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By R. E. Carter, F. D. Richardson

Self-diffusion coefficients have been measured for iron in wustite (700° to 1000°C) and for cobalt in cobaltous oxide (800&apos; to 1350°C) by means of radio-isotopes. Both sectioning and decrease of surface-activity methods have been used and a particular shortcoming of the latter method has been disclosed for wustite. The effects of oxygen pressure on the composition of cobaltous oxide and on the diffusion coefficient of cobalt in the oxide have been established. The effect of the preparation conditions of the cobalt-oxide specimens on the diffusion measurements has been determined. It has been concluded that diffusion of cobalt occurs via vacant cation sites and that a cobaltous-oxide disk reaches equilibrium with its environment in a time which is very short compared with that needed for diffusion of the radio-isotope. THE availability of radioactive isotopes in recent years has permitted the measurement of many self-diffusion coefficients which were hitherto impossible to determine. With the advent of radioactivity, the method of measuring diffusion coefficients has also changed. The earlier sectioning method by which the concentration profile of the diffusing species was determined in the diffusion specimen has often been rejected in favor of the decrease of surface-activity method first developed by Von Hevesy,&apos; and extended by Steigman, Shockley, and Nix,&apos; and Raynor, Thomassen, and Rouse." With the experimental arrangement where an infinitely thin deposit of tracer is diffused into a semi-infinite cylinder, the decrease in activity of the active face due to diffusion of the tracer into the specimen is measured by counting the active face before and after diffusion. Under these conditions, the appropriate solution of the diffusion equation is R = e*(l-<K/Z) [1] where R is the ratio of the counting rates after-to-before diffusion, $& is the Gaussian error integral of \/Z, and Z is defined as Z = p2Dt, p being the linear-absorption coefficient of the detected radiation in the diffusion specimen, D the self-diffusion coefficient, and t the diffusion time. In the older sectioning method the concentration distribution of the tracer is found after diffusion by analysing thin parallel sections cut from the active face of the diffusion specimen. As seen from the solution of Fick&apos;s second law for the distribution of an infinitely thin source after diffusion into a semi-infinite cylinder the log of the concentration plotted against x&apos; will be a straight line of slope log e/4 Dt. The diffusion coefficient thus can be calculated directly. The units of the tracer concentration are completely arbitrary, since any change in units does not change the slope of the log c vs x2 lot. Although both of the above methods have been widely used, a thorough experimental comparison does not appear to have been made. Birchenall and Mehl,&apos; during an investigation of the self-diffusion rate of a and r iron by the surface method using Fe" tracer, diffused and sectioned one welded couple. The diffusion coefficient from this run agreed with those by the surface method. Buffington, Bakalar, and Cohen," during an investigation on a and y iron

Jan 1, 1955

By C. R. Johnson, R. A. Greenkorn, E. G. Woods

A new method of reservoir evaluation called pulse-testins has been developed for describing formation properties between wells. Pulse-testing utilizes a sensitive differential-pressure gauge at a responding well to measure and record the response generated by a series of flow rate changes (pulses) at an adjacent or pulsing well. Since the pulse-test instruments have a sensitivity of about 0.001 psi, pulses of several hours or less in duration will generate a measurable response in most reservoirs. For this reason, many well pairs can be tested in a short period of time with little interference in field operations. Comparison of pulse-test results to conventional testing methods shows that the pulses obey unsteady-state, compressible-flow theory and thus provide a measure of both transmissibility (kh/µ) and storage (Fch). In additian, the method can be used qualitatively to describe communication across faults and between zones, and direction and tnagnitude of fracture trends. INTRODUCTION To obtain maximum usefulness of new reservoir analysis methods as well as to aid the field engineer in understanding local reservoir anomalies, improved methods are needed to describe heterogeneities in specific reservoirs. Optimum well spacing, equipment specifications, well completion design and especially the economics of pressure maintenance and secondary recovery programs depend on the extent and location of the heterogeneities that affect flow behavior in the field. One method for obtaining a measure of areal reservoir heterogeneity is an interference test. In the simplest interference test. constant-rate production or injection is initiated at one well and the effect of this flow is measured as pressure vs time at another well. Thus, during interference tests the flow characteristics of the formation are determined in situ. Despite their obvious usefulness in reservoir delineation. interference tests have not enjoyed frequent usage. Reasons for this have been the weeks or months required in many fields to obtain a pressure response measurable with conventional gauges, and the interruption of routine field operation during the field-wide shut-in normally required during these long times. Also, only average properties of the relatively large volume of the reservoir disturbed during these long times can normally be obtained — variations in properties between individual wells cannot be delineated. To eliminate these drawbacks of conventional tests, a special reservoir description technique called pulse testing&apos; has been developed. Pulse-testing has several advantages that make it more convenient and practical for field use than interference tests. Valid tests are more certain because use of a series of flow disturbances gives rise to a diagnostic pressure response that can more readily be distinguished from unknown trends in reservoir pressure and other "noise." The time required is only a fraction of that for an interference test because a special, high-sensitivity differential pressure gauge can detect a much smaller pressure change. Variations in properties between individual wells can be delineated because of the relatively small volume of the reservoir disturbed during these short times. Finally, wells other than the pulsing and responding wells do not have to be shut in or carefully regulated.

