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By C. E. Sims

In some experimental work conducted several years ago, it was noted that sulphur seemed to have a distinct influence on grain size of carbon steels. 111 order to check this observation, a series of S..A.E. 1040 steels was made with the normal composition held as nearly constant as possible. The steels were made with three sulphur levels, which were 0.012, 0.024 and 0.038 per cent sulphur, respectively. For each of the sulphur levels, steels were made with only silicon deoxidization and with aluminum additions of 0.1015, 0.025, 0.050 and 0.10 per cent. The melting medium was an acid-lined high-frequency induction furnace. These steels were forged and rolled and differentiall!. quenched from temperaturcs in the range of 1500O to 1800°F. After this, the A.S.T.M. grain size was determined and plotted as in Fig. I. It will be noted, first of all, that the aluminum-free steels had filler grain size with higher sulphur when heated to 1500, but that this condition was reversed at 1700°. When aluminum was added to produce fine grain size, the steels in the lowest sulphur level were fine-grained only to 1600°. and then only with an addition of one pound of aluminum per ton. The medium sulphur steels werc fine-grained to 1600' with a wider range of aluminum addition. The steels in the highest sulphur level were fine-grained at 1600° over a still wider range of aluminum additions and fine- grained at 1700° with an addition of one pound per ton. Fig. 2 shows curves of the grain-coarsening temperature for these steels and illustrates how sulphur and aluminum combine to give greater inhibition to grain growth than aluminum alone. Only the highest sulphur steels have a grain-coarsening temperaturc above 1700°.. At 1650°, the low sulphur steel is fine-grained only at its peak, while the highest sulphur steel is fine-grained over a wide range. In these tests, one pound of aluminum per ton gave the best results; this is equivalent to about 1 1/2 lb. per ton for commercial condition. IllcQuaid-Ehn tests made on these steels showed the same trend but to a lesser degree. The tests were repeated on a series of S.A.E:. 1015 steels with sulphur levels of 0.02 and 0.03j per cent. Aluminum additions were made in the range from 0.025 to 0.15 per cent. These steels were forged and rolled, normalized at 2000°F. to put them all in the same starting condition, then reheated to various temperatures from 1600" to 1800" and cooled at rates that would allow ferrite precipitation in the austenitic grain boundaries. The results of these tests arc shown in Fig. 3. It will be noted that. up to the temperature of 1650°, there is very little difference in the grain size obtained from the two levels of sulphur. .At temperatures of 1700° and 1750°, however, the lower sulphur steel was fine-grained only with an aluminum addition of 1 1/2 lb, per ton;

Jan 1, 1945

By Clarence Zener

The heat-treatment of steels will not pass from the stage of an art into that of a science until the mechanism of the phase transformations associated therewith is thoroughly understood. Such an understanding will involve two distinct types of inquiry: (I) the direction of the transformation, (2) the speed of the transformation. The first type of inquiry, which involves only the equilibrium relations between the various phases in steel, is the subject of the present and of a succeeding article; the second type, which involves the kinetics of transformations, will be the subject of a later article. In order that a theory of equilibrium relations may give useful information, certain experimental data must be put into the theory. It is customary for these data to be of a thermal nature. In the system discussed herein—steel—such thermal data are very scarce. In medium-alloy steels another type of data might possibly be used. In these steels the concentration of solute is so low that it may be possible to use the approximation of dilute solutions, an approximation that leads to linear relationships. The unknown functions, or constants, may then be determined in some cases from the binary iron-alloy system and in other cases from the ternary iron-carbon-alloy system. From the functions, or constants, so determined may then be computed the equilibrium relations in more complex medium-alloy steels. In the present article this second approach is used, the necessary experimental data 'being obtained from the simple binary and ternary equilibrium diagrams. Fundamental Equations In this article are derived the equilibrium relations between the gamma, alpha and cementite phases. In these three phases all important alloying elements except carbon form substitutional solutions, each alloying atom occupying a potential site for an iron atom. Carbon, on the other hand, forms an interstitial solution. In the face-centered cubic gamma phase, the interstitial positions are at the center of the unit cube and at the centers of the cube edges. There are therefore four interstitial positions per unit cell, or one per iron atom. In the body-centered cubic alpha phase, the interstitial positions are probably at the face centers, and also at the centers of the edges, which are crystallographically equivalent to the face centers. There are therefore six interstitial positions per unit cube, or three per iron atom. In cementite, (Fe, Alloy)3C, the carbon atoms may. be regarded as filling all the lattice positions of a given type. The introduction of the fundamental the of equilibrium has presented the author with a quandary. These equations are formally so similar to other equations that have been derived1,2 for related systems that they may appear to some readers

