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By E. C. Wright

THE bessemer process is nearly one hundred years old. William Kelly, the American inventor, was able to demonstrate that he had accomplished the pneumatic purification of molten pig iron as early as 1847; Henry Bessemer's English patent was granted in 1855. The application of this steelmaking process since then and the present position of bessemer steel are concisely discussed on pages 355 and 356 of the fifth. edition of "The . Making, Shaping and Treating of Steel." The great expansion of the automotive, machine-tool, chemical and oil industries after 1910 opened up a large market for special steels, whereas the output of steel before that time was mainly for structural purposes. The need for building more blast-furnace capacity complementary to bessemer operations, combined with the availability of the necessary amounts of steel scrap, both contributed to the extension of open-hearth plants at the expense of bessemer capacity. The ability of the open-hearth furnaces to consume virtually all types of raw materials as far as phosphorus content is concerned, and the need for selecting low-phosphorus ores of rapidly decreasing sources for the bessemer, also played a part in the reduction of bessemer steelmaking operations and the increase in basic open-hearth plants. As a consequence, the proportion of bessemer steel made in this country decreased from 65.7 per cent of the total in 1900 to 37.1 per cent in 1910, and only 6.8 per cent of the total in 1937. The metallurgical concepts existent between 1910 and 1920 caused the writing of many specifications of very low phosphorus and sulphur content, which definitely barred bessemer steel from many commodities. Now sulphur is being added to many open-hearth and bessemer steels in amounts far exceeding the maximum sulphur content of good bessemer steel. Rephosphorizing is also widely practiced for several specific applications. Even today, the chemical-analysis limits of many important steel specifications have an arbitrary and archaic tinge. The old standard "0.30 .to 0.60 per cent manganese" might be mentioned in this connection as similar to the rigid requirements for maximum sulphur and phosphorus that were established at least 25 years ago. The literature is full of vague and complex discussions of the effects of nitrogen and oxygen where these elements existed in steel in amounts less than 0.02 per cent. Many failures have been attributed to these elements without reasonable proof on which to base the conclusion. Methods of determining oxygen in steel require such complicated equipment that only a few research laboratories have the required apparatus. Even so, the accuracy of oxygen determinations in steel has been only recently reproducible. Up to the present time, no one has succeeded in obtaining a sample of molten steel that accurately indicates the full. oxygen content of the metal in the furnace or ladle because the molten sample

Jan 1, 1944

By J. M. Smith, D. Kunii, P. Adivarahan

Effective thermal conductivities were measured for seven samples of porous rocks through which gases or aqueous salt solution were flowing, parallel and countercurrent to the flow of heat. The results are analyzed in terms of the contributions of the solid and fluid phases to the total energy transfer. The solid contribution for the sandstone samples studied was found to be a Junction of the porosity and an effective thermal conductivity for the solid phase. The fluid contribution was a function of the Peclet number. Based upon the equations presented, the effective conductivity of the system can be estimated from the properties of the fluid, the flow conditions, and the porosity and pore-size distribution of the rock. INTRODUCTION Heat-transfer characteristics of porous media containing fluids are needed for the design and evaluation of thermal methods of petroleum production. The study reported here considers the problem of countercurrent flow of fluid and heat in sandstone rocks, and is a continuation of previous studies concerned with parallel and radial flow of energy and fluid in both rocks517 and beds of fine particles.6,10 In addition to these earlier works, Asaad,1 Kimura,4 Preston,8 Zierfuss and vlietll and waddams9 have reported effective conductivities for systems filled with stagnant fluids. There appears to be no published data on rocks through which fluids are flowing. The purpose of this study was to present such information and, particularly, to investigate the effects of properties of the rock and the flow rate on the results. The rock samples were naturally occurring sandstones from different locations and were similar to petroleum-bearing formations. The properties of the seven samples showing the range in porosities and permeabilities are given in Table 1. The mean pore sizes were calculated from mercury penetration data by averaging the radius with respect to pore volume. The details of this method and comparison with other procedures for estimating 7 are given elsewhere. Four fluids, nitrogen, carbon dioxide, helium and 10 weight per cent sodium-chloride solution were used with each sample. For Bartlesville sandstone, BA-5, runs were made at mean pressures from 15 to 250 psig using nitrogen. The other measurements were carried out at a mean pressure of 100 psig. The maximum temperature range eacountered was 70° to 300°F. The flow rate of fluid ranged from about 1.0 to 130 Ib/(hr)(sq ft), and this corresponded to a modified Reynolds-number range of 5 x 10-4 to 1.0. The variation in Prandtl number was 0.70 to 4.1. EXPERIMENTAL WORK The equipment consisted of apparatus to supply a constant flow of gas, or salt solution, at constant pressure to the bottom of a vertical test section, and metering and flow-regulation apparatus after the test section. The flow of salt solution was

