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By A. E. Jenkins, A. Jostsons

Isothermal sections of the Ti-0-H phase diagvam at 600°, 700°, and 800°C have been constructed from equilibrium hydrogen pressure measurements over a range of Ti-0-H alloys containing up to 34 at. pct 0. Oxygen reduces the hydrogen solubility at fixed hydrogen pressure but increases the terminal solubility in the a solid solutions at the a/(a + P) phase boundary. Metal-lographic studies of alloys annealed below the eutectoid temperature show that oxygen also increases the ter-ninal solubility of hydrogen in the a solid solution in equilibrium with the hydride phase. The effect of oxygen on hydrogen solubility is discussed in terms of the electronic and geometric structure of interstitial solid solutions. THE isothermal solubility of hydrogen in a Ti-0 alloys at 800°C has been measured by Hepworth and ~chuhmann' who subsequently used ternary Gibbs-Duhem integrations to calculate oxygen activities in binary Ti-0 alloys. The present study aims to extend Hepworth and Schuhmann's measurements to alloys richer in oxygen and to a range of temperatures. This paper presents the results of hydrogen equilibrium pressure/concentration measurements in Ti-0 alloys as well as observations on the effect of oxygen on the terminal solubility of hydrogen in a titanium. The thermodynamic properties of binary Ti-0 alloys, derived from these measurements, will be published separately.' EXPERIMENTAL METHODS Specimen Preparation. Ti-0 alloys were prepared from iodide-refined titanium and titanium dioxide obtained by hydrolysis of redistilled titanium tetrachlo- ride. Specimens containing up to 16 at. pct 0 were prepared by electromagnetic levitation3 whereas a conventional tungsten arc furnace with a water-cooled copper hearth was used to melt oxygen-rich alloys. The specimen homogeneity was indicated by the constancy of lattice parameters of samples from various parts of the ingot as well as by the sharpness of the reflections on X-ray powder patterns. Oxygen-rich specimens in the composition range (20 to 34 at. pct), where ordering has been ~bserved,~ were annealed for 300 hr at 600°C prior to use in hydrogen solubility measurements. Apparatus. The hydrogen pressure/concentration measurements were made with a modified Sieverts apparatus shown diagrammatically in Fig. 1. Specimens were placed in a clear silica tube and impurity pickup by direct reaction with silica was prevented by lining the heated end of the silica tube with thin molybdenum sheet. A double silica tube was required to eliminate loss of hydrogen by diffusion through silica at high temperatures and high hydrogen pressures, the space between the tubes being maintained at a hydrogen pressure equal to that above the specimen. Hydrogen was purified by diffusion through a Ag-Pd tube.= Hydrogen pressures were measured with a mercury McLeod gage in the range 0.001 to 4 Torr

Jan 1, 1968

By B. W. Gandrud

WET-PROCESS coal-washing tables as we know them today have been in use in this country for approximately 25 years. The literature records only a few table installations worthy of note prior to adoption of the present-day differential-motion table. According to Phillips,' six Campbell bumping tables were being operated by the St. Bernard Coal Co., Earlington, Ky., in 11893. As late as 1923, according to Richardson, 2 72 such tables were in operation in the Rosedale washery of the Cambria Steel Co., at Johnstown, Pa. Bumping tables probably were not used to any considerable extent except in the plant at Earlington, and at two or three plants in Pennsylvania, but they may be considered as forerunners of the present-day coal-washing table. The transition from bumping tables to the type of tables now in use signalized a revolutionary change in table design. The advantages of the new design over the old were so outstanding as to make its adoption inevitable. BUMPING TABLES Bumping tables, as the name implies, utilized a bumping action for conveying the refuse and discharging it over the refuse end. The tables were hung from rods attached to overhead supporting beams. A shaft and cam arrangement at one end of the table served as the actuating mechanism and imparted to the table an endwise, back-and-forth, swinging motion. A bumping block was fixed in the proper position at the shaft end, so that the table would strike against it at the end of each backward swing. The hanger rods or stirrups were so adjusted as to give the table a slight uphill slope toward the refuse end; that is, the end next to the driving mechanism. The feed box was near the upper end, of the table and designed to spread the mixture of coal and water over the width of the table. Wash water was added a short distance below the feed box with the table in motion and coal mixed with water being fed to it through the feed box, a certain amount of stratification took place, depositing heavy refuse at the bottom of the bed in contact with the surface of the table. Constant bumping and a certain amount of

Jan 1, 1943

By H. L. Gilbert, C. Travis Anderson, W. J. Kroll

IN a previous paper,1 the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.2 When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8in. in diameter. The supply of direct current of high amperage for producing the . desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flexible tubing of the movable electrode, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decided to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 1900°C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica according to the reaction: Si02 + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1948

By Earl S. Bardwell

The structural relations existing between cuprous oxide and copper were first systematically studied by Heynl; who suggested that a study of the microstructure of refined copper might be substituted for the analytical methods in vogue for determining the oxygen content of copper coming from the refining furnace. Hofman, Green and Yerxa,2 in their paper A Laboratory Study of the Stages in the Refining of Copper, working along the lines suggested by Heyn, showed that a study of the microstructure could be made to yield a correct estimate of the oxygen content of refined copper. In order to determine the oxygen content of the specimen of refined copper under examination a photomicrograph was first made. From the relative areas of copper and eutectic, the percentage of cuprous oxide and the corresponding percentage of oxygen were then readily calculated. It was found that the values for oxygen thus obtained corresponded closely with the analytical results. With the idea of utilizing this method of determining the oxygen content of each charge dipped from the refining furnaces at the Boston & Montana Reduction Plant, the physical testing laboratory was equipped with suitable apparatus for carrying out the work. It may be of interest to describe certain of the methods which have been worked out in this connection and give such data as have been obtained bearing on the effect of the oxygen content of refined copper upon its conductivity. Apparatus.—For the benefit of those who may be unfamiliar with metallographical apparatus and methods and may be interested to know what equipment is required, a few words with regard to the apparatus are in place at this point.

