Search Documents

By J. D. Alexander, W. L. Martin, J. N. Dew

This paper presents data obtained using a flood-pot technique to determine the fuel available and the corresponding theoretical air requirements for in situ combustion of crude oils. Since the technique is relatively quick and easy, it is a practical and convenient tool for evaluating reservoirs as fireflood prospects. It is also a research tool which facilitates systematic study of the variables affecting fuel availability and corresponding air requirements. The understanding of these variables is of prime importance to those concerned with the technical and economic development of in situ combustion as an oil-recovery process. The experimental results show conclusively that the fuel available for in situ combustion is not a constant but, rather, varies with crude-oil characteristics, porous-medium type, oil saturation, air flux and time-temperature relationships. Thus, the fuel availability for specified field applications should be determined using actual reservoir crude and core material and the process conditions expected during in situ combustion in the reservoir. INTRODUCTION In situ combustion is a thermal process for recovering crude oil from reservoirs. The thermal energy released during the combustion of a small amount of the oil in place aids in the displacement of the remaining oil. Numerous articles have been published describing the in situ combustion process giving detailed results of laboratory and field experiments.10 In order to engineer an in situ combustion project, a number of important factors must be considered and determined. These factors include: (1) the amount of fuel consumed per unit of reservoir volume swept by the combustion zone, (2) the composition of the fuel consumed, (3) the amount of air required to consume this fuel, (4) the portion of the reservoir swept by the combustion zone, (5) the appropriate air-injection rates and pressures, (6) the amount of oil that will be recovered, (7) the rate of oil production and (8) the operating costs. Nelson and McNiell1 recently have described a procedure which utilizes laboratory combustion-tube data as a basis for the calculation of some of these design factors. Various authors have attempted to describe the in situ combustion process mathematically, and considerable progress has been made. Analytical solutions to the problem of heat transfer from a moving combustion front have been obtained for linear and radial systems."-' All of the published results involve the assumptions that: (1) fuel concentration is constant throughout the reservoir, or that fuel concentration is inversely proportional to the velocity of the front for a given rate of oxygen consumption; and (2) the fuel reacts instantaneously with injected oxygen, while liberating a constant amount of heat per unit weight of fuel at all temperatures. It seems both desirable and reasonable to test the validity of these assumptions experimentally. This paper presents laboratory data which were obtained by means of a "fire flood-pot" method for determining fuel availability and composition, and the corresponding theoretical air requirements for in situ combustion of crude oils under variable conditions. The mechanics of the method are similar to a conventional tube-run experiment.' The important differences involve the size of the reservoir model used and the method for providing the experimental environment. The new method subjects conventionally-sized core samples or unconsolidated sands to a programmed environmental sequence similar to that experienced by a similar volume of rock during the approach and passage of a combustion front in a long tube or in an oil reservoir undergoing in situ combustion. Restored-state samples can also be used. The small samples and relatively simple techniques involved allow an experiment to be set up, run and calculated in about three 8-hour days. This is a considerable improvement over long-combustion-tube techniques which can require several days to run and several more work days to set up and calculate. All the runs presented were run at 40-psig injection pressure. Pressure was not considered as a variable for these experiments, since we previously had found that it had only a small effect on fuel availability up to 600 psig.APPARATUS AND MATERIALS APPARATUS The fire flood-pot apparatus consists of a consolidated

By W. N. Tanner

The wire-rope hoisting conditions at the mines of the Anaconda Coppcr Mining Co. in Butte, Mont, are very severe because of the conditions under which it is necessary to operate. A study was made, in the fall of 1919, for the purpose of changing these conditions in order to obtain longer rope and sheave life. There are at present in Butte hoisting engines equipped with wire rope as follows: 9 main hoists using flat ropes. 7 main hoists using 1 1/2-in. rope. 5 main hoists using 11/4-in. rope. 6 shafts using 11/8-in. rope. 2 chippy hoists using 11/4-in. rope. 9 chippy hoists using 11/8-in. rope. 15 shafts using 1-in. rope. 7 shafts using 7/8-in. rope. 1 shaft using 3/4-in. rope. In addition, there are a number of sinking engines wing 5/8-in, 3/4-in., 7/8-in., and 1-in. (15.9, 10, 22, and 25 mm) rope. THe flat ropes run from 1/2 by 71/2 in. (12.7 by 1905 mm.) to-3/8 by 4 1/2-in (9.5 by 114 mm.) and are used on the older hoisting engines, which arc set comparatively close to the shaft. Because of swelling and moving ground at some of the shafts, these ropes present certain difficulties ill operation that are more pronounced than with round ropes; they are, therefore, being superseded by round ropes as newer engines are being installed. They are, however, much more easily inspected and repaired than round ropes. In general, the practice in Butte is to use hoisting engines equipped with 12-ft. (3 7 m.) cast-iron drums, smooth faced, for 11/2-in. rope and 6-ft. cast-iron drums, smooth faced, lagged with 3/8-in. steel plate for 11/4 l1/8 and 1-in. (31.7, 28.6, 25 mm.) rope in main and chippy shafts. Cast-iron head sheaves, 12, 10, and 6 ft. in diameter, with grooves

Jan 1, 1923

By W. N. Tanner

The wire-rope hoisting conditions at the mines of the Anaconda Coppcr Mining Co. in Butte, Mont, are very severe because of the conditions under which it is necessary to operate. A study was made, in the fall of 1919, for the purpose of changing these conditions in order to obtain longer rope and sheave life. There are at present in Butte hoisting engines equipped with wire rope as follows: 9 main hoists using flat ropes. 7 main hoists using 1 1/2-in. rope. 5 main hoists using 11/4-in. rope. 6 shafts using 11/8-in. rope. 2 chippy hoists using 11/4-in. rope. 9 chippy hoists using 11/8-in. rope. 15 shafts using 1-in. rope. 7 shafts using 7/8-in. rope. 1 shaft using 3/4-in. rope. In addition, there are a number of sinking engines wing 5/8-in, 3/4-in., 7/8-in., and 1-in. (15.9, 10, 22, and 25 mm) rope. THe flat ropes run from 1/2 by 71/2 in. (12.7 by 1905 mm.) to-3/8 by 4 1/2-in (9.5 by 114 mm.) and are used on the older hoisting engines, which arc set comparatively close to the shaft. Because of swelling and moving ground at some of the shafts, these ropes present certain difficulties ill operation that are more pronounced than with round ropes; they are, therefore, being superseded by round ropes as newer engines are being installed. They are, however, much more easily inspected and repaired than round ropes. In general, the practice in Butte is to use hoisting engines equipped with 12-ft. (3 7 m.) cast-iron drums, smooth faced, for 11/2-in. rope and 6-ft. cast-iron drums, smooth faced, lagged with 3/8-in. steel plate for 11/4 l1/8 and 1-in. (31.7, 28.6, 25 mm.) rope in main and chippy shafts. Cast-iron head sheaves, 12, 10, and 6 ft. in diameter, with grooves