By J. D. Hanawalt, C. E. Nelson, J. A. Peloubet

THE subject of the salt-water corrosion resistance of magnesium alloys is somewhat like that of the pitting of stainless steels, in that it involves a relatively small percentage of the applications but receives a much greater proportion of the publicity. Actually magnesium alloys are in use in many exterior applications as well as interior, with no trouble from corrosion. Magnesium and its alloys have a striking stability against atmospheric attack, being far superior to iron. Specimens exposed unprotected to atmospheric weathering for 10 years show only a superficial surface-film formation. The basic nature of magnesium and of its important alloys is that they are also resistant to the attack of salt water even in an unprotected state, giving substantially no loss in weight after one year of alternate immersion in 3 per cent NaCl solution (Fig. I). This basic behavior is often masked because of the extreme sensitivity of these alloys to certain impurities and combinations of impurities. It is known, and the subject of increasing emphasis, that higher purity leads generally to greater stability for many materials, nonmetallic as well as metallic. However, a review of the literature on the corrosion factors in magnesium alloys shows that almost all researchers worked with base metal in which metallic impurities varied in uncontrolled amounts. The major factor, that of metallic impurities, probably greatly overshadowed the effects of minor ones such as flux inclusions, nonmetallic impurities, porosity, metallographic state, which these researchers presumed to study. In the present investigation the first observation of interest is that whereas magnesium of commercial purity (99.9 per cent pure) has a corrosion rate in alternate immersion in 3 per cent NaCl solution at room temperature of anywhere from 5 to 100 mg. per sq. cm. per day, the corrosion rate of high-purity magnesium is 0.15 ± 0.05 mg. per sq. cm. per day. The principle followed in the experiments was to add to such base magnesium other elements, singly and in combination, in controlled and known amounts and to observe the corrosion behavior of the resulting alloy. These experiments show the existence of what may be called "tolerance limits" of magnesium and some of its alloys for certain impurities. The extremely small percentages of impurities involved and the sharpness of the corrosion discontinuities appear to be quite unpredictable. In order to carry on this work, it was necessary to develop an analysis technique suitable to the problem. In some cases it was necessary quantitatively to analyze impurities to less than 0.001 per cent. The experimental data to be presented are based on observation of about 5000 alloy specimens and on more than 50,000 quantitative analyses. While the primary purpose of this paper is to present the experimentally obtained data on corrosion rates as a function of composition, and particularly to demon-

Jan 1, 1941

By F. Keller, R. H. Brown

BECAUSE of the extensive use of Alclad 24s alloy sheet in aircraft construction, there is much interest in the metallurgical changes caused by heat-treatment of this product.1,2 One of these changes is the result of the diffusion of soluble elements from the core into the coating during treatment. This paper deals with the thermal treatments that may influence diffusion and with the practical effects of diffusion on the serviceability of the product. As is well known, Alclad 24s-T sheet has a core of high-strength alloy combined with surface layers of relatively pure aluminum. The microstructure of a cross section of this product is shown by Fig. I. hot only does the relatively high-purity coating have a high resistance to corrosion, and hence serves as a mechanical barrier between the core metal and the corroding environment, but in addition this coating I exerts electrochemical protection over areas where the core may be exposed, such as cut edges. In addition, the coating affords electrochemical protection to projecting heads of *417S-T, 17S-T and 24S-T rivets, or attached members made from these alloys. Under some conditions of heat-treatment, however, diffusion of copper into the coating will alter the electrochemical relationship between the coating and the core to the extent that only partial protection will be obtained under some corrosive conditions. The reason for the electrochemical protection lies in the fact that the coating layers of pure aluminum are anodic to the alloy core. The addition of copper to aluminum produces alloys in which the potential is lower than that of the pure metal. Moreover, as the amount of copper in solid solution in z4S alloy is increased, the potential of the alloy becomes more cathodic. When heat-treated at 920°F. and quenched in cold water, 24s-T is about 0.16 volt cathodic to pure aluminum. However, copper will diffuse from the core into the coating, and if it reaches the surface the potential will be altered in a cathodic direction. Thus the potential dif-erence between the core and coating may be less than 0.16 volt, depending upon the thickness of the coating, and the time and temperature of heat-treatment. Of the methods available for determining the extent of diffusion of copper from the core into the coating of Alclad 24S-T, two are generally used; namely, the metallographic and the solution potential method.3 METALLOGRAPHIC METHODS Metallographic methods will reveal the progress of diffusion of copper into the coating. For instance, the diffusion zone in the coating intermediate between the coating surface and the core is shown in Fig. I. This photomicrograph is of a polished and etched cross section of 0.040-in. Alclad 24S-T sheet. Diffusion proceeds into the coating more rapidly along the grain boundaries than through the body of the grains. consequently, the diffusion zone is not of uniform width

Jan 1, 1944

By Eugene Grace

IN THE careers of the men to whom I have referred we find typified the development of the chief prob-lems of engineering. The first is to shape and direct the forces of nature and thus to bring the world's resources to add to the comfort and welfare of man-kind. That, in a word, is the problem of production. Engineers have made a supreme contribution to the solution of that problem. But I feel that we have two somewhat newer branches of engineering which must command more and more of our attention. Those are what might be termed commercial and human engineering. Of what value is all our efficiency in pro-duction if we do not distribute efficiently, economically and effectively? And of what value is any of it unless we can add to the happiness and deeper satisfaction of those engaged in industry, as well as those who enjoy its -products? I predict that the outstanding advances in business over the next ten years will be in improved merchan-dising and distributing methods. Herein lies a wide field of opportunity for the engineer. We have briefly reviewed certain qualities of engi-neers who have become successful business executives. Is it possible for us to say that the material success of all these men was due to any one characteristic com-mon to each one of them? Indeed, I venture to assert that there is one quality which, in the last analysis, is determining as to whether any roan shall realize material success in this world of ours. That quality-so notable in the character of each one of the men I have named-is sound judgment. Moments arise in every life when it is necessary to say "yes" or to say "no" to a particular proposition or to a proposed line of action. It is the man who says "yes" at the proper time and "no" at the proper time who, in the final analysis, realizes business success. The ability to do this wisely is the mark of sound judg-ment, which is necessary in a business executive. I have known many business men seemingly slow in their mental processes, possessed apparently, of little imagination and of none of the flair which gives fasci-nation to so many characters, and yet who, when crises come-be they big or be they little-are able so to steer their business courses that they move in the right direction instead of into shallow waters or upon the rocks of trouble.

