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By M. C. Lavine, H. C. Gatos, R. S. Mroczkowski

The structure of GaAs-Ge heterojunctions prepared by a back-melting process was studied by X-rav diffraction, melallographic, and electron-micro-analyzer techniques. The boundary region between the GaAs and the germanium was found to consist of a four-layered band. A discontinuity between the two inner bands was brought about by solidification occurring simultaneously from the GaAs and the germanium side. The junction material OH either side of the central discotinuity was found to have grown as a single Crystal with the orientation of the parent substrate. It was found essential to determine the GaAs-Ge phase diagram. This was accomplished by a series of alloys containing 0 to 40 wt pet GaAs. Over this range the diagram is a simple eutectic with the eutectic point at 74 wt pet Ge and 845 C. The limiting- solubility of Coils in germanium was found to bc less than 5 wt pet. The Kossel divergent-beam X-ray technique was used to study orientation relationships across the boundary lager. A great deal of effort has been recently expended on the electrical properties of heterojunctions. Little attention, however, has been given to the metallurgical variables which may be of importance in the formation of the junctions. The present work was undertaken to investigate some of the more pertinent metallurgical aspects of interface-alloyed GaAs-Ge heterojunctions. Such parameters as solidification processes, composition gradients, orientation effects, and the accommodation of crystal structures have been the objects of study in this program. EXPERIMENTAL PROCEDURES Phase Diagram. The phase diagram of the GaAs-Ge pseudobinary system was determined by means of cooling curves. A Bridgeman furnace was employed with the center section maintained at 1200°C and the upper section at 800°C. Melts varying from 0 to 40 at. pct in GaAs content were used. Each charge was incapsulated under a two-thirds atmosphere of argon in a carbon-coated quartz tube. Five min in the furnace hot zone provided rapid melting and homogenization. The capsule was then removed to the cooler portion of the furnace. Cooling times were of the order of 3 min. The resulting homogeneous microstructure indicated that equilibrium conditions were obtained by this procedure. Formation of Heterojunctions. Rectangular parallelepiped single-crystal samples were cut with the large faces of either the (l00), (110), or (111) orientation. The remaining four surfaces were also cut to specific orientations to permit accurate relative orientation of the GaAs-Ge pairs. The

Jan 1, 1965

Apparatus and a method for determining the volumetric behavior of hydrocarbons at pressures up to 10,000 psia and at temperatures between 0° and 460°F are described. The equipment is suitable for measuring the total volume of the system and the volume of a liquid phase as functions of state within these ranges of temperature and pressure. Introduction During the past two decades there has been a marked increase in the ranges of temperature and pressure encountered in underground hydrocarbon reservoirs of commercial interest. In addition, greater interest in the intensive characteristics of the fluids found in these reservoirs has developed. Apparatus Several types of apparatus have been developed in the authors' laboratory for volumetric measurements of hydrocarbon systems. The earliest equipment described1 was characterized by constant volume, and the weight of material present was varied systematically in order to attain the different pressures desired in the study. Later another apparatus2 was built in which the effective volume of the cylindrical cell, which confined a hydrocarbon sample of constant weight was varied by injection or withdrawal of mercury. The effective total volume of the equilibrium cell was measured by ascertaining the position of the mercury surface but no measurement could be made which gave knowledge of the volumes of individual phases existing within the hydrocarbon system. A third apparatus3 was designed for use at higher pressures and temperatures than the earlier equipment would tolerate. This apparatus was of the variable volume type but was built in the general form of a U-tube, the mercury level being measured at the surface which was not exposed to the hydrocarbon system. This arrangement avoided the need of subjecting measuring equipment to the extremes of temperature at which studies were made, but it gave no provision for measurement of the volumes of individual phases. Although this last apparatus was satisfactory as to accuracy and convenience for many purposes, need was felt for measurements of the volume of the liquid phase of the hydrocarbon system. For this reason a fourth equilibrium apparatus was designed and constructed, and it is the purpose of the present paper to describe it. The equilibrium cell has a working range of temperature from 0° to 460°F at pressures up to 10,000 psi. Provision for measurement of both total volume and liquid-phase volume makes it particularly suitable for the equilibrium study of heterogeneous systems consisting either of simple mixtures or of complex field samples of hydrocarbons. The general arrangement of the ap-

