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By H. l. Burghoff, E. C. Bohlen

The work reported in this paper was carried out to supplement the existing information concerning directional properties and recrystallization textures of annealed brass sheet and strip. These characteristics are of direct interest when the forming and drawing properties of such material are being considered. Among those who have made contributions in this field are Bass and G1ocker;l Bauer, Göler and Sachs;2 Phillips and Samans;3 Pratt;4 Price;5 Cook;6 Richards;7 Brick;8 and Brick and Williamson.9 These investigators have found, in general, that in brass strip that shows directional variations in properties, tensile strength has a minimum value and elongation has a maximum value at 45' to the rolling direction. The most pronounced directional properties have been found in material given the greatest reductions in rolling followed by high annealing temperatures. Recrystallization texture of brass has been variously reported as (II3)[II2], (ooi)[ioo], and a combination of (II0)[II5] and traces of the primary rolling texture, (110)[112]. The directional studies have been very informative, but actual tests appear to have been confined to material in its final condition. Tests at intermediate stages have received little attention although previous history of some materials has been partly considered. Perhaps the most comprehensive investigation was made by Cook,' who studied the directional properties of 70-30 brass strip for which the final and penultimate, or next to the last, anneals and the final reductions were varied. He found that, for any given combination of penultimate anneal and final reduction, the tendency toward the development of directional properties was reduced as the temperature of the final anneal was decreased. In addition to drawing cups and making tensile tests of the finished material at various angles to the rolling direction, he measured the frequency and the angles of twins in grains for several specimens. Plots of his twin counts showed directionality for the materials that produced eared cups. Test Materials and Equipment For this investigation, one commercial heat of 68-32 brass was cast in the form of bars for cold-rolling, I31/2 in wide and I1/2 in. thick. The analysis was as follows: 68.83 per cent copper, 0.04 per cent lead, 0.01 per cent iron, 31.12 per cent zinc (by difference). The bars were so processed to the final thickness, 0.020 in., as to obtain on this thickness all possible combinations of the variables listed below except those involving the sequence of 84 per cent penultimate reduction and 84 per cent final reduction: I. Penultimate reductions of 37 per cent, 50 per cent and 84 per cent; 2. Penultimate anneals at 800°, 900°, 1050° and 1200°F.; 3. Final reductions of 37 per cent, 50 per cent, 69 per cent and 84 per cent;

Jan 1, 1942

By E. C. Bohlen, H. l. Burghoff

The work reported in this paper was carried out to supplement the existing information concerning directional properties and recrystallization textures of annealed brass sheet and strip. These characteristics are of direct interest when the forming and drawing properties of such material are being considered. Among those who have made contributions in this field are Bass and G1ocker;l Bauer, Göler and Sachs;2 Phillips and Samans;3 Pratt;4 Price;5 Cook;6 Richards;7 Brick;8 and Brick and Williamson.9 These investigators have found, in general, that in brass strip that shows directional variations in properties, tensile strength has a minimum value and elongation has a maximum value at 45' to the rolling direction. The most pronounced directional properties have been found in material given the greatest reductions in rolling followed by high annealing temperatures. Recrystallization texture of brass has been variously reported as (II3)[II2], (ooi)[ioo], and a combination of (II0)[II5] and traces of the primary rolling texture, (110)[112]. The directional studies have been very informative, but actual tests appear to have been confined to material in its final condition. Tests at intermediate stages have received little attention although previous history of some materials has been partly considered. Perhaps the most comprehensive investigation was made by Cook,' who studied the directional properties of 70-30 brass strip for which the final and penultimate, or next to the last, anneals and the final reductions were varied. He found that, for any given combination of penultimate anneal and final reduction, the tendency toward the development of directional properties was reduced as the temperature of the final anneal was decreased. In addition to drawing cups and making tensile tests of the finished material at various angles to the rolling direction, he measured the frequency and the angles of twins in grains for several specimens. Plots of his twin counts showed directionality for the materials that produced eared cups. Test Materials and Equipment For this investigation, one commercial heat of 68-32 brass was cast in the form of bars for cold-rolling, I31/2 in wide and I1/2 in. thick. The analysis was as follows: 68.83 per cent copper, 0.04 per cent lead, 0.01 per cent iron, 31.12 per cent zinc (by difference). The bars were so processed to the final thickness, 0.020 in., as to obtain on this thickness all possible combinations of the variables listed below except those involving the sequence of 84 per cent penultimate reduction and 84 per cent final reduction: I. Penultimate reductions of 37 per cent, 50 per cent and 84 per cent; 2. Penultimate anneals at 800°, 900°, 1050° and 1200°F.; 3. Final reductions of 37 per cent, 50 per cent, 69 per cent and 84 per cent;

Jan 1, 1942

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963

NAME "Utah" is derived from the name of the Indian tribe, variously spelled "Yuta," "Ute," "Youta." "Uta." "Eutaw," and finally "Utah." It means "in the tops of the mountains," or "on the heights." The state emblem is the "Beehive," typical of industry. State nickname is "Beehive State." AREA Utah is the tenth state in area. It contains 84.990 square miles, of which 2.806 miles are water. When admitted as a territory in 1850. Utah included all the area from the east line of California to the summit of the Rocky Mountains between the 37th and 42nd parallels, which embraced practically all of the present state of Nevada, all of western Colorado, part of Idaho and part of Wyoming, in addition to the present area of Utah.

