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J. T. LITTLETON, JR., ? Corning, N. Y. (written discussion?).-This. discussion will add little that has not been brought out but will show how the problems encountered in the Corning Glass Works were overcome. The chief points of consideration in any equipment are, first, the work the equipment is called upon to do; second, the installation; and, third, the man who will use it. These three points should determine the type of apparatus adopted. If only rough measurements, merely a little better than the eye, are desired, the cost of the instruments should be considered; but if accurate temperature control is necessary, the cost of the equipment deserves only small consideration. There is no question that the real problem for any factory is the installation, making sure that the elements really give the temperatures desired; also, the instruments must be so designed that any man can use them.

Jan 12, 1919

By H. D. Newell

THERE has been much research and commercial development in recent years in the use of chromium and nickel in steels of various types, including those intended for high-temperature service. By "high-tem-perature steels" are meant those specifically designed for service at ele-vated temperatures in steam plants, oil refineries and other industries where high-temperature operations are conducted. This paper is devoted to some preliminary data on the effect of silicon on certain of the most popular chromium-molybdenum steels now being used in quantity by the refining industry and includes a short statement on the influence of copper in steels intended for high-temperature service.

Jan 1, 1937

By P. G. Meikle, C. T. Holland

The effect of the condition of friction upon the ultimate unit compressive strength as determined between the compressed faces of precisely machined coal specimens and specially prepared testing platens has been examined. Reductions of 30 to 40% in the ultimate unit compressive strength of these model coal pillars have been verified when lubricants areused between the faces as compared to non-lubricated faces. Increase in unit compressive strength due to confinement at each of three levels of friction appears to follow generally the widely accepted "1/2 power law", i.e. S - C (L/T)1/2 where S is the unit ultimate strength, C is a constant dependent on the coal being tested and the coefficient of friction acting at the compression surfaces and L and T are the least width and thickness of the specimen, respectively. Results suggest that the surface condition of both the specimen and platens should be mentioned in detail in conjunction with compression testing, for although the term (L/T)1/2 is adequate for all practical purposes, the coefficient C is directly dependent on the condition of interfacial friction, all else remaining constant. One phase of the investigation of the confining effect of friction on the ultimate unit compressive strength of small coal specimens has recently been completed at the School of Mines of West Virginia University. The efficient control of ground is of fundamental importance to successful mining operations and the design of support pillars has always presented the mining engineer with a difficult and intriguing engineering problem. Since about the turn of the century, many investigators have performed extensive laboratory tests on small coal specimens in efforts to solve some of the perplexing problems of strata control and pillar action in coal mines. A detailed review of this work would serve no purpose here, but a brief mention of the more significant contributions is in order. Muller16 was perhaps the first to illustrate the effect of confining pressure on the strength of coal specimens in compression. His work has recently been more carefully expanded by the experiments of Murrell17 in Great Britain. Rice and Enzian l9 observed that as the size of cubical test specimens increased, the unit compressive strength decreased. These observations were later supplemented by Lawall and Holland, 13 by Greenwald4,5 et a1 at the U. S. Bureau of Mines, by Gaddy3 as well as by Steart,22 Millard15 et a1 and Evans2 et al. Gaddy3 seems to have been first to quantify this relationship with his equation: S = K/vd , where S - ultimate unit compressive strength (psi), K = a constant dependent on the coal, and D =edge dimension (in inches). Holland7 concluded that the strength of coal as affected by lateral dimensions and thickness could be expressed as where K = a coefficient dependent upon the coal, L = least width of pillar (in.) and T = thickness of pillar (in.). Data supplied by this formula have been compared to the estimated stresses in pillars that had been standing for long periods in coal mines and in the cases so far studied the results indicate that the formula predictions are sufficiently accurate for engineering purposes (Holland11 ). This equation therefore is believed to be the simplest and most accurate tool available at the present time for approximating the strength of a coal pillar (over a specified range of L/T) in situ. However, Holland7,9 has indicated that friction between the coal pillars and the top and bottom rock

Jan 1, 1965

By B. H. Mot

Underground water has been one of the greatest problems in sinking mine shafts, sealing existing shafts, and driving headings under streams. In the preparation of a proposed shaft or existing shafts for elimination of water leakage, advances have been brought about through the use of a controlled grouting method. The modern method to divert water from proposed shaft sites is known to us as pre-grouting, and from existing shafts, as controlled pressure grouting. This method involves the solidification of the surface and rock by the injection of a liquid mixture of

Jan 1, 1949

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 A. E. J. Gallagher, W. D. Charles

The chapter is a review of published and unpublished data concerning energy usage and material wear in commercial crushing and grinding operations. Examples are given from practice and factors influencing power and wear are discussed.