Jan 1, 1914

By C. F. Smart

Since their comparatively recent development, the alloys of cadmium with silver and copper or nickel, and of cadmium with nickel alone, have been used somewhat extensively as liners for connecting rod bearings and main bearings of internal-combustion engines. In applications where, owing to high bearing loads and elevated operating temperatures, the life of bearings made from tin-base or lead-base alloys has been undesirably short, cadmium alloys have demonstrated considerable advantage. In applications where, because of deflection of the crankshaft or bearing supports, copper-lead bearing metals have resulted in scored shafts, cadmium alloys have been operated successfully. The somewhat serious drawback to these alloys in bearing service has been that they, in common with copper-lead and certain lead alloys, are susceptible to corrosion in the presence of lubricants containing organic acids. These acids may be fatty acids (such as oleic acid) derived from animal or vegetable oils that sometimes have been compounded with engine lubricants, or they may be compounds of an acid nature developed by the oxidation of some petroleum oils under operating conditions. The result of such acid attack on bearings is illustrated by the photograph, Fig. 1. The petroleum oils that are most readily oxidized to a corrosive condition, and the operating conditions under which such oxidation most readily occurs, are now rather well known among the technical organizations of both the petroleum and automotive industries. While means have been developed for inhibiting petroleum oils against such acid formation, the knowledge that this condition may be encountered has been a factor in restricting the wider use of cadmium alloys as engine bearings. It has appeared, therefore, that their value and use would be enhanced if they could be made corrosion-resistant to a degree compatible with the most severe operating requirements. Investigation, undertaken with this in view, indicated that the addition of fractional percentages of the metal indium to the cadmium bearing

Jan 1, 1938

By Richard E. Gray, Robert W. Bruhn

INTRODUCTION Underground coal mining has been practiced in the United States for over 200 years. Much early mining was not as efficient as today and unrecovered coal pillars, often of variable size and spacing, remain to support the overlying strata after mining has ceased. These conditions constitute a potential subsidence problem since the pillars will eventually fail. The possibility of subsidence above an abandoned mine must be anticipated except when total extraction has been achieved, permitting subsidence concurrent with mining, or when large coal pillars which have an adequate factor of safety for long-term support remain in the mine. Coal is found in 37 states and is mined under- ground in 22 states (HRB Singer, Inc. 1980). Underground mining produced 40 percent of the 7.5 x 10" kg. (830,000,000 tons) of U. S. coal mined in 1980 (Keystone, 1981). There are approximately 70,000 abandoned or inactive underground coal mines in the United States and approximately 2000 active underground coal mines (NAS/NAE, 1975). Underground coal mining in the United States will eventually extend beneath 162 x 109m2 (40 million acres). Thirty-two billion m2 (8 million acres) are already undermined (HRB Singer, 1977). Subsidence due to mining has affected more than 8 x 109m2 (2 million acres) in 30 states, 7.7 x 10 9m2 (1.9 million acres) from bituminous coal mining and the remainder primarily from anthracite mining (Johnson and Hiller, 1979). Subsidence from all other underground mines has affected only 6.9 x 10 7m2 (17,000 acres) (Johnson and Miller, 1979). Subsidence appears to be particularly widespread in two states, Pennsylvania and Illinois, although serious subsidence is found in localized areas of numerous other states (HRB- Singer, Inc. 1977). Host underground coal mining has occurred in the eastern United States, where the U. S. Bureau of Mines estimates 1.6 x 109m2 (398,600 acres) in urban areas in 18 states (out of a total 1.7 x 109m2 1418,400 acres]) are threatened by subsidence (Table 1) (Johnson and Miller, 1979). Pennsylvania and West Virginia contain 57 percent of the total threatened areas. The U.S. Bureau of Mines estimates the total cost to stabilize the estimated 1.7 x lo9m2 (418,400 acres) of subsidence prone urban land located above abandoned mines is over $12.5 billion (1978 costs).