Jan 1, 1923

By Philip D. Wilson

The mines of the Calumet & Arizona Mining Co. are situated in the Warren Mining District, Cochise County, Arizona, between Bisbee and Warren and adjoin those of the Copper Queen Consolidated Mining Co. and the Shattuck Arizona Copper Co. Paleozoic 1imestones.of considerable thickness have been intruded by granite porphyry. A great stock of the intrusive outcrops boldly near the city of Bisbee and is known as Sacramento Hill. From this central core the porphyry has tongued out into the limestone for many thousands of feet as dikes and sills of irregular shape and variable dimensions. Churn drilling has recently developed a large tonnage of secondarily enriched copper ore in the main porphyry mass of Sacramento Hill. While some ore has been found in porphyry in other parts of the district, it is relatively unimportant compared with that which occurs in the Paleozoic limestone as irregular lenses replacing favorable beds near porphyry contacts or associated with well-marked fracture zones often many hundreds of feet away from the intrusive. In a zone extending from Sacramento Hill for a distance of from 1,500 to 3,000 ft., the limestone has been extensively metamorphosed and in this contact metamorphic zone the ore occurs through a known vertical thickness of upward of 900 ft. and individual orebodies often show extension in a vertical direction of over 200 ft. At a greater distance from the intrusive stock, the ore occurs as lenses of greater horizontal than vertical dimensions with an average thickness of approximately 30 ft. An exception to this rule is found in the occasional steeply dipping mineralized fractures, almost true tabular veins, which are found long distances a way from the zone of contact metamorphism. The copper was probably introduced during or slightly later than the porphyry intrusion in the form of chalcopyrite and bornite. These primary copper minerals are always associated with pyrite and often occur as rich lenses in a huge mass or shell of pyrite carrying an insignificant percentage of copper. In many instances the copper-bearing solutions were preceded by siliceous solutions and these latter, often persisting during the period of mineralization, have thoroughly indurated the ore-

Jan 1, 1917

By William M. Boorstein, Robert D. Pehlke

The rates of solution (of hydrogen in liquid pure iron and in several liquid binary iron alloys were meas-ured using a constant volume technique. The rates of absorption and desorption were found to be equal un-der all experimental conditions. increasing concen-trations of S, Si, or Te decrease the rate of hydrogen uptake but additions of Al, B, Cr, Cu, or Ni have no measurable effect up to concentrations normally en-countered in steelmaking practice. No relation ship was found between the effect of an alloying element on the equilibrium solubility of hydrogen in liquid iron and its effect on the solution rate constant. Mathe-rnatical analysis of the data indicates that under the present experimental conditions the rate of reaction of hydrogen with liquid iron is controlled by transport of gas solute atoms in the metal phase. Comparison of the present resuts with data on nitrogen taken un der similar conditions establishes that the hydrody-nurnic conditions which exist near the surface of a metal bath are best approximated mathematically by a surface renewal model for the case of rapid in-ductive stirring and by a boundary layer model for more quiescent melts. HYDROGEN has long been recognized as being a detrimental constituent in steel. If dissolved in the molten metal in excess of its solid solubility, hydro-gen can be evolved during solidification and cause bleeding or porosity in ingots and castings. In the solid metal, lesser amounts play a definite role in causing other defects such as hairline cracks, blisters, and embrittlement. For significant refinements to be made in metallurgical procedures designed to control or eliminate hydrogen from liquid iron or steel dur-ing processing, available equilibrium solubility data must be supplemented with reliable fundamental in-formation pertaining to the kinetic factors involved in the transfer of hydrogen to or from the metal. The scarcity of such information in the literature prompted the present investigation. PREVIOUS RESEARCH Whereas much of the existing data on the solution kinetics of gases such as nitrogen were obtained during the course of thermodynamic investigations, the solu-tion rate of hydrogen has been found too rapid to be accurately determined by conventional solubility meas-urement techniques. Consequently, little work on hy-drogen solution kinetics has been reported in the lit-erature. Carney, Chipman, and crant1 attempted to study the rate of solution and evolution of hydrogen from liquid iron by employing a newly devised sampling method. Although no significant quantitative data could be obtained, it was observed that the rate of solution was approximately equal to the rate of evolution of hy-drogen from the melt. Karnaukov and Morozov2 stud-ied the rate of absorption and Knuppel and Oeters3 the rate of desorption of hydrogen from molten iron by measuring pressure changes with time in a constant volume system. Karnaukov and Morozov determined the hydrogen pressures over their inductively stirred melts with the aid of a McLeod gage and therefore, were forced to work at pressures not in excess of 40 mm of Hg. Their experimental data conformed to a mathematical correlation based on diffusion control: and the rate coefficients calculated on this basis were shown to be independent of the initial absorption pres-sure. These authors reported the solution rate of hy-drogen to be eight-to-ten times higher than they had found for nitrogen in a previous study. They also re-ported that under identical conditions, hydrogen dis-solves somewhat more slowly in iron-columbium alloys than in pure iron. Knuppel and Oeters found that the desorption of hydrogen from pure iron at 1600°C was controlled in all cases investigated by diffusion in the metal bath as long as bubble formation was sup-pressed. This was substantiated by Levin, Kurochkin, and umrikhin4 who studied the kinetics of hydrogen evolution from liquid (technical) iron while applying a vacuum. Salter5 measured the rate of hydrogen ab-sorbed by iron buttons, arc-melted by direct current, as a function of hydrogen partial pressure in a hy-drogen-argon atmosphere. A carrier gas technique was used for analysis of the hydrogen absorbed. The initial rate of absorption was found to increase di-rectly with the square root of the partial pressure of hydrogen. EXPERIMENTAL METHOD Because of the rapid uptake and evolution of hydro-gen by iron-base melts, a constant volume technique was devised in order to obtain meaningful kinetic data over the entire course of the solution process. Apparatus. A schematic view of the experimental apparatus is given in Fig. 1. The hydrogen-liquid iron reaction system consisted of a gas storage bulb con-nected to a meltcontaining reaction chamber through a normally-closed solenoid valve. The gas storage bulb, an inverted 250 ml round-bottomed Pyrex flask was joined to the inlet port of the solenoid valve by a glass-to-metal seal. A more detailed illustration of the reaction chamber is shown in Fig. 2. The design of the Vycor reaction bulb was essentially that de-scribed by Weinstein and Elliott6 with the exception of a shorter, larger diameter gas inlet for this kinetic study. In position, the reaction bulb was closely by an eight-turn coil of water-cooled copper tubing which, when energized by a 400-kc oscillator, provided the inductive heating source. The walls of the bulb were maintained relatively cool by circulating cold water along their outer surface, thus preventing