Jan 1, 1967

By T. M. Broderick

InveStIgations into the possibilities of economically mining and concentrating low-grade iron ores of the Lake Superior region are attracting increasing attention. Among the organizations that are carrying on the work are the United States Bureau of Mines, the State of Minnesota (which spends about $80,000 annually on problems of the iron and ferroalloy ores of Minnesota), and the State of Michigan (which spends about $10,000 annually of its iron-ore research). Several of the mining companies are also financing research. Of the states in the Lake Superior district, Minnesota has done most in iron-ore concentration. In 1930, thirty-seven concentrating plants were in operation on the Mesabi Range, beneficiating about one-third of the total ore shipped. About one-half of these plants reduced silica; the others reduced moisture or improved the structure of the ore.&apos; Research into the possibilities of magnetic concentration of the Eastern Mesabi magnetite ores indicates that vast tonnages of that ore may be utilized at a profit in the not distant future. Magnetic concentration has also been tried at Sellwood, Ontario, on the Moose Mountain deposit, and at the Berkshire mine in Wisconsin on the magnetic ores of the Western Gogebic Range. There have been few attempts to concentrate Michigan iron ores. In order to determine the possibilities of such concentration, iron-ore research has been carried on at the Michigan College of Mining and Technology for the past few years. After a general survey of the iron ores of the state, a program of more detailed experimentation was outlined, starting with work on the Ironwood formation of the Gogebic Range. The results of this research led to the belief that gravity methods will produce fairly satisfactory concentrates from the parts of the iron formation that are made up of comparatively thick alternating beds of rather high-grade ore and lean chert. About 85 per cent of the iron and steel produced in the United States comes from ores of the Lake Superior district. The reserves of direct

Jan 1, 1935

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By A. S. Emanuel

A correlation has been developed for calculating the phase behavior of, gas-condensate systems at reservoir conditions. The correlation is based on the principle of corresponding states and has been coded for an IBM 7094. Experimental K-values were determined for several gas-condensate systems at reservoir conditions to evaluate various semi-empirical parameters of the correlation. The approximate range of application of the correlation is 150 to 300F and 1,500 to 6,000 psi. INTRODUCTION The rapid development of digital computers during the past several years has made feasible the calculation of hydrocarbon phase behavior by methods based on rigorous thermodynamic principles. Good correlationsl have been developed for low to moderate pressures, but these techniques have not yet been extended successfully to reservoir fluids at high pressures. Consequently, the determination of phase behavior of oil and gas systems at reservoir conditions is still based almost entirely on generalized data correlations or on experimental studies of the fluid in question. While these methods have been used successfully many times, they do have inherent limitations that restrict their applicability. Generalized correlations, such as the NGShlA K-charts, are limited to the range of pressure, temperature and components for which the data were determined. The accuracy of these correlations is often questionable because the effect of total system composition is not well defined. Experimental studies offer a reliable method for determining phase behavior, but usually the studies are costly and time consuming. Recently, Leland and co-workers presented a new approach to calculating phase behavior from the principles of corresponding states.6-8 Corresponding states methods determine the thermodynamics properties of a given system by comparison with a reference substance whose properties are known. The accuracy of this approach depends on close chemical and structural similarity between the reference substance and the system in question and between components within the system itself. For high accuracy, it is usually necessary to correct for chemical and structural dissimilarities. In principle, however, the corresponding states method should be no less accurate at high pressures than at low pressures, provided reference substance properties are known. This paper describes an empirical modification of the basic correlation proposed by Leland, et al.6 for the specific purpose of calculating the phase behavior of gas-condensate fluids at reservoir conditions. The modified correlation, which has been programmed for an IBM 7094, may be used for either approximate or precise determination of fluid behavior depending on the amount of analytical and, experimental data available for the system. BASIC THEORY The basic theory of the corresponding states phase equilibria correlation was first published by Leland, Chappelear and Gamson.6 Subsequently, Leland, Chappelear and Leach published methods for improving the accuracy of the original theory.7-9 The aim of the correlation is to calculate the K-value of each component of a given system as a function of pressure, temperature, and over-all composition, where Once the K-values are known, the phase behavior may be determined directly by an appropriate flash calculation. The basic equation for calculating component K-values was taken from the work of Joffe. 4 For any component i of a mixture, the K-value is given by

