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By B. S. Norris, Charles R. Austin

The stresses which initiate deformation processes in metals are fundamentally important in the study of the mechanical properties of metals. A point of inflection in the load-elongation curves obtained for single crystals' has been rather too readily interpreted as a true yield point, and the critical resolved shearing stress on the plane of slip taken as a material constant. Even early work showed that the stress at this point varies with rate of loading, but it has not been generally appreciated that creep tests under static loads alone are suited for determining the existence or nonexistence of a yield point.* It has now been shown by Miller that single crystals of zinc3 when loaded statically begin to yield at loads too small to measure; as a result there is no case now known, apart from that cited in the present paper, in which a true critical stress for yielding has been demonstrated for single crystals of metals. The case of iron has especial interest: the existence of an upper and lower yield point and of an elongation at the yield point in ordinary iron and steel marks this substance as unusual, though the effects have been found to a very minor degree in other metals and alloys. $ Most alloys do not show such marked phenomena when appreciable yielding begins, and accordingly modern practice is to speak of the yield strength of such materials, a stress read from the load-elongation curve after elongation has begun, rather than yield point. The special behavior of iron suggests that it is more likely that single crystals of iron should have a true yield point than other metals. The study of the mechanical properties of metals and alloys requires a determination of the crystallographic mechanism of deformation, wlletller deformation proceeds by slip, twinning, or cleavage, or a combination of these, and a determination of the stresses that induce these modes of deformation. With this information, a study of the rates of work-

Jan 1, 1938

By B. S. Norris, Charles R. Austin

The stresses which initiate deformation processes in metals are fundamentally important in the study of the mechanical properties of metals. A point of inflection in the load-elongation curves obtained for single crystals' has been rather too readily interpreted as a true yield point, and the critical resolved shearing stress on the plane of slip taken as a material constant. Even early work showed that the stress at this point varies with rate of loading, but it has not been generally appreciated that creep tests under static loads alone are suited for determining the existence or nonexistence of a yield point.* It has now been shown by Miller that single crystals of zinc3 when loaded statically begin to yield at loads too small to measure; as a result there is no case now known, apart from that cited in the present paper, in which a true critical stress for yielding has been demonstrated for single crystals of metals. The case of iron has especial interest: the existence of an upper and lower yield point and of an elongation at the yield point in ordinary iron and steel marks this substance as unusual, though the effects have been found to a very minor degree in other metals and alloys. $ Most alloys do not show such marked phenomena when appreciable yielding begins, and accordingly modern practice is to speak of the yield strength of such materials, a stress read from the load-elongation curve after elongation has begun, rather than yield point. The special behavior of iron suggests that it is more likely that single crystals of iron should have a true yield point than other metals. The study of the mechanical properties of metals and alloys requires a determination of the crystallographic mechanism of deformation, wlletller deformation proceeds by slip, twinning, or cleavage, or a combination of these, and a determination of the stresses that induce these modes of deformation. With this information, a study of the rates of work-

Jan 1, 1938

By David J. Mack

THE structures and properties of the copper-aluminum alloys have been the subject of much study since the classic investigation of Carpenter and Edwards1 focused attention on the engineering utility of these alloys. It was recognized at an early date that the metallographic structures developed in the aluminum bronzes were similar to those developed in steels, both in the annealed and the rapidly cooled state. Most investigators have been concerned with the acicular, martensitic-like structure formed from the ß solid solution upon rapid quenching; the transformation of the ß under equilibrium cooling to a lamellar eutectoid having been relatively neglected. With the introduction in 1930 by Davenport and Bain2 of the isothermal transformation technique for studying eutectoidal decompositions, a new field was opened. Although an enormous amount of work has since been done on the isothermal transformation of steel, study of structurally analogous systems has been almost totally overlooked. The outstanding exception was the prize-winning paper† of Smith and Lindlief3 who investigated the decomposition of the ß phase in copper-aluminum alloys by isothermal methods. This was followed in 1934 by Wasserman's reviews of available information on analogous transformations in eutectoid alloys. Since that time no comprehensive study of isothermally transformed eutectoids analogous to steel has appeared, although many valuable contributions have been made to an understanding of the structures developed in such systems. Important papers have been published by Kurdjumow, Gridnew and co-workers, 5-17 Obinata,18,19 Greninger,20,21 and others .22.28 The work to be described in this paper was an out-growth of preliminary studies on the isothermal transformation of a eutectoid aluminum bronze, after it became apparent that the alloy under study was reacting somewhat differently than the similar alloy used by Smith and Lindlief. PRELIMINARY EXPERIMENTS The material used in this study was a high purity aluminum bronze especially prepared by Ampco Metal, Inc. It analyzed: Copper-88.o7 pct, Aluminum-11.89 Oct, Iron-0.02 pct, Manganese-0.01 pct, Others-Balance. Although some disagreement exists on the exact composition of the eutectoid, this alloy was believed to be of essentially eutectoid composition even though some pro-eutectoid* delta particles existed in the microstructure of furnace cooled specimens. Specimens transformed isothermally at temperatures slightly below the eutectoid showed relatively large amounts of pre-eutectoid delta, but as will be shown later, this results