Jan 1, 1948

By L. K. Oliver, Marshall

The use of model studies for the development of invasion patterns for cycling is .illustrated by model studies obtained with a recently developed apparatus in the solution of actual cycling problems. Introduction Depletion of a gas reservoir by cycling under pressure maintenance may be divided into three general phases. In the first phase, injection of dry gas is used to move all possible wet gas to producing wells prior to breakthrough of appreciable quantities of dry gas into producing wells. In the second phase, injection moves additional wet gas to producing wells while moderate quantities of dry gas are being produced. The third phase consists of production without injection to deplete the commercial gas reserve which remains after the cycling operation. Thus, in the first phase, a portion of the reservoir is invaded by dry gas, and the dry gas usually displaces something less than 100 pct of the wet gas from the invaded portions of the reservoir. The second phase enlarges the invaded portion of the reservoir and, at the same time, increases recovery from that zone invaded by dry gas in the first phase of the cycling operation. The result is an early yield of a substantial quantity of the liquefiable hydrocarbons in the reservoir with a minimum of the retrograde losses which occur in some reservoirs. The overall recovery from such an operation is usually high. The summation of the paths taken by dry gas in a cycling operation can be termed an invasion pattern. The use of electrical models to predict invasion patterns has been the subject of several contributions to the literature.1-3 The results of such model studies as applied to actual cases has been discussed by Kelton4 and Miller and Lents.= Recently, an improved apparatus for conducting potentiometric model studies has been developed, as described by Lee.V he purpose of this paper is to present model studies or invasion patterns obtained with this instrument in the solution of actual cycling problems. The percentage of displacement of wet gas within the invaded portion of the reservoir in cycling, increase in recoveries of wet gas by continuing cycling after dry gas breakthrough, recoveries of wet and dry gas by production after cycling, or economic factors in cycling are beyond the scope of this paper. Discussions which follow will be limited entirely to the development of suitable invasion patterns for cycling under pressure maintenance and the use of model studies therein. Discussion OF Results In using model studies to predict invasion patterns in cycling, some factors which influence the results are the following:

Jan 1, 1948

By A. M. Gavdin, F. W. Bowdish

Mineral dressing is an industrial art concerned with the treatment and separation of solids suspended in fluids. Knowledge and evaluation of the area of solid-fluid interface is important in all cases except those involving only large pieces of solid. In fact, many problems relating to comminution, to flotation, to thickening and classification, could be dealt with more rationally if the interfacial area were known. A number of methods have been proposed for the measurement of the surface of certain finely divided solids. Among them are methods using rate of dissolution of the solid,? its magnetic remanence,³ the turbidity of its suspension," and the character of the size distribution of the material.9 The first two are limited to one mineralogical species per sample; the third has certain optical limitations, especially for mineral mixtures, and the fourth is based on an extrapolation of uncertain validity. The need of a better and more general method of surface determination has long been felt, therefore. The method of P. H. Emmett,4 based upon the low-temperature adsorption of vapors, appears to fulfill this need. This method consists in determining the amount of nitrogen that is adsorbed by a given sample of solid at the temperature of boiling nitrogen. The more surface there is on the solid—both internal and external—the more nitrogen is abstracted. In actual operation, the method is somewhat less simple than has been stated so far, in that the nitrogen is adsorbed in an incomplete layer, the completeness and thickness of the layer being related to the pressure of the nitrogen in contact with the sample.2 This circumstance makes it necessary to determine the nitrogen adsorption for three or more values of the nitrogen pressure. Apparatus In the Richards Mineral Dressing Laboratories an Emmett apparatus has been built and tested (Figs. I and 2). A mechanical vacuum pump B and a mercury diffusion pump A work in series to give a high vacuum. The sample, placed in bulb D, can be evacuated by this pump train by suitable operation of the stopcocks in the glass tubing that connects the various parts of the apparatus. C is a McLeod gauge, used to ascertain the order of magnitude of the vacuum obtained, and not for accurate pressure measurements. Pressure measurements are made in the mercury manometer F and gas-volume measurements in the gas burette E. Gases are stored in flasks L (nitrogen) and K (helium), arranged so that definite quantities of these gases can be introduced into