Jan 1, 1947

By Clarence Zener

The heat-treatment of steels will not pass from the stage of an art into that of a science until the mechanism of the phase transformations associated therewith is thoroughly understood. Such an understanding will involve two distinct types of inquiry: (I) the direction of the transformation, (2) the speed of the transformation. The first type of inquiry, which involves only the equilibrium relations between the various phases in steel, is the subject of the present and of a succeeding article; the second type, which involves the kinetics of transformations, will be the subject of a later article. In order that a theory of equilibrium relations may give useful information, certain experimental data must be put into the theory. It is customary for these data to be of a thermal nature. In the system discussed herein—steel—such thermal data are very scarce. In medium-alloy steels another type of data might possibly be used. In these steels the concentration of solute is so low that it may be possible to use the approximation of dilute solutions, an approximation that leads to linear relationships. The unknown functions, or constants, may then be determined in some cases from the binary iron-alloy system and in other cases from the ternary iron-carbon-alloy system. From the functions, or constants, so determined may then be computed the equilibrium relations in more complex medium-alloy steels. In the present article this second approach is used, the necessary experimental data 'being obtained from the simple binary and ternary equilibrium diagrams. Fundamental Equations In this article are derived the equilibrium relations between the gamma, alpha and cementite phases. In these three phases all important alloying elements except carbon form substitutional solutions, each alloying atom occupying a potential site for an iron atom. Carbon, on the other hand, forms an interstitial solution. In the face-centered cubic gamma phase, the interstitial positions are at the center of the unit cube and at the centers of the cube edges. There are therefore four interstitial positions per unit cell, or one per iron atom. In the body-centered cubic alpha phase, the interstitial positions are probably at the face centers, and also at the centers of the edges, which are crystallographically equivalent to the face centers. There are therefore six interstitial positions per unit cube, or three per iron atom. In cementite, (Fe, Alloy)3C, the carbon atoms may. be regarded as filling all the lattice positions of a given type. The introduction of the fundamental the of equilibrium has presented the author with a quandary. These equations are formally so similar to other equations that have been derived1,2 for related systems that they may appear to some readers

Jan 1, 1947

By F. C. Kelley, L. L. Wyman

In order to clarify and amplify the existing data concerning the action of the cementing material in cemented tungsten carbide alloys, the authors have initiated this investigation of the entire range of cobalt-tungsten carbide alloys. Inasmuch as the ultimate objective is relative to what actually goes on during the sintering of cemented tungsten carbide materials, this work was necessarily restricted to heat treatments similar to those used in actual production of these materials. In the course of numerous experiments, the authors have noted several conditions that indicated that there was a solubility to be considered. Among these factors are the following: 1. Many of the alloys showed a much larger amount of binding constituent to be present than could possibly be accounted for by the cobalt content. 2. In many areas, grains of the carbide constituent are much larger than the particles of carbide originally added. In addition, these grains are of very regular contour. 2a. In samples of cemented tungsten carbide which had been fused in the atomic hydrogen torch in the presence of excess binder constituent, immense grains are formed, and their shapes are very regular. This is also true when the cemented tungsten carbide of 13 per cent. Co content is fused alone in the atomic hydrogen torch. Contrary to general expectation, chemical analysis of this material, after fusion in the atomic hydrogen torch, checks the analysis of unfused material. 3. In making the cemented tungsten carbide materials by the process of exerting the pressure at the time of heating a certain portion of the ' contents squeezed out of the mold. Chemical analysis has shown that this material contains approximately 12 to 20 per cent. of tungsten. The microstructure shows a cored dendritic structure interlaced with eutectic network, and some graphite, as shown in Fig. 1. 4. Thermal analysis of these materials has consistently indicated an arrest point close to 1350" C.