Jan 1, 1947

By J. W. Spretnak, G. W. Cunningham

Grain growth across the bond region in Pressure bonded copper was found to be mainly dependent upon the presence or absence of microvoids, but it was also found that prior history, bonding pressure, bonding time, and bonding temperature are important variables. An increase in pressure, time, or temperature tends to promote grain growth in the interfacial region. Polygonization is observed after pressure bonding except for specimens previously annealed at temperatures on the order of 1800°F or higher. The dislocation density in bonded specimens was found to be greater in the bond region. THE bonding of metals by the application of gas pressure at elevated temperatures is a relatively new process, having been developed over the past 10 years. The technique, as described by Paprocki, Hodge, and Boyer,l is unique in that assemblies of many parts and complex shapes can be bonded with a negligible amount of deformation. The process thus differs metallurgically from pressure welding, cold welding, and recrystallization welding in that deformation occurs only in a microscopic region whereas, in general, the welding requires severe deformation and may extend the contact surface by a factor of 3 to 10 during the welding. From a practical standpoint, pressure welding is not amenable for bonding large surfaces. During the time in which Paprocki and coworkers were deve1oping the process, West2 established aproc-ess,for bonding aluminum to uranium, and Barnes and Maze? developed a gas-pressure-bonding technique for nickel and copper. Recently, Fugardi and Zambro4 have used equipment similar to that developed by Paprocki and coworkers to establish parameters for bonding stainless steel, aluminum, and zirconium. Most of the investigations on pressure bonding have been empirical in nature and, although methods have been developed for bonding such metals as molybdenum, columbium, titanium, zirconium, and stainless steel, the information concerning the mechanism of bonding is limited. Several workers5"7 have studied the pressure bonding of dissimilar metals in order to gain information on diffusion and formation of inter-metallic phases under application of pressure. Clapson and Robbins8 have shown by a series of annealing studies that voids in the interfacial boundary of roll-bonded copper can prevent movement of the boundary until the voids are spaced far enough apart to prevent pinning. They also indicated that recrystallization and grain growth can eliminate the voids. In this paper it is shown that voids are the major detriment to grain growth across pressure-bonded interfaces, but it is also shown that prior history, bonding pressure, bonding time, and bonding temperature are

Jan 1, 1962

By Howard Evans

Moderate but substantive gains were recorded in 1972 in the minerals processing industry. In the area of mill design, a number of large plants under construction during the past two to three years were tuned up and went into production. The application of operating controls has also made some significant strides. Progress here has been made in the areas of on-stream particle size analysis, on-stream x-ray analysis, slurry transportation, tripper control, flotation reagent control and digital control of grinding circuits. The major contributions to improved equipment are coming from smaller specialized equipment makers.

Jan 2, 1973

By R. K. Hopkins

Fox a great many years fusion welding has been used in and around petroleum refineries, but it is only within six or seven years that the more important pressure vessels have been constructed by this process, because before that time the properties of fusion welds would not withstand such rigorous service. Since the adoption of fusion welding for the construction of this equipment, the refiner has required pressure vessels suitable for operation over a very wide range of conditions. On the one hand, vessels must operate at extremely high temperatures, in the range of 950° to 1000° F., and on the other vessels must be suitable for operation at sub-zero temperatures down as low as -75° F. Also, vessels are required suitable for operation at pressures upwards of 1000 lb. per sq. in., and as low as a 29-in. vacuum. In addition, vessels are required to withstand the attack of very corrosive mediums. It has been a rather difficult task for the fabricator to meet all of these requirements, but as a result of the extensive research carried on by steel manufacturers and several fabricators of class I vessels, practically all of these demands have been met. In order to meet the refiners' requirements for this wide range of conditions, the fabricator has worked closely with the metallurgist. This has enabled him to choose the proper base metal for each service condition, but it has been the fabricator's problem to develop a welding rod and welding technique, as well as a heat-treatment, that would produce in the welded vessel characteristics in and around the weld comparable to those in the base metal. Where corrosion is not a serious problem, and where the operating temperatures are not too high, ordinary carbon steel has served very well. But when corrosion is serious, and/or when the temperatures are either very high or very low, it is necessary to use some form of alloy steel to give satisfactory service.