Jan 1, 1982

By Guy Borden, Michael J. Rzasa

Laboratory data on bubble point pressures and reservoir volume factors have been correlated as functions of solution gas-oil ratio, calculated gas gravity of the pentanes-and-lighter fraction of the entire fluid, differential residual oil gravity, and reservoir temperatures. INTRODUCTION Several correlations of crude oil properties have appeared in the literature. D. L. Katz4 in 1942 presented five methods of predicting oil shrinkage. these being of decreasing accuracy for decreasing amounts of information available. M. B. Standing- in 1947 published three correlations of laboratory flash vaporization data of California crudes. From values of GOR (gas-oil ratio), gas gravity, liquid gravity, and temperature, his correlations will predict bubble point pressure, formation volumes of bubble point liquids, and two-phase formation volumes. Curtis and Brinkley2 in 1949 presented several correlations. From the gas-oil ratio, an approximation of reservoir volume factor and barrels of condensate recoverable per barrel of reservoir space may be obtained; along with liquid gravity and reservoir temperature, the GOR will allow prediction of bubble point pressure. These last cor- relations seem to be more qualitative than quantitative. Generally, laboratory bottom hole sample tests furnish information on solution gas-oil ratios, residual oil gravities. bubble point pressures, viscosities of oils, liquid shrinkages, and occasionally gas gravities. Each of these data has its own applications and use in reservoir engineering calculations. The particular uses of correlated bottom hole sample data are found in (1 Providing a basis for obtaining estimates of formation crude properties in fields where bottom hole sampling is impractical or impossible. (2) Greatly reducing the time in obtaining the desired information. (3) Determining the applicability of the results from various bottom hole samples to particular field problems. (4) Avoiding, in many cases, the uncertainties of sampling by replacing it with an element over which greater control can be exercised. (5) Permitting use of preliminary field data in application of production procedures before a bottom hole sample can be obtained and analyzed in the laboratory. (6) Serving as a check on data which may appear out of line. (7) Estimating for a particular type crude the appropriate equilibrium constants by working backward from the bubble point pressure. (8) Estimating original or other past history properties of reservoirs that were not sampled in the past. PROCEDURE Application of the published correlations4,6 to Stanolind laboratory data indicated that the general scheme presented by Standing" could give dedrable results if changes were made in parameter positions and scales. The correlation curves were drawn with all the variables having consistent gradations except the temperature increments which were drawn in to best fit the data. The variables from available Stanolind laboratory data are defined below: (1) Gas-oil Ratio: Gas is liberated at reservoir temperature by differential vaporization (or rather by a series of flashes, approaching differential vaporization) and measured at atmospheric pressure and temperature, at which the compressibility factor is assumed to be unity. The oil is the residual liquid remaining after the pressure has been reduced to atmospheric. For the gas-oil ratio both volumes are corrected to standard conditions of 14.7 psia and 60°F. (2) Gas Gravity: It was decided to arbitrarily divide the hydrocarbons of the entire bottom hole sample into pentanes-and-lighter and hex-anes-and-heavier, and use a calculated gas gravity of the pentanes-and-lighter for a correlating variable. (Sample calculation is shown in Table 111.) (3) Liquid Gravity: This is the API gravity of the residual liquid from the differential vaporization. The gravity is measured at room temperature and corrected to 60°F.

Jan 1, 1950

By Kenneth C. Vincent, A. M. Gaudin

In a study1 of the action of amyl xan-thate on chalcocite in water suspension, it was found that if the xanthate is added in relatively large quantity the xanthate group can be accounted for in three forms: (1) as xanthate ion remaining in water, (2) as benzene-soluble cuprous xanthate on the chalcocite, (3) as a benzene-insoluble coating on the chalcocite. Reduction in the amount of xanthate added leads to disappearance of form I then of form 2. With minute quantities of added xanthate, substantially all the reagent is of the "unleachable" kind. Yet this unleach-able xanthate can be dissolved by pyridine to form a soluble cuprous xanthate complex, and it is sufficient in effectiveness to make chalcocite flotable even if insufficient in quantity to form a complete mono-molecular film on the mineral. In that study it was also found that chalcocite abstracts cuprous xanthate from benzene so1ution, in what may (or may not) be a case of molecular adsorption. It seemed desirable, therefore, to study further the "unleachable" xanthate on the chalcocite, and particularly to ascertain whether it is formed as a result of the benzene leach or is actually formed during the conditioning of chalcocite in aqueous xanthate solution. A 'splendid tool to make such studies has recently been perfected; that is, the use of radioactive spies or tracer atoms. With this tool, it was thought possible to answer the problem stated above, but, unfortunately, this did not prove to be true. Answer to the flotation question was clouded by the existence of rapid and selective diffusion of copper atoms in the solid mineral—a phenomenon that was totally unexpected yet remains interesting and perhaps important. Method of Radioactive Spies The method of radioactive spies is discussed in many places. Two convenient references are the article by Evans2 and the book by pollard and Davidson.3 The method was first developed by van Hevesy and paneth in 1013, when only natural radioactive isotopes were available. These isotopes are few in number, and so the method remained limited in scope. Recently the synthesis of over 350 active isotopes of all the known stable chemical elements4 has opened widely expanded possibilities for the method, A fundamental tenet of the method is that a radioactive atom and a nonradio-active atom are exactly alike until disintegration of the radioactive atom. Then, by its sudden death, the spy reveals its location. The relative abundance of spies at various locations makes it possible to ascertain the relative abundance of the corresponding nonradioactive atoms at the same times and locations. A second fundamental tenet of the method of radioactive tracers is that the radioactivity lies in the nucleus of the atom: transfer of radioactivity from one