Jan 4, 1928

By L. W. Kempf

ALUMINUM alloys, in common with most other metallic alloys, exhibit slight density changes with variations in temper achieved by heat-treatment, which usually are the result of the variation with tem-perature of the solid solubility of the various alloy constituents in the solvent metal. Changes in density are, of course, most marked in conditions that exhibit the maximum variation in solid solubility of the constituents. In aluminum alloys these conditions usually prevail when alloys are quenched from just below the melting point and are subsequently reheated to some lower temperature. Since commercial heat-treatments may be of this type, the density changes, although small (of the order of 0.3 per cent which may be compared with the density change of about 1.5 per cent involved in the transformation, at ordinary temperatures, of gamma to alpha iron during the hardening of steel), may in some specific applications necessitate quantitative con-sideration. This phenomenon has been investigated extensively in the laboratories of the Aluminum Company of America over a period of years. A number of investigators1-5 have observed and measured the density changes accompanying the heat-treatment of aluminum alloys. In general, these changes have not been directly translated to dimensional changes and their significance has been overlooked to some extent by the practical user of aluminum alloys. It is the purpose of this paper to consider some practical aspects of these density and dimensional changes. These density changes were given some consideration in 1917 in connection with the use of aluminum-alloy pistons for aircraft engines. Investigations by Lea and Shakespear were reported in some confidential reports of the British Advisory Committee for Aeronautics, Light Alloys

Jan 1, 1936

By T. H. Courtney, G. W. Pearsall, J. Wulff

The mechanism, of the decrease in transition temperature of Nb3Sn was studied. Presintered Nb3Sn powder compacts were heated in a dynamic vacuum at elevated temperatures. Loss of tin resulted from these heat treatments and transition temperature as a function of tin loss was discontinuous at a critical value of tin loss. In general, decreases in transition temperature were correlated with deviations from AS a class, the A15 structure-type (also known as Cr3O or ß W) compounds have the highest superconducting transition temperatures.' In this class are stoichiometry and presence of vacancies in niobium sites. The effect of vacancy distribution on the physical properties of Nh3Sn is considered. It is concluded that the close-packed atomic A chain in the A3B A15 structure must be preserved both in coutinuity and direction if good superconducting properties are to he obtained. tempting to associate these high transition temperatures with the most unique crystallographic feature of the A3B structure: the three close-packed, orthogonal chains of A atoms.'0"' There are at least three principal mechanisms by which the perfection of these "A-atom chains" could be interrupted: changing stoichiometry, inducing disorder, or introducing vacancies. Departures from stoichiometry in either direction in V3Ga lower the transition temperature.7'8 In niobium-

Jan 1, 1965

By Oliver Bowles

WAR necessities have spurred inventive genius in many fields. A grinding mill without any moving grinding parts stirs the imagination. Among the new and striking accomplishments in the heterogeneous group of nonmetallic industrial minerals is the use of an electric arc to speed up manyfold the difficult and delicate task of drilling a microscopic hole in a diamond, the hardest of all known substances. Outstanding in the field of optical research is the ability that man has developed to improve upon nature by making in the laboratory optical crystals many times larger than those usually found in rocky crevices. These are merely samples of numerous events and circumstances of noteworthy import, many of which are recorded in this review. Termination of the second World War in 1945 permits an appraisal of the effects of the conflict and the probable effects of the coming restoration of a peacetime economy on the nonmetallic mineral industries. Some industries were stimulated greatly by the war, notably mica, quartz crystal, graphite, spinning asbestos, potash, fluorspar, barite, and refractories. The large-tonnage industries connected with the building trades, however, were forced to curtail their activities, except where their products were needed for wartime construction. Their reconversion to peacetime production will not be difficult.

Jan 1, 1946

By W. A. Straw

IN the manufacture of telephone apparatus a number of nonferrous sheet metals are blanked and formed to produce a wide variety of parts, which are generally small in size because of space and weight requirements. Many are given sharp bends in forming, so that they may be assembled into compact units. This study covered sheet metal of the alloys of brass, phosphor bronze and nickel silver that are most extensively used by our company. In general, the sheets range from 0.005 to 0.100 in. in thickness and from 1/4 hard to extra spring temper in hardness. As many parts function as flat springs, and others require the maximum stiffness for structural reasons, a large percentage of the metal is used in the hard and spring tempers. So, because of the necessity for the minimum radius of bend consistent with the maximum in hardness, there has been a need for information as to the forming characteristics of these sheet metals in the various alloys, tempers and thicknesses. The literature yields relatively little regarding such forming characteristics, so that designers of apparatus and tools have been largely dependent upon past experience or tool tryouts for guidance. In presenting tabular data intended as a basis for selecting the temper of the metal and radius of the bend, we recognize the influence of many other factors which are not covered in this study. For example, the angle of the bend and conditions of the metal, such as grain size and presence of impurities, as well as conditions of the fabricating process, such as rate of forming and adjustment of the tools, may all affect the result. In addition, a bumping operation subsequent to forming, which is frequently used to set the bend, increases the strain on the metal. We wish to emphasize the fact that this is not considered a scientific investigation of the formability of materials or an attempt to correlate forming, characteristics with various other properties of the metals, except in so far as such properties are controlled by commercial limits on composition and temper.