Jan 1, 1931

By William Hurst

Muskat's depletion performance equation is here derived considering the expansion behavior of the reservoir hydrocarbon system and a simple fractional-flow equation. This nietkod of derivation leads logically to the two extensions that follow. The first of these is concerned with gravity segregation in a depletion-drive reservoir. The second is concerned with including an empirically determined tern? for water influx in the performance equation. The more general equation for gravity segregation when there is a primary gas cap and empirically-determined water influx is stated for completeness. These equations have been found useful in reservoir performance calculations in Eastern Venezuela. A discussion on the methods of solving these equations follows, and considers firstly the effect of taking finite intervals in the numerical integration, and sec-ondly, methods of incorporating the time functions involved in segregation in with the expansion behavior. The paper concludes with a brief general discussion on further extensions to the depletion performance equation. INTRODUCTION The two fundamental sources of energy by which oil is produced from a reservoir result from pressure depletion inside the boundaries of the reservoir and fluid encroachment across the boundaries of the reservoir. The wells in either case form low pressure outlets through which oil and gas may be produced by the expansive force of the reservoir fluids and associated encroaching fluids. When the reservoir pressure is higher than the bubble-point pressure of the oil, so that there is no free gas in the reservoir, these expansive forces are the only ones available for the production of oil. However, when the reservoir pressure is less than the bubble-point pressure of the oil, free gas is vaporized as the pressure falls. With both oil and free-gas phases present, the additional forces of gravity and capillarity may operate on the gas-oil system, as they have previously operated on the oil-interstitial water system. Gravity tends to segregate the free gas from the oil due to their density difference. Capillarity opposes and eventually balances gravity as the more extreme free gas and oil saturations are reached, preventing the independent move- ment of free gas until it is above a certain saturation, and the independent movement of oil when it is below a certain saturation. The type of depletion performance equation chosen for predicting the future performance of a reservoir depends on the amount of past history available. When the reservoir is somewhere past the halfway mark in depletion, some form of decline curve is often used. With less past history, material balance equations which incorporate empirical factors based on the past performance are often used. When, however, the amount of past history is small, the Muskat depletion performance equation will usually be used. The distinguishing feature of this type of equation is that empirical factors based on the over-all or macroscopic reservoir behavior are almost or entirely absent. Each parameter affecting the reservoir performance is ascribed an independent set of values based on measurements made on laboratory samples; that is, incorporating microscopic empirical factors. In establishing Muskat-type depletion performance equations, it is necessary to consider the reservoir as consisting of a number of associated blocks, in each of which the saturations and pressures may be considered uniform, and in each of which all substances have uniform pressure-volume characteristics. Thus, a primary gas cap can usually be considered as one block and an aquifer as another. Gravity segregation may be negligible for practical purposes when the rock and oil properties are adverse and/or the dip or thickness of the reservoir is too small. In this case the whole oil leg may be considered as one block, except in very large reservoirs. In very large reservoirs the fluid and rock properties may vary enough, particularly in the dip direction, for it to be necessary to divide the oil leg into a number of blocks, in each of which the relevant quantities may be considered uniform. When gravity segregation of the oil and free gas is not negligible, it is necessary to consider the space occupied by the initial oil leg as divided into two blocks, a secondary gas cap and an effective oil leg, in each of which saturations may be considered to be uniform. The total volume of these two blocks is thus constant, but the secondary gas cap grows continuously at the expense of the oil leg. Muskat1 derived depletion performance equations for the basic case of an oil reservoir with closed boundaries and without segregation, and for the case of an oil

By L. L. Swift

AT the present time there are four base metals being used for automo-tive bearing alloys. Of course there are numerous variations in the amounts of alloying elements added to each base metal and nearly all of these alloys have the conventional, if not classical duplex structure; that is, they are composed of a hard constituent embedded in a soft matrix. The well-known theory is that the former will wear well, while the latter will be plastic enough to allow the bearing to be broken in and conform to the contours of the shaft. The requirements of the modern bearing have been most aptly described by W. M. Corse: In order to meet the engineering demands of today a good bearing metal must be able to carry the weight of the shaft and stand up under steady or suddenly applied loads, or even blows in some types of service. A certain amount of plasticity is desired to compensate for minute irregularities in the shaft or bearing surface, and to permit yielding, thereby avoiding dangerous stresses in bearing and shaft and pre-venting overheating and rapid wear of parts. Less plasticity is required in a bearing metal if the surfaces of bearings and journals are machined accurately, aligned, and kept in alignment. It is desirable, of course, that a bearing metal have a low coeffi-cient of friction. Under most operating conditions the friction depends on the unit pressure of the bearing, the speed, the temperature, and the properties of the lubricant. A good bearing metal must have a low rate of wear to reduce the necessity for frequent replacements, and adjustment of the bearings. It must wear more rapidly, however, than the journal or shaft running on it, because replacement of the journal or shaft is more difficult and costly than replacement of the bearing.1 The hardness of the bearing alloy is a property closely related to several of the foregoing. With a duplex microstructure, the measure-ment of hardness with any of the usual commercial devices means little. The Bierbaum method of measuring the hardness of the individual constituents was developed to fill this need.