Jan 1, 1982

By Charles A. Ashburner

' I. Natural-Gas Explorations. The rapid development of the natural-gas* industry in Western Pennsylvania, and the great economy which results from its use, both for manufacturing and domestic purposes, has led to an inquiry as to the occurrence of this gaseous mineral in all thickly populated and large manufacturing centers of the United States. Natural-gas springs are to be found in almost every State in the Union, and in many States gas has been obtained in wells sunk either for water, oil, or gas, or in search of solid mineral deposits. The occurrence of natural gas is, however, not dependent upon mere chance, as is popularly supposed, but upon the existence of special geological phenomena; this fact is now recognized by professional men and by many practical men concerned either in the exploration for or in the use of this gas. The desire among our leading manufacturers, to emulate Pittsburgh, has led to the sinking of many wells in many localities, in search of natural gas. Some of these wells are now being located and drilled under the direction of professional experts, but many more have been, and are still being located by "quack " explorers, who often depend upon spiritualistic communications, or the diviningrod, or by intelligent persons, who are ignorant, however, of the geological and physical conditions under which gas has already been found. My attention has recently been directed to a number of these exploring operations where holes have been drilled, and, after failing

Jan 1, 1887

By William B. Plank

ENGINEERING students to the number of 73,269 had been enrolled in United States and Canadian schools on Nov. 5, 1945, but, as shown in the following tables, even this sizable number will not greatly remedy the 150,000 deficit reported by Vannevar Bush, director of the U. S. Office of Scientific Research and Development, to exist in the engineering and scientific man-power supply. These figures were received in advance from the Society for the Promotion of Engineering Education, and are given in detail in the January 1946 issue of the Journal of Engineering Education. Although the enrollment on Nov. 5 was an increase of 76% over the low of 41,632 in 1944-45, it was still 36% below the peak enrollment in 1941-42 of 115, 228. These figures include both undergraduate students and graduate students in the schools of the United States and Canada and are therefore comparable. As was to be expected, almost half of this enrollment is in the first or freshman year and 25% of the total are veterans. Also, 1,850, or about 2.5%, are women. A measure of the seriousness of the engineering graduate supply in these two countries is indicated by the trend of the number of first degrees that have been conferred during this period of scarcity:

Jan 1, 1946

By Frank Reiber

The study of earthquakes long ago developed the fact that by study-ing the travel .times of the various groups of waves from the same earthquake, as received on seismographs :it varying distances, major discont'inuities in the earth's crust, could be reasonably well defined. Using this original discovery, and adapting the mathematical methods originally devised in seismology for determining the depth below the surface at which such discontinuities occur, other investigators were able to develop a new branch of seismology which promises to be extremely useful in extending the boundaries of our information on local conditions Below the earth's surface. As an outstanding example of the applications of this work, we have the so-called " seismograph " exploration of the Gulf Coastal region, which has resulted in the discovery of a large number of salt domes, from many of which oil fields may be developed. The original seismological investigations, from which different major discontinuities in the earth's crust were deduced, as well as these later successful experiments in locating salt-dome structures, involve relatively simple problems. In each case we arc dealing with surface materials in which elastic waves will be propagated with a fairly definite velocity. Under this material we have something quite different', in which the elastic waves will be propagated with a much higher velocity. The transition from one medium to the other is likewise relativtly abrupt. For example, in the Gulf Coastal region the sedimentary formations have a velocity of 6000 or 7000 ft. per sec., while the velocity of elastic waves in the cap rock of a salt dome may exceed 15,000 ft. per sec. Under such conditions, delineation of the formation is a relatively simple matter, and, furthermore, there is very little opportunity for ambiguous results. Development of Elastic-wave Method The success of this Gulf Coast work immediately suggested the advisability of attempting to extend elastic-wave methods to a point

Jan 1, 1929

By E. C. Harder

The situation in the United States, at the present time, regarding the supply of manganese ores and alloys of manganese is one of great seriousness and is likely to become increasingly so while the European war continues. The two principal iron-manganese alloys, ferromanganese and splegel-eisen, are indispensable in steel manufacture, being used extensively in the Bessemer and open-hearth processes. Spiegeleisen, the lower alloy, contains between 15 and 25 per cent., and ferromanganese, the higher alloy, between 60 and 80 per cent., of manganese. Besides manganese the alloys contain iron and carbon. On the market ferromanganese is usually quoted on the basis of 80 per cent. manganese, and spiegeleisen on the basis of 20 per cent. manganese. The consumption of ferromanganese has been increasing during recent years at the expense of spiegeleisen, because larger quantities of the latter must be used to accomplish the same purpose with the result that the amount of carbon introduced with it into the molten metal is frequently injuriously great. Manganese ore proper, in the form of manganese dioxide, is used extensively in many chemical industries, especially for oxidizing purposes. It is also used for the manufacture of both wet and dry electric cells and in the manufacture of paints and dyes. The manganese ore used in this country has been derived hitherto from three principal sources: Southern Russia, Southern British India and East Central Brazil. The following tables show the quantity of manganese ore imported from these countries, and (for comparison) the domestic production, during 1912, 1913 and 1914. The imported manganese ore has been used largely in the manufacture of iron-manganese alloys and in addition large quantities of the alloys themselves have been imported, chiefly from Great Britain, Germany and other European countries.