Jan 1, 1925

By M. A. Scheil

Austenitic stainless alloys are susceptible to stress-corrosion cracking which may occur under certain corrosion environments irrespective of their susceptibility to intergranular corrosion. Test samples are described for investigating stress-corrosion susceptibility of alloys for industrial equipment. A laboratory test using a solution of magnesium chloride boiling at 309 F. was found to produce transgranular cracks in several alloys investigated and in types 347 and 316 stainless steel tubing a residual stress of the order of 10,000 psi. was observed to initiate cracking. The susceptibility to stress-corrosion cracking as judged by the boiling magnesium chloride test indicates that alloys may be selected which will withstand a high stress in service Stressed specimens of stainless alloys included in a corrosion testing program will aid in determining the acceptibility of these fabricated alloys, when stressed, to the service conditions.

Jan 1, 1945

By Harry L. Washburn, Robert L. Llewellyn, W. J. Halvorsen

Many of the problems that occur in the preparation plant originate from practices in the mine. Impurities in raw coal can be in the seam itself or from extraneous material taken in mining from the roof or bottom. In the case of underground mines, the choice of mining equipment will affect the size consist and the amount of extraneous material included with the coal. Also, governmental regulations concerning the degree of rock dusting, gobbing underground, and cleanup have increased the dirt in raw coal. Sulfur dioxide emission standards, on the other hand, are pressuring the coal industry to clean coal more thoroughly. Coal supplied for coking purposes is nearly all upgraded by washing, while for the largest market, electric power generation, a high proportion is shipped as a raw product with processing, in whole or in part, only necessary when excess impurities are mined with the coal. This chapter will deal primarily with plants that process or wash coal to some extent (Fig. 1) and only incidentally with mines shipping raw run-of-mine coal crushed to a top size of, usually, 51 to 102 mm (2 to 4 in.), with little, if any, other treatment. JUSTIFICATION FOR COAL PREPARATION During the past decade, major changes have occurred affecting the market, profit, and long-range planning of the coal industry. Mining companies have become "partners" with consumers at many new and some old mines, both for steam and metallurgical coals. Coal properties have become "assigned" tonnages at mutually agreed upon conditions and prices. Lower unit-train tariffs have been instrumental in helping coal markets to compete against oil and nuclear energy. Coal prices for power plants are still on a Btu (British thermal unit)

Jan 1, 1981

By Leonard B. Lipson

Boyer, Morgan and Muskat,' with improvements by Morgan, McDowell, and Doty,l and Laird and Putnam,' have described a scheme for the determination of fluid saturatic in porous media by measuring the x-ray linear absorbing power of particular fluids in the media. This method is one of several which depend on the linear absorbing power of the fluids in the porous medium. Other examples of linear absorption methods involve measurement of dielectric constant, gamma ray absorption, and ultrasonic attenuation. It is the purpose of this note to demonstrate by theortical considerations that the absorption versus saturation curve for a linear absorption method is not necessarily a single valued function of the saturation. Such non-unique behavior must be considered and evaluated before suitable saturation determinations can be made by a linear absorption method. To illustrate the discussion, examples will be given only for the simplest cases of combinations of two different dielectrics. The dielectric constant method was chosen for illustration because it was thought to demonstrate most graphically the point in question. According to Argue and Maass,4 the resultant dielectric constant of a combination of two different dielectrics depends on the orientation of the dielectrics in the electric field of the test condenser used to measure the dielectric constant. One ease involves alternate slabs of dielectrics E1 and E2 perpendicular to the electric field of the test condenser, as shown in Fig. 1A. For this case: l/'E, = A/E, + B/E,.......(1) where E,,, is the dielectric constant of the combination, A is the ratio of the path length through dielectric E, to the distance between the plates of the condenser (assuming the dielectrics have the same cross sectional area as the condenser), and B is the ratio of the path length through dielectric E2 to the distance between the plates of the condenser. It will be noted that the constants A and B are numerically equal to the fractional "saturation" of the region between the test plates of the condenser by the two dielectrics E1 and E2, respectively. Another case involves alternate columns of the two dielectrics parallel to the electric field and forming a continuous path between the condenser plates, as shown in Fig. 1B. For this case: E., = AE1 + BE2.........(2) where E., is the dielectric constant of the combination, A is the ratio of the cross sectional area of dielectric E, to the cross sectional area of the condenser plates (assuming the lengths of the dielectrics equal the distance between the condenser plates) and B is the ratio of the cross sectional area of dielectric E2 to the cross sectional area of the condenser plates. As before the constants A and B are the effective "saturation" of the condenser by the two dielectrics. Still another case is described by Lichtenecker5 where dielectric E2 is shown in the form of small particles distributed at random in dielectric E1. This is shown in Fig. 1C. For this case: log Em = A log E1 + B log E2.....(3) where Em is the dielectric constant of the combination. A is the ratio of the volume of dielectric E1 to the volume of the condenser, i.e., the effective "saturation" of the condenser by dielectric E,. B is the ratio of the volume of dielectric E2 to the volume of the condenser, i.e., "saturation" of dielectric El. Equations (l), (2) and (3) are plotted in Fig. 2 for E1 = 2.5 (oil) and E2 = 80 (water). Equations (1) and (2) may he thought of as representing the limiting cases of the configuration of two fluids which might be expected to exist in a porous medium. Equation (3),