Jan 1, 1947

By W. R. Hibbard, Ming-Kao Yen

Various rationalizations of preferred orientations in cold worked polycrystalline metals have been based on the operation of at least two three2 five, an indefinite number, and all,6 slip systems of the type occurring in single crystals. Pickus and Mathewson3 suggested that the cold rolling texture in face-centered cubic metals could be rationalized on the basis of two or more operating slip directions symmetrically disposed about the direction of flow in such a manner that the resolved shear stress factor is equal for all operating slip systems and lattice rotations cancel each other. The importance of the direction of flow, the necessity for the operation of slip systems capable of producing the required changes in external dimensions, the maintenance of a common surface between adjacent grains and a symmetrical arrangement of the operating slip systems in order to produce an end orientation which is stable under additional deformation lead to the following rationalization of textures based on the type of slip systems operative in single crystals. The rationalization is intended to explain why certain orientations are suitable for deformational flow without a change in orientation and thus are stable end orientations or ideal texture orientations. It does not attempt to explain how the grains of a randomly oriented polycrystalline aggregate will reach this orientation. The rationalization is based on the following four postulates: 1. The ideal textures for polycrystalline aggregates are the result of reorientations of individual crystals toward the same stable end orientation at which no further reorientation will occur even during additional deformation. Since, in simple slip, the relative orientations of the stress axis and the active slip system determine the change in orientation during slip, it is considered that the orientation of the stress axis with respect to the ideal texture determines what slip systems must be active to retain the stable end orientation. Therefore the stable end orientation should be a symmetrical one around the stress axis with respect to the active slip systems such that lattice rotations resulting from slip will cancel each other and prevent a resultant change in orientation. (Rotational symmetry only—not translation, inversion, nor others—is considered here.) Thus a metal under a pure stress should develop a texture consisting of one or more of the crystallographically symmetrical directions, <100>, <110> or <111> for cubic metals or <0001>, <1010> or <1120> for hexagonal close-packed metals, parallel to the stress axis. 2. Since the active slip direction is the direction of glide during simple slip and thus the direction of maximum shear movement, in the ideal texture the active slip

Jan 1, 1949

By Marshall, L. K. Oliver

The use of model studies for the development of invasion patterns for cycling is .illustrated by model studies obtained with a recently developed apparatus in the solution of actual cycling problems. Introduction Depletion of a gas reservoir by cycling under pressure maintenance may be divided into three general phases. In the first phase, injection of dry gas is used to move all possible wet gas to producing wells prior to breakthrough of appreciable quantities of dry gas into producing wells. In the second phase, injection moves additional wet gas to producing wells while moderate quantities of dry gas are being produced. The third phase consists of production without injection to deplete the commercial gas reserve which remains after the cycling operation. Thus, in the first phase, a portion of the reservoir is invaded by dry gas, and the dry gas usually displaces something less than 100 pct of the wet gas from the invaded portions of the reservoir. The second phase enlarges the invaded portion of the reservoir and, at the same time, increases recovery from that zone invaded by dry gas in the first phase of the cycling operation. The result is an early yield of a substantial quantity of the liquefiable hydrocarbons in the reservoir with a minimum of the retrograde losses which occur in some reservoirs. The overall recovery from such an operation is usually high. The summation of the paths taken by dry gas in a cycling operation can be termed an invasion pattern. The use of electrical models to predict invasion patterns has been the subject of several contributions to the literature.1-3 The results of such model studies as applied to actual cases has been discussed by Kelton4 and Miller and Lents.= Recently, an improved apparatus for conducting potentiometric model studies has been developed, as described by Lee.V he purpose of this paper is to present model studies or invasion patterns obtained with this instrument in the solution of actual cycling problems. The percentage of displacement of wet gas within the invaded portion of the reservoir in cycling, increase in recoveries of wet gas by continuing cycling after dry gas breakthrough, recoveries of wet and dry gas by production after cycling, or economic factors in cycling are beyond the scope of this paper. Discussions which follow will be limited entirely to the development of suitable invasion patterns for cycling under pressure maintenance and the use of model studies therein. Discussion OF Results In using model studies to predict invasion patterns in cycling, some factors which influence the results are the following:

Jan 1, 1948

By A. M. Gavdin, F. W. Bowdish

Mineral dressing is an industrial art concerned with the treatment and separation of solids suspended in fluids. Knowledge and evaluation of the area of solid-fluid interface is important in all cases except those involving only large pieces of solid. In fact, many problems relating to comminution, to flotation, to thickening and classification, could be dealt with more rationally if the interfacial area were known. A number of methods have been proposed for the measurement of the surface of certain finely divided solids. Among them are methods using rate of dissolution of the solid,? its magnetic remanence,³ the turbidity of its suspension," and the character of the size distribution of the material.9 The first two are limited to one mineralogical species per sample; the third has certain optical limitations, especially for mineral mixtures, and the fourth is based on an extrapolation of uncertain validity. The need of a better and more general method of surface determination has long been felt, therefore. The method of P. H. Emmett,4 based upon the low-temperature adsorption of vapors, appears to fulfill this need. This method consists in determining the amount of nitrogen that is adsorbed by a given sample of solid at the temperature of boiling nitrogen. The more surface there is on the solid—both internal and external—the more nitrogen is abstracted. In actual operation, the method is somewhat less simple than has been stated so far, in that the nitrogen is adsorbed in an incomplete layer, the completeness and thickness of the layer being related to the pressure of the nitrogen in contact with the sample.2 This circumstance makes it necessary to determine the nitrogen adsorption for three or more values of the nitrogen pressure. Apparatus In the Richards Mineral Dressing Laboratories an Emmett apparatus has been built and tested (Figs. I and 2). A mechanical vacuum pump B and a mercury diffusion pump A work in series to give a high vacuum. The sample, placed in bulb D, can be evacuated by this pump train by suitable operation of the stopcocks in the glass tubing that connects the various parts of the apparatus. C is a McLeod gauge, used to ascertain the order of magnitude of the vacuum obtained, and not for accurate pressure measurements. Pressure measurements are made in the mercury manometer F and gas-volume measurements in the gas burette E. Gases are stored in flasks L (nitrogen) and K (helium), arranged so that definite quantities of these gases can be introduced into