Jan 1, 1917

By David White

Attention has been given to the sources and supply of the raw vegetal matter and the conditions of its submission to the process of sedimentation. An original and most valuable review has been made of the more important or significant chemical compounds originally contained in the organic dct,ris, and of the biochemical changes undergone by the latter during deposition. Consideration also has been given to the factors controlling the selective biochemical decomposition, in whole or in part, of this debris, and the deposition, as sediments, of the undecom-posed plant structures and compounds, together with more or less of the so-called "ulmic," or "humic," organic decomposition products in colloidal so1ution. Biochemical Changes End in Peat Formation The biochemical process terminates in the peat stage of coal formation, and with the cessation of this process organic sedimentation is completed. All subsequent changes result from geological causes and conditions. The deposits are in the form of peats of different types, organic muds, oozes, etc. They are essentially uncompressed and are wholly uncon-solidated, and their water content is great, amounting to over 85 per cent, near the surface of the deposit. Many of the chemical compounds remain as in the once living organisms; others are biochemically broken down and new ones formed. Geochemical and Geophysical Changes in Buried Deposits Subsequent Changes " Dynamochemical" The changes which subsequently take place through dehydration, lithification, and simultaneous progressive chemical alteration, by which organic sediments are advanced to brown lignite, subbituminous, bituminous, semianthracitic, and graphitic ranks, are geochemical and geophysical, and the process, which really is metamorphic,2 takes place under dynamic influences. In fact, the essential changes, including loading,

Jan 1, 1925

By Edward A. Capillon

The problem of scrap is probably of greater importance in the pro duction of gold, silver and other precious metal alloys than is the case for base metals and alloys. Remelting of gold and silver scrap in the shop is always a costly process because it involves losses by oxidation of thc base metals in the alloy with a consequent increase in the percentage of precious metal. This is most marked in the case of alloys containing the low-boiling and easily oxidized metals zinc and cadmium. Since it is not generally feasible to assay every shop remelt it follows that the possibilities of lost values arc large. So-called rolled gold and silver plate is made by soldering or welding the precious metal alloys onto base metal. Such plate when defective must be sent to the refinery to recover the gold and silver values, thereby involving additional expense in the form of refining charges. It is obvious therefore that gold and silver alloy scrap is an important item in manufacturing cost and must be reduced to a minimum. The amount of scrap resulting from poor metal will depend on a number of factors in the manufacturing operations, not least among which is the melting and casting practice. The notes which follow are a summary of experiments performed at various times to determine what variables in melting and casting are influential in the production of sound alloys. Metals Used in Alloying Pure gold, that is, gold of 24-kt. value is very much too soft for jewelry purposes and it is therefore always alloyed with other metals to increase its hardness and resistance to wear. For the same reason pure silver is seldom used alone but is alloyed with copper, the standard alloy being sterling silver which contains 92.5 per cent. silver and 7.5 per cent. copper. The metals commonly used for alloying gold are silver, coppcr, nickel and zinc. In addition to hardening the gold and producing alloys of different karat values the use of these metals makes possible the production of gold alloys of various colors such as yellow, red, green and white. The gold-silver-copper alloys vary in color from light greenish-white through green, yellow and red depending on the relative amounts of the three metals. Green or yellowish-green colored golds

Jan 1, 1930

By W. M. Yim

Experimental results are presented which indicate that transverse striations in horizontal zone-leveled Bi-Sb alloy crystals are due to irregular growth rate resulting from thermal fluctuations in the melt (Iring gowth. Thc thermal fluctutations arose from two different sources. The first type was brought about by periodic fluctuations in the furnace temperature. The second type can be attributed to turbulent therrrol conlcclion in the trzelt near the solid-liquid inteyace. Tile arrzplitlcde ond fvequency of the tetiperaticre fluctlrations vesultity from llle lhevnal con1,ecrrell. The striation spacings in Lhe crystals covvelale well with the periodicity 0.f the tempevature flueluatiors. Altliough the strialiors represenl corrlpositiozul inhoiHogeneity oh a rzicroscule, less than f.z cil. be1 S6 in Best's as deterrirzed by electron-pro be chalq'sis, the slriations roerre fbund to ILUL' no rrleusuanble effect on electical vesistirity rwr on weak field macgnetoresistance of. the Bi-Sb a1lu.y in the ternpevutue ),unge 4.Polo 300°K. DURING the course of an investigation on the horizontal growth of semimetals,' it was found that crystals of Bi-Sb alloys contained many closely spaced parallel arrays of striations. These striations occurred perpendicular to the growth direction and parallel to the solid-liquid interface. We shall refer to them as transverse striations, or just striations'', to distinguish them from lineage substructures or longitudinal striations which form parallel to the growth direction and have been known to be associated with cellular structures.' Similar transverse striations have been reported previously to occur in other materials prepared by horizontal growth: metals,4 semiconductors,5 as well as their alls. - Various methods of crystal preparation have apparently little effect on the occurrence of the transverse striations. They form whether the crystals were grown by the vertical Czochralski technique, withe1' or without'3- rotation, or by the horizontal zoning methd.- Thus, the transverse striations are not limited to any one class of materials, nor to any particular method of preparation. It is likely, therefore, that all of the observed transverse striations may have some common cause. Previously, workers agreed that periodic changes in the growth rate bring about the striations. However, no agreement exists as to the origin of the growth-rate fluctuations. Some attributed the discontinuous growth to a purely external cause, such as fluctuations in the furnace temperature, jerky motions in the crystal pulling mechanism, or a nonsymmetrical temperature distribution in the melt (in the case of crystals grown by the Czochralski technique with rtation). Others looked for the cause in some fundamental property of the growth process itself. For instance, a certain degree of supercooling is required to initiate growth from the melt. But, with further growth, the degree of supercooling decreases because of the liberation of the heat of solidification at the solid-liquid interface. Thus, crystal growth would be brought to a halt until sufficient supercooling is resotred and the cycle begins again.3'11 According to this model, periodic fluctuations in the melt temperature should exist at the solid-liquid interface. Since the periodic fluctuations in growth rate would result in changes in the segregation coefficient of solute atoms, crystals containing the transverse striations may, in some cases, show a periodic impurity fluctuation along the length, resulting in a degradation of electrical properties. The resistivity striations in doped germanium'9-10 or lnsbB are well-known examples of this microsegregation. The present work was undertaken to explain the exact origin of the transverse striations, and to assess the extent of their effect on chemical homogeneity as well as on electrical properties of Bi-Sb alloy crystals. Results from our previous study of the crystal growth of Bi-Sb alloys1 indicated that the transverse striations may arise from the temperature fluctuations in the melt during growth. This paper will show that the melt temperature fluctuations are indeed responsible for the occurrence of the transverse striations. I) EXPERIMENTAL Although the transverse striations have been observed in all slow-grown Bi-Sb alloys across the entire compositional range, we selected a composition, Big3Sbs, for the present study in view of the extensive data available on the crystal growth of this alloy from a previous study.' High-purity bismuth and antimony, both a 6-nine grade by the manufacturer's emission spectrographic analysis, were used throughout. Independent mass-spectrographic analysis showed, however, that the starting materials were more nearly a 5-nine grade. each containing metallic impurities of approximately 10 ppm atomic. In zone-leveled Big5Sb5 alloys, the total metallic-impurity content was slightly lower, about 7 ppm atomic, indicating that some degree of purification was achieved during the growth. None of the electrically active impurities, such as tin and lead (acceptors) and tellurium and selenium (donors), were present in significant quantity in undoped Bi95Sb5. Typical analysis of the undoped Bi95Sb5 alloy is shown in Table I. Nonmetallic impurities, such as carbon and oxygen, were detected, sometimes as much as 100 ppm, in both the starting materials and the zone-leveled alloys: but the data were only qualitative. Temperature fluctuations in the melt were monitored over 1 or more days by means of a 5-mil chromel-