Jan 1, 1947

By Kenneth C. Vincent, A. M. Gaudin

In a study1 of the action of amyl xan-thate on chalcocite in water suspension, it was found that if the xanthate is added in relatively large quantity the xanthate group can be accounted for in three forms: (1) as xanthate ion remaining in water, (2) as benzene-soluble cuprous xanthate on the chalcocite, (3) as a benzene-insoluble coating on the chalcocite. Reduction in the amount of xanthate added leads to disappearance of form I then of form 2. With minute quantities of added xanthate, substantially all the reagent is of the "unleachable" kind. Yet this unleach-able xanthate can be dissolved by pyridine to form a soluble cuprous xanthate complex, and it is sufficient in effectiveness to make chalcocite flotable even if insufficient in quantity to form a complete mono-molecular film on the mineral. In that study it was also found that chalcocite abstracts cuprous xanthate from benzene so1ution, in what may (or may not) be a case of molecular adsorption. It seemed desirable, therefore, to study further the "unleachable" xanthate on the chalcocite, and particularly to ascertain whether it is formed as a result of the benzene leach or is actually formed during the conditioning of chalcocite in aqueous xanthate solution. A 'splendid tool to make such studies has recently been perfected; that is, the use of radioactive spies or tracer atoms. With this tool, it was thought possible to answer the problem stated above, but, unfortunately, this did not prove to be true. Answer to the flotation question was clouded by the existence of rapid and selective diffusion of copper atoms in the solid mineral—a phenomenon that was totally unexpected yet remains interesting and perhaps important. Method of Radioactive Spies The method of radioactive spies is discussed in many places. Two convenient references are the article by Evans2 and the book by pollard and Davidson.3 The method was first developed by van Hevesy and paneth in 1013, when only natural radioactive isotopes were available. These isotopes are few in number, and so the method remained limited in scope. Recently the synthesis of over 350 active isotopes of all the known stable chemical elements4 has opened widely expanded possibilities for the method, A fundamental tenet of the method is that a radioactive atom and a nonradio-active atom are exactly alike until disintegration of the radioactive atom. Then, by its sudden death, the spy reveals its location. The relative abundance of spies at various locations makes it possible to ascertain the relative abundance of the corresponding nonradioactive atoms at the same times and locations. A second fundamental tenet of the method of radioactive tracers is that the radioactivity lies in the nucleus of the atom: transfer of radioactivity from one