Jan 1, 1969

By C. C. Templeton, J. C. Rodgers

A key step in feed water treatment for generating wet steam for thermal oil recovery is the removal of calcium and magnesiunt hardness by cation-exchange series softening. Knowing the solubility of any scale forming salts in brines at elevated temperatures is necessary for fixing the level to which the feed water must be softened. Such calcium sulfate solubility data, previously not available above 392F, were determined by the authors in a flow equilibrium apparatus mud will be reported elsewhere. These data were used to develop a method for predicting the solubility of anhydrite in hot water or steam droplets for saturated steam pressures as high as 2,000 psig (637F). (The calcium sulfate solubility product is represented by a combination of two factors, one reflecting the effects of ionic strength and the other accounting for the effects of complex ion formation in either calcium-magnesium-rich or sulfate-rich brines.) The method is applied to a calcium-magnesium-rich brine If moderately high salinity from a pilot hot-water flood, I nd to several sulfate-rich, low-salinity feed waters and l lowdown (cooled steam droplets) samples from steam s ak operations. The predicted calcium hardness levels corresponding to the calcium sulfate solubilities agreed reasonably well with the results of laboratory solubility determinations run on the field samples. Further testing of the method is needed for brines of other composition classes. Existing field cation exchange softeners in the cases tested are performing adequately since all the samples were found to be undersaturated with respect to calcium sulfate at their operating temperatures. Introduction Prevention of scaling caused by precipitation of calcium sulfate (anhydrite) is of considerable concern in connection with thermal recovery processes using wet steam or hot water. To avoid anhydrite precipitation in a heated system, an engineer must keep the product of the calcium and sulfate concentrations in the water or steam droplets below the value of the solubility product of anhydrite for the temperature and brine composition in question. Usually it is most practical to keep the concentration product lower than the solubility product by keeping calcium low in the presence of high sulfate, or by keeping sulfate low in the presence of high calcium. This can be done by a choice of combinations of natural waters and water treatment processes (such as series cation exchange softening to remove calcium). Until recently, few anhydrite solubility data, particularly for solutions containing other salts, were available for temperatures above 392F (211 psig steam); Marshall, Slusher and Jones&apos; studied the CaS0,-NaCI-H,O system up to 392F and surveyed the work of previous investigators. To model natural brines, one needs to study the solubility of anhydrite in aqueous solutions of sodium chloride, sodium sulfate, calcium chloride, magnesium chloride and their mixtures. Since steam pressures as high as 2,000 psig (637F) may be involved in thermal oil recovery projects, a solubility study was conducted between 482 and 617F.&apos; Discussed in this paper is the application of these data to the prediction of anhydrite precipitation in some practical steam soak and hot-water injection projects. Any simple method for predicting the solubility of an inorganic compound over a wide range of temperatures and solution compositions must be based on some assumptions, and therefore must yield approximate results. On the one hand, natural brines contain too many ionic species for all to be included in a simple scheme; on the other hand, there is no adequate theoretical basis for the exact prediction of solubility in even simple solutions of mixed electrolytes. However, it is possible at a given temperature to base a reasonable prediction scheme on two phenomena:&apos;-&apos; the increase in solubility with increasing total concentrations of all ions (as measured by the ionic strength; see the Appendix), and an increase due to formation of cornplexes between calcium ions and sulfate ions and between sulfate and magnesium ions. Stiff and Davis&apos; developed such a scheme for predicting the solubility of gypsum (CaSO, ¦ 2H,O) in brines at temperatures u~ to 212F. However, for the higher temperaturei of present interest, the stable solid phase is anhydrite (CaSO,). This study involves a two-part method for predicting anhydrite solubility products. First, one predicts a value K, for a given ionic strength I and a given temperature T corresponding to mo./msr, = 1 from data of the CaS0,-NaCI-H,O system. Second, one determines a group of factors F .= F(Ca) • F(Mg) • F(SO,), where the individual factors account for increases in the solubility product due to complex formation by high concentrations, respectively, of calcium, magnesium and sulfate. Combining the two parts, one obtains the solubility product in molalities as

Jan 1, 1969

By A. C. Dittrick

THE Simon-Carves washer, originally known as the Baum jig washer, was first built in Europe about 1892. It was probably the first washer to use intermittent pressure of air on water in one part of the wash box to obtain water pulsations in another part. This type of washer was also the first to successfully clean various sizes in the same unit. Previous practice was to size closely before washing. Today there are several large firms abroad, and a few in the United States, that are constructing the Baum type washer. The design of all is practically the same, their differences being only in details. In 1928, the Hanna Coal Co. first gave consideration to the question of coal cleaning. It was believed at that time that by efficient removal of so-called noncombustibles appearing in the Pittsburgh No. 8 seam, certain markets that had been lost due to poor preparation might be recovered. Mechanical cleaning and mechanical loading were under consideration. This type of cleaning was considered the most practical means of removing impurities in the sizes below 4 in. It was decided to adopt mechanical cleaning and develop a system of mechanical loading that would be successful on No. 8 coal.

Jan 1, 1935

By George A. Colligan, John M. Lo

Electrical resistivity as a function of temperature was investigated in undercooled gallium and under-cooled Ga-In alloy of eutectic compositian to examine structural changes in undercooled melts. A continuous linear extension of the resistivity was determined for 99.999 pct pure gallium when undercooled below the stable Ga(l)-liquid, and the metastable Gafl)-liquid equilibria. In icndercooled Ga-In, a significant continuous negative departure from linear resistivity behavior was observed below the eutectic temperature. All resistivity measurements were made by the four-point probe technique. ThE temperature range for investigations into the physical properties of liquids before freezing has been greatly extended with the undercooling of massive melts of pure metals and alloys. Experimental determinations of thermal and transport properties and diffraction patterns in undercooled systems should throw further light on the structural behavior of liquids. Many measurements showing prefreezing anomalies in viscosity1&apos;5 have been regarded677 as evidence for structural groupings in the liquid state. However, the majority of viscosity results,~)~-~~ conforming to the law 17 =A exp(~/RT), do not support theories of atomic aggregation. For the system Cd-Sb, which exhibits a metastable solid phase, Fisher and Phillipsg reported that, in undercooled alloys, the activation energies for viscous flow below the stable liquidus are much higher than those above it. Similarly, Miller et a1." observed a doubling of the activation energies for electrical conductivity in undercooled Cd-ib alloys. These effects were suggested as indicative of atomic association and clustering in the liquids at lower temperatures. With the recent establishment of metastable phases in pure gallium22 and its alloys,23 attempts were made during this investigation to undercool bulk samples and to determine the temperature dependence of electrical resistivitv. Pure gallium, when undercooled below -17°C at atmospheric pressure, can crystallize to either a stable Ga(1) phase (mp, 29.78"C) or a metastable phase identi-