Jan 1, 1951

By Leonard B. Lipson

Boyer, Morgan and Muskat,' with improvements by Morgan, McDowell, and Doty,l and Laird and Putnam,' have described a scheme for the determination of fluid saturatic in porous media by measuring the x-ray linear absorbing power of particular fluids in the media. This method is one of several which depend on the linear absorbing power of the fluids in the porous medium. Other examples of linear absorption methods involve measurement of dielectric constant, gamma ray absorption, and ultrasonic attenuation. It is the purpose of this note to demonstrate by theortical considerations that the absorption versus saturation curve for a linear absorption method is not necessarily a single valued function of the saturation. Such non-unique behavior must be considered and evaluated before suitable saturation determinations can be made by a linear absorption method. To illustrate the discussion, examples will be given only for the simplest cases of combinations of two different dielectrics. The dielectric constant method was chosen for illustration because it was thought to demonstrate most graphically the point in question. According to Argue and Maass,4 the resultant dielectric constant of a combination of two different dielectrics depends on the orientation of the dielectrics in the electric field of the test condenser used to measure the dielectric constant. One ease involves alternate slabs of dielectrics E1 and E2 perpendicular to the electric field of the test condenser, as shown in Fig. 1A. For this case: l/'E, = A/E, + B/E,.......(1) where E,,, is the dielectric constant of the combination, A is the ratio of the path length through dielectric E, to the distance between the plates of the condenser (assuming the dielectrics have the same cross sectional area as the condenser), and B is the ratio of the path length through dielectric E2 to the distance between the plates of the condenser. It will be noted that the constants A and B are numerically equal to the fractional "saturation" of the region between the test plates of the condenser by the two dielectrics E1 and E2, respectively. Another case involves alternate columns of the two dielectrics parallel to the electric field and forming a continuous path between the condenser plates, as shown in Fig. 1B. For this case: E., = AE1 + BE2.........(2) where E., is the dielectric constant of the combination, A is the ratio of the cross sectional area of dielectric E, to the cross sectional area of the condenser plates (assuming the lengths of the dielectrics equal the distance between the condenser plates) and B is the ratio of the cross sectional area of dielectric E2 to the cross sectional area of the condenser plates. As before the constants A and B are the effective "saturation" of the condenser by the two dielectrics. Still another case is described by Lichtenecker5 where dielectric E2 is shown in the form of small particles distributed at random in dielectric E1. This is shown in Fig. 1C. For this case: log Em = A log E1 + B log E2.....(3) where Em is the dielectric constant of the combination. A is the ratio of the volume of dielectric E1 to the volume of the condenser, i.e., the effective "saturation" of the condenser by dielectric E,. B is the ratio of the volume of dielectric E2 to the volume of the condenser, i.e., "saturation" of dielectric El. Equations (l), (2) and (3) are plotted in Fig. 2 for E1 = 2.5 (oil) and E2 = 80 (water). Equations (1) and (2) may he thought of as representing the limiting cases of the configuration of two fluids which might be expected to exist in a porous medium. Equation (3),

Jan 1, 1951

By Clintford R. Jones, Om P. Pande

This chapter presents a survey of instrumentation and control systems used on ball mill circuits from the past to the present. It is based on the concept of optimization of plant practice, and addresses the influence of the circuit design on the control strategy and on the instrumentation philosophy. Methods of optimization of the grinding circuit, within the constraints of the mill design requirements, are reviewed. The modern use of automation and circuit optimization is critically reviewed for known and possible conceptual control loops. A comparative study of circuit variations due to instrument hardware, location and installation is provided. Future trends i.e., computer control (DDC) and the effects on both the control stratagems and the optimization stratagems are described.