Jan 1, 1967

By Akinobu Kasami, Keiji Maeda, Makoto Naito, Masaharu Toyama

Gap electroluminescent diodes have been prepared by the vapor phase diffusion of zinc into n-Gap crystals which were grown from a gallium solution (10 wt pct Gap) doped with tellurium and Ga203. A marked improvement in the efficiency of the red electrolumines -cence has been achieved by heat treatment after diffusion. External quantum efficiencies of diodes annealed under optimum conditions are 0.2 to 0.6 pct at room temperature, or about 200 times higher than the efficiencies of diodes quenched after diffusion. The optimum dopant concentrations in the gallium melt from which the crystals were grown are 3to6 x at. pct Te and 4 to 8 x 10-2 mol pct Ga203. The efficient diodes are characterized by linearly graded junctions with an i-layer 0.1 to 0.2u thick. Annealing increases the emission intensity by a factor of 20 to 50 and decreases the current density to 1/3 to 1/8 that of quenched diodes at a given bias. The decrease in current is attributed to an annihilation of deep recombination centers in the depletion layer. The increase in emission intensity is interpreted in terms of an increase in lifetime of minority carriers and an increase in the relative intensity of red-to-infrared emission. The dependence of these quantities on the tellurium and oxygen doping levels is also discussed. A number of studies have been made of the red light emission from for ward-biased Gap diodes.' At room temperature this emission band is centered at 7OOO? with a spectral width of nearly 1000?. Low-tempera-ture photoluminescence indicates that this emission is due to either the radiative annihilation of an exciton bound to a pair of zinc and oxygen atoms substituting on nearest neighbor lattice sites2,3 or the radiative recombination of an electron bound to this Zn-O pair with a hole bound to an isolated zinc shallow acceptor.3 An emission band is also observed with a spectral peak at 9800?. This infrared emission has been shown to be due to the recombination of an electron trapped at an isolated oxygen deep donor with a hole trapped at an isolated zinc acceptor.4 The red emission from Gap diodes is fairly efficient at room temperature because the nearest neighbor Zn-0 pair forms a deep electron trap at 0.3 to 0.4 ev below the edge of the conduction band.2'4 In diodes grown by liquid epitaxy an external quantum efficiency of 2.1 x 10-2 (photon/electron) has been attained by heat treatment at relatively low temperatures.5 This heat treatment was found to increase the efficiency by a factor of 3 to 6. However, no detailed studies have-been reported on the effects of heat treatment. We can only cite Onton and Lorenz's work6 on the change ; in the relative intensity of red-to-infrared emission. Heat treatment has also been tried on junctions built in during growth, but contrary to expectations the efficiency decreased. In-diffusion is a simple and controllable method of fabricating p-n junctions. For Gap, zinc is generally used to form a p-type layer on n-type crystals. The emission efficiencies of in-diffused diodes are, however, extremely low in comparison with liquid epitaxial diodes.' Although efficiencies as high as 2 x 1O-3 have been reported, values from 10-6 to 10-4 are generally obtained by typical diffusion techniques. Out-diffused diodes are known to be a little more efficient than in-diffused diodes. Nevertheless, the quantum efficiency is at most 7 x 10- 3 and ordinarily of the order of 10-4.8 NO results have been reported on heat treatment of either in-diffused or out-diffused diodes. This paper reports a marked improvement in the efficiency of the red emission observed for in-dif-fused diodes as a result of heat treatment after diffusion. The method described reproducibly yields diodes with external quantum efficiencies of 2 to 6 x 10-3. The observed dependence of efficiency on annealing time and on doping level will be discussed in terms of the lifetime of minority carriers and the formation of Zn-O complex pairs. EXPERIMENTAL A) Diode Fabrication. The n-Gap crystals used in this study were grown from a saturated gallium solution by a slow cooling method.8 The Gap content in the gallium melt was fixed to 10 wt pct corresponding to a growth temperature of about 1100 Tellurium was chosen as the n-type dopant and added to the melt in concentrations ranging from 0.001 to 0.06 at. pct. Oxygen was added in the form of Ga2O3, whose concentration was varied from 0.004 to 0.2 mol pct. The resulting crystals were platelets with well-developed (111) surfaces. Typical electrical properties were Hall mobilities of 130 to 30 sq cm per v-sec and carrier concentrations of 1016 to 10" cm-3 at room temperature. Diodes prepared from crystals with relatively low doping levels, in which u = 130 to 100 sq cm per v-sec and n = 0.6 to 6 x 1017 Cm-3, were examined in detail. The p-n junctions were produced in these n-Gap crystals by the diffusion of zinc from the vapor phase by the following procedure. The platelets were carefully lapped on both sides to a thickness of 150 to 200 u while maintaining the (111) orientation. After being etched in hot aqua regia, the crystals together with the zinc were sealed in an evacuated 12 mm ID quartz ampoule 20 cm long. The crystals and the zinc were then separated from each other at opposite ends