Jan 1, 1935

By Donald D. Carr, Lawrence F. Rooney

Perhaps no other mineral commodity in this volume has as many uses as limestone and dolomite. These carbonate rocks are the basic building blocks of the construction industry, the material from which aggregate, cement, lime, and building stone are made. Carbonate rocks, and their derived products, are used as fluxes, glass raw material, refractories, fillers, abrasives, soil conditioners, ingredients in a host of chemical processes, and much more. Although the use of limestone and dolomite goes back before recorded history, new uses and products are continually being found. Carbonate rocks form about 15% of the earth's sedimentary crust and are widely available for exploitation. Found extensively on all continents, they are quarried and mined from formations that range in age from Precambrian to Recent. Reserves of carbonate rock are large and will last indefinitely, although high-purity deposits may be absent or have limited availability in certain areas. Limestone and dolomite are so useful and so abundant that in 1981 about 644 million tons were produced in the United States. In fact, about 75% of all stone quarried or mined in the United States was carbonate rock. Sand and gravel was the only mineral commodity produced in greater quantity. In this chapter we have sought to provide the general reader an overview of carbonate rocks, their composition, distribution, production, and uses, with emphasis on developments since 1960. In doing so we borrowed extensively from our report on the applied geology of limestone and dolomite (Rooney and Carr, 1971). The literature on the limestone and dolomite resources of the United States and Canada is so vast and diverse that one can easily become mired down in print. We tried to list those references that are easily accessible and that provide the economic geologist with a starting point for more intensive study. The table listing selected references on limestone and dolomite resources in Canada and the United States reflects our attempt to be selective rather than exhaustive and to direct the reader to the best sources of detailed information. Geology Mineralogy The principal carbonate rocks used by industry are limestone and dolomite. Limestones are sedimentary rocks composed mostly of the mineral calcite (CaCO3) and dolomites are sedimentary rocks composed mostly of the mineral dolomite (CaCO3 • MgCO3). Aragonite (CaCO3), which has the same chemical composition as calcite but a different crystal structure, is economically important only in modern deposits, such as oyster shells and oolites. Aragonite is metastable and alters to calcite in time. Some other carbonate minerals, notably siderite (FeCO3), ankerite (Ca2MgFe (CO3)4), and magnesite (MgCO3), are commonly found associated with limestones and dolomites but generally in minor amounts. Because of their similar physical properties, the carbonate minerals are not easily distinguished one from the other. Specific gravity,

Jan 1, 1983

By Scott Howard

MANGANESE being perhaps the least expensive of the metallic alloying elements that can be advantageously added to iron in considerable quantities, the basic characteristics of its alloys with iron are properly receiving much attention at present. In the course of a dilatometric investigation of this system several years ago, the writer observed certain transformation phenomena not found in other iron-base alloys. The interpretation of those effects was not evident from the information then available, but recent X-ray studies clear up at least one anomaly and permit a more satisfactory description of the results than would have been possible otherwise. Aside from the new phenomena observed, the effect of manganese on the Ar3 transformation is of timely interest because of its bearing on the critical compositions of austenitic alloys, the applications of which are now being greatly extended. It is known that the properties of these alloys are unstable unless the Ar3 transformation occurs at a temperature considerably below atmospheric and that manganese is very effective in depressing the temperature of this transformation. The writer aims to establish a simple general relation which expresses the location of Ar3 quantitatively in terms of the content of the common alloying elements used in steel. A step in that direction is taken here. Early dilatometric investigations1 indicated that only one transformation other than the eutectoid A1 occurs in the high-iron alloys of the iron-manganese system. Dejean represents the Ar3 point as falling to 0° C. with a manganese content of 11 per cent and carbon content of between 0.30 and 0.40 per cent. Esser and Oberhoffer,2 using alloys low in carbon (under 0.03 per cent), arrived by extrapolation at 14 percent for the manganese content at which Ar3 is depressed to 0° C. Not until both low carbon contents and alloys having a manganese content

Jan 1, 1931

By Charles S. Barrett, Robert F. Mehl, Dana W. Smith

The Widmanstatten figures found in the steels have been long recognized and in some aspects carefully studied,' especially as they occur in cast hypoeutectoid alloys. Aside from the practical importance of the structures obtained in the steels by various heat treatments, a study of the characteristics of these figures is interesting because of the rich opportunity the system affords to obtain new data on the mechanism of segregation from solid solutions. This opportunity is twofold: first, by changing composition within the austenite range the proeutectoid precipitate may be changed from that of ferrite to that of cementite, thus offering the same opportunity for changing the type of precipitate while maintaining the same basic lattice as that afforded by the Cu-Zn alloys;2 and second, the eutectoid inversion leads upon drastic quenching to the formation of martensite, a Widman-statten figure of unique interest from the crystallographic viewpoint, particularly in comparison with those formed on slow cooling.3 We have, therefore, two types of structure to study: that formed on slow cooling of hypoeutectoid and hypereutectoid alloys, and that formed on quenching hypoeutectoid, eutectoid, and hypereutectoid alloys. For each of these types of structure we require the crystallographic plane in the mother austenite along which the precipitate forms (we shall see that the precipitates in these alloys are invariably platelike in form), and also the orientation of the precipitate upon this plane. Some of these