Jan 1, 1982

By R. K. Hopkins

For 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 with-stand 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 require-ments, but as a result of the extensive research carried on by steel manu-facturers 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 Robert Keeney

Before the outbreak of the war in 1914, the only electric-furnace smelting plant operating on a commercial basis west of the Mississippi River was an electric pig-iron plant in California; rare metal ores were not smelted, concentrates of molybdenum, tungsten, uranium, and vanadium ores being shipped east for reduction. Practically no- chrome ore was being mined, and only comparatively small amounts of manganese ore. Today there are two electric smelting plants in California, one in Washington, one in Iowa, and four in Colorado; two plants are under construction in California, and one in Montana. Ores of manganese, chromium, molybdenum and tungsten are now smelted in the West, and although uranium and vanadium concentrates are still shipped to the East, they will probably be treated in western plants in a short time. The four electric-furnace plants in Colorado are listed in Table 1. TABLE 1.-Electric Smelting Plants in Colorado Capacity, Company, Location Kilowatts Products . Tungsten Products Co Boulder 800 Ferrotungsten, ferromolybdentun. Boulder Tungsten Production Co. . Boulder 400 Ferrotungsten. Ferro Alloy Co Utah Junction 1200 Ferrochrome, ferrotung-sten. Iron Mountain Alloy Co Utah Junction 3000 Ferromanganese. Power for all of these plants is supplied by the Colorado Power Co.

Jan 8, 1918

By Guillermo Zuloaga

THE iron deposits of the Imataca Range of Venezuela, which occur along the Orinoco River, in the northern border of the Guayana High-lands, have lately attracted attention on account of their economic possibilities. Many deposits occur in this area; some of slight economic importance and others that may rank with the largest masses of high-grade iron ore of the world. The geology and the character of the ores seem to be remarkably similar to those of the large iron deposits of Brazil. In the investigation of the Venezuelan deposits a definite relationship has been found between the mineralization of the large orebodies and igneous intrusions, especially norites and granites. The following paper is the result of a field and laboratory investigation of the ore deposits. The field work was done during the months of February and March of the year 1929, partly in the company of Prof. W. H. Newhouse. The laboratory studies have been made in the Massachusetts Institute of Technology, under the supervision of Profes-sor Lindgren and Professor Newhouse.

Jan 1, 1933

By C. S. Samis, J. C. Mitchell

Sodion activity data have been obtained for the Na-A1 system for sodium concentrations in aluminum between NN, = 25 . 10-and 300 x 10'. This concentration intert-a2 encompasses those sodium concentrations nor1)zally encountered in aluminum reduction cell operation. The sodium activity data were measured by a two-phase equilibration of sodium between a lead and an aluminam rich phase. The Na-Pb system was emplojed as a reference for the determination of the actiz7itj 0.f sodium. The activity of sodiin in aluminuwz exhibits large positi2.e deviations frorn ideality and a strong dependence, on concentration below NN, = 100 x 1K6. The inteated data indicate that the activity of aluminium is equal to its mole fraction over the range of miscibility of the Na-A1 sgstem. The data on the Na-A1 binary have been combined with experimental data on the cryolite-A1 system at 1025°C to obtain the activities of Na F and AlF, in liquid cryolite oz2er the cornposition 1-ange encountered in aluminum cell operation. The results are in agreement with activities calculated from the NaF-AlF, phase diagram. ALUMINUM is produced commercially by the electrolytic reduction of aluminum oxide dissolved in molten cryolite. There is considerable controversy over the actual mechanism of the discharge processes, but sodium potentials in the systems appear to play an important role in the reduction mechanism. The metal-salt reaction involving NaF and aluminum to produce A1F3 and sodium is responsible for the presence of sodium in the aluminum metal phase. Additional sodium may be produced from the simultaneous deposition of sodium and aluminum at the cathode as a result of a cathodic overvoltage. runert' has suggested that sodium gas at atmospheric pressure would be the result of reaction between cryolite and aluminum at 1000°C. Subsequent investigations have shown that production of sodium at atmospheric pressure does not occur. These later investigations can be conveniently separated into two categories. The first involves sodium, aluminum, and cryolite, in which the sodium activity was measured. The second includes a lead phase for sodium activity measurement. Jander and errmann,' studied the reaction: at 1090°C in alumina crucibles under an atmosphere of dry, oxygen-free nitrogen. The equilibrium constant for the reaction was expressed in terms of concentration. Their results in Fig. 1 show an increase in sodium content of the aluminum with increasing NaF/A1F3 weight ratio. Pearson and waddington3 performed similar experiments at 1000°C. Their results are included in Fig. 1. Dewing and ollinshead have measured the sodium content of aluminum as a function of the NF/AF, ratio at 1025"C, Fig. 1, and ewin' measured the sodium content of the aluminum in a system involving the solid reactants NaF, cryolite, and liquid aluminum. This reaction is different from those discussed above. Two solid phases, NaF and Na3A1F6, and a liquid aluminum phase were present. The sodium concentration in the aluminum was determined by the temperature. Dewing's measurements covered the temperature range 679" to 896°C. Omo, Matsushima, and 1t02" investigated the equilibrium 6NaF ential thermal analysis. Stokes and Frank6 determined sodium activities by