Jan 1, 1931

By D. L. Martin, E. R. Parker

IN a previous paper, one of the authors observed that the rate of cooling from the anneal prior to testing greatly influenced the life of copper under sustained load at 200°C. Furnace-cooled bars of oxygen-free copper (with, and without silver) had a life four to twenty-five times that of the water-quenched specimens. The addition of 0.054 per cent silver to the oxygen-free copper increased the life at a stress of 20,000 lb. per sq. in. from about 2 hr. to 50 hr. Fractures in these bars were intercrystalline. An explanation was advanced to account for the profound influence of cooling rate on the rupture properties at 200°C. The suggestion offered was that at the high annealing temperature the minor constituents are distributed at random. By water quenching, this condition is maintained at room temperature, whereas furnace cooling permits some segregation at the grain boundaries. The higher concentration of the minor constituents in the grain boundaries results in a strengthening, so that a longer life at a given stress and temperature results. Small amounts of cadmium or manganese have also been found to increase the life of copper at 200°C., and to a much greater extent than silver .2 The increase in the long-time strength of copper resulting from small additions of cadmium or silver appears to be related, indirectly at least, to the higher softening temperatures of such alloys. The elements, such as silver or cadmium, which greatly increase the rupture life of copper also cause large increases in the softening temperature. As little as 0.05 per cent of cadmium or silver is sufficient to raise the softening temperature more than 100°.3,4 The effects of cooling rate and of minor constituents on the rupture properties are of considerable fundamental as well as practical interest; therefore a more detailed study of their nature was conducted and is reported in this paper. EXPERIMENTAL PROCEDURE Materials The materials studied in this investigation may conveniently be classified in two groups: one consisting of a wide variety of commercial coppers, and the other composed of special high-purity, laboratory-prepared coppers. The commercial materials were tested to determine whether or not the effect of cooling rate occurred with all coppers, whereas the high-purity coppers were investigated in order to establish a basis for evaluating the effect of minor constituents on the rupture properties. In Table I are given the analyses of the coppers tested. The samples I to 6 are commercial materials and were obtained for the most part from stock supplies.*

Jan 1, 1943

By Paul J. Bennett, James E. Castle

The sillimanite family of minerals, including kyanite, sillimanite, and andalusite, are anhydrous aluminum silicates with the formula A12O3-SiO2. Dumortierite and topaz are also included in this group because they are closely allied in composition and thermal behavior. However, neither are mined commercially today. They are typical metamorphic minerals which are found in metamorphic rocks on every continent. Sillimanite minerals are prized chiefly for their refractoriness and are important components in a broad range of acid refractory products, especially in mortars and castables. World production of sillimanite minerals is currently about 400,000 tpy and has been increasing at the rate of 3 to 8% a year for many years (Anon., 1972). While these minerals have widespread occurrence, the consumption of sillimanite minerals is concentrated in the relatively few highly industrialized areas where refractories are manufactured, and which in turn are typically close to the major iron and steel producing regions of the world. Thus northern Europe,. England, the United States, and Japan are the principal consumers of refractories and sillimanite minerals. Of these countries only the US is a significant producer. Uses of Kyanite The following specifications are typical for the domestic kyanite industry: Raw Kyanite Concentrates Chemical Analysis 56% AI2O3 min 0.1% CaO max 42% SiO2 0.1% MgO max 1% Acid soluble 0.3% combined Fe2O3 alkali max 1.2% TiO2 max Available Sizes 35, 48, 100, 200, and 325 mesh The largest use for domestic kyanite, both raw and calcined, is in the manufacture of refractory mortars, cements, castables, and plastic ramming mixes. In these applications kyanite constitutes from 10 to 40% of the mixture, the balance being refractory clays and coarser grog materials. A certain proportion of raw kyanite is used to offset the shrinking of the clay binder, whereas the calcined kyanite is used in the coarser sizes for body. Certain high grade refractory shapes and kiln furniture are composed chiefly of graded sizes of calcined kyanite bonded with a little ball clay. In most applications, however, kyanite is used only to fortify the mix or as a minor ingredient. Some manufacturers of mullite brick use domestic calcined kyanite for the fine-grained portion of the brick, but seldom in quantities exceeding 10% by weight. Kyanite is used by ceramic manufacturers of wall tile and sanitary ware to offset shrinkage and cracking after firing. Indian kyanite has traditionally been used to make the coarse grog sizes needed for the manufacture of mullite brick, and for the grog portions of mortar, cement, and castable mixes. It has been largely replaced, however, by synthetic mullite, high fired flint, and diaspore clay or calcined bauxite for other applications. Indian kyanite has been available in lump as well as in granules and concentrates, as are sillimanite materials from India and South Africa. Andalusite is available as 8 mesh granules and as fines with chemical analyses not unlike those of domestic kyanites. From time to time and from place to place minor amounts of other aluminum silicate minerals such as dumortierite, topaz, and pyrophyllite have been made available at various prices and specifications, but have not been significant factors in the refractory industry. A mixture of kyanite and sillimanite of relatively fine grain-size and of low iron content was at one time offered to the molding sand industry by the Du Pont Co. as a byproduct from their deposits of heavy