Jan 1, 1967

By A. M. Rahm

PROBABLY the majority of red brass sand castings are judged merely on the basis of outside appearance and the quality of machined surfaces. Many castings, however, must individually withstand a hydraulic or air-pressure test before being accepted as parts of more complicated machin-ery. Finally, there remains a comparatively small group of castings intended for uses of considerable responsibility where only the highest possible characteristics of the metal are acceptable, and for these specially cast test bars are required. The shape of the cast piece from which the test bar must be detached varies greatly from one country to another. The test bar as specified in the American Society for Testing Materials Specification B62-36 is widely used by the American foundry industry. The actual test piece is at the bottom of the cast block and has a riser about six times its mass. It is obvious that this test bar has an advantage over the actual casting. The latter rarely possesses a riser of as much as 30 per cent of its own weight and that riser cannot generally be located in so convenient a manner. Therefore, the characteristics of the test bar cannot possibly correspond to those of the casting itself. It must be taken into consideration that red brass if melted and cast in the best possible manner may show a tensile strength of 40,000 lb. per sq. in. with 35 per cent elongation in 2 in. Such a test bar would indicate that the metal was nearly perfect from the viewpoint of its gas and inclusion content. Barring some accidental defect, a casting cor-responding to such a test bar could be accepted as being quite sound. However, actual specifications do not demand such high characteristics; indeed, few specifications require over 30,000 lb. per sq. in. and 20 per cent elongation, while one Federal specification demands merely 27,000 lb. per sq. in. strength and 15 per cent elongation. It is obvious that

Jan 1, 1939

By Waldemar Lindgren

CONTENTS. [ ] THE following pages are a resun16 of some of the conclusions reached during a study of the copper-deposits near Clifton The field-work was finished in 1902 and a complete report is now in the press. A preliminary description of the district was published in 1903, in Bulletin U. S. Geological Survey, No. 213. pp. 133-140

Jan 1, 1913

By T. C. Boberg, R. B. Lantz

This paper presents a method for calculating the producing rate of a well as a function of time following steam stimulation. The calculations have proved valuable in both selecting wells for stimulation and in determining optimum treatment sizes. The heat transfer model accounts for cooling of the oil sand by both vertical and radial conduction. Heat losses for any number of productive sands separated by unproductive rock are calculated for the injection. shut-in and production phases of the cycle. The oil rate increase caused by viscosity reduction due to heating is calculated by steady-state radial flow equations. The response of successive cycles of steam injection can also be calculated with this method. Excellent agreement is shown between calculated and actual field results. Also included are the results of several reservoir and process variable studies. The method is best suited for wells producing from a multiplicity of thin sands where the bulk of the stimulated production comes from the unheated reservoir. The flow equations used neglect gravity drainage and saturation changes within the heated region. INTRODUCTION This paper presents a calculation method which can be used to predict the field performance of the cyclic steam stimulation process. The calculation method enables the engineer to select reservoirs that have favorable characteristics for steam stimulation and permits him to determine how much steam must be injected to achieve favorable stimulation. While the calculation represents a considerable simplification of physical reality and the results are subject to numerous assumptions which must be made about the reservoir, it has been found that realistic calculations can be made of individual well performance following steam injection. The duration of the stimulation effect will depend primarily on the rate at which the heated oil sand cools which, in turn, is determined by the rate at which energy is removed from the formation with the produced fluids and conducted from the heated oil sand to unproductive rock. A complete mathematical solution to this problem is a formidable task, and finite difference techniques would undoubtedly have to be used. The calculation method pre- sented here utilizes analytic solutions of simple related heat transfer and fluid flow problems. The method is sufficiently simplified that it can be used as a hand calculation, although the calculations are somewhat lengthy and laborious. For that reason, the analysis was programmed for an IBM 7044 digital computer. Well responses observed at the Quiriquire field in eastern Venezuela&apos; have been matched using this program after making suitable approximations for reservoir and wellbore conditions. One of the most valuable uses of this calculation method is to assess the effect of reservoir and proc-cess variables on the stimulation response. This paper contains results of several studies made of key reservoir and process parameters. Among the most important of these is the influence of prior wellbore permeability damage. If a well is severely damaged prior to stimulation, a higher stimulation response will be observed than if it is undamaged. If a portion of this damage is removed, a permanent rate improvement will occur. THEORY I)ES(:KJJ&apos;TION OF CALCULATION METHOD The process of cyclic steam stimulation is essentially one of reducing oil viscosity around the wellbore by heating for a limited distance out into the formation through the injection of steam. Suitable modifications of the calculation technique presented here can be made so that stimulation of wells by hot gas injection or in situ combustion can also be calculated. A schematic drawing of the heat transfer and fluid flow considerations included in the calculation method is shown in Fig. 1. In brief, the calculation assumes that the oil sand is uniformly and radially invaded by injected steam. For wells producing from several sands, each sand is assumed to be invaded to the same distance radially. In calculating the radius heated rn energy losses from the wellbore and conduction to impermeable rock adjacent to the producing sands are taken into account. After steam injection is stopped, heat conduction continues and oil sands with r < ra cool as previously unheated shale and oil sand at r > r, begin to warm. The effect of warming of oil sand out beyond r, has little effect on the oil production rate compared to the effect of cooling of the oil sand nearer the wellbore than ra. Thus, in computing the oil production rate, an idealized step function temperature distribution in the reservoir is assumed where the original temperature exists for r > rn and where an average elevated temperature exists for r < rn. The average temperature in the oil sand for the region r < rn is computed as a function of