Jan 1, 1947

By E. C. Bitzer

The primary object of the work described in the following pages was to simplify the equipment in the separating circuit of the heavy-media process by substituting a spiral classifier for the separatory cone. Mechanical considerations were the leading attraction and the best that was hoped for on metallurgical performance was that the new vessel would give results equal to those obtained by conventional equipment. Tests have demonstrated in commercial operation on iron ore that the mechanical advantages of the spiral separator are about as predicted; also, the metallurgical performance is superior to the cone on the ores treated. Treatment of iron ore involves the separation of two products: a concentrate that sinks and a float product that contains true float material plus a controlled division of interfering middling. The middling material is heavier than the average specific gravity of the separating medium. Recent work with the spiral separator on Tri-State zinc ore showed that the middling material had to be recovered as concentrate because this fraction contained the bulk of the zinc in the ore. It has been demonstrated that it is possible to make three products with the new separator on an ore such as this: a float tailing, a float middling, and a high- grade heavy sink product. It appears from this last work that the new separator has definite mechanical and metalluigical advantages over any type of separating cone for treating feed that contains large amounts of material of a specific gravity close to that of the separating medium. However, either type of separator should perform equally well, metallurgically, on feed that is free of middlings. Each series of experiments with the spiral separator has required additional work to fully develop the possibilities of the machine. For this reason the paper is divided into chronological parts. History of Development A drag-type classifier was first proposed as a substitute for the cone separator by Butler Brothers technicians during the initial tests with galena medium at Crosby, Minn., in 1937. The desire for finding a substitute for the cone arose from trouble with interfering middlings and certain operating disadvantages of the cone. The possibility of using a spiral classifier was also suggested at this time by Emmett Butler and C. J. Abrams. However, inability to satisfactorily recover fine galena, which was used as a medium, terminated all development work at Crosby. During the winter of 1937--1938 investigation started on magnetic medium with concurrent development of the inverted or closed-top cone, which was found necessary to eliminate iron-ore middlings with the float product. About

Jan 1, 1949

By Ming-Kao Yen, W. R. Hibbard

Various rationalizations of preferred orientations in cold worked polycrystalline metals have been based on the operation of at least two three2 five, an indefinite number, and all,6 slip systems of the type occurring in single crystals. Pickus and Mathewson3 suggested that the cold rolling texture in face-centered cubic metals could be rationalized on the basis of two or more operating slip directions symmetrically disposed about the direction of flow in such a manner that the resolved shear stress factor is equal for all operating slip systems and lattice rotations cancel each other. The importance of the direction of flow, the necessity for the operation of slip systems capable of producing the required changes in external dimensions, the maintenance of a common surface between adjacent grains and a symmetrical arrangement of the operating slip systems in order to produce an end orientation which is stable under additional deformation lead to the following rationalization of textures based on the type of slip systems operative in single crystals. The rationalization is intended to explain why certain orientations are suitable for deformational flow without a change in orientation and thus are stable end orientations or ideal texture orientations. It does not attempt to explain how the grains of a randomly oriented polycrystalline aggregate will reach this orientation. The rationalization is based on the following four postulates: 1. The ideal textures for polycrystalline aggregates are the result of reorientations of individual crystals toward the same stable end orientation at which no further reorientation will occur even during additional deformation. Since, in simple slip, the relative orientations of the stress axis and the active slip system determine the change in orientation during slip, it is considered that the orientation of the stress axis with respect to the ideal texture determines what slip systems must be active to retain the stable end orientation. Therefore the stable end orientation should be a symmetrical one around the stress axis with respect to the active slip systems such that lattice rotations resulting from slip will cancel each other and prevent a resultant change in orientation. (Rotational symmetry only—not translation, inversion, nor others—is considered here.) Thus a metal under a pure stress should develop a texture consisting of one or more of the crystallographically symmetrical directions, <100>, <110> or <111> for cubic metals or <0001>, <1010> or <1120> for hexagonal close-packed metals, parallel to the stress axis. 2. Since the active slip direction is the direction of glide during simple slip and thus the direction of maximum shear movement, in the ideal texture the active slip