Jan 1, 1983

By Fred Chappell

Pyrophyllite, a hydrous aluminum silicate, physically similar to talc, receives its name from the Greek word Pyr, for fire and phyllite, a rock or stone. Firestone refers to its first recorded use as firestones or hearthstones. Composition and Properties Pyrophyllite is an aluminum silicate A12O34SiO2H2O (alumina 28.3 pct, silica 66.7 [ ] pct, water 5.0 pct) (Table 1). Vanderbilt1 gives pH value of pyrophyllite as 5.6 to 8.4. Pyrophyllite is usually white or cream, though it may be found in shades of pale green, pale yellow, buff or light gray, and in darker shades and other colors principally due to oxidation of contained iron minerals. It is opaque to translucent in thin sections. Its hardness is 1 to 2 in the Mohs scale. Its specific gravity is 2.8 to 2.9. Its luster is pearly to dull; it is recognized chiefly by its micaceous structure and cleavage, and its soft greasy feel. Two other varieties occur, one in which there are radiated needles in the crystalline form, and there is also a massive homogeneous structure found. Fine grinding reduces pyrophyllite to fiat plates or scales but aggregates of minute foliated plates may be formed.1 Distribution of Deposits Pyrophyllite is found in metamorphic rocks throughout the world but it is only in comparatively recent years that it has assumed much commercial importance. The principal

Jan 1, 1960

By E. M. Wise

PLATINUM and palladium are the most generally useful, most ductile and least rare members of the platinum family. They have many impor-tant applications in the pure state but for other applications it is fre-quently desirable to harden them and otherwise modify their properties by alloying small amounts of the other platinum group metals with them. These alloys are frequently required to withstand very drastic forming operations and to possess certain mechanical properties to fulfill specific requirements. For these reasons a knowledge of the tensile properties and annealing characteristics of pure platinum and palladium as well as their more useful commercial alloys is important to the user, and the fabricator. The present work was undertaken to fill this need. Rather brief (5 min.) annealing treatments were employed to render the data of maximum practical value and all tests were conducted upon 0.050-in. dia. wire, initially reduced 50 per cent in area by cold drawing, for the same reason. CONCLUSIONS 1. Pure (thermocouple grade) platinum reduced 50 per cent by cold drawing exhibits the following tensile properties: ultimate tensile strength, 36,000 lb. per sq. in.; proportional limit, 27,000 lb. per sq. in.; elongation, 2.5 per cent in 2 in.; reduction in area, 95 per cent. When fully annealed by treatment at 1100°C. its properties are: ultimate tensile strength, 20,700 lb. per sq. in.; elongation, 30 per cent in 2 in.; reduction in area, 93 per cent.

Jan 1, 1934

By W. W. Anderson, D. G. Girton

The photoluminescence of Pr, Nd, Ho, Er, Tm, and Yb in CdS, and Ho, Er, Tm, and Yb in ZnSe has been observed from crystals Prepared by diffusion using rare earth metals and an excess chalcogen pressure. For a given temperature, time, and chalcogen pressure the spectral characteristics were very reproducible from run to run, and the emission intensity for Nd, Er, and Yb in CdS was as high or higher than the best vapor phase doped crystals we have grown. For a few rare earths it was found that certain conditions of diffusion tend to yield optimum rare earth emission intensity with respect to the background lattice emission. Photoluminescence measwements of Yb in CdS as a function of depth gave a profile which was neither a Gaussian nor complementary error function. Part of the profile appears to arise from a fast component of the diffusion and the other part from a slow diffusing component. At 960°C and 33 atm S pressure, a com -plimentary error function approximation of the slow diffusing component gave a diffusion coefficient of D = 1.3 x 10-9 sq cm per sec. MOST of the studies of emission from rare earth ions in II-VI compounds have been reported on crystals doped during growth,1,2 although Kingsley and Aven prepared ZnSe:Er by diffusion for paramagnetic resonance and fluorescence studies. Pappalardo and Dietz prepared CdS:Yb by diffusion, but they made optical absorption measurements., We know of no study on the properties of rare earth diffusion in the II-VI compounds. To date we have diffused Pr, Nd, Ho, Er, Tm, and Yb into CdS, and Ho, Er, Tm, and Yb into ZnSe and observed the rare earth emission spectra. For a given temperature and chalcogen pressure, the emission characteristics are very reproducible from run to run and for Yb, Nd, and Er in CdS, as good as the best crystals we had prepared by doping during vapor phase growth.2 The emission of Pr, Ho, and Tm has been observed in CdS prepared by diffusion for the first time. Previous attempts2 to prepare these later three materials by vapor phase growth were unsuccessful. The problem of obtaining reproducible characteristics in II-VI semiconductor compound work is well known.5 Not only is it difficult to reproduce results from one laboratory to another but it is sometimes difficult to reproduce results from one growth run to another under ostensibly identical conditions within one laboratory. This situation has been particularly bothersome in research on the luminescence of rare earth activated ZnS1 and Cds2. Crystals from one vapor phase growth run would show very strong rare earth line emission while crystals from a nearly identical run would show no rare earth emission. It was also observed on occasion that the intensity of the rare earth emission was not constant over the entire volume of a single crystal. MATERIAL PREPARATION AND INSTRUMENTATION Vapor phase grown boules of CdS were supplied by Dow Corning. This material was characterized by a free electron concentration of n - 3.5 x 1015 cm-3 and Hall mobility of 350 sq cm per v sec at room temperature. There were microscopic voids and decorated precipitates in some samples. The precipitates annealed out at diffusion temperatures but the voids remained. Single crystal rectangular samples of mm dimensions were sawed from the boules. The ZnSe was polycrystalline, UHP grade from Eagle-Picher. Poly-crystalline samples were sawed from the ingots. The samples were lapped, polished on one side, etched in a solution of 0.5 M K2Cr2O7 in 16 N H2SO4, and thoroughly washed in distilled water. A sample, excess sulfur (or selenium), and 5 mg of rare earth metal (turnings) were sealed in a 3.6 cm3 quartz ampoule at about 2 X 10-5 torr. The high chalcogen pressure used (1 to 30 atm) prevented thermal etching of the crystals and affected the diffusivity and solubility of the rare earth ions in the crystal lattice. For meaningful or reproducible results, it is thus necessary to specify the vapor pressure at which the diffusion was carried out. It is assumed that a negligible amount of the chalcogen was used in the formation of rare earth sulfides or selenides Our sulfur vapor pressure calculations are based on data assuming S2, S6, and S, molecules only in which case the equilibrium constants are given by6 where the pressures are expressed in torr. Selenium vapor consists of a mixture of Se2, Se4, Se6, and Se6 molecules. The selenium vapor pressure was calculated using equilibrium constants given by The status of the rare earth source during diffusion is unknown, i.e., the partial pressures of the rare earth metal and of the rare earth chalcogenides has not been determined. All emission spectra were recorded at 77°K on a Perkin-Elmer model 98-G spectrometer using a 640 line per mm grating. No correction was made for the spectrometer and detector spectral sensitivity. Excitation was by means of an XBO 1600 w xenon arc