Jan 1, 1970

By M. T. Simnad, R. F. Mehl, L. Yang

Techniques for studying marker movement in K-Rb interdiffusion have been worked out. The results indicate that Rb diffuses faster than K and that the ring mechanism of diffusion cannot be the dominant one operating in this case or probably in cases involving other alkali metals, despite their low ion core repulsive energies. SEVERAL theoretical attempts have been made in the past decade to elucidate the mechanism of diffusion in body-centered-cubic metals. No general agreement, however, has been reached by different authors. Zener,1 and later LeClaire,2 on the basis of a correlation between the entropy of activation for self-diffusion and the temperature dependence of the elastic constants, predicted that a ring mechanism should operate in the diffusion of body-cen-tered-cubic metals. Paneth3 calculated the activation energies of various ring, vacancy, and interstitial mechanisms for the self-diffusion in alkali metals and concluded that the most likely one was based on the linear motion of "crowdions," which is in fact a different form of interstitial diffusion. Fumi,1 however, showed that the experimental values of the activation energies for self-diffusion in the alkali metals could be better accounted for if the diffusion process in these metals was assumed to follow a vacancy mechanism. The same conclusion was reached by Kojima5 for the self-diffusion in lithium. Experimental evidences published during the past few years seem to exclude the ring mechanism as the predominating one in the diffusion of body-centered-cubic metals. For instance, maker movement has been observed in ß-brass, first in this laboratory" and later by Resnick and Baluffi.5 Shewmon and Bechtoldh also found marker movement in the body-centered-cubic system Ti-Mo and showed that the argument which led Zener and LeClair to favor a ring mechanism was not incompatible with a vacancy mechanism. In spite of this, it seemed to the authors that further experimental tests should be made by studying the Kirkendall effect in body-centered-cubic systems that characteristically have small ion core repulsion, such as the alkali-metal systems. Since the ion core repulsion term constitutes the main part of the activation energy needed for the rotation of a ring, such a test should be the most critical of all. The system K-Rb was chosen for experimental study because these metals form a continuous series of solid solutions. Experimental Investigation Owing to the extremely active nature of these two metals, a brass dry box (18 x 11 x 10 in.) was built for making the diffusion couple. It had a big lucite window on top, two side ports through which neo-prene-rubber gloves were inserted, and another side port covered with an optically flat-glass window for microscopic examination of the sample. Inside the box there were a circulating fan driven with a rotating horse-shoe magnet located outside the box, a heater used to generate potassium vapor for getter-ing the box, and a cold trap for keeping the inside of the box cool. Chemically pure grade K and Rb were triple distilled before they were transferred in vacuum into cylindrical steel molds kept in pyrex-glass ampules, Fig. 1. The latter together with the tools needed for making the diffusion couple were put into the dry box. After the box was flushed with purified argon and gettered with potassium vapor, generated from a heated steel crucible inside the box, the glass ampules were broken and the mound on the top of the alkali-metal ingot was cut off with a razor blade to yield a flat surface. To make the diffusion couple, one K ingot and one Rb ingot were pushed out of the molds together with their steel supports by screwing a metal plunger into the bottom of each mold. They were then laid on a brass cradle inside the assembling carriage (shown separately in Fig. 2) with the flat faces opposite to each

