid withdrawals and how the reservoir pressure changes as fluids are produced from the reservoir; that is, on how effectively the aquifer maintains pressure by replacing withdrawals. inasmuch as pressure changes, fluid withdrawals, contact positions, and produced gas-oil and oil-water ratios are interdependent, the analysis and prediction of the performance of a reservoir produced in a given way must take into account this interdependence throughout depletion. This paper presents an analysis which, within the limitations of the assumptions made, yields an engineering approach to predicting future performance based on reservoir pressure and production history. The most significant assumption is the method of extrapolation of future gas-oil and water-oil ratios. The extrapolation procedure smoothly increases both ratios to preselected values as the remaining oil column undergoes a specified decrease in thickness. This preselection is made on the busis of previous field experience in depletion of similar reservoirs under similar conditions. For computing future performance a vdumebic balance L combined with the differential equation defining pressure distribution in the aquifer to obtain positions of water-oil and gas-oil contacts. From these positions are extrapolated produced water-oil and gas-oil ratios. Reservoir performance can be investigated when oil production rates are dependent upon various factors including the performance of the reservoir itself. Examples of practical application of the procedure are included. INTRODUCTION To predict performance of water-drive reservoirs with gas caps and thin oil columns, it is necessary to describe the motions of the fluids within the reservoir during the entire production period to depletion. These motions depend on the pressure changes and on the withdrawal of oil, gas and water. Production of oil from the oil zone primarily causes water to move in to take its place; production of gas from the cap tends to cause oil to migrate into its place. In addition, the volumes of oil and gas remaining in the reservoir depend on changes in the pressure, since a decrease in pressure causes fluid expansion, gas liberation and oil shrinkage. A method of relating the future pressure to total withdrawals is used to describe the motions of fluids within the reservoir under conditions arising in possible modes of production. The analysis is based on two relationships and will reduce the problem to one amenable to digital computation. The first of these concerns the dependence of the pressure distribution in the entire aquifer furnishing the water drive upon the total reservoir withdrawals. This dependence is dictated by the permeability distribution and the extent of the aquifer; at present, such information is most readily obtained from the performance history by means of the resistancecapacitance reservoir analyzer. The second relation involves withdrawals, pressure in the reservoir, and movement of oil, gas, and water within the reservoir. The analysis is subject to certain simplifying assumptions that are necessary to permit solution of the problem. A comparison of the methods of this paper with those presently practiced is pertinent. One method of analysis is to use the reservoir analyzer to predict reservoir behavior based on aquifer characteristics determined from production history. Inasmuch as the total withdrawal rate depends upon the gas-oil and water-oil ratios, which depend in turn upon, among other things, the positions of the gas-oil and water-oil contacts, these ratios must be assumed in advance. In this paper these ratios are, instead, related to the computed positions of gas-oil and water-oil contacts. Thus, our method can be applied to problems in which the oil production rate is limited by produced gas-oil ratio, or to problems in which it is desired to determine the variable gas injection rate that will maintain the gas-oil or water-oil contact stationary. These problems cannot be worked satisfactorily on the analyzer. Another method presently used is based on a paper by Hurst.' Since his procedure is dependent upon using the solution of the heat flow equation, which requires constant permeability within the aquifer, and our procedure recognizes variations of permeability in

By R. G. Robins

The processing of gold bearing sulphide minerals which contain arsenopyrite and various complex arsenic sulphides results in arsenic containing emissions and effluents which are suspect in relation to clean air and clean water standards. Removal of arsenic from gaseous emissions is briefly reviewed. The use of lime to stabilise aqueous residues as either calcium arsenate or calcium arsenite is shown to be inadequate for long term disposal since both compounds are converted into calcium carbonate due to the influence of carbon dioxide in the atmosphere. Mixed calcium arsenate-phosphate residues are similarly unstable, but present better stability than the straight calcium compounds. Alternative disposal methods are reviewed whereby the arsenic is converted to more stable compounds, such as barium arsenate, titanium (IV) arsenate, and arsenic sulphide.