Jan 1, 1970

By V. Koump, R. H. Tien, W. J. Kim

This paper presents an approximate solution of the problem of freezing of a binary alloy. he alloy is in the form of a one-dimensional slab of finite thickness. The surface temperature of the slab is assumed to be constant and lower than the solidus (or eutectic) temperature. The densities of the liquid and the solid are assumed to be equal. For a given binary alloy system, initial concentration of solute and surface temperature, the solution yields a) the temperature distribution in the solid skin, b) the temperature, concentration, and solid fraction distribution within the solid-liquid region, and c) the positions of the liquidus and the solidus (or eutectic) fronts as a function of time. The results of calculation for Fe-C and Fe-P systems are presented. In this investigation we are considering the problem of solidification of a binary alloy. The alloy is in the form of a one-dimensional slab of finite thickness. The molten alloy is initially at liquidus temperature. At time zero the surface of the slab is reduced to a temperature T, < Te,, where Te, is the solidus (or eutectic) temperature and T, is a constant. The densities of solid and liquid alloys are assumed to be equal and independent of temperature and composition. A qualitative picture of solidification of an alloy, under these conditions, is illustrated in Fig. 1. During the initial stage of solidification, before liquidus front reaches the center of the slab, freezing proceeds by propagation of two isothermal fronts, the liquidus front and the solidus (or eutectic) front. The fraction of solid at the liquidus front is zero; the fraction of solid at the solidus front is unity, The solid fraction and the temperature distribution between the two fronts and the width of the solid-liquid region change with time. During the later stage of freezing, after the liquidus front reaches the center of the slab, the liquidus front disappears. The solid fraction and the temperature at the center of the slab, as well as throughout the solid-liquid region, are now changing with time. The solidification is completed when the fraction of solid at the center of the slab reaches unity. In solution of this problem we seek to determine a) the temperature distribution in the solid, b) temperature, concentration,