Jan 1, 1933

By S. R. B. Cooke, S. W. Clark

Adsorption of calcium and magnesium by quartz was determined over a wide pH range using flame photometry for solution analysis. A parallelism was noted between calcium adsorption at alkaline pH and flotation of activated quartz by means of various fatty acid collectors. Abstraction of calcium from 100 ppm solutions increased above pH 10.5 until all of the calcium was removed at pH values between 12 and 12.5. Calcium was desorbed from the quartz over the pH range 12.5 to 13.0 and returned to the solution. Precipitation of magnesium hydroxide prevented measurement of magnesium adsorption above a pH of 9.9. A calcium adsorption isotherm determined at pH 9 matched measurements of barium adsorption by other investigators over the range where adsorption corresponded to the equation of a Freundlich adsorption isotherm. In accordance with the Gouy-Chapman theory for adsorption in the diffuse layer, adsorption of the divalent cations under these conditions was four times the adsorption of monovalent sodium. Activation of quartz by multivalent metal cations in flotation using anionic collectors has been studied by many investigators. The occurrence of activator cations in the water of flotation mills makes depression of silaceous gangue very difficult. Alternatively, in some flotation systems it is practical to cause activation of quartz so that it is floated from the desirable mineral values. The present study was initiated to investigate the activation of quartz by measuring adsorption of calcium and magnesium ions as a function of solution pH. Early empirical tests showed that quartz would be activated to flotation using anionic collectors if any of a number of divalent or trivalent metallic cations were present in the pulp.1*2 Subsequent studies by Clemmer,3 Cooke and Digre,4 Cooke,5 Schuhmann and Prakash,6 and Cooke, Iwasaki, and Choi,7-8 showed that flotation depended strongly upon the alkalinity of the flotation pulp, the concentration of the activating cations, and the chain length and structure of the organic collectors used. The concept of the electrical double layer has been applied to the case of the quartz-aqueous solution interface by Gaudin and Fuerstenau,9-10 and by de Bruyn 11 to explain the activation of quartz by multivalent metal cations. Studies of the surface of quartz by Gaudin and Fuerstenau9,10,12 and by Li " using the streaming potential technique contributed much information on the electro kinetic condition of the surface of quartz in the presence of various organic and inorganic ions. Measurement of adsorption of ac-

Jan 1, 1969

By T. V. Philip, R. E. Lenhart

When commercial silicon iron sheets of varying magnetic quality are isothermally annealed at high temperatures, extremely large grains develop in the material having good magnetic properties. These grains are of the (110) [001] orientation and are formed by secondary recrystallization. The primary driving force for this secondary recrystallization is grain boundary free energy. For the secondary grains, activation energies of 103 kcal per mole for nucleation, and of 75.5 kcal per mole for growth, were obtained. The activation energy for nucleation of the secondary grains is consistent with a model involving redistribution of a precipitate acting as the primary grain growth inhibitor. SINGLY oriented silicon iron sheet was first produced in 1935.1 The material as commercially produced today has a very highly developed preferred orientation or texture; up to 95 pct of the grains are crystallographically oriented with their (110) planes in the plane of the sheet and their [loo] directions parallel to the rolling direction. This texture, usually written as (110) [00l], is referred to as the "GOSS" or the "cube-on-edge" texture. Because the magnetic properties of this material are superior to those of the nonoriented sheets in the direction of rolling, the oriented silicon iron has acquired tremendous industrial importance especially in the manufacture of transformer cores and other electrical equipment. The commercially produced material is essentially an iron-silicon alloy containing about 3 1/4 pct Si with minor impurities totaling less than 0.15 pct. The silicon steel heat is melted in the open hearth or electric furnace. The ingots are hot rolled, with or without being slabbed, to strips of 0.100 to 0.080 in. thickness. They are then cold reduced to an intermediate thickness, recrystallized, cold reduced to final thickness, decarburized, and finally annealed at a high temperature. During this high-temperature anneal, extremely large grains with the cube-on-edge texture are produced in the sheet. Several papers have appeared in the literature2-10 relating to the production of the Goss-textured material. Most of these describe the textures produced on cold rolling and on subsequent annealing of single crystal or polycrystalline silicon iron. May and Turnbull11,12 have recently shown the necessity of a second-phase dispersed impurity in the material for the production of the Goss texture. However, none of these papers describes in detail the nucleation and growth kinetics of the (110) [001] grains during the final high-temperature anneal.* The present work, therefore, is an attempt to understand the nucleation and growth kinetics of the cube-on-edge grains in the silicon iron sheet during the final high-temperature anneal.