Jan 1, 1959

By D. H. Polonis, Gary A. Dreyer

This investigation involved a study of the reactions occurring during aging of supersaturated a phase in a CIL-Si alloy. The aging processes at temperatures below 552°C were studied by means of metallography, microhardness, and electrical resistivity measurements. During the initial stage of aging in the temperature range 275o to 525oC an anisotropic phase, which is visible in the form of striations in the micro-structure formed prior to the appearance of the -phase. This transition phase has been designated k' due to its structural similarity to the k phase. The rate of K' formation during aging increased with aging temperature. At 450o and 525°C the reaction appeared to reach completion before significant amounts of precipitation were observed. The overall precipitation reaction in this system involved four stages: formation of formation of at a grain boundaries, growth of particles in 7-egions, and coagulation of into large particles. The relative role of each of these processes is dependent on the temperature of aging. The formation of phase from supersaturated a during aging increases the electrical resistivity and slightly increases the hardness of a 4.9 pct silicon alloy. The formation of during aging decreases the electrical resistivity and increases the hardness until coalescence of particles begins during the final stages of aging. The coalescence of results in a decrease of both electvical resistivity and hardness. THE available literature does not record a detailed analysis of the aging processes in Cu-Si alloys. Such an analysis has been difficult due to both the limited data available and misleading microstructural observations which have been reported. Previous work suggests that a rather complicated series of processes may be involved in the aging of supersaturated a. The present investigation is concerned with an analysis of the sequence of these aging processes in a 4.9 pct Si alloy. The currently accepted version of the Cu-Si equilibrium diagram, Fig. 1, was published by C. S. Smith in 1940.' This diagram shows a eutectoid at 5.2 pct Si with the high temperature phase, having its composition range entirely to the right of this value. By quenching alloys in the composition range 4.6 to 5.2 pct Si from the region, Smith was able to retain the phase. However, this phase exhibited a striated microstructure which was anisotropic to polarized light. These striations were suggested by Smith to be duplex twins. Using an oscillating crystal X-ray method Barrett2 studied alloys containing 4.0 to 5.4 pct Si quenched from the and regions. The striations observed in quenched specimens were attributed by Barrett to quenching stresses. He found that striations could also be formed by deformation after quenching and identified them as stacking faults in alloys containing 4.0 to 5.0 pct Si. Barrett related the striations in alloys containing 5.0 to 5.4 pct Si both to stacking faults and to a metastable phase which he called The striated structure reported by smith' was also obtained by Hoffmann, et al. 3 By deeply etching their specimens the anisotropic phase on the surface was removed, leaving a structure which was microscopically similar to pure copper. By means of X-ray analysis before and after deformation at room temperature it was concluded that the anisotropic phase was metastable This conclusion has been questioned by Barrett who attributes the discrepancy to superposition of k and lines on the powder patterns of Hoffmann, et alm3 The decomposition of supersaturated according to smith' and Anderson,4 is very sluggish. However, Nony and Dreyer,5 and Hoffmann, et al.' found that deformation increases the rate of decomposition. X-ray studies by Hoffmann, et al on

Jan 1, 1962

By Carl Henrich

I have read with particular interest that portion of the discussion by Anton Eilers referring to the high-lime (and also high-alumina) slags made by August Raht in 1881, while smelting the Horn Silver ores at Franklin, Utah. The two analyses of such slags, furnished by Mr. Raht to Mr. Eilers are: (a) Not determined in this analysis. (b) Not given in Mr. Eilers' paper. Oxygen ratio, A1 as base. I. 0 in acid: O in base:: 18.1:18.9:: 0.96:1 11. 0 in acid :O in base:: 18.7:17.5::1.06:1 Average: 18.4:18.15=1.01:l Oxygen ratio, AI as acid. I. O in acid: O in base: :23.2:13.8:: 1.68:1 11. O in acid: O in base::23.1:13.5:: 1.76:1 Average: 23.15:13.4 = 1.73:l By assigning to alumina the the of a base, Mr. Eilers deduces the formula 3Feo.-2SiOa + 4Cao.2SiO². The nearest approach to a simple formula expressing the average composition of these slags, which I can figure, is 9RO.Al2O3.6SiO2. Allowing a ratio of 4Feo : 5Cao, we have for this formula:

Jan 1, 1917

By N. C. J. Ros

The paper deals with pressure gradients occurring in flowing and gas-lift wells, a knowledge of which can be applied to the determination of optimum flow-string dimensions and to the design of gas-lift installations. The study is based on a pressure-balance equation for the pressure gradient. It appears that a pressure-gradient correlation of general validity must essentially consist of two parts-—one part being a correlation for liquid hold-up and the other part being one for wall friction. Dimensional analysis indicates that both liquid hold-up and wall friction are related to nine dimensionless groups. It is shown that in the field of interest only four groups are really important. On the basis of these four groups a restricted experimental program could be selected that nevertheless covered practically all conditions encountered in oil wells. This experimental program has been carried out in a laboratory installation. Three essentially different flow regimes were found. The pressure gradients in these regious are presented in the form of a set of correlations. Comparison of these correlations with a few available oilfield data showed excellent agreement. INTRODUCTION Prediction of the pressure drop in the flow string of a well is a widely known problem in oilfield practice. Accurate data on the pressure gradient of a simultaneous flow of gas and liquid in a vertical pipe are especially useful for the determination of optimum flow-string dimensions. It is well known that with moderate gas and liquid flows such a vertical string acts as a "negative restriction". The pressure drop decreases (1) when the throughput through a given pipe increases, and (2) when at a given throughput the cross-sectional area is decreased. The reason is that, with increasing velocities, the flow becomes more agitated so that the gas slips relatively more slowly through the liquid. With the resulting increase in gas content in the string, the static head decreases. When the area becomes very small, however, the high velocities entail great wall friction, which causes an increase in pressure drop. For a given flow, therefore, minimal pressure drop is obtained by using a certain cross section. This means that, in principle, each well can be provided with an optimum flow string for minimum pressure drop and, hence, maximum possible production rate. The procedure for the selection of the optimum string has been discussed by Gilbert.' A necessary tool in the procedure, however, is accurate knowledge of the pressure gradient to be expected for various values of the governing variables. Another application of pressure-gradient data lies in the field of gas-lift practice: they provide a means of determining the optimum gas-injection rate, optimum injection pressure and optimum injection depth. Much work has already been done in the study of the pressure gradient of vertical gas-liquid flow. Poett-mann and Carpenter2 presented a pressure-gradient correlation based on measurements in wells. This correlation has been found to provide accurate predictions in high-pressure wells and in high-production wells for flow through both tubing and annuli.2-5 However, when their method is checked on low pressure-low production wells or on wells with viscous crudes, serious discrepancies are found. As we shall see in the next section, this is due to the fact that their correlation factor, representing all irreversible energy losses, is given as a function of only one correlation group. Some important variables, such as gas-liquid ratio and liquid viscosity, are not incorporated in this group so that their specific effects are not accounted for. To study also the mechanism of vertical gas-liquid flow outside the ranges covered by the Poettmann-Carpenter publication and extensions, a laboratory investigation has been carried out. This study is founded on a pressure-gradient equation that is based on a pressure balance. To reduce the number of test runs required, a dimensional analysis has been carried out, followed by a selection of relevant dimensionless groups. These groups guided a subsequent experimental study, and with their aid the experimental program could be minimized while still covering the majority of the situations encountered in oilfield practice. In this paper the choice of a formula for the pressure gradient is discussed first. This is followed by a brief description of the experimental setup. Subsequently, the dimensional analysis is discussed and the relevant dimensionless groups are selected, resulting in the experimental program required. The general relationships of pressure gradient and liquid hold-up are then described; various flow patterns and a certain flow instability (so-called "heading") are discussed and a set of correlations is presented which shows a good agreement with the measurements and a few available field