Jan 1, 1967

By Robert I. Jaffee, Bruce W. Gonser

RECENT work by the authors1 established the constitutional diagram of the gold-germanium system. Of particular interest in the simple euctectiferous system was the eutectic alloy at 12 per cent Ge, which melted at the very low temperature of 356°C. and had an unusually fine eutectic structure. It was of interest to investigate the effect of third components on the melting point, microstructure, and strength of this alloy, and in this work the effect of copper is discussed rather completely, with less complete data on the effects of silver, platinum, nickel, and zinc. No reference in the literature has been found on ternary systems with gold-germanium. MATERIALS AND ALLOYING As in the work on the binary system, gold-germanium, the germanium used in this investigation was the cyanide-reduced, 99.9 per cent product, produced by the Eagle-Picher Co. Fine gold sheet from Handy and Harmon, pure platinum sheet from the American Platinum Works, copper magnet wire from Anaconda, nickel wire assaying 99.6 per cent Ni, and electrolytic zinc were used for alloying. To make the alloys, charges of the pure metals were put in a graphite crucible and melted in an atmosphere of pure hydrogen. The temperature was brought up to about 1050°C., and the metal allowed to freeze in the crucible. Except with alloys containing zinc, melting losses were consistently less than a few milligrams. When zinc was a component, weight losses up to half the weight of the zinc present were incurred, and the alloy compositions were calculated by assuming the entire weight loss to be that of zinc. In all other cases the composition of the alloys could safely be taken as that of the charge. The ingots, as solidified, were segregated, the heavier primary phases being at the bottom and sides of the ingots and the lighter primary phases at the top, but by sectioning the entire ingot vertically for microscopic examination, this factor could be evaluated. Ingots for microscopic examination weighed one gram, and those for thermal analysis weighed three grams. THERMAL ANALYSIS In this work, the eutectic line composition and thermal arrests were desired, and, after microscopic exploration had established the position of the eutectic line at a given percentage of the third component, a thermal analysis was run at that composition. The method of thermal analysis used in the work on the binary Au-Ge system,1 a method particularly well suited for a small quantity of material, was used in this work. Clearly defined arrests were obtained, although with some alloys containing platinum

Jan 1, 1946

By Walter H. Munk

Generation of Waves by storms, and the transformation of waves in shallow water by local bottom topography are briefly reviewed. A detailed description of water motion in waves explains the nature and distribution of wave forces. A numerical example dealing with forces and moments against vertical piles summarizes the principles involved. Introduction The oil industry is moving into the open waters of the Gulf of Mexico. The design and construction of offshore drilling rigs present a number of difficult problems, among them problems involving the action of waves on fixed and floating structures. This paper deals with our present knowledge of ocean waves as it pertains to these problems, and the principles involved in computing wave forces against fixed structures. It is hoped that the more difficult case pertaining to floating structures can be discussed at a later time. None of the engincering aspects of the problem are entered upon in this paper, yet an understanding of the principles presented here should be helpful in the solution of practical problems. Waves are capable of exerting almost unbelievable forces. During a gale, waves at the harbor entrance of Amsterdam Canal in Holland lifted a 20-ton concrete block, which was resting on the bottom in 12ft of water, and deposited it on top of a pier which was 5 ft above the high water mark. At Wick Breakwater in Scotland, a mass of large stones in cement and bound together with iron rods, weighing 1350 tons, was broken loose and moved bodily! But one need not go to Holland or Scotland to find evidence of damage that waves are capable of inflicting (Fig I and 2). What is the mechanism by which waves are capable of exerting such enormous forces? To answer this, we must consider briefly the nature of wave motion. When a wind blows over a wheat field, waves appear to travel across the field, whereas the wheat itself remains rooted, slowly swinging back and forth. Similarly, in the case of water waves, the waveform travels swiftly over the water surface, whereas the water particles oscillate back and forth, but scarcely advance. The speed of the wave form is called wave velocity, the speed of the water particles is called orbital velocity. This fundamental difference between wave velocity and orbital velocity was already recognized by Leonardo da Vinci. Orbital velocity is generally much slower than wave velocity except for a breaking wave, a case which is of particular importance in the application to engineering problems. Forces exerted by the waves on obstacles