Jan 1, 1938

By Mark J. Klein

An internal-friction profile induced by nitrogen in Cr-35 at. pet Re was studied as a function of nitrogen concentration and heat treatment. From these studies, the solubility of nitrogen in this alloy was deduced. The equilibrium solubility of nitrogen in chromium does not appear to be substantially changed by the addition of 35 at. pet Re to chromium. However the precipitation kinetics of nitrogen from solution are significantly decreased. IT has been found that rhenium has a beneficial effect on the low-temperature ductility of Group VI-A metals. As part of a study to investigate the mechanism of this increased ductility, it was of interest to compare the concentration of interstitials retained in solution in one of these ductile bee alloys with the concentration retained in solution in its base metal. In this regard, a study of the solubility of nitrogen in ductile Cr-35 at. pet Re was selected for this phase of the investigation because the solubility of nitrogen in the base metal, chromium, has been determined over a fairly large temperature span.1-3 In addition, nitrogen is known to have an embrittling effect on chromium,4 but does not appear to have a comparable embrittling effect on Cr-35 at. pet Re.5 The experimental method selected for this study was the measurement of internal friction. This technique allows interstitial-concentration measurements to be made in bee metals that are sensitive to small changes in the concentration of a particular interstitial, even when other interstitials are present. When subjected to a cyclic stress, interstitial atoms in solid solution give rise to an internal-friction peak whose origin is the stress-induced ordering of interstitials into preferred lat- tice sites. These internal-friction peaks signify a dissipation of elastic energy which is greatest when the period of oscillation is comparable with the relaxation time for the attainment of an equilibrium interstitial distribution. For dilute interstitial binary alloys, the height of the internal-friction peak is proportional to the concentration of interstitial atoms in solid solutions. snoek8 has shown that the internal friction, Q-1, may be expressed by the equation where A is the relaxation strength, ? is the angular frequency, and 7 is the relaxation time. The relaxation strength, A, is proportional to the concentration of interstitials taking part in the relaxation if no interaction occurs between solute atoms. Thus values of peak height, which can be determined as a function of temperature, give a measure of the relative concentration of interstitial atoms in solution at various temperatures. If equilibrium has been attained, the peak heights will be proportional to the interstitial solubilities. The constant that relates A to the interstitial concentration can be determined experimentally from peak-height measurements as a function of concentration for specimens of constant crystallographic orientation. When this has been done, Q-1 measurements can be used to determine solubilities according to the equation C - KQ-1 where C is the soluble interstitial concentration and K is a constant that can be experimentally determined. It is possible, however, that lattice imperfections may bind interstitials to certain lattice sites. Internal friction does not measure these interstitial~, but does measure interstitials which are free to move in the normal lattice sites when subjected to an applied oscillating stress. On alloying the pure metal with a substitutional

Jan 1, 1965

By P. L. Rittenhouse, M. L. Picklesimer

A rapid and seniquantitative method of determining prefered orientation on large numbers of. Zircaloy-2 specimens was desired. knoop microhardness measurerrzetzls were irvestigated as a solldtion to this pro6lem. The variation of Knoop microhardness measurerlerzts on selected planes as a function of 'irzdenle axis relutilje lo cryslallograplzic or fabrication divectals were used to corzstrrcl a polar coordinate hardness contour map. With use of an empirical relationslip between the single-crystal hardnesses and those of the polycrystalline material conentional pole figures could be constructed which compare favorably also obtained. To determine preferred oriention qualitatively from hardness data requires a minimum of twelve measurements per plane on three, preferattention to grain size, specimen prepartion, and in-rreinetzt, and analjlsis is of the order of- 45 to 60 rrin. THE design of structures from Zr alloys requires consideration of preferred orientation and the resulting anisotropy of mechanical properties. Rapid and semi-quantitative methods of evaluating anisotropy and of determining preferred orientation are needed for quality control and for examining the large number of test specimens required in development programs. The variation of Knoop microhardness with indenter orientation has been studied in single crystals of several hcp metals including titanium.' beryllium,' magneium, and zinc.4 The maximum hardness observed on any crystallographic plane other than the basal plane invariably occurred when the long axis of the Knoop indenter was either parallel or perpendicular to the projection of the [ OOOI.] direction on the plane of examination. When the major slip mode was (0001)(i2i0j the maximum hardness occurred at the parallel positio! but when the operating slip system was {10i0) (i210) the hardness was a maximum perpendicular to the [0001] projection. A minimum hardness was always observed at a rotation of 90 deg from the maximum. It follows that the orientation of the projection of the [0001] can be determined on any non-basal plane by making hardness measurements at a number of indenter orientations. The determination of the orientation of the [0001] projection on two non-parallel, preferably orthogonal, surfaces of the specimen will allow location of the [0001] direction in the specimen. It seems possible that such measurements could be used to examine, at least qualitatively, the preferred orientation existing in polycrystalline hcp materials. An investigation of the microhardness anisotropy in Zircaloy-2 was undertaken to ascertain whether these measurements could be used for this task. EXPERIMENTAL PROCEDURE Single crystals of Zircaloy-2 were grown by an a-8-a annealing sequence using electron-beam heating.= The orientation of the crystals was determined by a conventional back-reflection Laue technique. The crystals were then mounted on a goniometer head and the desired crystallographic faces were milled and chemically polished. Polycrystalline Zircaloy-2 specimens were prepared from fabricated sheets or plates. Inverse pole figures for these materials were obtained using the X-ray diffraction techniaue described by Jetter, McHargue, and illiams.' A Wolpert-Greis Micro-Reflex hardness-testing machine was used to make the Knoop microhardness measurements. The single-crystal and polycrystalline specimens were loaded to 0.5 and 2.0 kg, respectively. Determination of the scatter of hardness numbers as a function of applied load for several indenter orientations on several specimen surfaces showed that the loads selected were the lightest consistent with minimum scatter. Heavier loads did not appreciably decrease the scatter and produced hardness impressions too large to be conveniently measured with the equipment used. Seven crystallographic planes of the single crystals were examined, while six planes of examination were used in studying Zircaloy-2 polycrystals. The specimens were rotated 10 to 15 deg after each measurement and from four to eight impressions were made at each angle of rotation. RESULTS The two angles which were used to relate crystallographic directions and planes in the hcp cell to the planes of examination of the single crystals are shown in Fig. 1. 8 is the angle between the c axis. [0001]. and the normal, N, to the plane of examination. a is the angle between the long diagonal of the Knoop indenter and the projection of the c axis on the plane of examination. For exampIe, if P = 90 deg and a = 0 deg, the plane of examination is of the family