Jan 1, 1949

By E. C. Bitzer

THE primary object of the work described in the following pages was to simplify the equipment in the separating circuit of the heavy-media process by substituting a spiral classifier for the separatory cone. Mechanical considerations were the leading attraction and the best that was hoped for on metallurgical performance was that the new vessel would give results equal to those obtained by conventional equipment. Tests have demonstrated in commercial operation on iron ore that the mechanical advantages of the spiral separator are about as predicted; also, the metallurgical performance is superior to the cone on the ores treated. Treatment of iron ore involves the separation of two products: a concentrate that sinks and a float product that contains true float material plus a controlled division of interfering middling. The middling material is heavier than the average specific gravity of the separating medium. Recent work with the spiral separator on Tri-State zinc ore showed that the middling material had to be recovered as concentrate because this fraction contained the bulk of the-zinc in the ore. It has been demonstrated that it is possible to make three products with the new separator on an ore such as this: a float tailing, a float middling, and a high grade heavy sink product. It appears from this last work that the new separator has definite mechanica1 and metallurgical advantages over any type of separating cone for treating feed that contains large amounts of material of a specific gravity close to that of the separating medium. However, either type of separator should perform equally well, metallurgically, on feed that is free of middlings. Each series of experiments with the spiral separator as required additional work to fully develop the possibilities of the machine. For this reason the paper is divided into chronological parts. History of Development A drag-type classifier was first proposed as a substitute for the cone separator by Butler Brothers technicians during the initial tests with galena medium at Crosby, Minn., in 1937. The desire for finding a substitute for the cone arose from trouble with interfering middlings and certain operating disadvantages of the cone. The possibility of using a spiral classifier was also suggested at this time by Emmett Butler and C. J. Abrams. However, inability to satisfactorily recover fine galena, which was used as a medium, terminated all development work at Crosby. During the winter of 1937--1938 investigation started on magnetic medium with concurrent s development of the inverted or closed- top cone, which was found necessary to eliminate iron-ore middlings with the float product. About

Jan 1, 1947

By C. R. McEwen

The displacement equations of Buckley and Lever-ett&apos; have been successfully applied to the prediction of oil recovery in frontal drives for a number of years. Commonly, the capillary pressure term is omitted from Leverett&apos;s fractional flow formula. The resulting satura-tion-vs-distance curves become multi-valued, however. Buckley and Leverett, recognizing that the neglect of capillarity was most likely the cause, proposed that this part of the solution he ignored. An ingenious method of propagating a discontinuity in place of the multi-valued portlon of the curve was devised by Cardwell using "non-capillary displacement theory". However, it would seem that a completc description of the displacement pracess would require the inclusion of capillary forces. Three publications on displacement theory have appeared in which capillary pressure was included. Ter-williger. et al&apos;, calculated saturation profiles which matched those which they observed when gas displaced water vertically downward. Based on their study, Jones-Parra and Calhoun5 roposed a method of computing saturation distributions sufficiently removed in time from the initial conditions so that all saturations in the flood front region were assumed to move with the same velocity. This latter assumption corresponds to the tangent construction on the flowing fraction-vs-satura-tion curve proposed by Welge." A numerical solution to the problem of water displacing oil from a water-wet porous medium was recently presented by Blair, ef at&apos;. The initial conditions included a uniform saturation slightly above interstitial water saturation. that is, the permeability to water ahead of the front was not zero. This appeared to result in a region of slowly rising water saturation ahead of the front, at least for the particular set of relative permeability and capillary pressure data used to illustrate the computation. The authors also postulated an "end-effect" at the outflow face of the system, whereby no water could pass out of the system until the water saturation had built up to a high value. The saturation profiles computed under these assumptions show water accumulating at the downstream end of the system while the flood front proper is still traveling toward the outlet. The purpose of this paper is to present the results of a numerical solution to the one-dimensional water-flooding equation in which no outlet end-effect is considered and where there is no flow of water ahead of the flood front. It should be noted that the contemporary paper of Fayers and Sheldon8 deals with the problem under discussion. For a thorough treatment including both capillarity and gravity the reader is referred to their paper.