Jan 1, 1949

The Iron and Steel Committee of the American Institute, of mining and Metallurgical Engineers held a joint session with the American Foundrymen&apos;s Association during the Annual Meeting of the Institute in February, 1928, for the purpose of discussing blast-furnace operations and the character of pig iron and castings. Dr. Richard Moldenke presided. H.. H. Sweetser, who was named on the program as the presiding officer of the session, was unable to be present, but sent a letter in which he said: " The meeting we had here last year and the meeting held in Chicago last June showed a desire on the part of blast-furnace men and users of pig iron to get the facts regarding the influence on castings made from pig iron produced in blast furnaces under varying conditions of temperature, mixture and local furnace operations. It has been my hope that at this Round Table we might he able to formulate a series of tests that, would give us the desired information. "Several independent blast-furnace investigations have. been, and still are being, carried on in different sections of the country. The furnaces investigated include a southern furnace, a middle-west furnace, a western furnace and a Chicago district furnace. The results so far show distinct characteristics for each of the four furnaces. It is possible that a furnace in the eastern part of the United States would be different from all the others. "It is hoped that a plan of action can be worked out at your meeting today whereby the IT. S. Bureau of Mines will be able, to carry on more extensive work in connection with the research departments of the different iron and steel companies and the big consumers of pig iron. "No one group can get all of the, information but if the different investigations can be coordinated it will he possible for us to (Iran. conclusions regarding the effects of varying conditions in blast-furnace practice on the pig iron produced and the castings made there from." DISCUSSION R. Moldenke, Watehung, N. J.—I was across the -water this summer and saw some of those interested in an investigation of this kind. &apos;I&apos;hey told me that in Germany, where they had a joint committee of blast-furnace operators and foundry-

By R. A. Morgen

THE binary system lead-antimony has been the subject of compre-hensive investigations in these laboratories by Dean1 and his associates. The effect of a third constituent on this system, particularly on the lead-rich alloys in which dispersion hardening ,was found, has a commercial value as well as an academic interest. This paper covers the effect of the addition of copper, bismuth and tin, all of which are likely to be found in commercial lead-antimony alloys, and is divided into three parts, as follows: I. The System Lead-Antimony-Copper II. The System Lead-Antimony-Bismuth III. The Lead Corner of the System Lead-Antimony-Tin These three systems are of three different types, and hence may be considered as covering three general kinds of additions. Bismuth forms no compounds with either lead or antimony and forms solid solutions with both. Copper forms several compounds with antimony as well as solid solutions but with lead it forms a two liquid layer system and no appreciable solid solution. Tin is soluble in both lead and antimony in the solid state and also forms a compound with antimony. The effect of small amounts of bismuth on the lead-antimony alloys is small, having no appreciable effect on the solubility of antimony. The temperature of the solidus floor is lowered appreciably by the presence of bismuth, cutting down the range of heat treatment. Copper, on the other hand, due to compound formation, increases the apparent solubility of antimony. The excess antimony is tied up with the copper finally and so is not available for dispersion hardening. The net result of addition of small amounts of copper is to shift the dispersion hardening peak of the

Jan 1, 1927

By J. L. Lamon, W. Crafts

Study with the electron microscope of the carbides in vanadium-chromium-molybdenum steels after tempering up to 1000 hr at 600 teelsto 1400°F confirmed that alloy carbides are formed at the secondary hardening temperature by decomposition of the plate-like iron carbides. It was also demonstrated that vanadium carbide persists as much smaller particles than do chromium- or molybdenum-bearing carbides. Conditions conducive to the formation of fine vanadium carbides are indicated to be favorable for high temperature strength. IN order to determine the effects of long exposure at high temperatures on vanadium-bearing steels, a survey has been made of their hardness and carbide structure. The behavior of carbides in the tempering of martensite was studied by X ray diffraction and electron microscope examination of electrolytically extracted residues in greater detail than in an earlier investigation.&apos; A group of steels with about 0.25 pct carbon and containing chromium up to 5 pct, molybdenum up to 1 pct, and vanadium up to 1 pct was either quenched or annealed and then tempered for peri- ods of up to 1000 hr at 600° to 1400°F. Their hardness after tempering agreed with the Hollomon and Jaffe2 relation of equivalency of time and temperature, and with the degree of secondary hardening predicted from composition. Further, the appearance of the carbides indicated that the time and temperature equivalency relation was also applicable to the degree of carbide development. The mechanism of the tempering of martensite was demonstrated more clearly than in the earlier study. It was confirmed that carbides develop from martensite as poorly defined plates of the Fe2C type carbide followed by thickening of the plates with a transition to Fe,C. Finally the plate structure deteriorates into a lacy mass from which alloy carbides emerge as chunky particles that grow slowly with further increase of tempering temperature. Vanadium carbide derived from tempered martensite was found in characteristically small particles that tended to grow very slowly. The addition of chromium or molybdenum to a steel with predominant vanadium carbide tended to introduce carbides of a chromium- or molybdenum-bearing type having a somewhat larger particle size. The Cr,C, type carbide particles were larger than those of the V,C, type and somewhat smaller than the carbides in steel containing both Cr,C and M,C. Similar observations were made of the carbides in the pear lite of annealed steels. It appeared that high temperature properties would be benefited by the retention of the fine carbide particles that result from a balance of composition and heat-treatment designed to produce a maximum amount of vanadium carbide. Procedure: The steels used in the investigation were made with a base of Armco iron in a high-frequency furnace at the Union Carbide and Carbon Research Labs., Inc. The steels were deoxidized