Jan 1, 1967

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

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

By Sumner M. Anderson

Any discussion of outside support to Latin American mineral industries must concede at once the pre-eminent role of U. S. industry and business. American capital has developed the great copper resources of Chile and Peru, the lead-zinc of Peru and Mexico, the bauxite of Surinam and Jamaica, the petroleum and iron ore of Venezuela. American consumers have provided the market for their products. U. S. companies operating south of the border have trained Latin American geologists, engineers, chemists, and skilled labor-including metal, mineral, and fuel technicians-to new and greater competence. The industrial demands of World War II drastically altered world economics and concepts of U. S. foreign mineral requirements. In this country discovery of vital mineral resources fell far behind the alarming depletion rates, and there was new appreciation of the actual and potential importance of the world's less extensively explored areas. During the war and afterward, the task of supplying the nation's mineral requirements became greater than private industry could carry alone, and the Government assumed a position of continuing support.

Jan 11, 1958

By Reno H. Sales

Jan 1, 1914

By W. L. Crentz, E. E. Donath, D. Doherty

Maurice Rey—The influence of cyclone diameter upon the fineness of separation is an important point which, however, cannot be discussed adequately if the injection pressure or the rate of flow are not specified. Perhaps some light can be thrown on the matter by using the formulas derived by Dahlstrom. Let us consider several geometrically similar cyclones where the apertures e and b are equal and proportional to the diameter D and which are operated with the same pressure drop. Eq 8 of Dahlstrom's paper can be written: Q Q = K D'. " or. if F is constant: Q = K D18 K is a constant of proportionality. Introducing this value of Q in eq 13 gives elimination efficiency = K D0' " Elimination efficiency, in the terminology of Dahlstrom, means the diameter of particles, in microns, which divide equally between the underflow and the overflow. This denomination is regrettable and it would be preferable to call it diameter of separation or characteristic size or any other name connoting a size rather than an efficiency. Whatever the name used, the above equation shows a slow increase in the fineness of separation when the diameter of the cyclone decreases. For example, if a 14-in. cyclone gives a 400-mesh separation (37 microns), geometrically similar cyclones, having the same pressure drop will give separations at the sizes shown below.

Jan 1, 1951

By E. E. Donath, W. L. Crentz, D. Doherty

Maurice Rey—The influence of cyclone diameter upon the fineness of separation is an important point which, however, cannot be discussed adequately if the injection pressure or the rate of flow are not specified. Perhaps some light can be thrown on the matter by using the formulas derived by Dahlstrom. Let us consider several geometrically similar cyclones where the apertures e and b are equal and proportional to the diameter D and which are operated with the same pressure drop. Eq 8 of Dahlstrom's paper can be written: Q Q = K D'. " or. if F is constant: Q = K D18 K is a constant of proportionality. Introducing this value of Q in eq 13 gives elimination efficiency = K D0' " Elimination efficiency, in the terminology of Dahlstrom, means the diameter of particles, in microns, which divide equally between the underflow and the overflow. This denomination is regrettable and it would be preferable to call it diameter of separation or characteristic size or any other name connoting a size rather than an efficiency. Whatever the name used, the above equation shows a slow increase in the fineness of separation when the diameter of the cyclone decreases. For example, if a 14-in. cyclone gives a 400-mesh separation (37 microns), geometrically similar cyclones, having the same pressure drop will give separations at the sizes shown below.