Jan 1, 1984

By R. W. Raymond

I wish to call the attention of the Institute to a curious subject, brought to my notice last summer by Mr. Begger, the accomplished metallurgist of the smelting-works of the Boston and Colorado Company at Black Hawk, near Central City, Colorado. At these works, the richest auriferous sulphurets of Colorado (particularly copper pyrites) are smelted in reverberatories, together with roasted tailings (iron pyrites), and the gold and silver are concentrated into a new, artificial sulphide, or copper matte, containing $1500 and upwards of the precious metals per ton, and this is shipped to Swansea. I will say in passing, that this shipment of an unrefined product, like the similar shipments from Utah and Nevada to San Francisco, Chicago, St. Louis, Newark, New York, and Europe, of crnde argentiferous lead or "base bullion," is not a sign of incomplete metallurgy here, but has a sound business reason. The separation of the precious metals in the West would be more expensive, to begin with ; and then it would necessitate the movement of these metals by express, . - at high rates and risk, to commercial centres or coining mints, while the base metals having no home market, must be shipped and sold at little or no profit. At present, the gold and silver, safely packed, as it were, in the base metals, are transported with safety as ordinary freight; and the base metals probably more than pay cost of shipment and separation. To return to the Black Hawk reverberatories. On a recent occa-

By K. R. Evans

The yield and fracture characteristics of a Ti-8 pct A1 alloy have been examined at room temperature as a function of exposure temperatures to 1700°F. Em-brittlenzent of the alloy is observed to occur following exposures below 1280°F, the critical temperature for formation of ordered Ti3Al particles. Presence of Ti3Al particles results in an increase in the yield and flout stresses which, for a given exposure time, are a maximum at the critical temperature. Embrittlement is attributed to the occurrence of plastically induced fracture controlled by the increase inflow stress. This interpretation is compatible with the decreasing ductility and increasing crack popagation rates observed with increasing exposure time below the critical temperature. Slip line observations and measurements of the gain size dependence of the yield stress indicate that the slip character of the alloy is not influenced by exposure treatments below the critical temperature. ThE potential usefulness of Ti-A1 alloys in structural applications has prompted considerable interest in studies of their microstructure and mechanical characteristics. The relatively recent surge of interest in the system and at the same time its complexities are indicated by the fact that despite numerous recent efforts14 there has not even been general agreement upon a phase diagram for the system. However, most of the Ti-A1 alloys of commercial interest range in aluminum content from 5.0 to 8.5 wt pct where most investigators achowledge the existence of the ordered Ti41 phase. Goldak and parrs confirmed the existence of Ti41 from X-ray diffraction analysis of the stoichiometric composition while Blackburn6 has determined its presence in commercial Ti-8 pct A1 alloys by electron diffraction analysis and dark field transmission microscopy. The embrittlement of Ti-8 pct A1 alloys was initially reported by Crossley and carew7 who showed that aging in the temperature range of 750" to 1110°F resulted in extreme brittleness. This behavior was later confirmed and correlated by Soltiss to the presence of long-range order in the commercial Ti-8 pct Al-1 pct Mo-1 pct V alloy (Ti-8-1-1) which exhibited anomalous creep and yield strength behavior at 950°F. This investigation was designed to study the mechanical characteristics of a binary Ti-8 pct A1 alloy in order to further examine the nature of the embrittlement behavior reported for the alloy system. EXPERIMENTAL PROCEDURE A Ti-8 pct A1 binary alloy was obtained from the Wah Chang Co. in the form of 0.050 in. sheet. The chemical composition of the alloy is given in Table I. Heat-treatment of the alloy was conducted in evacuated vycor capsules for the tensile sDecimens (1.25 bv 0.25 in. gage section) and in evacuated stainless steel jackets for the crack growth-rate panels. All specimens were annealed at 1700°F for 24 hr and water quenched before an exposure at elevated temperatures. Tensile testing was conducted at room temperature in an Instron testing machine equipped with a pushbutton control for instantaneous control of the cross-head motion. In this manner the change in stress, Aa, accompanying an increase in strain-rate by a factor of 10 was measured immediately after yielding. The crack growth-rate panels used were 3 by 18 in. with a precrack 0.33 in. long cut into the center of the panel. The panels were cycled at a maximum gross stress of 40,000 psi at a maximum to minimum tension stress ratio of 20. Cycling of the specimens was continued until the crack propagated the width of the panels. The crack length was intermittently measured during slow crack growth. EXPERIMENTAL RESULTS Correlation of Embrittlement to the Critical Temperature for Ordering. Blackburn6 has found that the critical temperature, T,, for the formation of Ti41 in a Ti-8 pct A1 alloy with an interstitial content on the order of that given in Table I is approximately 1245°F. The relationship between the ductility of the binary alloy used in this investigation and T, was estimated from tensile tests on specimens which were exposed for 24 hr at various temperatures followed