By Robert H. Aborn, J. J. B. Rutherford

It is now well known that troublesome intercrystalline corrosion may occur in austenitic stainless steels following exposure of the metal to a temperature within the range 1000° to 1500° F. (540° to 815° C.). The present paper describes a satisfactory method of estimating the extent of such corrosion, based on the measurement of the electrical resistance of a specimen before and after attack. This new method enabled us to study quantitatively the effect of several factors upon intergranular corrosion in the 18 Cr, 8 Ni type of alloy. The results show that susceptibility to this attack increases with increasing carbon content and grain size and appears to pass through a maximum for certain combinations of temperature of sensitization and period during which the alloy was maintained at that temperature; and are in complete accord with our interpretation of the mechanism of this phenomenon. The method is probably applicable to other metals or alloys subject to intercrystalline attack, such as the aluminum alloys of the duralumin type. The methods hitherto in use for estimating the degree of intergranular attack fall into three types: (1) microscopic examinationll (2) macroscopic examination of fractures, and (3) determination of the time required for complete failure or disintegration.2 None of these lends itself very well to a measurement of the extent of corrosion. The first two are qualitative in nature and the third provides an arbitrary value largely dependent on individual judgment, since failure is a progressive phenomenon and not a sudden event. Our experience is that weight-loss determinations, although valuable in some types of corrosion investigations, bear no simple relation to intercrystalline corrosion in this type of alloy, as is to be expected since the phenomenon probably involves only the thinnest films between adjacent metallic grains. Measurement of electrical resistance has been used recently in the study of some types of corrosion,3 but seems not to have been applied to

Jan 1, 1932

By Thomas Darlington

The obligation of an employer to the State requires certain things of him as matters of good citizenship: for instance, that his workmen shall have a living wage, that child labor shall not be employed, that injuries from accidents shall not make workmen a charge upon the State, and that the laborer's children shall have opportunity for education and to become good and useful citizens. Affairs of this kind are not taken up as philanthropy, for the officials of a corporation or a large manufacturing concern may not feel at liberty to spend the funds of their company as prompted simply by motives of kindliness; but they may spend company money on such matters because it is good business. For years, the poisonous effects of lead, phosphorus, and dust have been emphasized in books on industrial hygiene and their elimination has been urged; but the more important and everyday physiology of the workman himself has been neglected. Part of my object in writing this paper is to show how our knowledge of physiology may be applied to working conditions in everyday life. In the interest of industrial laborers, accident compensation laws have been enacted in 33 States. This has been carried forward rapidly, because it has been shown that it pays both employer and employee. A further step is the recognition of sickness and disablement independent of accidents, not only because of their immediate cost to the worker and to the employer, but because continued efficiency in work and business depends largely upon health. Some measure of the importance of health in industry can be gained by the knowledge that records kept by some companies which now make this the subject of careful inquiry show that the time lost by employees, through illness, is several times as much as that lost as the result of industrial accidents. It is true that accidents frequently result in permanent disability or death, but it is equally true that illness is also a cause of permanent disablement or death. Thus the chief difference is that the loss to the employee through accidents occurring in the course of his employment is now generally recognized as a cost

Jan 1, 1918

By A. D. Zunkel, A. H. Larson

Equilibrium arsenic contents of Pb-As alloys in contact with PbO-As2O3 slags containing less than 30 mol pct As2O3, were determined at 650°, 700: and 750 C in an inert at?rzosphere. In this temperature range, the arsenic content of the alloy increased with increasing temperature in the single-phase liquid slag region and decreased with increasing temperature in the two-phase slag region and the single-phase solid-solution slag region. The PbO-As2O3 phase diagram below 22 mol pct As2O3 was determined by thertrzal analysis and by application of a log ?As2O3/?PbO vS log XAs2o3 /x3pbO plot determined from the equilibrium actiuity data. The resulting phase diagram was not well-defined since the eutectic temperature was not detected in the thermal analysis experiments, although a region of terminal solid solubility of As2O3 was found. Results from the phase diagram determination are compared with an existing diagram in the literature. THIS experimental investigation is an extension of a study by the authors1 on the slag-metal equilibria in the systems concerned with commercial lead refining processes such as softening and dross fuming. The first part of this investigation was a study of the slag-metal equilibria in the Pb-PbO-Sb2O3 system. The only experimental work previously done on the Pb-PbO-As2O3 system was by Pelzel2,3 in which the phase diagram for the PbO-As2O3 system was determined below 50 wt pct As2O3 and the equilibrium constant for the reaction 3Pb + As2O3 + 3PbO + 2As was determined as a function of temperature. No slag-metal equilibrium data have been determined. It is due to the scarcity of information regarding the Pb-PbO-As203 system that this work was undertaken. This paper describes the determination of the slag-metal equilibria in the Pb-PbO-As203 system by equilibrating Pb-As alloys with PbO-As2O3 slags in an inert atmosphere, the effect of 1 wt pct additions of bismuth and copper on the slag-metal equilibria, and the PbO-As2O3 phase diagram both by thermal analysis and the use of the slag-metal equilibria data. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade and assayed as follows: 1) 99.8 pct PbO (0.014 pct insoluble in CHJCOOH, 0.02 pct not precipitated by H2S, 0.1 pct CaO, and 0.08 pct SiO2); 2) 99.95 pct As2O3; 3) 99.99 pct Pb; 4) 99.0 pct As; 5) 99.99 pct Cu; and 6) 99.97 pct Bi. Room-temperature X-ray patterns revealed no detectable impurities in any of these materials. Apparatus for Equilibrium and Thermal-Analysis Determinations. The resistance-heated crucible furnace used in this investigation employed nichrome elements and was mounted so that it could be raised to surround the reaction tube during each experiment and, subsequently, lowered. A schematic diagram of the apparatus is shown in Fig. 1. Each charge was heated in a 3+-in.-OD by 31/2-in.-high 416 stainless-steel crucible placed in a 41/4-in.-1D by 18-in.-long fused-silica reaction tube which was closed at one end. On a shoulder around the crucible was placed a 3: -in.-OD by 12-in.-long open-end fused-silica condenser tube. The open end of the reaction tube was covered by a water-cooled brass cap with ports for 1) admitting an inert atmosphere to the system through a stopcock, 2) introducing a stainless-steel, motor-driven, paddle stirrer into the crucible, 3) evacuating the system with a mechanical vacuum pump, and 4) sampling the melt with Vycor sampling tubes. The brass cap was fitted to the open end of the reaction tube with a silicone gasket and collar clamp. The furnace temperature was controlled by a Barber-Coleman Capacitrol controller and a chromel-alumel thermocouple. Due to the corrosiveness of the melt, the controlling thermocouple also served as the measuring thermocouple. The temperature of the melt was calibrated against the controller temperature and was checked periodically during each test with a Vycor-enclosed calibrated chromel-alumel thermocouple. The temperature measurement and control can be considered accurate to ±3°C. Procedure. The charge placed in the crucible for each experiment consisted of 1000 g of Pb-As alloy and 300 g of PbO-As2O3 slag. The crucible was then placed in the reaction tube, the condenser tube was placed on the shoulder of the crucible, the silicone gasket and brass cap were fitted on the open end of the reaction tube, and the entire system was evacuated and filled with argon ten times. After the last flushing, a positive argon pressure of 1 psig was impressed on the system. The furnace was then raised to sur-