Jan 1, 1951

By R. W. Regehr, R. A. Burmeister

Epitaxial growth of GaAs 1-xPx on germanium substrates was achieved using an open tube vapor transport system. The compositional range of 0.3 < x < 0.4 was examined. The best results were obtained with (311) orientation of the germanium substrate. The physical and chemical properties of the resulting layers were investigated using several techniques. Spectrographic analyses of the layers indicate substantial incorporation of germanium into the GaAs t-X Px layer. Evidence is presented which indicates that this incorporation occurs via a vapor phase transport process rather than by solid phase dijfu-sion. Electrical measurements suggest that the germanium thus incorporated behaves predominantly as a deep donor in the compositional range of 0.33 < x * 0.40 and has a deleterious effect upon the luminescent properties of GaAs1-x Px. The increasing technological importance of GaAs1-xPx for use in light-emitting devices has led to an evaluation of several aspects of existing growth processes. The method most commonly used to prepare GaAs1-xPx for electroluminescent device applications is vapor phase epitaxial growth on GaAs substrates.&apos;-4 In a typical electroluminescent diode structure the active region of the diode is entirely within the epitaxial layer and thus the electrical properties of the substrate are relatively unimportant since it is effectively a simple series resistance (assuming hetero-junction effects to be negligible). The use of germanium rather than GaAs as the substrate material is of interest for several reasons. First, GaAs of reasonable structural quality has been epitaxially grown on germanium4-2 and it is reasonable to expect that GaAs1-xPx could subsequently be deposited on the GaAs layer. Second, germanium substrates are readily available with both lower dislocation densities and larger areas than GaAs. Finally, single crystals of germanium are more economical than GaAs single crystals. The principal objective of the present investigation was to test the feasibility of growing GaAs1-xPx epi-taxially on germanium substrates, and to evaluate the properties of such layers with regard to electroluminescent device requirements. The approach used was to a) demonstrate epitaxial growth of GaAs1-xPx on germanium, and b) characterize the relevant structural, electrical, and optical properties of the GaAs1-xPx layers. The possibility of germanium incorporation into the grown layers was of special interest since there was some indication of this in previous studies of GaAs growth on germanium.5&apos;11,12 Although a study of the electrical properties of germanium in GaAs1-xPx was not an intent of this investigation, several features of the electrical properties of the layers grown in the present study which appear to be due to germanium are described. EXPERIMENTAL PROCEDURE The open-tube vapor transport system used for the epitaxial growth of GaAs1-xPx is illustrated in Fig. 1. This system utilizes the GaC1-GaC13 transport reaction and is similar in most respects to the larger system described elsewhere.&apos; The germanium substrates were n-type, with a resistivity of 40 ohm-cm (Eagle-Picher Co.). These were cut to the orientations of {100), {111), and (3111, and were mechanically polished and chemically etched in CP-4 (5 min at 0°C) prior to growth. In some cases, a GaAs substrate was employed in addition to the germanium. The orientation of the latter was {loo}, and they were also mechanically polished and chemically etched prior to growth. The initial composition of the deposited layer was pure GaAs. After approximately 10 microns of GaAs was deposited on the germanium substrate, the phosphorus content of the layer was gradually increased over a distance of approximately 15 microns to the desired concentration and maintained at this value throughout the remainder of the growth. Typical operating parameters used during growth are given in Table I. Selenium was used as a n-type dopant in several runs to facilitate comparison of the electrical properties of the layers grown on germanium with those of layers grown on GaAs substrates, which are usually doped with selenium. The concentration of H2Se in the gas phase was adjusted to a value which would normally yield a carrier density of 1 to 5 x 101 7 at room temperature in layers grown on GaAs substrates. The terminal surfaces of the epitaxial layers were examined by optical microscopy for structural characteristics. Laue back-reflection photographs (Cu radi-ation) were also made on the terminal surface to verify the epitaxial nature of the deposit. After these steps

Jan 1, 1970

By F. N. Ward, E. H. Bailey

Camp and sample-site methods useful for determining about 0.5 to 16 ppm of mercury in soils and rocks have been devised to complement the analytical methods already widely used in geochemical prospecting. In the camp-site procedure the sample solution is obtained by digesting the finely powdered sample with hot nine-molar sulfuric acid and bromine, the latter generated in place. The solution is buffered at a pH of 4 and the mercury is extracted into a relatively small volume of an organic solvent. Estimations are made by comparing the color of the mercuric dithizonate extracted from the sample with that extracted from a standard. In the sample-site method the mercury is volatilized as the iodide and the latter is dissolved in a buffer solution from which the mercury dithizonate is extracted as in the camp-site method. The estimation is made by a similar comparison with standards or by comparing the color of the mercuric dithizonate with artificial standards prepared from Orange II, an azo dye. Except for the establishment of standards, the time required by an experienced analyst seldom exceeds 10 min for a camp-site determination and 5 min for a sample-site determination. Camp-site determinations are useful for commodity studies and intensive exploration programs; sample-site determinations are applicable to extensive and reconnaissance-type geochemical prospecting programs. The results obtained on samples taken along traverses above known mercury ore deposits in the California Coast Range and western Nevada demonstrate the usefulness of both methods in geochemical prospecting. The increasing use of the mercury content of soils, rocks, plants, or water in geochemical prospecting emphasizes the need for analytical methods which are sensitive and at the same time require a minimum of readily available equipment. Sensitive methods based on the absorption of ultraviolet light by mercury vapor are common in the literature31 12. Although none of these methods have been used to analyze the large number of samples required in geochemical prospecting, they could be extremely useful except for the expensive instrumentation usually required to make the methods quantitative Also, such methods are perhaps too sensitive for field use, especially around areas of possible contamination. Other methods involve the distillation of mercury from a relatively large sample and subsequent collection of the vapors in nitric acid6. The mercury is then estimated by titration with a suitable reagent such as thiocyanate. These methods are not trace methods because the actual amount of mercury measured is often as great as 50 to 100 milligrams. Also, such methods are unsuitable for geochemical prospecting because of the amount of equipment necessary and the time required. Still other methods involve colorimetry, and the sensitive reaction between dithizone and mercury (11).. is the basis for a number of reports on the determination of mercury in biological materials 5,7. Moreover, by the judicious use of solvent extraction and suitable complexing agents, the dithiaone method can be made almost specific for mercury. However, none of the dithizone methods have yet been applied to the determination of mercury in soils and rocks. In most colorimetric methods he sample solution