Jan 1, 1968

By I. J. Hegyi, J. J. Tietjen, H. Nelson, J. I. Pankove

The fabrication of p-n junctions in GaAsl-,P, alloys by a vapor-phase gowth technique has for the first tirne resulted in room-temperature injection lasers capable of operating over a broad range of wavelengths extending into the visible region of the spectrum. The shortest wavelength achieved to date is 6750A at room tetnperature. In addition, at 78°K the threshold current density values for these lasers are generally the lo~vest reported, and the emitted radiation extends to the lozc,est wavelength ever attained (6350A). With lasers fabricated from material containing 14 pct Gap, quanticm efficiencies of 26 pct and peak power outputs of 25 zu were obtained at room temperature. ALTHOUGH room-temperature operation of GaAs injection lasers has been well-documented,&apos;-5 the operation of GaAsl-,P, (x > 0) laser diodes has been restricted to relatively low temperatures.8-&apos;0 This has been previously attributed5, 7, 10-12 partially to the difficulty of preparing single-crystalline GaAsl-& alloys having a high degree of chemical homogeneity and purity. Also, with these materials it has been difficult to prepare high-quality, abrupt p-12 junctions by diffusion techniques; and, in turn, this has made it difficult to obtain optimum electrical properties for room-temperature operationL3 in the resulting laser diodes. As a result, GaAsl-,P, laser diodes have not been efficient enough to permit operation at room temperature. For example, using diffused structures, only a few diodes were obtained which could be operated even close to room temperature (255K)." Recently, a vapor-phase growth method of preparing epitaxial deposits of GaAsl - .P, alloys has been described,14 and the high-purity and homogeneity of these materials has been previously demonstrated. Of special significance, with this technique, n- or p -type doping can be initiated or discontinued at any time and at almost any rate during the crystal growth so that the donor and the acceptor concentrations can be easily controlled to obtain desired impurity profiles. This permits high-quality, abrupt p-TZ junctions to be vapor-phase grown entirely during the crystal growth process, so that diffusion or other p-n junction fabrication processes are unnecessary. After growth, the device does not have to be heated to elevated temperatures, which avoids the possible unwanted introduction and motion of both impurities and lattice defects. Using the vapor-phase growth method cited above, over 300 room-temperature injection lasers have been prepared from GaAsl-,P, alloys having compositions in the range of 0 5 x 5 0.41. These lasers have emitted cohe~ent radiation in the spectral range of 8350 to 6350A at 78°K or from 9000 to 6750A at room temperature. The threshold current densities of the best lasers are independent of the alloy composition over the range 0 < x < 0.2 and compare favorably with values for good GaAs lasers.&apos; MATERIAL PREPARATION Multilayer, epitaxial deposits of GaAsl-,P, alloys are prepared by a vapor-growth technique described elsewhere.14 With this technique, the individual layers which comprise the multilayer structure are prepared sequentially in the deposition apparatus without interrupting the crystal growth. The epitaxial layers are deposited on GaAs substrate surfaces oriented normal to the ( 100) direction. The substrate wafers employed in this study were usually doped with tellurium to an electron concentration of approximately 2 x 10" per cu cm. To avoid strains, the first 10 to 15 p of the deposited material is uniformly graded from pure GaAs to the specific GaAsl- ,P, alloy composition of interest. The GaAsl - ,P, alloy growth is then continued to form a layer of constant composition having a thickness in the range of 25 to 75 p. Both the graded region and the layer of constant composition are doped with selenium to an electron concentration of about 2 x 10" per cu cm. The p region of the diode is then incorporated in the crystal by abruptly changing the dopant concentrations in the vapor phase to facilitate doping with zinc. This layer has a hole concentration of approximately 3 X 1019 per cu cm and typically is 50 p thick. DEVICE FABRICATION In general, the GaAs substrate and the region of graded composition are removed. Ohmic contacts are made to the n-type side by tin evaporation and to the p-type side by an electrodeless nickel deposition. This is followed by an electrodeless deposition of gold on both sides. The crystal wafer is then cleaved along (110) planes and sawed into rectangular parallelepipeds. Typical dimensions are 100 by 300 for the junction area and 100 µ for the diode height. The diodes are either soldered to a copper stud or pressure-mounted in a copper clip. RESULTS AND DISCUSSION Approximately 400 laser diodes having compositions in the range of 0.41 have been prepared by the method described above. Each laser was routinely tested at liquid-nitrogen temperature. The lasers were operated with l-psec current pulses at a repetition rate of 60 pulses per sec. The parameters of greatest practical interest are the photon energy or wavelength of the laser output and the threshold current density. Fig. 1 shows the variation of photon energy with alloy composition at 78°K. The composition was determined from the lattice constant of the material obtained by X-ray back-reflection measurements. Although there

Jan 1, 1968

By Robert Mehl

METALLURGISTS are properly interested in papers dealing with subjects ranging from the theories of the metallic state to very practical details on the use of metals. A review of theoretical metallurgy naturally excludes papers concerned with the usefulness of metals and limits itself to those concerned purely with the science of metals. Even in this more limited field the reviewer is confronted with thousands of papers dealing with facts and theories of metallic behavior, from which he can select only a few hundred. The selection is necessarily highly arbitrary. Certain classes of papers definitely fall within the scope of this review. Thus, papers on the deformation of metals, on the structure of alloys, on recrystallization, to select only a few, are fully represented. Other subjects, which verge on what is generally accepted as the science of metals, such as the magnetic properties of metals, the less familiar electrical properties and theories, adsorption of gases by metal surfaces, and the like, are treated scantily. Particular attention is given to reviews of subjects that fall with in the groups chosen; in a summary such as this, which is largely in the nature of a progress report, capably written reviews are of importance, particularly since the monograph and text book literature is so meager in this field.