Jan 1, 1962

By H. Rush Spedden, A. M. Gaudin

IN the belief that a critical study of its operating problems might be a sound investment, the Cuban American Manganese Corporation initiated an ore-treatment research in cooperation with the Massachusetts Institute of Technology One of the early objectives of this research naturally became the relationship of the microscopy of the Cuban ores of the Corporation to their flotation treatment The operations in Cuba have already been described by F S Norcross, Jr 7 and the laboratory study of manganese oxide flotation goes back a number of years 4 Broadly speaking, the difficulties encountered in the flotation of manganese ores are that the consumption of reagents is extremely high, the concentrate contains more silica than is desirable and the tailing losses are relatively high An appreciable betterment on any of these scores would achieve a definite betterment in costs, quantity of minable ores, and quality of product The microscope study discussed in this paper was made on samples from the Quinto mine, from the Ponupo mine, and from mill products at various stages of passage of the ore through the mill The writers have had access to Company records and in particular to the petrographic studies made on thin sections of ore by the late Professors R J Colony and Philip Krieger, of Columbia University They acknowledge their debt to both of these men for the help derived from the reports Manganese oxides are black, friable, smudging It is therefore, very difficult to judge operations by inspection The mineralogy of manganese compounds seems to be confused, and the authors believe that many more minerals have been described than actually exist Much of this difficulty is due to the prevalence of the structural conditions that will be discussed further in this paper, namely, the porosity and the friability of the ores, and the extremely intimate association of minute manganifeous mineral crystals with impurities of various sorts By all odds the most important manganese mineral in Cuba is the one that in this paper is called "psilomelane " The name "psilomelane" has been used in so many different ways that the choice of it for this ore may not be approved by all However, it seems to be the best under the circumstances This mineral accounts for about 97 per cent of the manganese in the ores of the Quinto and Ponupo mines and in the mill feed The remaining odd 3 per cent consists mostly of pyrolusite together with minor amounts of other manganese oxide minerals DESCRIPTION OF PSILOMELANE Aggregate Structure In grains or lumps, psilomelane has a characteristic fibrous appearance and seems

Jan 1, 1942

By W. L. Saunders

It is now generally admitted by experts that at least so far as rapid progress is concerned the Alpine system of tunnel-driving is superior to any other. This is perhaps natural in view of the record of experience in driving tunnels through the Alps. These great mountain-chains cannot be treated in the ordinary way by shaft-sinking and driving headings, thus multiplying the points of attack. The work must be done from the ends only, hence speed in driving is of the utmost importance ; and, as necessity is the mother of invention, the concentration of effort to make progress has resulted in an organization and in mechanical appliances that have produced results so much in excess of the usual practice, even in America, that a discussion of the subject in detail should be of much value to the engineer and contractor. The first Alpine tunnel mas the Mont Cenis, length 7.5 miles, driven with a progress that averaged about 7.75 ft. per day. Next came the Saint Gothard, 9.5 niiles long, 18 ft. per day; Arlberg, 6.5 miles long, 27.25 ft. per day; Simplon, 12.25 miles long, 36 ft. per day. The figures represent progress when driving from two headings, so that by dividing them in two we get the daily single-heading progress. The latest of the Alpine tunnels is the Loetschberg, now being driven. In this work the world's record has been beaten by a single day's record in one heading of 36 ft. and by an average daily record in one heading of 29.5 feet. The Alpine range forms a natural barrier between a large section of northern and southern Europe. This range extends from the southeast of Prance to the frontier of Hungary, betveen Italy and the plains of sonthern Germany. The contour