By John Wulff, Robert Kamm, Steinberg Morris

In powder metallurgy it has often been observed that shrinkage may occur in one direction and growth in another during sintering. Even in long-time sintering experiments the rate of shrinkage may be different in different parts of the compact. In the fabrication of some parts requiring a constant permeability it is even questionable in some cases whether pressing from one direction should be attempted. These observations require for their interpretation a more detailed study of green or pressed density than has heretofore been available. Usually average density measurements of the whole compact are made and in some cases carefully cut sections are measured. A different approach to the problem was first mentioned by Rakowskil and also used by Balshin.2 Balshin&apos;s diagram is reproduced in Fig I and schematically shows the result of pressing three layers of metal powder with fine intervening layers of graphite. The retarding effect of the die walls and a qualitative example of the density distribution is evident. More quantitative information about the distribution of density within a cold-pressed powder compact would be useful in showing the variation in density in as as influenced by the type of poKder, shape of die, lubricatioll during the process, and other variables. Furthermore, information about the cracking of cold-pressed compacts may be obtained from an analysis of the stress distribution within a, powder compact, and some information about the stress distribution can be obtained in turn from the derlsity and strain distributions. A more detailed report on some of the present experiments appears in reference 3. Present Investigation In order to ascertain the density gradients in cold-pressed metal powders, a deformable lead grid within the powder was employed. After pressing in cylindrical di" the ejected compact was radiographed, giving a pattern of the deformed grid. From the radiograph density and deformation from point to point is readily measured. From the radiograph strain distribution and stress trajectories were also determined. The latter also permits the determination of the coefficient of friction at the die wall. This technique indicates that the densest Part of a compact pressed from one side is at the top outer circumference and the least dense region at the bottom circumfercnce near the stationary plunger. For Some heights of compacts the density at the axis is such that the lower density is at the top rather than at the bottom. SO irregular a density distribution is due primarily to die-wall friction. As the ratio - diameter to height of compact is increased the die walls play a correspondingly smaller role. More uniform density

Jan 1, 1947

By John Wulff, Steinberg Morris, Robert Kamm

In powder metallurgy it has often been observed that shrinkage may occur in one direction and growth in another during sintering. Even in long-time sintering experiments the rate of shrinkage may be different in different parts of the compact. In the fabrication of some parts requiring a constant permeability it is even questionable in some cases whether pressing from one direction should be attempted. These observations require for their interpretation a more detailed study of green or pressed density than has heretofore been available. Usually average density measurements of the whole compact are made and in some cases carefully cut sections are measured. A different approach to the problem was first mentioned by Rakowskil and also used by Balshin.2 Balshin&apos;s diagram is reproduced in Fig I and schematically shows the result of pressing three layers of metal powder with fine intervening layers of graphite. The retarding effect of the die walls and a qualitative example of the density distribution is evident. More quantitative information about the distribution of density within a cold-pressed powder compact would be useful in showing the variation in density in as as influenced by the type of poKder, shape of die, lubricatioll during the process, and other variables. Furthermore, information about the cracking of cold-pressed compacts may be obtained from an analysis of the stress distribution within a, powder compact, and some information about the stress distribution can be obtained in turn from the derlsity and strain distributions. A more detailed report on some of the present experiments appears in reference 3. Present Investigation In order to ascertain the density gradients in cold-pressed metal powders, a deformable lead grid within the powder was employed. After pressing in cylindrical di" the ejected compact was radiographed, giving a pattern of the deformed grid. From the radiograph density and deformation from point to point is readily measured. From the radiograph strain distribution and stress trajectories were also determined. The latter also permits the determination of the coefficient of friction at the die wall. This technique indicates that the densest Part of a compact pressed from one side is at the top outer circumference and the least dense region at the bottom circumfercnce near the stationary plunger. For Some heights of compacts the density at the axis is such that the lower density is at the top rather than at the bottom. SO irregular a density distribution is due primarily to die-wall friction. As the ratio - diameter to height of compact is increased the die walls play a correspondingly smaller role. More uniform density

Jan 1, 1947

By Nicholas J. Grant, John Chipman

A full understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization;the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag—i.e., equilibrium conditions—and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck:20 V radio = % CaO/%SiO, Körber and Oelsen&apos;s _ % CaO&apos;. 100/% CaO + % SiO2 where (%CaO&apos;) = % CaO- 1.18% P2O5. Herty&apos;s B ratio = % CaO - (0.93 . % SO2) - (1.18% P205) Among others there appear the following: 20 References are at the end of the paper.