Jan 1, 1935

By J. M. Woodall

GuAs crystals which have been grown in quartz boats by the horizontal Bridgman method in the pvesence of Ga20 vapov have beetz found to have carrier and donor distributions which do not correspound to those expected from simple dopant seg-vegation during directional freezing; Instead, the carrier distribution is determined by the heat-trentnzent history of the crystal, while the donor distribution, zohiclz is principally due to silicon, is fixed by the pozuth rate, the geo)tlet.ry of the crystal growth vessel, and tlze initial Ga20 pressure. WHEN semiconducting materials are made into doped crystals by the normal freezing method,&apos; they usually exhibit doping variations along the growth axis. If a) there is no dopant diffusion in the solid, b) the dopant is distributed uniformly in the melt, and c) the distribution coefficient, k, does not vary with composition, then the doping variation along the growth axis is represented by the equation: where C is the doping level in the solid at a point where a fraction g of the original liquid has frozen, and Co is the mean concentration. When the dopant is either a singly ionized shallow donor or shallow acceptor, C also represents the carrier concentration. Even though this equation accurately describes the dcping profiles of a large number of normal freeze systems, there are several special systems for which Eq. [I] does not apply. One such system is the horizontal Bridgman method for preparing oxygen-grown GaAs crystals using quartz vessels. Several workers2"* have shown that GaAs crystals grown by the horizontal Bridglnan method using quartz vessels are generally contaminated with silicon in concentrations in excess of 5 < 10lG atoms per cu cm. This contamination is ascribed to a reaction: occurring at the walls of the crystal-growth vessel which liberates silicon into the melt and Ga2O vapor. It has been shown4 that this reaction, and, hence, the silicon contamination, can be suppressed by the addition of oxygen to the crystal-growth apparatus. It is the purpose of this paper to describe a special apparatus capable of yielding single crystals of GaAs grown in the presence of oxygen and to describe both the kinetics of silicon suppression in this system and the relationship between the carrier concentration profile and the silicon concentration profile. EXPERIMENTAL-CRYSTAL GROWTH A schematic diagram of the apparatus used in the oxygen addition experiments is shown in Fig. 1. The most important features of this apparatus are: a) the use of a sand blasted quartz boat, h) a quartz rod of length 1, with a hole of cross section A, that is placed near the boat to limit the free space volume V, over the melt during the growth, and c) the temperature gradient at and near the solid-liquid interface. Sand blasting the boat is necessary to prevent wetting of the melt. The quartz rod retards the diffusion of the GazO vapor away from the melt to the colder portions of the ampoule. A crystal is prepared by first loading a 5.5-in. boat, which has been cleaned in aqua regia, with 40 g of 99.9999 pct Ga along with 1 to 8 mg of Ga203 powder. GazO3 is a convenient source of oxygen since it reacts with gallium at the melt temperature to form Ga20 vapor, the species which apparently controls the suppression of silicon contamination. The loaded boat, the quartz rod, and the 99.9999 pct As are placed in the ampoule as shown in Fig. 1. Generally, GaAs seeds were not used since most of the unseeded growths resulted in monocrys-tals. The ampoule is evacuated to 10-5 Torr and sealed off. The GaAs melt is synthesized by placing the ampoule into a two-zone horizontal Bridgman furnace. The two zones are separated by several sandwiched layers of -in. Fibre-Fax board drilled with holes slightly larger than the OD of the ampoule. This causes a very large temperature gradient between the two zones, which is necessary for single-crystal growth. The two-zone furnace is mounted on a stand fitted with a roller bearing which allows uniform motion of the furnace in a horizontal direction. A uniform velocity of the stand is achieved by the use of a windlass device which winds up a wire attached to the stand. Movement of the solid-liquid interface is accomplished by fixing the position of the ampoule and moving the stand. Growth rates investigated in this experiment were between 0.4 and 1.2 in. per hr. The composition of the melt is fixed by maintaining an arsenic reservoir at 618°C. The stand is moved away

Jan 1, 1968

By James M. Stapleton

It has long been recognized by blastfurnace men that correct top distribution of materials is very important in efficient and economical furnace operation. Thousands of experiments on top design, filling, sizing, and other operations have been carried out to improving furnace performance by securing uniform distribution. Many of these experiments have worked out satisfactorily and have been passed along to the industry. Many of them have been discarded and forgotten. It has been the custom to judge the results of such experimentation by the results shown in improved or lowered furnace efficiency. While the effect on furnace practice will have to continue to be the final criterion of experimental changes, it has always been a desire of blast-furnace men to ascertain the reason for failure or success. Efficiency in the blast furnace approaching the maximum can be measured in several ways: (1) by actual operating results as revealed in the coke rate and tonnage figures, and (2), in the degree to which the top gas approaches the limiting ratio of CO/CO2 for the reduction of iron oxide by CO gas. This ratio is shown in the equilibrium curve in Fig. I for the system Fe-O-C and CO2-CO-C. The closer the top gases approach this limiting ratio (set at 1.08 by Martin1 because of the effect of limestone calcination) the more efficiently we may expect a furnace to operate. The fact that low CO/CO2 ratios parallel eficient operating performance caused us to investigate the cause of good or poor distribution and the effect of filling and other changes on furnace operation. Heretofore it has been possible to take a sample of furnace gas (usually from the dust catcher) and from it determine how closely the reducing gases were to the ideal or limiting value as set by the equilibrium diagram. However, to find just where in the top area the distribution was distorted and the top-gas CO/CO2 ratios were distant from equilibrium values has been a difficult and expensive investigational procedure. In an effort to overcome this difficulty, apparatus was designed to take gas samples and temperatures across the top radius of the furnace. It was hoped that with the aid of this apparatus traverse sampling of the ascending gases could be simplified, and the cost of sampling substantially lowered. Routine experimenting could then be maintained and results checked with furnace operation. It must be emphasized that a traverse sampling is necessary for a true picture, as single samples at any one point are unreliable. This statement can be verified by an examination of Tables 3 to 6, showing results obtained at our furnaces in a large number of tests. Apparatus The design of the equipment for taking the samples was governed by the need for providing a simple, routine test that could be performed fairly quickly without adversely affecting normal furnace operation.