Jan 1, 1968

By T. F. Baily

During the period of the war, in both this country and Canada, a number of attempts were made to make pig iron from steel scrap in the electric furnace, and a considerable tonnage of white pig iron was produced, the silicon and manganese additions being made with ferroalloys; but it is believed that the experiments conducted. at Canton, Ohio, in

Jan 1, 1930

By Nicholas J. Grant, Italo S. Servi

THE creep and stress rupture properties of three grades of aluminum have been reported in a previous paper.' It was found that the stress coefficient of the creep rate and of the rupture time changes at the transition from low temperature-type to high temperature-type deformation. The transition corresponds to the equicohesion for grains and grain boundaries. In order to support the conclusions obtained from the examination of creep and stress rupture data, the deformed specimens were observed metallographically and a few special tests were conducted. The results of these qualitative observations are given in the present paper. Experimental Procedure and Results Table I gives the types of aluminum specimens.' The creep and stress rupture tests were conducted in simple tension at constant stress. Further details on the experimental techniques have been given.' The test bars were electropolished in a perchloric-acetic mixture before testing and were observed after testing without any further preparation unless otherwise specified. Observations of specimen cross-sections were made after electrolytic polishing and etching. The samples were extended along a direction parallel to the longer side of the micrographs of Figs. 12 through 27. The log-log plots of stress vs. minimum creep rate for the three grades of aluminum appear in Figs. 1 and 2. The reference numbers on each curve help relate the photographs to the conditions of testing, indicating where high temperature-type deformation and failure prevailed and where low temperature behavior prevailed. Deformation of Single Crystals at Very High Temperature: An annealed, high purity aluminum specimen was slightly strained at one end and re-annealed. A large single crystal was formed at the strained end of the specimen during re-annealing; the other end remained polycrystalline (see Fig. 3). A stress of 50 psi was applied to the cold specimen to avoid loading at 1100°F. The temperature was then raised to 1100°F, kept at 1100°F for 3 hr, and lowered again to room temperature. Fig. 4 shows the appearance of the specimen after testing. The single crystal deformed by gliding along parallel planes, while the polycrystalline part deformed mainly by grain boundary flow. Some grain growth occurred in the polycrystalline part. Another high purity specimen, which had two large single crystals at the two ends and a polycrystalline zone in the middle portion, was tested at 1000 °F under a stress of 100 psi. The appearance of the sample after test is shown in Fig. 5. Even though considerable slip occurred in the single crystals, the fracture occurred in the weaker polycrystalline portion. Evidence of Grain Boundary Migration during Creep Testing: A high purity, coarse grained specimen, which had a large crystal in the middle portion (see Fig. 6) was tested at 700°F under a constant stress of 175 psi for 30 hr. The appearance of the specimen after testing (Fig. 7) indicates that the large crystal deformed by gliding along parallel planes, while the rest of the specimen deformed mainly by grain boundary flow. Microscopic examination showed clear evidence of grain boundary flow and grain boundary migration, an example of

Jan 1, 1952

By R. C. Hepworth

Heaving in roads built on the Mancos Shale is a serious problem in east-central Utah. Heaves are expressed as local bumps, general rises and severe cracking of the pavement. The heaves usually occur in shale road cuts and generally show a seasonal cycle, which reaches a maximum development in the winter. The presence of certain salts, absorption of moisture and physical properties of the subgrade materials were considered, in Utah, to be the main factors in the heaving mechanism. Work done on similar problems elsewhere and studies conducted by the author indicate that the latter two factors are the most important. Results of this investigation indicate that heaving areas are associated with slaking shale or expansive clays, with and without salts present. Laboratory studies show that the initial moisture content of remolded samples and the desiccation history of un- disturbed samples have a major effect on swelling. Swell tests on compacted samples at various temperatures indicate that water has more influence on swell than temperature, except for samples containing sodium sulphate, which swelled with decreasing temperature. Chloride salts inhibited swelling. Tests on shale cores indicate that the stability of slaking shale can be preserved by maintaining its original moisture content. It is concluded that shales and expansive clays, when exposed in road cuts, become desiccated and are subject to expansion when moisture is subsequently available. The seasonal cycle of heaving may possibly be explained by the annual moisture excess and deficiency. To minimize the problem, freshly exposed shale should be kept wet, and the thickness of the subbase and base courses should be increased. The Utah State Department of Highways has been plagued for many years with a distressed condition that develops in roads constructed on the Mancos Shale. Locally these distressed areas are known as heaves, frost boils and alkali boils. These names refer to the surface expression, time of year