Jan 1, 1912

By M. R. Lorenz

Efficient visible light emission from p-n junctions in semiconductors is currently achieved in the four materials, Sic, GaP, ]Ga1-xAs and GaAs1-x,. Recent advances in materials preparation and p-n junction formation are briefly reviewed. The radiative recombination processes in the different materials depend largely on the band structure and the impurity states of each material. The spectral distribution of the emission ranges from the blue in Sic, to green in Gap, yellow in Sic and red in Gap, Ga1-x AlxAs and GaAs1-x Px. The origin of the various processes are discussed. The conversion of the electrical power into optical power and the measurement of the conversion efficiency are reviewed. The currently maximum quantum efficiencies at 300°K are: 3 pct in GaP(red), 1 pct in SiC(yellow), 0.1 pct in GaP(green), 0.2 pct in Ga1-x AlxAs at 66001, and 0.1 pct in GaAs1-x Px at 6800. The brightness and the interplay of the quantum efficiency and the luminous efficiency are given detailed consideration. VISIBLE light generated by the application of a direct current to a semiconductor crystal was first observed by Lossev1 in 1923. Light emission came from naturally occurring junctions in Sic crystals but little was known then with regard to the mechanism of charge transport and light emission. Some nearly 30 years later and with a vastly increased understanding of semiconductors the phenomenon of electroluminescence was studied in more detail, for example in p-n junctions of germanium.2 In these early studies, the efficiency of converting the electron current into a photon current was very low and therefore aroused little interest toward practical application. More recently it became apparent that in certain materials, for instance GaAs, and under certain conditions, the conversion efficiency was not low at all.3 The subsequent discovery of the p-n junction laser4-6 provided the impetus for increased studies of electroluminescence. Light emitted from GaAs occurs in the infrared region of the electromagnetic spectrum and is not visible to the eye. At nearly the same time the use of GaAs1-xPx led to laser action at low temperatures which was visible to the eye.7 Later a red light emitting diode, made from Gap, was reportedS which emitted incoherent radiation at 300°K with an external quantum efficiency of about 1.5 pct. The fact that such efficient devices were obtainable led to a more concentrated effort in the search for highly efficient room-temperature semiconductor light sources. It is some of this later work on p-n junction luminescence with which we will be concerned here. Since our aim is centered on visible light, with hv =1.8 ev ( ?=7000?), only the wider band gap semiconductors are of interest, i.e., Eg 1 1.8 ev. Although many compounds meet this criterion, only a limited number of those are also good semiconductors, i.e. contain low resistance n and p regions. Some of the more promising candidates are listed in Table I. We will only be concerned with light generation from a p-n junction. This limitation excludes essentially the group II-VI binary compounds, although we will briefly review the case of ZnTe and the solid solution ZnTe1-xSex. As we will show they may contain a p-n junction but only of a special kind. Most of the discussion will deal with the four materials, Sic, Gap, Gal-xAlxAs, and GaAs1-xPx. These appear to be at the present time the best visible light emitting semiconductors. In the following sections we will briefly consider: 1) the electrical properties of p-n junctions; 2) some recent advances in materials preparation; 3) the formation of p-n junctions; and then in somewhat greater detail we will consider: 4) the various radiative recombination processes; 5) the measurement and observation of the external quantum efficiency; 6) the luminous efficiency; 7) the brightness of light emitting diodes (LED'S). THE P-N JUNCTION The p-n junction in a semiconductor crystal is the interface between two differently doped regions. More specifically the p region is doped predominantly with acceptor impurities and the n region contains predominantly donor impurities. The energy band structure of a degenerate p-n junction at thermal equilibrium is shown in Fig. l(a). The excess electrons on the n side of the junction are confined to this region by the barrier potential Eg. Similarly the excess holes on the p-side of the junction are confined to the p-region by a similar potential barrier. If we now apply a dc voltage V such that the p region is made positive and the n region negative, the barrier potential EB is reduced by the applied voltage, V and the junction is said to be forward biased. With the barrier potential lowered, electrons and holes can drift toward the p region and n region, respectively, see Fig. l(b). The current voltage characteristics of p-n junctions in most wide band gap materials can be described by the relation: J = Joexp(eV/BkT) [1] where the functional form of Jo is determined by the recombination mechanism. Jo is generally a complicated parameter which depends on a number of different factors including temperature, junction width, bias voltage, and carrier lifetimes. The parameter B also depends on the recombination mechanism but

Jan 1, 1970

By William J. Harris, Morris Cohen

INTRODUCTION THE recent application of lineal analysis1,2 to the austenite-martensite reaction has made possible a quantitative study of the kinetics of this transformation during rapid cooling. Martensite range curves can thus be constructed to portray the onset of the reaction at [M.] and its subsequent progress as a function of temperature down to and below the ambient. It now seems in order to investigate other aspects of the martensite transformation, using this quantitative method of approach. One of the least understood characteristics of the austenite-martensite reaction is that of stabilization which has been defined by Troiano and Greninger3 as "a lowering of [M.], resulting from aging, without change in chemical composition of the parent solid solution." In other words, if the hardening quench is arrested at a predetermined subcritical temperature (Th) for a sufficient period of time, more austenite may be retained at a given lower or reference temperature (Tr) than if the steel had been cooled directly and rapidly to Tr in the first place. For the purposes of the work at hand, the extent of stabilization produced by the isothermal treatment at Th, is measured explicitly in terms of the excess austenite [(S)] that exists in the steel at Tr, over and above the amount that is normally present after direct quenching to Tr. Tr is conveniently taken to be room temperature, but this choice is not essential and is sometimes undesirable. The holding temperature (Th) may be above or below [M], and still cause stabilization depending upon the chemistry of the austenite. Stabilization has been found to occur in the presence of bainite4 and of martensite5,6,7,8 as well as in the absence of either.9 The phenomenon of stabilization is not concerned with (and may even be obscured by) ferrite formation or any other type of phase change occurring at Th that alters the chemistry of the remaining austenite. Such a structural change would obviously influence the martensite transformation during subsequent cooling. Stabilization, however, is more subtle; it appears to manifest itself without detectable variation of the austenite composition, whether in the presence or absence of transformation products. There are relatively few direct references to stabilization in the literature. The stabilizing effect of room temperature aging and tempering on the subzero transformation of retained austenite has been clearly shown in plain carbon,6.8 low alloy 6.7.8 and high alloy tool steels.10,5 Starting with the as-hardened steel, the degree of stabilization increases with tempering time and temperature through