Jan 1, 1970

By M. H. Harris

A solution has been obtained to the problem of calculating flow into a cased and perforated well. Equations describing the idealized system were solved by numerical analysis techniques on a high-speed digital computer. Computer experimentation indicated that the results are within 3 per cent of the exact solution. Computed results are presented as an apparent skin effect, on a series of dimensionless working curves. Productivity ratios can be rapidly calculated from these data for the wide range of wellbore and reservoir properties actually encountered in field practice. Any reasonable vertical unisotropy ratio can be included in the computation. Productivities can be calculated for wells perforated in a regular pattern, a single horizontal plane or a vertical line on one side of the casing. Solutions for asymmetrical perforation patterns can he easily obtained from the working curves. Solutions for flow into sells completed with a horizontal notch are also provided. Results show that productivity can be increased by extending perforation penetration. This is especially true for shallow penetrations. The highest productivity is obtained when perforations are arranged in horizontal planes, as opposed to a vertical line on one side of the casing. Four or five perforations in one plane will approach the maximum productivity. The effect of perforation hole diameter is small, and is rioticeable only in shallow penetrations. INTRODUCTION The perforating method of well completion has been successfully and widely used in most producing areas. In the past, the desired perforation results were achieved by simply shooting numerous large holes in the casing. A perforating scheme for an area, or particular well, was established by evaluating two types of experimental data: the well flow index and the productivity ratio.' 3 The well flow index test is a means of determining the relative flow capacity of perforations in a linear system. This test also gives information on the perforation size, shape and hole damage which can be expected under well-bore conditions. However, relative flow data from this test cannot be accurately tarnsformed into the radial wellbore system. Thus, no true indication of the productive capacity of a perforated well can be obtained from the well flow index test. A well productivity ratio is derived from electrolytic models built to simulate perforated wells. Available productivity ratio data 2,3 are limited in that all important variables are not extensively evaluated. For example, data are limited to well radii of 3 and 6 in., and to maximum perforation penetration of 1 ft. Practically no information is available on the pattern of flow into a perforation. The effect of various perforation patterns on well productivity has not yet been determined and the effect of perforation diameter has not been thoroughly studied. Also, it will be shown that this type of electrolytic model data is probably in error by as much as 10 per cent or more. Modern completion techniques such as limited-entry perforating, single-plane fracturing, steam and hot air injection and chemical consolidation of incompetent formations all rely on injection and/or production from a limited type of completion. These completions may consist of several high-capacity perforations or a horizontal notch which is equivalent to an infinite number of perforations in one plane. Proper design of these new completion techniques requires, in part, accurate estimates of a well's productive capacity. Data on perforated and notched well productivity have been determined in this investigation. Results are presented as a function of the pertinent variables. Equations describing the idealized system were solved by numerical analysis techniques on a high-speed digital computer. DESCRIPTION OF PROBLEM PRACTICAL APPLICATION The computed results can be applied to wells which meet several general specifications. An external drainage radius of the well must be known or assumed, but the well need not be drilled on a regular pattern. The well must be cased and cemented through the entire producing interval. And, the casing must be perforated with one or more horizontal planes of perforations. The perforation pattern itself must conform to three geometrical requirements. 1. The perforations in a plane must divide the plane into equal angular segments (Fig. 1). Four perforations per plane would be 90" apart. 2. Perforations in a plane must be directly above or beneath perforations in adjacent planes. For two shots per plane, perforations would lie in the BB' plane (Fig. 1). 3. Horizontal planes must have equal vertical spacing and be separated from the top and bottom of the formation by one half the spacing interval. Single planes of perforations should be in the middle of the formation. This is shown in Fig. 2 where h is the formation thickness in a single plane conlpletion or the spacnig interval in a multiple plane completion. The spacing interval at the top and bottom of the formation may vary somewhat without causing an appreciable error in the productivity calculation if the formation is reasonably thick and there are many horizontal planes of perforations. A special provision has been made to calculate the productivity ratios of wells with uneven spacing intervals, or for the case where a single plane of perfora-