Jan 1, 1965

By John J. Croston

In the closing months of 1936 the copper industry gave every evidence that it was at last on the threshold of an improved era. At the beginning of the year prices stood at 91/4c, which in itself was a great improvement over prices prevailing for the three previous years. Industry generally was showing signs of moving forward in this country, and business was definitely good in certain foreign quarters. The threat of war and preparations for rearmament in Europe and Asia acted as a further stimulus to purchasing. By midsummer the situation had so improved and stocks had been so reduced that the cartel of foreign producers (including American producers with foreign mines) decided to increase the production quota to 75 per cent on Aug. 1. Large-scale buying gave continued strength to the price and by Oct. 1 the quota was increased to 80 per cent, and again on Oct. 15, to 85 per cent. Notwithstanding this the price of copper continued its advance and on Nov. 1, with stocks declining continuously, the cartel increased operations to 95 per cent, then to 105 per cent on Nov. 5. In the meantime the domestic producers, because of the great increase in home consumption, had increased their production by nearly one-half. At the close of the year copper sold at 126 per pound, and since the turn of the present year has reached 17c. This rapid increase has not been wholly justified. Much of the increase was due to the legitimate demands of recovering industry, but rearmament orders plus accumulation of reserve stocks in case of war, purchases in anticipation of labor strikes and purely speculative activities on the London Metal Exchange accounted for the balance. Certainly in view of the state of industry and the general world price level, it appears unnecessarily high. Talk of a copper shortage is sheer nonsense, the recent condition in the market being created by overbuying, leaving but a small volume for speculative supplies. It takes some months for an increase in mine output to reach the market, but production is again overtaking apparent consumption, stocks have begun to increase, and this, together with the reopening of many small

Jan 1, 1937

By R. W. Balluffi, R. Resnick

NUMEROUS investigations of chemical diffusion in a brass have been made and the results are collected in several places.1-3 This work has been mainly concerned with the determination of the chemical diffusivity as a function of composition and temperature. In 1947 Smigelskas and Kirken-dall&apos; showed that zinc and copper diffuse at different rates in face-centered-cubic brass, and since then, a number of efforts have been made to determine the intrinsic diffusivities of zinc and copper in this alloy.1, 5-9 Horne and Mehl8 in particular have recently determined the intrinsic diffusivities as functions of temperature and composition using sandwich-type couples and inert markers. Inman et al." also have determined the intrinsic diffusivities in homogeneous alloys using tracer techniques. When the present work was started, no information of this type was available. Consequently, measurements of the intrinsic diffusivities were made as a function of temperature at a constant composition of 28 atomic pct Zn with vapor-solid diffusion couples where the zinc was diffused into the diffusion couple from the vapor phase. The application of these couples to the study of diffusion in a: brass has been described previously.0,7 The temperature dependence of the intrinsic diffusivities was found to follow the relation D, = A, exp(-Hi/RT) and the values of Hzn, and Hcu, were found to be closely the same. It is emphasized, however, that the chemical dif-fusivity (D = N1D2 + N2D1) is a composite diffusivity and does not necessarily follow this exponential form. It is usually found to do so within experimental error for substitutional alloys because the heats of activation of the intrinsic diffusivities generally are not greatly different.&apos;" Also, at the onset of this work, there was no information available concerning possible unequal diffusion rates of individual components and the existence of a Kirkendall effect in alloys with other than face-centered-cubic structures. Since then, two reports indicating a Kirkendall effect in body-centered-cubic ß brass have appeared. Landergren and Mehl" have published a note describing Kirkendall diffusion experiments with sandwich-type couples. Inman et a1.9 also find a Kirkendall effect in this alloy using the tracer technique. In the present work, several aspects of the Kirkendall effect in ß brass were further investigated using vapor-solid couples. Two different couples were used, one in which the zinc was diffused into the specimen from the vapor phase and the other in which the zinc was diffused out of the specimen into the vapor phase. Briefly, the existence of a Kirkendall effect is confirmed and it is found that Dzn/Dcu = 3 at about the 46 atomic pct composition in this alloy at 600°, 700°, and 800°C. As a result of the unequal diffusion rates of zinc and copper, volume changes occur and subgrain formation is observed in the diffusion zone. In addition, significant porosity is produced by the precipitation of supersaturated vacancies. Diffusion in this alloy is therefore outwardly similar to diffusion in a brass where these effects are also observed, a Brass Experimental Methods—The use of vapor-solid couples in studying diffusion in a brass has been described in previous articles.6,7 The method briefly consists of sealing a copper specimen with Kirkendall markers initially placed on its surface in an evacuated quartz capsule along with a large zinc source of fine a brass chips and then diffusing the zinc into the specimen through the vapor phase. The zinc concentration at the specimen surface rises rapidly enough to a value near that of the a brass source so that the surface concentration may be regarded as constant during diffusion. Under these boundary conditions, values of the chemical diffu-sivity may be obtained by applying the Boltzmann-Matano analysis to the concentration penetration curve, and the intrinsic diffusivities may be obtained from Darken&apos;s5 equations when the velocity of marker movement is known. The diffusion specimens were made from OFHC copper in the form of disks 3.2 cm diam and 0.5 cm thick with faces surface-ground parallel to within +0.001 cm. Markers in the form of fine alumina particles <0.0002 cm diam were placed on the specimen surface. These specimens were then sealed in quartz capsules along with enough a brass chips of a 30.0 atomic pct Zn composition to keep the source concentration from decreasing by more than 0.3 atomic pct Zn as a result of the loss of zinc to the specimen during diffusion. The quartz capsules which were initially evacuated to a pressure of