Jan 1, 1948

By William J. Craig, Harold L. Walker

INDUSTRY has for many years recognized the dependence of certain mechanical and physical properties, as well as workability, upon grain size variations in brass. Although the dependence of properties upon grain size has been recognized there are not many instances where a planned program of testing has been conducted and where the only intentional variable has been grain size. In particular the literature is limited with respect to the effect of grain- size on the endurance limit, though there are many industrial applications where the brasses are subjected to cycles of repetitive stresses. LITERATURE A number of the physical and mechanical properties of a given brass sheet, in the annealed condition, will depend upon: (I) The ready-to-finish grain size before final rolling, (2) the percentage deformation by cold working, and (3) the time and temperature of annealing, The first and second variables affect the recrystallized grain size, and the third variable affects the coalesced grain size. Gibbs1 has shown the effect of two different ready-to-finish grain sizes upon the tensile strength and hardness of deep drawing brass strip after a definite amount of cold rolling. The smaller the ready-to-finish grain size, the higher the tensile strength and hardness, but with lowered ductility, Gibbs also demonstrated, for a given time and temperature of anneal, that the tensile strength, hardness, and elastic limit are higher for the smaller ready-to-finish grain size, but the elongation is lowered, Townsend and Greenall2 have reported data which show that cold working increases the tensile strength, hardness, and load carrying ability of deep drawing brass sheet under reversed stress. Greenall and Gohn3 have reported data which show that the smaller grain sizes have higher tensile strength and hardness properties, and the data also show that increased cold working increases the tensile strength and hardness properties of deep drawing brass sheet. Kommers4 has reported data for tests of brass of known ready-to-finish grain size, a specific amount of cold reduction, and annealed at different temperatures above and below the recrystallization temperature. Kommers' results indicate that annealing below the recrystallization temperature does not change the tensile strength and hardness properties, but the endurance limit may be increased from 22,000 to 28,000 psi. The increased endurance limit is explained as resulting from the reduction of internal stresses by a stress-relief anneal. Burghoff5 and associates have reported data on creep tests, over

Jan 1, 1948

By Edwin Hopkins

THE year 1923 started a few days after the Venezuelan Oil Concessions, Ltd., discovered a 140,000-bbl. well at. La Rosa and a well of between 2500 and 5000 bbl. at La Paz, on the opposite side of Lake Maracaibo. These nearly simultaneous events changed, overnight, the general aspect of oil affairs in Venezuela. Up to that time, big things had been expected by the companies then in the district, but many major companies had shown little interest in the country. Within a few weeks the Pure Oil. Co. and the Gulf Oil Corpn. entered the field and acquired large properties. The Texas Co. purchased several concessions and the Standard of California, Atlantic Refining Co., and Mexican Petroleum Co. established offices. Representatives of many other companies visited the district during the first few months of the year. The sudden influx of buyers naturally caused a great rise in prices and this, together with overproduction in the United States, doubtless caused the slowing up of concession transfers in the latter part of the year. The following property transfers occurred: (1) The Gulf Oil Corpn. contract with the Maracaibo Oil Exploration Corpn., whereby the Gulf acquired the right to select 100,000 acres from the Maracaibo's zones. (2) The Gulf Co. purchase of one-quarter interest in seven concessions of the New England Oil Corpn., Ltd. (3) The Gulf Oil Corpn. purchase of several concessions of Kunhardt and others in the Perija district. (4) The Gulf Oil Corpn. purchase of certain portions of the one-kilometer Lake zone that were not covered by parcels or Government reserves (namely the "sobrantes"). (5) Pure Oil Co. purchase of all Government reserves turned back by Maracaibo Oil Exploration Corpn. in the districts of Mara and Miranda. (6) Standard Oil Co.: of New Jersey deal with the British Controlled Oilfields, Ltd., for control of approxi-mately the eastern third of the .district of Buchivacoa, state of Falcon. (7) Royal Dutch deal with the British Controlled Oilfields, Ltd., for the control of the central third of the district of Buchivacoa, Falcon. (8) The Texas Co. purchase of several concessions in Perija and one west of Mene Grande on the east side of Lake Maracaibo. (9) Purchase by the British Equatorial Oil Co., Ltd., of Goverment reserves corresponding to certain Creole Syndicate parcels under the margin of Lake Maracaibo near La Paz. (10) The Lago Petroleum Co. acquired a concession on all of Lake Maracaibo except a 1-Km. strip along the shore.