Jan 1, 1967

By William Rawles

THIS report is the first of a series planned by The Mineral Inquiry, organized by the American Institute of Mining and Metallurgical Engineers to make factual studies of the world's mineral resources in their political and international relations. The efforts of The Inquiry are directed toward filling certain notable gaps in available information, without duplication of many other investigations touching this field which are being conducted by other organizations, public and private. Much of its work is indirect-suggesting topics for study by other individuals and organizations and aiding in their planning and correlation. The present report is designed to show the nationality of the commercial control of mineral resources, in addition to the geographic distribution of production by nation-in other words, the overlapping of political and commercial control. Detailed accuracy cannot be claimed for the figures presented. For some companies division of ownership by nationality has been very difficult to ascertain, as many companies are reluctant to dis-close the extent of their holdings in other corporations, and the impossi-bility of tracing all stock ownership is obvious. Also there are frequent changes in the distribution of stock control. The percentages given rep resent only the participation that has been identified definitely, even though it is known in some cases with fair certainty that larger interests exist, as, for instance, American participation in foreign chromite companies. In bringing together these figures we have had the cordial co-operation of the United States Bureau of Mines, the United States Geologi-cal, Survey, the Mineral Division of the Bureau of Foreign and Domestic Commerce, the Brookings Institution, and of many specialists connected with the mineral industries covered. The report does not cover the entire list of minerals: Coal, although it is one of the most important minerals, was omitted because not more than one or two per cent of the world's production comes from mines that are owned by companies foreign to the countries where the coal is produced. Others, such as gold, are omitted because sufficient data have not yet been accumulated. It is hoped that some of these may be covered in subsequent reports. It is not our purpose here to discuss the significance of the figures sub-mitted, but only to point out the general nature of the problems on which they have a bearing.

Jan 1, 1933

CONTENTS PAGE PEIRCE, CARL-Making Rimmed Steel. Discussed by L. F. Reinartz. H. D. Hibbard, C. L. Kinney, Jr., A. H. Woodward, V. B. Buck, A. L. Feild, J. V. W. Reynders 1 SCHROEDER, F. W., and LARSEN, B. M.-Progress Report of the Effect of the Open-hearth Process on Refractories. Discussed by D. A. Lyon 12 KEATS, J. L., and HERTY, C. H.-Elimination of Metalloids in the Basic Open-hearth Process. Discussed by J. V. W. Reynders 14 Making Rimmed Steel Discussion of paper by CARL PEIRCE, presented at the New York fleeting and issued, as Paper No. 1563-C, with MINING AND METALLURGY, March, 1926. L. F. REINARTZ, Middletown, Ohio.-Mr. Carl Peirce has presented a valuable paper on a subject that has been very widely discussed in recent years, especially since the demand for high finish, deep drawing and other grades of sheet steel in the lower carbon ranges has become an important factor in the steel business. Steel of this analysis has been produced for many years, but the product for which it was made did not require the extra care in the steel plant that it does today. It must now be worked down into thin sheets for special purposes and undergo many severe finishing processes both in the steel mill and in the fabricating plants. Mr. Peirce's paper has outlined in a concise and logical manner the steps which must be taken in manufacturing such steels. The secret of successs is attention to details of well known steel practices. I agree with him that quality steels of this class cannot normally be made out of inferior raw materials. Scrap should be clean and if possible not too variable in analysis. Galvanized scrap or babbit are particularly objectionable. Scrap should be in such physical condition that undue delays are not encountered in charging the furnace. Limestone should preferably contain over 95 per cent. available calcium carbonate, and be free from clay or other foreign substances. Almost universal practice shows that 10 per cent. limestone is required for proper slag volumes to protect the metal from over oxidation. The use of 8 per cent. limestone makes the operation less fool-proof.