Jan 1, 1943

By James M. Stapleton

It has long been recognized by blastfurnace men that correct top distribution of materials is very important in efficient and economical furnace operation. Thousands of experiments on top design, filling, sizing, and other operations have been carried out to improving furnace performance by securing uniform distribution. Many of these experiments have worked out satisfactorily and have been passed along to the industry. Many of them have been discarded and forgotten. It has been the custom to judge the results of such experimentation by the results shown in improved or lowered furnace efficiency. While the effect on furnace practice will have to continue to be the final criterion of experimental changes, it has always been a desire of blast-furnace men to ascertain the reason for failure or success. Efficiency in the blast furnace approaching the maximum can be measured in several ways: (1) by actual operating results as revealed in the coke rate and tonnage figures, and (2), in the degree to which the top gas approaches the limiting ratio of CO/CO2 for the reduction of iron oxide by CO gas. This ratio is shown in the equilibrium curve in Fig. I for the system Fe-O-C and CO2-CO-C. The closer the top gases approach this limiting ratio (set at 1.08 by Martin1 because of the effect of limestone calcination) the more efficiently we may expect a furnace to operate. The fact that low CO/CO2 ratios parallel eficient operating performance caused us to investigate the cause of good or poor distribution and the effect of filling and other changes on furnace operation. Heretofore it has been possible to take a sample of furnace gas (usually from the dust catcher) and from it determine how closely the reducing gases were to the ideal or limiting value as set by the equilibrium diagram. However, to find just where in the top area the distribution was distorted and the top-gas CO/CO2 ratios were distant from equilibrium values has been a difficult and expensive investigational procedure. In an effort to overcome this difficulty, apparatus was designed to take gas samples and temperatures across the top radius of the furnace. It was hoped that with the aid of this apparatus traverse sampling of the ascending gases could be simplified, and the cost of sampling substantially lowered. Routine experimenting could then be maintained and results checked with furnace operation. It must be emphasized that a traverse sampling is necessary for a true picture, as single samples at any one point are unreliable. This statement can be verified by an examination of Tables 3 to 6, showing results obtained at our furnaces in a large number of tests. Apparatus The design of the equipment for taking the samples was governed by the need for providing a simple, routine test that could be performed fairly quickly without adversely affecting normal furnace operation.

Jan 1, 1943

By T. A. Wright

THE SAMPLING of waste materials containing copper, lead and tin has taken on a new significance within recent years, and is of increasing importance, on account of the entry of some of the copper refineries into this field and the tendency towards consolidations among the smelters. In the past, such material was sold on the basis either of a rough or grab sample or of casual inspection of the lot. The two principal sources of this waste are the processes of fabrication and the scrapping of automobile, electrical, plumbing, railroad and other equipment. In both cases much material can be sorted, salvaged and sold by classification and grade to be melted "as is" or with the addition of new or virgin metal. The increasing care in classifying exercised in the large manufacturing plants tends to increase the proportion of this usable scrap; on the contrary, the increasing use of more complex and special non-ferrous alloys tends to make sorting and grading more difficult in turnings, borings, clippings, etc., and consequently is making sampling of more moment. In tin, lead, aluminum, and zinc furnace by-products such as ashes, drosses, skimmings, etc., the trade practice of evaluation has not varied much. For instance, tin drosses, battery lead, and aluminum skimmings are ordinarily sold on what is called "metallic button" or "metallic recovery" or "metallic yield." Copper and lead waste, however, is being sold more and more on actual copper and lead contents based on sample and chemical analyses. This paper will be devoted chiefly to the sampling of materials suitable only for refining and recovery of one or more of the metals present. The methods described are often based on the fact that but one metal, such as copper, is to be paid for. The loss of volatile constituents in melting does not appreciably affect the final copper result, as the "after-melting" assay can he readily calculated to the "before-melting" basis, but if smelter efficiency continues to increase, so that in time zinc, for instance, may be recovered on a paying basis, the method of sampling dirty brass, for example, will have to be changed also. As a matter of fact, we may expect that improved refining processes will make possible the partial recovery of lead and tin which are now lost.

Jan 1, 1928