Jan 1, 1951

By P. Greenfield, C. C. Smith, A. M. Taylor

The Mg-Zr alloy ZA and Mg-Mn alloy AM503(S) are shown to have a markedly improved resistance to creep deformation after suitable heat treatments. This improvement makes them suitable for certain stress-bearing fuel element components in nuclear reactors. The extent of strengthening is described and an explanation of the behavior of both materials is given, based on a combination of strain-aging and grain growth. The increase in operating temperatures of fuel element components in Calder Hall type nuclear reactors has necessitated the development of magnesium base alloys with a very high resistance to creep at temperatures up to 500°C. Such alloys are not required for fuel element cans, which require high-creep ductility rather than strength, but for can supporting and stabilizing components, which are needed to support the imposed loads without deforming more than about 1 pct in times of up to 40,000 hr. The amount and type of alloying addition made to magnesium for these parts is limited by the necessity of keeping the cross-section to thermal neutrons as low as possible. The alloys must also possess a high resistance to oxidation in CO2. Alloys which have been developed for this application include ZA, an alloy of magnesium with 0.5 to 0.7 pct Zr and AM503(S), an alloy of magnesium with 0.5 to 0.75 pct Mn. In the as-extruded condition these alloys are very weak and ductile in creep but it has been found that they can be strengthened to a significant extent by heat treatment. This paper describes the method of developing a high-creep resistance in ZA and AM503(S), the extent of the strengthening produced and discusses the probable mechanisms of strengthening. TEST MATERIALS Specimens were taken from typical casts of ZA and AM503(S) alloys extruded into 2 1/4-in.-diam bars, supplied by Magnesium Elektron Ltd. Typical analyses of the bars were as follows: The as-extruded mean grain diameter was 0.001 to 0.002 in. for the ZA alloy and 0.003 in. for the AM503(S) alloy. EXPERIMENTAL METHODS Extruded bars of ZA alloy, 2 1/4 in. in diameter and 9 in. long, were heat treated in electrical resistance furnaces in an atmosphere of flowing CO2 containing 50 to 300 ppm water, thereby reducing the extent of oxidation compared with that which would have occurred in air. Heat treatments were carried out at 600oc for times of 8, 24, 48, 72, and 96 hr and material was subsequently both furnace cooled and water quenched. In order to measure the effect of time of heat treatment, specimens were creep tested at 400°C and 336 psi for about 1000 hr. Subsequently, the behavior of material heat treated for 96 hr at 600°C and furnace cooled was tested at a variety of stresses from 200° to 500°C. Tests were also conducted at 200o and 400°C on material in the as-extruded condition for comparative purposes. With the AM503(S) alloy, only the effect of heat treatment at 565°C for 4 hr was examined. It has been shown1 that such a heat treatment produces marked strengthening in this alloy. Tests on this material were conducted at a variety of stresses at 200°, 300°, and 400oc with comparative tests on as-extruded material at 200o and 400°C. The creep tests were carried out on machines using dead-weight loading and direct micrometer strain measurements on specimens 5 in. long and 0.357 in. diameter. At temperatures of 400° C and below, the creep tests were conducted in air, but at higher temperatures an atmosphere of CO2 was used. Grain size measurements were made on ZA in the extruded and heat treated states and on each specimen after creep testing. This was done by a line count of a minimum of 20 grains in two or three random fields in the longitudinal and transverse directions. The same method was used for measuring the grain size of as-extruded AM503(S), but the grain size of the heat treated material was so large that this method could not be employed. For heat-treated AM503(S) the large grained characteristics (between 0.1 and 1 in.) were confirmed by the measurement of individual grains. In the case of the ZA alloy, specimens taken from various stages in the program were analysed for hydrogen by a combustion method. Material in various states was also analysed for the soluble and insoluble zirconium content by dissolving in dilute hydrochloric acid. This technique has been useda for the determination of amounts of zirconium present