Jan 4, 1926

By Albert E. Reed

The development of the modern highspeed vibrating screen, together with the increasing availability of long-lasting stainless-steel screen cloth for relatively fine-mesh separations, means that more screen circuits will be used in the future. It seems pertinent therefore to examine a few characteristics of screen-circuit products, and especially the points of difference as compared with products of classifier circuits. The most noticeable change that takes place when substituting screening for classification in a grinding circuit is a substantial drop in the circulating load, owing to the greater ease with which the "fines" leave the circuit. Where circulating loads of 500 to 600 per cent are considered fairly normal in classifier grinding circuits, the grinding circuit equipped with screens for equivalent work will have a circulating load of only 20 to 75 per cent. As a result, the products of screen circuits will show a minimum of overgrinding or sliming as compared with a classifier circuit. The desirability of this characteristic will naturally vary according to the metallurgical requirement in each case. Because screen separations make a sharper division according to particle size, the products of screen circuits can be expected to show greater crowding of particles near the point of separation. These changes in product characteristics are so important that other factors, both in the grinding and concentration processes must be adjusted if the operator is to take full advantage of the increased tonnages and higher efficiencies available to him through the use of the screen circuit. One factor that too often is overlooked when changing to screen circuits is the importance of adjusting the ball-mill or rod-mill charge, to compensate for: (I) increased tonnage of new feed, (2) decreased circulating load, or (3) more granular character of feed. These same factors should also be taken into consideration for their effect on the various types of concentration or flotation equipment that may follow the screen circuit. Over a period of years, this equipment has generally been designed and adjusted to the product of the classifier, therefore it seems obvious that some research on the adjustment and adaptation of concentrating and flotation equipment to screen-circuit products will be most profitable to the operators. To illustrate the points mentioned above, the results from three recent installations follow, with data on the comparative characteristics of screen and classifier circuits. A range of separation from 10 to 48 mesh has been chosen, using two general types of screening equipment and two types of classifiers. The first of the installations of which the results are to be examined is that of an iron-ore installation where eastern magnetite was being concentrated prior to sintering. Fig. I shows the original grinding circuit, using classification, while Fig. 2 shows the same circuit equipped with a

Jan 1, 1947

By Albert E. Reed

The development of the modern highspeed vibrating screen, together with the increasing availability of long-lasting stainless-steel screen cloth for relatively fine-mesh separations, means that more screen circuits will be used in the future. It seems pertinent therefore to examine a few characteristics of screen-circuit products, and especially the points of difference as compared with products of classifier circuits. The most noticeable change that takes place when substituting screening for classification in a grinding circuit is a substantial drop in the circulating load, owing to the greater ease with which the "fines" leave the circuit. Where circulating loads of 500 to 600 per cent are considered fairly normal in classifier grinding circuits, the grinding circuit equipped with screens for equivalent work will have a circulating load of only 20 to 75 per cent. As a result, the products of screen circuits will show a minimum of overgrinding or sliming as compared with a classifier circuit. The desirability of this characteristic will naturally vary according to the metallurgical requirement in each case. Because screen separations make a sharper division according to particle size, the products of screen circuits can be expected to show greater crowding of particles near the point of separation. These changes in product characteristics are so important that other factors, both in the grinding and concentration processes must be adjusted if the operator is to take full advantage of the increased tonnages and higher efficiencies available to him through the use of the screen circuit. One factor that too often is overlooked when changing to screen circuits is the importance of adjusting the ball-mill or rod-mill charge, to compensate for: (I) increased tonnage of new feed, (2) decreased circulating load, or (3) more granular character of feed. These same factors should also be taken into consideration for their effect on the various types of concentration or flotation equipment that may follow the screen circuit. Over a period of years, this equipment has generally been designed and adjusted to the product of the classifier, therefore it seems obvious that some research on the adjustment and adaptation of concentrating and flotation equipment to screen-circuit products will be most profitable to the operators. To illustrate the points mentioned above, the results from three recent installations follow, with data on the comparative characteristics of screen and classifier circuits. A range of separation from 10 to 48 mesh has been chosen, using two general types of screening equipment and two types of classifiers. The first of the installations of which the results are to be examined is that of an iron-ore installation where eastern magnetite was being concentrated prior to sintering. Fig. I shows the original grinding circuit, using classification, while Fig. 2 shows the same circuit equipped with a

Jan 1, 1947

By W. A. Backofen, D. Lee

The deformation of textured sheet of titanium and several of its all-a (hcp) alloys was investigated with two kinds of experiments: tension testing along different directions in the plane of the sheet, and combined-stress loading along the principal axes of anisotropy (the rolling and transverse directions). Texture and plastic anisotropy were evaluated with pole figures and by measurement, as a function of orientation, of the tensile transverse-strain ratio, or R parameter. The results as a whole can be rationalized qualitatively with the present understanding of deformation mechanisms in titanium. Quantitative agreement between the orientation dependence of tensile yield strength and the Predictions of continuum ANISOTROPY in the properties of engineering materials is more the rule than the exception because anisotropy in structure is so common, and the one generally follows the other. Two broad categories of structural anisotropy are represented by mechanical fibering and crystallographic texture. The former is important in many aspects of fracture.' The latter has more significance for yielding and plastic deformation, theory, using the R measurements, was relatively poor. However, in tension-tension quadrants of the yield-locus diagrams, the difference between theory and experiment was hardly more than 10 pct. The maximum texture-hardening effect was found in a 4Al-1/4O2 alloy to be nearly 50 pct. In the compression-compression quadrant, {1012} deformation twinning prevented the locus from expanding much beyond the Position predicted for isotropic material. With increasing temperature the trend in R was downwards, approaching unity (isotropy) near the a-transus temperature; an accompanying development was large amounts of neck-free extension. which are of special concern in this paper. The tendency has been to view crystallographic texture more as a liability or curio than as an asset. The prominent exception is found in silicon-ferrite sheet for power-transformer cores, which is processed to develop a new optimum texture for high electrical efficiency. Yet it should be possible to find other examples, involving other kinds of properties. More specifically, there is good analytical reason to expect improved combined-stress yielding resistance in suitably textured material,2,3 and it has now been shown by experiment that texture hardening or softening is a potentially useful phenomenon in certain engineering devices and processes.'-I To date, work has included measurements of the transverse (width to thickness) strain ratios in the

Jan 1, 1967