Jan 1, 1947

By G. Bruggeman, K. G. Kreider

Grain boundary dij]usion coefficienls were measured in tungsten between 1400° and 2200° C and can be expressed by the equation sq cm per sec This activation energy confirms some eavlier estimates made .from tungsten sintering experiments. Grain boundary diffusion was found to occur in sub-bozrndavies having -misorientations of less than 10 deg. The actiuation energy for this subboundavy diffusion is equal to that for dijjusion in incoherent grain boundaries with in the limits of error. This is shown to be consistent with the dislocation model of Low-angle boundaries wheve diffusion occlcvs along- the dislocation 'YPipes" comprising -tile boundary. RECENT investigations of the sintering of tungsten powders all report activation energies which are considerably less than the activation energy for tungsten volume diffusion. Kothari' reports a value of 100 * 5 kcal per mole, Hayden and Brophy' obtained 90 kcal per mole, and Vasilos and smith3 found 110.7 kcal per mole from their sintering studies. Since most determinations of the activation energy for volume diffu-sion4-' fall between 120 and 160 kcal per mole (the true value seems most likely to be nearer 150 kcal per mole), the conclusion is drawn that the mass transport leading to densification during sintering is accomplished by grain boundary diffusion. This interpretation is consistent with various diffusion models of the sintering process. 10-12 Vasilos and Smith calculate diffusion coefficients from their data which fit the equation D * 1.36 x 10* exp(-llO,700/HD However, no direct measurements of tungsten grain boundary diffusion have been made. Furthermore, considerable disagreement exists between the directly measured values of tungsten volume diffusion.'-' In order to corroborate the inferred results of the sintering experiments concerning grain boundary diffusion and to provide accurate diffusion data essential to the analysis of the kinetics of creep, oxidation, precipitation, and so forth, the present work was undertaken to measure self-diffusion in single-crystal and polycrystalline tungsten between 1400" and 2200°C. It is within this temperature range that tungsten sintering is done, the re crystallization of tungsten occurs, and the widest application of tungsten as a high-temperature material will probably be made. EXPERIMENTAL PROCEDURE Radioactive WlE5 was produced by irradiating tungstic acid in a neutron flux of 1.2 x 1012 neutrons per sq cm per sec for 36 hr. A 2-week waiting period was allowed for the decay of w"~ also produced by the irradiation. (w"~ has a half-life of 24 hr.) The half-life of the remaining isotope was determined to be 75 days confirming the presence of w lE5 and the absence of any undesired radionuclide. Specimens 4 in. in diam and $ in. thick were cut from polycrystalline swaged tungsten rods (recrystal-lized) and from Linde single-crystal rods. Chemical analyses of these materials appear in Table I. Actually upon closer examination, the single-crystal specimens were found to consist of several subgrains separated primarily by tilt boundaries in which the misor-ientation ranged from 3 to 10 deg. Thus, it was possible to measure boundary diffusion coefficients in these low-angle subboundaries as well as in the incoherent boundaries of the polycrystalline specimens. The two faces of each specimen were ground flat and parallel within 0.0001 in. The radioactive tungstic acid was dissolved in concentrated ammonium hydroxide, placed on the ground flat of the specimen, and evaporated to dryness. The oxide was then reduced in hydrogen at 1000°C resulting in a layer of wlE5 approximately 1 p thick. The diffusion anneals were performed in vacuum in a tantalum resistance furnace. Time at temperature ranged from 10 hr at 1400°C to 2 hr at 2200°C. The penetration profile was determined by measuring the residual activity after successive removal of surface layers by grinding on metallographic polishing paper. Extreme care was exercised to insure that sections were always taken normal to the diffusion direction; this was verified repeatedly by checking that front and back surfaces of the specimen remained parallel. The activity was measured with an end-window Geiger-Mueller counter. The sides and edges of the specimen were well-shielded to eliminate possible effects due to surface diffusion. The weight of the

Jan 1, 1968

By G. Caetani, E. Burt

Jan 1, 1907

By Robert Archer

IT is now well known that the structure of aluminum-silicon alloys can be refined in a rather remarkable manner, with consequent improvement of physical properties, by certain treatments applied to the molten metal shortly before casting. The differences between the treated and the untreated alloys are so marked that special terms are used to distinguish them, the untreated alloys being referred to as "normal" and the treated alloys as "modified." The first practical method of accomplishing this result was that of A. Pacz,1 which consists in treating the molten metal with a, salt flux of which the, active ingredient is sodium fluoride. The result can also be brought about, and in a more economical manner, by the addition of small quantities of metallic sodium (or potassium) to the molten alloy shortly before casting.2 The action of the Pacz flux evidently consists essentially in the production of free sodium by the reaction of sodium fluoride with aluminum. The changing of a normal alloy to a modified alloy is referred to as "modification' and any process for accomplishing this result is a "modifying" process. Modified aluminum-silicon alloys were introduced several years ago, and it has been demonstrated both in the laboratory and in commercial practice that it is no simple matter to produce castings having the maximum or nearly the maximum properties which under favorable circumstances can be obtained. The alloys are rather sensitive to small changes in chemical composition, and the modifying process must be carried out in a very particular manner to obtain the best results. Extensive experimental work has been carried out in the laboratories of the Aluminum Company of America with the object of determining the conditions that must be observed to make these alloys of the greatest possible