Jan 1, 1970

By Donald W. Barnett

U.S. environmentalists have tended to oppose all new energy developments. Their efforts may be counterproductive because opposition to, say, offshore oil directly leads to the continued use of other energy sources that may have a higher social cost. Rather than attempting to eliminate all pollution from energy production, which would be prohibitively expensive, one should minimize the social cost of energy production for the given demand. Linear programming is used to rank various oils (California State and O.C.S., Gulf of Alaska, Prudhoe Bay, Athabasca tar sands, oil shale and certain foreign crudes) in terms of their social desirability. The objective is to minimize the cost of supplying the California market, subject to resource, sulphur and oil spill constraints. Social desirability is indicated by the inclusion of the oil in the optimal solution and the size of the associated shadow price. the larger the shadow price, the greater the benefits of increased production. The more negative, the greater the cost associated with forcing consumption of that fuel. The environmental shadow prices indicate the size of the trade-off between a particular environmental standard and minimum cost. The trade-offs can be surprisingly large. any reasonable spill standard can be achieved by changing the development pattern. Generally, the further offshore, the smaller is the environmental degradation, but the more expensive is the oil. Foreign oils can be economically and environmentally inferior to domestic oils. Crude from the California O.C.S., San Joaquin Valley end Prudhoe Bay appears a valuable resource, while the Gulf of Alaska, synthetic and foreign crudes appear marginal to submarginal.

Jan 1, 1977

By H. W. Miller, V. H. Wilhelm

During 1932 the oil industry persistently endeavored to maintain a rate of production that would permit a profitable price structure. Much effort was concentrated on curtailment of both production and drilling. The tendency in curtailment was to shut in reserves where closely held and not subjected to drainage, and to allow town-lot fields such as Long Beach, Santa Fe Springs, Playa Del Rey and Huntington Beach a greater percentage of allotment. Marginal wells were given special consideration; only a small percentage of curtailment wag required, making their operations profitable. Naturally the decline in production of town-lot fields, under slight curtailment, is very rapid, hence production that is restricted in fields controlled by major interests at the present time will profit considerably in the future, as California reserves do not appear adequate to sustain heavy withdrawals over a long period of time. California production during 1932 was much greater than additions to reserves during the year. The state produced 10,701,238 bbl. of crude oil less in 1932 than in 1931, while total stocks (all petroleum commodities) decreased 1,589,524 bbl. Had all operators kept strictly within their allotted 'production, the total crude production decline would have been approximately 20,000,000 bbl. and total stock decrease 3,000,000 barrels. Estimated proven oil reserves for California were 3,965,000,000 bbl. on Jan. 1, 1932, as compared with 3,784,120,000 bbl. as of Jan. 1, 1933, a decrease of 180,880,000 barrels. Approximately 85 per cent of the 178,127,794 bbl. of oil produced during 1932 was withdrawn from old reserves in settled fields and the remaining 15 per cent from new sources such as Kettleman Hills North Dome, Belridge, San Miguelito and Dominguez deep zone. The oil reserves of Kettleman Hills North Dome are estimated to be approximately 50 per cent of the total oil reserves, of California and they may be drawn upon at a much greater rate than the remainder of the state's oil fields.

Jan 1, 1933

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By R. S. McCaffery, D. E. Krause

There has been some discussion among blast-furnace operators regarding the relative merits of tuyeres of the converging type and tuyeres designed in an attempt to produce a diverging jet of air. An article1 on Progress in German Blast Furnace Practice indicates the interest in this subject abroad. This article illustrates a diverging type of tuyere which is shown here in Fig. 1A. The design appears to be rather poor as regards known properties of air flow. The adoption of this tuyere, the arlicle states, resulted in a decrease of blast pressure of about 4 Ib. per sq. in. and an increase of the output of the furnace. If the improvements mentioned are due entirely to the change in tuyere design, the subject of tuyere design seemed worthy of investigation and this paper is a report of such work. Because of the gain in efficiency brought about by the use of a diverging tuyere in the German plant, it was thought desirable to investigate the shape of the air streams issuing from various types of tuyeres to ascertain whether the gain was due to the tuyere itself or to the distribution of the air in the furnace. Since it is difficult to do experimental work on a full-sized furnace, or even on full-sized tuyeres, and because of the equipment available for the work, it was decided to carry out the work on scale models of tuyeres. Therefore, in this work, single tuyeres were used and the blast discharged into the atmosphere. The shape of the air stream was determined by means of a Pitot tube suitably supported in the air stream at various positions. The air was furnished by a Roots blower driven by a 10-hp. direct-current motor having field control, and capable of discharging 250 cu. ft. per min. with a pressure on the discharge of 4 in. of mercury. A modern blast furnace with 21-ft. hearth requires about 50,000 cu. ft. per min. of free air at from 16 to 23 Ib. per sq. in. pressure, depending upon the type of burden. This pressure is the total pressure required to force the air through the burden and through the tuyeres. Upon computation the pressure drop through the tuyeres is about 1 to 2 lb. per sq. in. By making the tuyeres to a one-fifth scale, and by using a pressure of 1.5 in. of mercury, the shape of the air streams should be

Jan 1, 1931