Jan 1, 1961

By H. W. Mead, C. E. Birchenall

The rates of growth of graphite nodules in cast irons are calculated for a model of a growing graphite sphere surrounded by a shell of austenite through which carbon and iron are diffusing. The carbon is supplied by a cementite-austenite mixture at the outer edge of the shell. The calculated rates from carbon diffusion agree fairly well with the measured values, but the rates based on iron self-diffusion are much too low. Because the iron must be removed for the process to continue, o plastic deformation mechanism is suggested. THERE has been an unfortunate tendency in the literature of growth and dissolution reactions to identify the slope of a plot of the logarithm of the growth or dissolution rate vs reciprocal of temperature with the activation energies determined by diffusion measurements in chemically similar systems. If the solubility limits at the growing or dissolving phase interfaces change appreciably with temperature, such procedures may lead to serious errors in specifying the mechanisms controlling the rates of these processes. A reaction involving the simultaneous growth of graphite from and dissolution of cementite in austenite will be discussed here to show that substantial oversimplifications have been made in earlier studies of this process. From a dilatometric study of the overall y-range graphitization process, Bunin and Danil&apos;chenko&apos; found an apparent activation energy of 90 kcal per g-atom. They concluded that, since this value was much nearer the approximately 68 kcal per g-atom observed for self-diffusion in pure iron than it was to 32 kcal per g-atom for diffusion of carbon in iron, the rate-controlling process must be the diffusion of iron away from the growth interface to provide space for graphite to grow. Bunin and Salli&apos; bolstered this agreement with the observation that graphite forms preferentially at surfaces, cracks, and pores where free volume is present initially. Ziegler, Meinhart, and DeaconQ ad found an apparent activation energy for graphitization of 98 kcal per g-atom. This value, like that of Bunin and Danil&apos;chenko, applies to nucleation and growth occurring simultaneously. It is not generally assumed that nucleation is entirely diffusion-controlled. Treatments such as prior cold-working and prequenching, which strongly affect the rate of graphitization, would be expected to have little effect on diffusion processes occurring at the graphitization temperature. In any case 90 kcal per g-atom is not particularly close to the 54 kcal or lower to be expected for diffusion of iron which is carbon-saturated.&apos; The presence of silicon in iron is said to reduce the activation energy for diffusion,&apos; so its presence in cast irons would be expected to have a similar effect. The growth rates of nearly spherical graphite nodules have been studied by Brown and Hawkes." The initial rate of growth before impingement of adjacent carbon-depleted areas was found to be parabolic, and rate constants were measured at several temperatures. Their apparent activation energy for the growth process only was roughly 45 kcal per mol. Burke and Owen&apos; made growth-rate measurements on several alloys, recording appreciable induction periods, initial nucleation rates, and average radial growth rates based on an assumed linear rate of radial growth. They found that increased silicon content increases the ovel-all reaction rate and the initial rate of nucleation, and decreases the induction period. Assuming 1) spherical nodules. 2) constant volume rate of nucleation, 3) austenite in equilibrium with cementite at positions where the cementite is not depleted, and 4) a constant diffusion distance during the growth of a nodule, they calculated an apparent overall activation energy of 68 kcal per mol, which was related to an activation energy for nucleation of 79 kcal per mol and activation energy