Jan 1, 1970

By Blake M. Loring, Robert A. Colton

MeltiXg procedures for most metals and alloys usually include some provision for the control of oxygen, since this element frequently has some undesirable effect on the properties of the metal or alloy concerned. In the melting of the various bronzes, this is especially true, since oxygen can be introduced into the melt in a number of ways, most of which are difficult to control. In making bronzes from virgin materials, oxygen is usually present in the commercial grades of copper used; electrolytic fire-refined copper ingots usually contain from 0.02 to 0.05 per cent oxygen. When ingot metal or scrap bronze is used in the charge, oxides are almost always present to some degree. Under certain melting conditions and in certain types of melting equipment the atmosphere over the metal may be highly oxidizing. This, of course, may be desirable in the melting practice used, but is certain to introduce appreciable amounts of oxygen into the melt, and that may not be entirely desirable. From the foundry viewpoint oxygen may have several harmful effects on bronzes. The formation of excessive amounts of oxides may produce drossy metal, which, in turn, means dirty castings and a potentially high rejection rate. It is claimed, too, that oxides in the metal may combine with hydrogen to form steam and thereby produce porosity in certain of the bronzes. The presence of certain refractory oxides, such as SnOz, may be undesirable from the viewpoint of making machining difficult, or as possible stress-raisers in the metal matrix. It is often said that excessive oxide present in the liquid metal makes the metal run sluggishly. Since it appears impractical to try to control the amount of oxygen introduced into the metal beyond taking the economical limit of precaution about charging dirty scrap, it would seem' that control of the oxygen content of the liquid metal offers the most promising approach to this problem. This might be done by using slags, or covers, or by the use of some element or compound added to the melt to remove oxygen preferentially. Most aspects of this problem have been considered and considerable work has been done along these lines. A reconsideration of the problem is indicated, however, by the controversial nature of the evidence at hand, especially on the possibility of using a chemical deoxidizer to control the oxygen content of bronzes. Choice of Deoxidizer The choice of the chemical agent selected as a deoxidizer would naturally depend first on the alloy in which it is to ~he used: in this particular case the alloy is Navy gun metal. In Table. I are listed a group of elements that might be considered as deoxidizers for bronze, with some of their properties that should be considered in