Jan 3, 1924

By John G. Koert, Koert D. Burnham, John G. Broughton

Wollastonite in Essex County, New York, occurs as a typical contact mineral in a series of rocks metamorphosed by anorthosite. Sole current use is in various types of electric welding fluxes. Its uniform lathlike shape suggests its use as a specialized filler. Introduction Wollastonite (CaSiO3) was first noted in the vicinity of Willsboro, Essex County, New York, about 1810 by Dr. William Meade, and described from the same locality in 1821 by Lardner Vanuxem.' Recent exploration and development indicate that the deposit is of adequate size for continued exploitation on a larger scale than the present operations. The only other known occurrence of like magnitude in this country is in Kern County, California.* Wollastonite has been reported from Michigan, Pennsylvania, and Lewis County, New York, but these are little more than mineral localities. Geology The Essex County wollastonite has been found outcropping at numerous separate localities in a belt of contact metamorphosed sediments, 1/4 mile wide, which begins 2 miles southwest of the village of Willsboro and trends N. 70" W. for approximately 6 miles (Fig. I). In this belt, the pre-Cambrian Grenville has been injected and partially replaced by the more liquid portions of an anorthositic magma. Bud-dington and Whitcomb3 have described the rock in this contact metamorphosed belt as "Mixed gneisses: Grenville mafic, pyroxenic and garnetiferous gneisses and skarns* with local nearly uniform garnet or pyroxene layers and with gabbroic anorthosite sheets. A few limestone layers." These rocks are underlain, presumably at no great depth, by gabbroic anorthosite gneiss, the typical Whiteface border facies of the Adirondack anorthosite massif. The occurrence of wollastonite in large quantities was discovered during the quarrying of the garnet-rich layer that overlies the wollastonite at one opening. Further prospecting revealed its presence elsewhere in the belt, overlain in most places by the garnet. Accurate tracing of the wollastonite is difficult, owing to the glacial cover and to the fact that the weathered surface of the mineral has a dark, dirty brown color, and that the wollastonite itself has been dissolved more or less completely along the outcrops. It has, however, been noted at 10 localities within the skarn belt in the first 2 1/2 miles from its southeastern end. It has not been found in the northern half of the belt and therefore may be limited to the southern half. At the Fox Hill quarry, which is the main opening, 150 ft. have been exposed, showing an aggregate thickness of 30 to 35 it. Of

Jan 1, 1948

By Koert D. Burnham, John G. Broughton, John G. Koert

Wollastonite in Essex County, New York, occurs as a typical contact mineral in a series of rocks metamorphosed by anorthosite. Sole current use is in various types of electric welding fluxes. Its uniform lathlike shape suggests its use as a specialized filler. Introduction Wollastonite (CaSiO3) was first noted in the vicinity of Willsboro, Essex County, New York, about 1810 by Dr. William Meade, and described from the same locality in 1821 by Lardner Vanuxem.' Recent exploration and development indicate that the deposit is of adequate size for continued exploitation on a larger scale than the present operations. The only other known occurrence of like magnitude in this country is in Kern County, California.* Wollastonite has been reported from Michigan, Pennsylvania, and Lewis County, New York, but these are little more than mineral localities. Geology The Essex County wollastonite has been found outcropping at numerous separate localities in a belt of contact metamorphosed sediments, 1/4 mile wide, which begins 2 miles southwest of the village of Willsboro and trends N. 70" W. for approximately 6 miles (Fig. I). In this belt, the pre-Cambrian Grenville has been injected and partially replaced by the more liquid portions of an anorthositic magma. Bud-dington and Whitcomb3 have described the rock in this contact metamorphosed belt as "Mixed gneisses: Grenville mafic, pyroxenic and garnetiferous gneisses and skarns* with local nearly uniform garnet or pyroxene layers and with gabbroic anorthosite sheets. A few limestone layers." These rocks are underlain, presumably at no great depth, by gabbroic anorthosite gneiss, the typical Whiteface border facies of the Adirondack anorthosite massif. The occurrence of wollastonite in large quantities was discovered during the quarrying of the garnet-rich layer that overlies the wollastonite at one opening. Further prospecting revealed its presence elsewhere in the belt, overlain in most places by the garnet. Accurate tracing of the wollastonite is difficult, owing to the glacial cover and to the fact that the weathered surface of the mineral has a dark, dirty brown color, and that the wollastonite itself has been dissolved more or less completely along the outcrops. It has, however, been noted at 10 localities within the skarn belt in the first 2 1/2 miles from its southeastern end. It has not been found in the northern half of the belt and therefore may be limited to the southern half. At the Fox Hill quarry, which is the main opening, 150 ft. have been exposed, showing an aggregate thickness of 30 to 35 it. Of

Jan 1, 1948

By E. T. Dumble

Introduction..........914 I. Topography,........915 The Nueces Basin........915 The Coastal Slope...........918 Streams..........919 II. Geology..........921 Eocene..........923 Basal Beds .......923 Lignitic Stage........923 Atascosa Sections......924 International and Great Northern Sections .. . 928 Leona Sections.......929 Nueces Sections....929 Rio Grande Sections.....930 Lower Claiborne Stage......932 Marine Beds ........933 Atascosa Sections....... 933 International and Great Northern Sections .. . 934 Frio County Sections,.....935 Rio Grande Sections.....936 Yegua Clays........938 Atascosa Sections......938 Tilden Sections.......941 International and Great Northern Sections .. . 942 Rio Grande Sections.....942 Fayette Sands........945 Atascosa Sections......946 Tilden Sections......948 Rio Grande Sections.....950 Frio Clays........953 Atascosa-Frio Sections.....953 Tilden-San Diego Sections....955 Rio Grande Sections......955 Neocene ....966 Oakville Beds.......957 Lapara Beds,....... 987 Nueces Sections......958 Bartlett's Ford Sections.....959 Fort Merrill Section......963 Lapara Sections,.....964 Tilden-San Diego Section.....967 Lee Tiendas.......969

Jan 1, 1903