Jan 1, 1962

By M. C. Flemings, T. Z. Kattamis

Dendrite morphology and grain size were studied in bulk samples of iron and nickel base alloys under-cooled up to 300°C. In the alloys studied, dendrite morphology gradually changes with increasing undercooling from the usual dendritic structure to a structure composed of cylindrical dendrite arms. At a critical undercooling of approximately 170°C in these alloys there is an abrupt transition to a fine-grained structure of spherical morphology. Final dendrite-arnz spacing of melts nucleated at less than the critical undercooling decreases with increasing undercooling and with decreasing distance from a chilled surface. Grain size of melts nucleated at greater than the critical undercooling decreases similarly with these factors. It is concluded that structure coarsening, with reduction of surface area as driving force, is the principal mechanism determining final dendrite-arm spacing in melts nucleated at small undercoolings and grain site in melts nucleated at large undercoolings. IN solidification of highly undercooled melts, nuclea-tion and growth of the solid is accompanied by a rapid release of latent heat of fusion. The heat release is sufficiently rapid in bulk specimens that it takes place essentially adiabatically with respect to the surroundings; hence the specimen heats up ("recalesces") to some maximum recalescence temperature. For bulk liquid metals and alloys, a simple thermal balance shows the undercoolings obtainable in bulk samples are not sufficient to lower the maximum recalescence temperature below the equilibrium solidus temperature. Hence, some liquid always remains at the end of recalescence; this liquid must solidify by rejection of heat to the surroundings. Metals, including iron and nickel base alloys, normally freeze with only a few degrees of undercooling. In general, nucleation begins on impurity particles present in the metal, at a "heterogeneous nucleation temperature" that is quite close to the equilibrium liquidus temperature. Very small droplets of metal can be undercooled considerably before nucleation occurs,1-4 presumably because subdivision of the liquid reduces the probability of solid impurity in a given droplet. Following early work on metal droplets,&apos; a series of studies has shown that it is possible, without great difficulty, to undercool bulk samples of many metals and alloys. Undercoolings obtainable are approximately two tenths of the melting point for nickel, iron, copper, and other metals and alloys.5-9 Specimen sizes have generally been in the range of 50 to 500 g. Studies on undercooling to date have been concerned primarily with techniques of undercooling and with nucleation and growth kinetics. Only limited consideration has been given to dendrite morphology in under- cooled alloys. One such study, in bulk Cu-Ni alloy,8 showed that at small undercoolings a typical dendritic structure was obtained. At undercoolings the order of 175°C the structure of a Cu-40 pct Ni alloy became "ray or starlike", and a dense network of subbound-aries appeared. At still larger degrees of undercooling, of the order of 250°C, the structure became more random and included an ensemble of globular forms. Comparable results were obtained by walker10 on Cu-Ni alloys, and by Kamenetskaya et al.11 in research on Cu-Ni, Sb-Bi, Fe-Ni, and Fe-Cr alloys. In this work, study was made of the processing parameters influencing dendrite morphology and grain size in undercooled alloy melts. Experiments were specifically designed to show the effects of coarsening ("ripening") during solidification on final casting morphology. EXPERIMENTAL PROCEDURE Apparatus used was patterned after that of Walker,10 Fig. l(a). Melting was by induction under reduced pressure of helium. Two different types of crucible materials were used; there was no difficulty in obtaining substantial undercooling in both types of materials. Alumina crucibles were used for the bulk of the runs made, with a glass coating separating the metal from the crucible walls. Other runs were made using fused silica crucibles with or without slag coating. A graphite susceptor was employed around the crucible to aid in melting and to reduce melt stirring. The major portion of the experimental work was on

Jan 1, 1967

By Cyril Stanley Smith

Although alloys of copper and silicon were examined several years ago,&apos; and their excellent mechanical properties were shown, it was not until C. B. Jacobs 2 introduced manganese in small quantities to the alloys that they became of commercial importance. A few years ago The American Brass Company took over the patents and commenced to manufacture the alloy under the name "Everdur." The present study of the constitution of the ternary system was undertaken in order to reach a fuller understanding of the behavior of the alloy. Review of Previous WORK on the BinaRy Systems There have been no papers published dealing with the constitution of the ternary system, although some tests of the mechanical properties have been described," which indicate that there is a change in solubility with temperature. Copper-silicon System The copper-silicon system has been studied in detail by the author and is described in two papers published in 1928.V he portion of the diagram up to 8 per cent. silicon, as determined by this research, is reproduced in Fig. 1. The author&apos;s previous papers include a complete review of the work of other investigators and it is not necessary to deal further with this system here. Copper-manganese System The copper-manganese system has been investigated by several workers, notably Lewis,5 Wologdine,6 Sahmen7 and Schemtschuschny,

Jan 1, 1930

By Mark C. Malamphy

The occurrence of outcrops of bituminous schists and sandstones impregnated with heavy asphaltie petroleum first directed attention to the São Pedro area as a possible source of commercial production of petroleum. Since 1920, more than 20 wells have been drilled in this area. The discovery of oil shows and small quantities of natural gas in some of the early wells led to the continuation of drilling in the hope that more important findings would result. During the early part of 1934, detailed magnetometer observations were made in this area, and a considerable number of torsion balance stations were occupied. The results of these geophysical observations help considerably to clarify the structure of the area and the very considerable amount of geologic information available makes possible a much more exact interpretation of geophysical anomalies. In presenting the results of these observations, and interpretation of the geophysical data, certain actual case problems are included; i.e., geophysical anomalies due to anomalous masses of which the forms and positions are more or less known. Although anomalies due to igneous intrusions are probably more important to geophysicists in Brazil than in other countries, these data have a certain interest for all geophysicists, particularly because they were obtained in the south magnetic hemisphere, where the lines of magnetic force are directed upward, and in a region of moderately low inclination. This is considered as a geological-geophysical problem, and only passing mention will be given to the petroleum possibilities of the area. General Geology The location and general geology of the São Pedro area are shown in the sketch map of Fig. 1, which is adapted from the geologic map of South Brazil compiled by Oppenheim1,†- who gives the geologic column of South Brazil (So Pedro and vicinity) as follows:

Jan 1, 1940