Jan 1, 1946

By Blake M. Loring, Robert A. Colton

MeltiXg procedures for most metals and alloys usually include some provision for the control of oxygen, since this element frequently has some undesirable effect on the properties of the metal or alloy concerned. In the melting of the various bronzes, this is especially true, since oxygen can be introduced into the melt in a number of ways, most of which are difficult to control. In making bronzes from virgin materials, oxygen is usually present in the commercial grades of copper used; electrolytic fire-refined copper ingots usually contain from 0.02 to 0.05 per cent oxygen. When ingot metal or scrap bronze is used in the charge, oxides are almost always present to some degree. Under certain melting conditions and in certain types of melting equipment the atmosphere over the metal may be highly oxidizing. This, of course, may be desirable in the melting practice used, but is certain to introduce appreciable amounts of oxygen into the melt, and that may not be entirely desirable. From the foundry viewpoint oxygen may have several harmful effects on bronzes. The formation of excessive amounts of oxides may produce drossy metal, which, in turn, means dirty castings and a potentially high rejection rate. It is claimed, too, that oxides in the metal may combine with hydrogen to form steam and thereby produce porosity in certain of the bronzes. The presence of certain refractory oxides, such as SnOz, may be undesirable from the viewpoint of making machining difficult, or as possible stress-raisers in the metal matrix. It is often said that excessive oxide present in the liquid metal makes the metal run sluggishly. Since it appears impractical to try to control the amount of oxygen introduced into the metal beyond taking the economical limit of precaution about charging dirty scrap, it would seem' that control of the oxygen content of the liquid metal offers the most promising approach to this problem. This might be done by using slags, or covers, or by the use of some element or compound added to the melt to remove oxygen preferentially. Most aspects of this problem have been considered and considerable work has been done along these lines. A reconsideration of the problem is indicated, however, by the controversial nature of the evidence at hand, especially on the possibility of using a chemical deoxidizer to control the oxygen content of bronzes. Choice of Deoxidizer The choice of the chemical agent selected as a deoxidizer would naturally depend first on the alloy in which it is to ~he used: in this particular case the alloy is Navy gun metal. In Table. I are listed a group of elements that might be considered as deoxidizers for bronze, with some of their properties that should be considered in

Jan 1, 1946

By W. S. Stahmann, F. W. Bowdish

Previously published experimental data showing that both collectable and non-collectable sulfide films may be formed on chrysocolla were analysed, and chemical mechanisms were proposed for the formation of the films. A special technique was developed by which the quantity of sulfur adsorbed was determined for samples sulfidized under different conditions of pH and soluble sulfide concentration. The data on sulfur adsorption were used together with the expression for the equilibrium constant for the proposed reaction to indicate the validity of the chemical mechanism theory. A recent paper 1 about contact angle studies on chrysocolla reported the effects of pH value and sodium sulfide concentration during sulfidization upon the character of the surfaces produced. In each experiment the surface of a specimen of chrysocolla was prepared by grinding it with fine abrasive and washing it in tap water. The specimen was then placed in the sulfidizing solution for 10 min, rinsed in tap water, treated for 15 min in a solution containing 30 mg of potassium amyl xanthate per liter, rinsed in distilled water, and tested for air adhesion in a contact angle apparatus. The results, when plotted as in Fig. 1, showed an island representing conditions giving air adherent or collectable surfaces surrounded by conditions giving non-collectable surfaces. Particular interest may be attached to the region of non-collectability to the right of and above the island in Fig. 1, and to the boundry curve separating these two regions. It is apparent that at any pH from 4.0 to 6.0, where a collectable surface may be produced, a sufficient increase in the sulfide concentration results in a non-collectable surface. Thus it appears that too much soluble sulfide has a depressing effect upon the mineral, just as it has in sulfide flotation. This paper presents some speculations regarding the chemical mechanisms by which the collectable and non-collectable sulfide films may be formed and reports on a physical-chemical study intended to support these speculations. THEORETICAL CONSIDERATIONS The experimental results presented in the previous paper were analysed in several ways in an attempt to understand better the chemical mechanisms involved. For several points on the boundary to the right of the region of contact in Fig. 1, molar concentrations of H+, OH-, HS-, and S= ions, as well as various ion concentration products, were calculated. Following the reasoning of Wark and Cox, 2,3 no single kind of ions may be credited with causing depression of the surface because none of them have a constant con-

Jan 1, 1968

U.S. Steel Uncovers Massive Iron Ore Deposits in Nevada United States Steel Corporation has confirmed that mineral investigation in Lyon County, Nevada. has been under way since 1960. Confirmation followed press reports of a statement attributed to a Nevada State inspector of mines to the effect that the Corporation has found a major iron ore deposit that may also contain copper ill West Central Nevada. Drillings over the years in a number of locations have indicated extensive iron ore bodie containing a possible quarter of a billion tons of ore of a basically magnetite composition. analyzing less than 40% iron, which would require beneficiation for commercial use. Some of these deposits are deep- lying while others would permit open pit mining. These bodies contain copper in quantities of approxiimately 0.3%. More recent drilling in another area has disclosed evidence of additional deeply-lying deposits of a lower fe content but with more promising indications of copper. A realistic estimate of fe and cu ore reserves cannot be made until more drilling is completed.