Jan 1, 1957

By S. Ramachandran, R. A. Walsh, J. C. Fulton

A method has been developed for calculating the oxygen content of commercially melted stainless steels. Application of thermodynamics to the de-oxidation reaction in straight chromium and Cr-Ni stainless steels has resulted in a set of equations DURING the past 30 years, many rewarding developments have resulted from the application of physical chemistry to steelmaking. A need still ex- which permits the calculation of oxygen contents. The model was programmed for computer calc~ilations. The validity of the method was demonstrated on routine oxygen samples from numerous commercially melted heats of stainless steel. ists for further progress in the use of thermodynamics to meet the more stringent requirements for cleaner steel. Current electric furnace practices have been developed around minimizing residual-oxygen content, one of the most important factors controlling the inclusion content of stainless steels. The residual oxygen is controlled by the use of deoxidizers during the finishing period and a number of empirical rules have been evolved. Although this feature of electric furnace practice has long been in use, only in recent years has funda-

Jan 1, 1963

By Herbert Clark Hoover, Lou Henry Hoover

SINCE I have written of the varied work of pre- paring the ores, I will now write of the various methods of smelting them. Although those who bum, roast and calcinea the ore, take from it something which is mixed or combined with the metals ; and those who crush it with stamps take away much ; and those who wash, screen and sort it, take away still more; yet they cannot remove all which conceals the metal from the eye and renders it crude and unformed. Wherefore smelting is necessary, for by this means earths, solidified juices, and stones are separated from the metals so that they obtain their proper colour and become pure, and may be of great use to mankind in many ways. When the ore is smelted, those things which were mixed with the metal before it was melted are driven forth, because the metal is perfected by fire in this manner. Since metalliferous ores differ greatly amongst themselves, first as to the metals which they contain, then as to the quantity of the metal which is in them, and then by the fact that some are rapidly melted by fire and others slowly, there are, therefore, many methods of smelting. Constant practice has taught the

Jan 1, 1950

By Charles D. Walcott

The following acts of the Directors are reported for the information of members At a meeting held June 20, 1907, Dr. Charles D. Walcott, Director of the U. S. Geological Survey, Washington, D. C., having been recommended by unanimous vote of the Council, was unanimously elected an Honorary Member of the American Institute of Mining Engineers, in recognition of his personal services to American geology, and of his generous co-operation with this Institute, to the Transactions of which he has not only himself made valuable contributions, but has also encouraged the preparation of such contributions by the members of the U. S. Geological Survey under his charge, his liberal policy in this respect having gone so far as to permit the preliminary publication by the Institute of important results reached by the geologists of that Survey, even before their final and full publication as public documents. This wise and generous course has not only brought the U. S. Geological Survey into intimate and sympathetic relations with the mining industry of the world, but has also enriched the Transactions of the Institute, especially in the department of the science of ore-deposits, with many valuable papers. At a meeting held Jan. 14, 1908, Mr. Charles Kirchhoff was unanimously re-elected a Trustee of the United Engineering Society, to serve for a second term of three years. At a meeting held Feb. 18, 1908, directly after the adjournment of the annual meeting of the Institute, the following officers were elected for the ensuing year: President, James Gayley: Vice-President, James Douglas; Secretary, R. W. Raymond; Treasurer, Frank Lyman.

Mar 1, 1908

By John F. Elliott, John P. Hager

The standard free energies of formation of the lowest stable sulfides of chromium, molybdenum, and tungsten in equilibrium with the corresponding metal hazle been determined by reacting the sulfide and metal with H2(g)/H2S(g) mixtures. The reaction is A method for estimating the standard ~nolav entropies and standard entropies of formation at 298°K of the sul-fides of refractory metals is presented. The standard free energies of formation of the lowest sulfides of the metals in group VIa of the periodic table are probably best determined with the reaction* is known with greater accuracy than is that property for any other sulfur-bearing compound or solution which might serve as a reference phase to establish the chemical potential of sulfur for the essential re- However, there still remain significant problems to the use of Reaction [I] in studying these sulfides. First, the equilibrium gas ratios (Ph2S/PH2) are very small, and with the most stable sulfides in the series the ratios tend to be at the limit of the range for precise chemical analysis (10-4); and second, the reaction rate for the formation or reduction of these sulfides appears to be relatively slow. A primary reason for the latter problem is that the gas phase near the equilibrium concentration has very little capacity for transport of sulfur. It is to be noted that the thermo-dynamic properties obtained from the experimental results by Eq. [I] apply for 1 g-atom of sulfur in the metal-saturated compound even though the exact composition of the compound has not been determined. The work reported here is a study of the standard free energies of formation of the lowest sulfides of chromium, molybdenum, and tungsten, and of copper, by Reaction [I]. In planning the experimental program, it was decided that the technique that has been used previously3"&apos; could be used with modification and that an improved analytical method was needed for determining H2S in the gas phase. THE EXPERIMENT The once-through flow of gas was selected in preference to recirculating the gas, a) because of the low sulfur capacity of the gas, b) because of the relatively slow rate of reaction and the danger of the

Jan 1, 1968