Jan 1, 1956

By J. B. Newkirk

IN 1939 Bitter and Kaufmann1 suggested that iron, precipitating from a copper-rich, Cu-Fe solid solution, appears initially as coherent particles of r-Fe which transform to the body-centered-cubic form of iron when the alloy is cold worked. Since then there has been considerable discussion, supported only by indirect evidence, regarding the validity of the concept. For example, Reekie, Hutchison, and Hether-ington2 interpreted the changes in electrical resistance accompanying the aging of Cu-Fe specimens in terms of a coherent 7-Fe precipitate which transformed to the incoherent a-phase during long aging or cold working. Greninger- ound that Cu-Fe alloys which had been water quenched from 1050" and then held at 650°C for 3 hr changed from weakly to strongly ferromagnetic as the aged wire was subsequently cold worked. He also found diffraction lines corresponding to body-centered-cubic iron in Debye-Scherrer patterns given by aged and worked specimens but lines corresponding to only one face-centered-cubic phase in specimens which had been aged but not worked. Knoppwost,&apos; and later Cech and Turnbull,5 found that aged Cu-Fe specimens showed a slight increase in ferromagnet-ism after they had be? cooled in liquid nitrogen. Very recently Denney6 followed the kinetics of the precipitation reaction as indicated by the saturation magnetization, hardness, and diffuse X-ray effects. The experimental results reported by all of the authors mentioned above are readily explained in terms of the Bitter and Kaufmann concept. However, most of the evidence is indirect when used to define the structural changes involved. It was the aim of the present investigation to determine the mechanism of precipitation of iron from a Cu-Fe solid solution in the light of available published information and with additional new and more direct experimental data. Experimental Method At 1060°C copper will contain up to 3 atomic pct Fe in equilibrium solid solution.7 The solvus slopes rapidly toward lower iron concentration, so that at 600°C only about 0.5 pct Fe remains in solution at equilibrium. Below the eutectoid temperature (850°C), the iron-rich phase in equilibrium with the copper-rich solid solution consists of body-centered-cubic a-Fe. Above 850 °C the equilibrium iron-rich phase is face-centered-cubic r-Fe. The alloy to be studied was made by melting electrolytic iron and OFHC copper by induction under vacuum in an Alundum-lined crucible. The metal was held molten for about 5 min, after which time the power was turned off and the crucible was tipped about 70" to promote directional solidification. The resulting ingot, containing 2.5 wt pct Fe by analysis, was clean, large grained, and free of gross segregation. Slices % in. thick were cut from the ingot, rolled to 1/8 in. in thickness, homogenized in hydrogen at 1060°C for 24 hr and, finally, quenched in cold water. Specimens for all subsequent tests were made from these slices. Squares measuring about 1 cm on a side were cut from the slices to make specimens for studying hardness and microstructure. Wires (0.020 in.) for the Debye-Scherrer survey were drawn from 1/8 in. sq rods which had been cut from the homogenized slices. Large crystals for observing diffuse X-ray diffraction effects were prepared by mechanically

Jan 1, 1958

By W. H. Ashby, R. W. Cassingham, C. R. Blomberg, J. B. Justins

The Brookhaven field is one of several Basal Tuscaloosa reservoirs located in south-central Mississippi. It is a standstone reservoir, of erratic deposition and with several faults, having an approximate subsea depth of 9,800 ft. A large variation in permeability exists with a weighted average being 256 md. Estimated average interstitial water saturation is 45 per cent. The undersaturated reservoir fluid exhibits marked differences in physical properties with measured saturation pressures ranging from 733 to 2,255 psi. Early rapid decline in reservoir pressure caused the operating interests to unitize the field and initiate a program of pressure maintenance by gas injection. At the time gas injection was commenced, the reservoir pressure had fallen to nearly half of the original pressure with only 4.5 Per cent of the original oil in place produced. The reservoir pressure has since been maintained at approximately 2,750 psig, and cumulative production to date is 17 per cent of original oil in place. An analysis of field performance during gas injection is presented in detail. The program of pressure maintenance by gas injection is considered to be a success, since the expected ultimate recovery has been increased and the current production rate is in excess of 2 per cent of original oil in place per year. Performance has been better, anticipated ultimate recovery is larger, and total production costs are lower than for a similar Basal Tuscaloosa reservoir nearby, even though that field appears to have a more effective natural water drive. INTRODUCTION The history of the Brookhaven Unit is a testimonial for unitization and for the application of engineering techniques in the operation of an oil field. The operating and royalty interests in this field have mutually benefited from their early recognition of the need for unitization and pressure maintenance and from the forthright manner in which these were accomplished. The tangible benefits accruing to the participants in the Unit are: (1) income from gasoline plant products, (2) reduced lifting and operating costs from those of competitive operation, (3) maintenance of high levels of current income by mitigation of the inevitable decline in production rates inherent to natural depletion, (4) an increase in ultimate recovery of about 40 per cent over natural depletion operations. This paper should properly be considered a progress report; however, the performance of the field after five years of pressure maintenance clearly indicates that the ultimate success of the project is assured. LOCATION AND GEOLOGY The Brookhaven field is located in south-central Mississippi, about six miles from the town of Brookhaven. Production at Brookhaven

Jan 1, 1955

By J. M. Davey

Lead-zinc sulphide ores at Mount Isa are currently treated at the rate of 180,000 long tons per 28 day period in the No. 2 Concentrator of Mount Isa Mines Limited. Prior to June 1966 lead-zinc ore was treated in part of the No. 1 Concentrator up to a rate of 70,000 long tons per period. Since 1955, two major changes in ore type being processed have occurred. Because of these changes, problems arising from treatment of the ore have altered and during the period several major changes in practice have been advocated and experimentally tested. Most of these flow sheets were developed with a view to overcoming one major problem in the ore. These were invariably abandoned as the Mount Isa lead-zinc ore contains a number of equally major problems all of which must be overcome in the treatment process. MINERALOGY The orebodies are situated in the Mount Isa Shale Group which is Proterozoic in age (Carpentarian System). The sediments consist dominantly of fine grained dolomitic, quartzo-feldspathic shales and siltstones. Specifically, the Mount Isa orebodies lie in the Urquhart shale formation which is characterised by sediments of high albite and orthoclase content denoting a large volcanic component. The Urquhart shales are approximately 3,500 feet thick and extend at least north and south of Mount Isa for 20 miles in each direction. In the area of the silver-lead-zinc orebodies the Urquhart shales are highly pyritic and have a relatively high carbon content. The

Jan 1, 1970