Jan 1, 1947

By Morris Steinberg, John Wulff, Robert Kamm

IN powder metallurgy it has often been observed that shrinkage may occur in one direction and growth in another during sintering. Even in long-time sintering experiments the rate of shrinkage may be different in different parts of the compact. In the fabrication of some parts requiring a constant permeability it is even questionable in some cases whether pressing from one direction should be attempted. These observations require for their interpretation a more detailed study of green or pressed density than has heretofore been available. Usually average density measurements of the whole compact are made and in some cases carefully cut sections are measured. A different approach to the problem was first mentioned by Rakowski1 and also used by Balshin.2 Balshin&apos;s diagram is reproduced in Fig r and schematically shows the result of pressing three layers of metal powder with fine intervening layers of graphite. The retarding effect of the die walls and a qualitative example of the density distribution is evident. More quantitative information about the distribution of density within a cold-pressed powder compact would be useful in showing the variation in density in compacts as influenced by the type of powder, shape of die, lubrication during the process, and other variables. Furthermore, information about the cracking of cold-pressed compacts may be obtained from an analysis of the stress distribution within a powder compact, and some information about the stress distribution can be obtained in turn from the density and strain distributions. A more detailed report on some of the present experiments appears in reference 3. PRESENT INVESTIGATION In order to ascertain the density gradients in cold-pressed metal powders, a deformable lead grid within the powder was employed. After pressing in cylindrical dies the ejected compact was radiographed, giving a pattern of the deformed grid. From the radiograph density and deformation from point to point is readily measured. From the radiograph strain distribution and stress trajectories were also determined. The latter also permits the determination of the coefficient of friction at the die wall. This technique indicates that the densest part of a compact pressed from one side is at the top outer circumference and the least dense region at the bottom circumference near the stationary plunger. For some heights of compacts the density at the axis is such that the lower density is at the top rather than at the bottom. So irregular a density distribution is due primarily to die-wall friction. As the ratio of diameter to height of compact is increased the die walls play a correspond¬ingly smaller role. More uniform density

Jan 1, 1947

By Nicholas J. Grant, John Chipman

A full understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization;the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag—i.e., equilibrium conditions—and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck:20 V radio = % CaO/%SiO, Körber and Oelsen&apos;s _ % CaO&apos;. 100/% CaO + % SiO2 where (%CaO&apos;) = % CaO- 1.18% P2O5. Herty&apos;s B ratio = % CaO - (0.93 . % SO2) - (1.18% P205) Among others there appear the following: 20 References are at the end of the paper.

Jan 1, 1947

By L. F. Terry, H. K. Ihrig, D. J. Sabin, Ralph E. Davis

This paper presents the results of a study of the comparative values of the several fuels commonly used by industrial plants. It shows that the energy actually recovered from any fuel and turned into useful work is dependent upon several factors: (1) the total energy available in the fuel, (2) energy losses resulting from combustion reactions and (3) energy losses dependent upon the mechanics of the firing operation. The chemistry of combustion and the losses resulting therefrom are discussed. The Advantages and disadvantages of the several mechanical methods of firing and the resulting heat losses in each are developed. Data obtained from several typical fuel operations, where careful records have been maintained, are presented to show that the practical results in the actual operation are in harmony with the theoretical results developed in the earlier part of this paper. Water power and solid, liquid or gaseous fuels are at present the only commercial sources of energy. The economic utilization of any one of them depends, in the final analysis, on the cost of energy per unit of finished product to which the energy is applied. The location of the plant utilizing the particular fuel chosen is a large factor in the original choice. The cost per unit at its original natural source, or even in its delivered form, is not always the final measure of its worth. The use of electricity as a source of energy illustrates this to the extreme. Electric current produced from water power is very cheap in certain localities. In Norway, current is sold as low as ½0# per kw-hr., while in dry cells it costs as much as $10 per kw-hr. Yet the sale of dry cells is a large business. The selling price of gas also varies widely. In some localities natural gas for the manufacture of carbon black sells for as low as $0.02 per million British thermal units, while artificial gas for domestic purposes sells for as high as $6 per million B.t.u. Obviously the cost per unit of energy is not the final determining factor in its purchase. Any discussion of the economic utilization of fuels must include costs in relation to the units of finished material manufactured. In large central power generating stations, this is the over-all cost per kilowatt-hour, and in ceramic firing the cost per unit of finished product of a certain quality is the criterion of economic utilization.

Jan 1, 1931

By J. W. Hickman

Most of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.&apos; In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,~ nickel,= chromium,= copper,z tungsten,s molybdenum,3 beryllium,&apos; uranium,&apos; thorium,&apos; titanium6 and zirconium6 while investigations are in progress on tantalum and columbium. The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally. Examples of solid solutions which may present difficulties are MOO* and WOp, Fe304 and FeO.CrnOa since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of loglo Kg for the several temperatures. AF"B = -RT In KR AF°R and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the the given in I 1 to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium oxide to form