Jan 1, 1970

By A. G. Jordan, W. Jeitschko, Paul A. Beck

The occurrence qf the V phase structure /Zr,Co,Ge, type) in ternary syste7ns (titanium, zivconium, niobium, lanta1urn) -(nickel, cobalt, iron)-(silicon, germanium) was incestigated. Nine V silicides and four V gertrlanides were found and their lattice constants are reporled. The lattice constants of twenty-one preri-ously identified E phases (TiNiSi type) are given. The average atomic volumes of these phases are discussed in relation to similar binary phases. ThE occurrence of a phase Ti4Ni4Si7 was first reported by Westbrook. DiCerbo, and peat' who gave it the name "V phase". They also reported the existence of an E phase TiNiSi. Subsequently a systematic study was undertaken in this laboratory to explore the occurrence of E' and V phases3 in related ternary systems. In the meantime the crystal structure of the E phase TiNiSi 4 and of the V phase Zr4CO4Ge 75,6 was determined. In the present paper the details of the V phase investigation and the lattice constants of the E and V phases are presented. V PHASES Alloy specimens of approximately 10 to 15 g were prepared by arc melting under argon (99.996 pct Ar) atmosphere. The starting materials were all of purity higher than 99.9 pct, with the exception of cobalt. which contained 0.14 pct Fe as the only major impurity. The weight losses were in all cases less than 2 pct, in most cases less than 1 pct. The samples were encapsulated in fused silica tubes with sufficient argon to yield about 1 atm pressure at the annealing temperature. After the homogenization anneal. Table I. the specimens were water-quenched. A representative portion of each specimen was then examined metallographically (etchant: 20 pct HNO,. 10 pct HF. 25 pct glycerine, 45 pct H20). Only minor amounts of second- and third-phase particles were observed in the specimens listed in Table I, with the exception of alloys Zr4Fe4Si7 and Ta,Fe,Si,. which contained an estimated 10 pct by volume of foreign phases. X-ray powder photographs were taken with a Seeman-Bohlin type focusing camera and Fe-KO radiation. Of the thirty possible combinations of elements in the ternary systems (titanium, zirconium. vanadium. niobium. tantalum)-(iron. cobalt, nickel)-(silicon. germanium) thirteen V phases could be identified. In the remaining seventeen ternary systems and also in the systems Cr-Ni-Si and (M0.W)-(Ni.Co)-Si no V phase was found at the composition 4:4:7 after annealing at temperatures between 900" and 1200'C. For the determination of the lattice constants of the V phases Debye-Scherrer photographs were taken using the asymmetric film arrangement and CrKcr radiation (ka1, = 2.28962A). Using the positional parameters, as determined6 for Zr,Co,Ge,. Table 11. intensity calculations were carried out for each of the V phases with the aid of a computer program.: Thus unequivocal indexing of the diffraction patterns was greatly facilitated. The lattice constants. Table I. were then computed by a least-squares fit of the high-angle lines with f (0) = cos2 Q as extrapolation function. Only few. if any. very weak impurity lines were observed, with the exception of the three iron alloys Zr,Fe,Si7. Zr4Fe,Ge7. and Ta,Fe,Si7. The agreement

Jan 1, 1970

By J. T. Norton, N. J. Grant, A. M. Gervais

An investigation of the creep deformation of coarse grained specimens of high purity aluminum in the temperature range 800' to 1150°F, permitted the formulation of a theory explaining the formation of kink bands. The X-ray Laue back-reflection technique was used in conjunction with metallographic studies to determine the crystallographic elements involved in kinking and to measure the rotations of the bands. THAT metals deform by the formation of kink bands was first shown by Orowan1 in 1942. He manually compressed cadmium single-crystal wires, the basal planes of which were parallel to the wire axis and to the direction of compression. He found that kink bands formed quite suddenly. Similar experiments were performed by Hess and Barrett2 on zinc with a hydraulic testing machine to permit slower more careful compression. They observed that kink bands formed progressively with increasing compression. Recently Washburn and Parker3 observed the formation of kink bands in zinc single-crystal specimens during tension creep experiments. Each of these authors observed the formation of kink bands but did not make a complete analyses of the crystallographic relationships. In addition to these studies on hexagonal metals, extensive investigations of kink bands formed during deformation of aluminum in tension at room temperature have been reported. Two types of deformation bands have been observed during the deformation of aluminum at room temperature. These are: 1—kink bands: these exhibit a sharp curvature of the lattice along certain surfaces, and 2—bands formed by secondary slip along certain regions. As has already been shown by Honeycombe,4 it is important to point out the difference characterizing the two types of deformation bands. In the first case. for moderate deformation, only one system of slip planes normally is active; in the second case, however, two slip systems are active in the deformation bands. The latter have a rumpled surface because of the action of the two slip systems. In the present work only the first type of band was studied and to avoid any confusion the term kink band will be used exclusively in the discussion which follows. Honeycombe' observed that very narrow kink bands (width, 0.01 mm) formed along the (110) planes during the deformation of high purity aluminum at room temperature. He observed narrower ones in commercially pure aluminum and found also that their width decreased with decreasing temperatures. Chen and Mathewson5 reported the formation of kink bands during tensile testing of single crystals of high purity aluminum at room temperature and pointed out that some rotation occurred about a [211] direction. The influence of the bending moment on the formation of kink bands was illustrated by the experiments of Rohm and Kochendorferl0 who used a Polanyi apparatus to obtain pure shear during tensile testing of high purity aluminum single crystals. Under such conditions only one slip system was active and no kink bands were observed; consequently, no noticeable asterism was detected after deformation. The influence of the bending moment will be discussed later. Calnan8 gave a detailed account of the work performed on kink bands obtained during deformation of aluminum at room temperature. Because no explanation of the process of kink band formation in creep was given in the previous investigations and because some of the above observations are vital to the following discussion the brief review of the literature has been given. It is proposed in the present work to provide an explanation of kink band formation during creep deformation at elevated temperatures. Results and Discussion Kink bands were observed to form during tensile creep testing of high purity (99.995 pct) aluminum specimens, having a very large grain size, in the temperature range 800" to 1150°F. These observations were made in grains which occupied the whole cross section of the specimen. The specimens were originally round (diameter, 0.187 in.; gage length, 1 in.) and had parallel flats milled to permit easier metallographic and X-ray observations. The final

Jan 1, 1954