Jan 1, 1949

By Dr. O’Neil Thomas J., Donald W. Gentry

"We can easily represent things as we wish them to be..” -Aesop INTRODUCTION The first eight chapters of this book have primarily addressed the concepts and fundamentals associated with project valuation, particularly as they apply to mining-related projects. Specific emphasis was placed on the engineering and economic parameters and estimates necessary for quantifying line items in pro forma income statements and the subsequent calculation of net annual cash flows. Given these estimates of relative benefits, costs, and annual cash flows for a project, it then becomes necessary to convert these estimates into measures of relative desirability or attractiveness. The criteria and techniques typically utilized to determine project acceptability or desirability are, then, the topics of discussion in this chapter. Before proceeding it may be advantageous to put the problem of project evaluation into proper perspective by reiterating some of the fundamental concepts developed in Chapter 1. The basic premise set forth in this book is that the objective of the firm should be to maximize its value to its owners (stockholders&apos; wealth). This value or wealth is represented by the market price of the firm&apos;s common stock; consequently, the primary objective of the firm can be restated as one of maximizing the value (price) of the firm&apos;s common stock in the marketplace over the long term. This price, in effect, is an indicator or index of the market&apos;s perception of the company&apos;s progress and a reflection of the investment, financing, and dividend decisions made by corporate management. These three major decisions are inter- related and jointly impact the market price of the firm&apos;s stock. Therefore, if the objective of maximizing the value of the firm to its stockholders is to be achieved, an optimal combination of the three decisions will be necessary. It is important to emphasize that maximizing stockholder wealth is not the same as profit maximization or even the maximization of earnings per share. Corporate managers making decisions based on the objectives of maximizing profits and/or earnings per share must recognize that these objectives do not consider: (I) the timing or duration of expected returns, (2) the business and financial risks of the promised earnings, or (3) the dividend policy of the firm. Obviously all of these factors are of concern to the company&apos;s stockholders and will have an effect on the market value or price of the firm&apos;s common stock. Maximizing market price per share, or wealth maximization, is therefore the appropriate corporate objective and

Jan 1, 1984

By E. T. Turkdogan, L. E. Leake

A number of measurements have been made on the vapor pressure of pure iron at 1600°C. Experiments were carried out by the transportation method in which a sample of iron is exposed in a furnace to a stream of pure argon, metered at a predetermined flow rate for a specified period of time. The vapor pressure was obtained from the weight loss of the sample. A detailed diagram of the apparatus used for the experiments is given in Fig. 1. It consisted of a horizontal molybdenum-wire-wound furnace fitted with a recrystallized alumina tube 1 1/8 in. internal diam. The boats, 1 by 3/16 by 1/8 in., were fired in argon at 1600°C to constant weight before use. After this treatment, subsequent heating of the boats to 1600°C gave little or no further change in weight, e.g. ±0.05 mg in 24 hr. The furnace and reaction tube were separately fed with argon from two independent flowmeters. These were connected to a common supply source via an argon purification furnace containing metallic titanium sponge at 700°C, and an anhydrone drying-tower. A rotary displacement-type meter was included in the gas train to provide a direct means of measuring the total volume of gas passed through the reaction tube. The material used was vacuum melted high-purity iron in the form of wire 2mm in diam. The following impurities were present in the iron: 0.008 pct C, 0.002 pct Si, 0.005 pct Mn, 0.008 pct S, 0.001 pct P, 0.01 pct Ni, 0.001 pct Cr, 0.006 pct Cu, and 0.001 pct Al. Samples consisting of three small pieces of this wire were laid end to end in a recrystallized alumina-combustion boat, and were separated by small fragments of alumina. The wire samples were then melted in argon to form spherical beads 2 to 3 mm in diam. After weighing, the boat with its contents was placed on the boat carrier and introduced into the cool end of the reaction tube. The entire furnace system was then flushed with argon for 30 min. At the end of this period, the flow of argon to both furnace and reaction tubes was adjusted to the desired level; then the boat was slid rapidly into the hot-zone of the reaction tube. After a known volume of gas had passed through the reaction tube, the boat was withdrawn quickly to the cool end of the furnace. When quite cool, the boat was removed from the fur-mace and placed in a desiccator for subsequent re-weighing. The semi-micro balance used in these experiments had a sensitivity of 0.005 mg. The above procedure was repeated at several flow rates within the range of 25 to 300 ml per min. The flow of argon in the annular space between the two tubes was at a rate of 300 ml per min in all experiments. During all the experiments the furnace temperature was maintained at 1600° ± 5°C by means of a temperature controller. The temperature of the reaction zone was measured with a Tinsley high precision disappearing filament pyrometer which was initially calibrated against a Pt-13 pct Rh/Pt thermocouple; the errors due to temperature measurements were within * 5°C. RESULTS Assuming that the iron vapor is in the monatomic state, the vapor pressure can be calculated from the weight loss of the sample and the volume of the carrier gas. The results obtained are plotted in Fig. 2 against the rate of flow of argon through the chamber containing liquid iron beads. At low flow rates, the thermal diffusion of iron gives an apparent high vapor pressure, but at high gas flow rates, the carrier gas is not saturated with the vapor, and therefore, low vapor-pressure values are obtained. This is now a well-known phenomenon. There is a distinct inflexion of the curve at about 120 to 160 ml per min rate of argon flow and the vapor pressure of iron within this

Jan 1, 1961