Jan 2, 1926

By John Chipman, Carl F. Floe

A year ago the authors published a paper on the solubility of sulphur dioxide in molten copper.l The data in that paper agreed closely with that obtained by previous investigators, which, however, did not agree with the theoretical predictions for solubility of triatomic gases of this type. It has generally been assumed that the reaction of solution is: 6Cu(l) + SO2(g) = Cu2S (in Cu) + 2 Cu2O (in Cu) [I] _ (CU2S)(CU2O)2 K = (Cu)6(Pso2) [2] Neglecting the slight change in copper concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume of gas absorbed, it follows that this volume should be proportional to the cube root of the pressure. It was found that a plot of the volume absorbed versus the cube root of the pressure gave a straight line, but that this line did not pass through the origin. Calculations of the equilibrium constant for the reaction showed that it was fairly constant for pressures above 100 mm. but that actually it approached zero at lower pressures. The conclusion was made therefore that the solubility as determined could not be expressed by Eq. I or by any other simple equation, particularly at low pressures. Other investigators have concluded that the solubility of sulphur dioxide in copper as well as in several copper alloys is more nearly proportional to the square root of the pressure.* Such a conclusion, however, does not satisfactorily account for the results, even when rather complicated mechanisms for the solution are assumed. The highly improbable speculations of Lepp2 and of Schneider and Esch3 based upon hypothetical dissociation pressures of Cu2O and CU2S dissolved in copper illustrate the type of reasoning that has been used to account for the discrepancy. In the discussion of the previous paper, the authors pointed out that the discrepancy might possibly be due to impurities in the copper, although the purest form available was used. Further consideration of the problem suggested that the impurities likely to have the greatest effect on the solubility of so2 in copper were oxygen, sulphur and carbon. Accordingly, further experiments have been made to show the effects of these elements. Experimental Methods The apparatus used for measuring solubility was essentially the same as that shown in the previous paper. However, since it was desired to make measurements at low pressures, a McLeod gauge was added and 6-mm. glass tubing was substituted for the capillary. This increased the "hot volume" considerably but was necessary in order to obtain good vacuums in a reasonable length of time. A mercury diffusion pump was also installed.

Jan 1, 1942

By Carl F. Floe, John Chipman

A year ago the authors published a paper on the solubility of sulphur dioxide in molten copper.l The data in that paper agreed closely with that obtained by previous investigators, which, however, did not agree with the theoretical predictions for solubility of triatomic gases of this type. It has generally been assumed that the reaction of solution is: 6Cu(l) + SO2(g) = Cu2S (in Cu) + 2 Cu2O (in Cu) [I] _ (CU2S)(CU2O)2 K = (Cu)6(Pso2) [2] Neglecting the slight change in copper concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume of gas absorbed, it follows that this volume should be proportional to the cube root of the pressure. It was found that a plot of the volume absorbed versus the cube root of the pressure gave a straight line, but that this line did not pass through the origin. Calculations of the equilibrium constant for the reaction showed that it was fairly constant for pressures above 100 mm. but that actually it approached zero at lower pressures. The conclusion was made therefore that the solubility as determined could not be expressed by Eq. I or by any other simple equation, particularly at low pressures. Other investigators have concluded that the solubility of sulphur dioxide in copper as well as in several copper alloys is more nearly proportional to the square root of the pressure.* Such a conclusion, however, does not satisfactorily account for the results, even when rather complicated mechanisms for the solution are assumed. The highly improbable speculations of Lepp2 and of Schneider and Esch3 based upon hypothetical dissociation pressures of Cu2O and CU2S dissolved in copper illustrate the type of reasoning that has been used to account for the discrepancy. In the discussion of the previous paper, the authors pointed out that the discrepancy might possibly be due to impurities in the copper, although the purest form available was used. Further consideration of the problem suggested that the impurities likely to have the greatest effect on the solubility of so2 in copper were oxygen, sulphur and carbon. Accordingly, further experiments have been made to show the effects of these elements. Experimental Methods The apparatus used for measuring solubility was essentially the same as that shown in the previous paper. However, since it was desired to make measurements at low pressures, a McLeod gauge was added and 6-mm. glass tubing was substituted for the capillary. This increased the "hot volume" considerably but was necessary in order to obtain good vacuums in a reasonable length of time. A mercury diffusion pump was also installed.

Jan 1, 1942

By Benjamin C. Allen

The surface tensions of liquid chromium and manganese were determined by a modification of the dynamic drop-weight method and found to be, respectively, 1700 * 50 and 1100 * 50 dynes per cm at their melting points. Molten drops were formed LITTLE is known about the surface tension of liquid chromium and manganese, even though they are technologically important metals and widely used in steelmaking. In the past, direct determinations have been hampered by their high reactivity on the lower end of a vertically held rod inductively heated under argon. The technique essentially reproduced surface tensions reported for liquid nickel and zirconium using static drop-shape methods. and vapor pressure. In this work, surface tensions were measured by the drop-weight method, using induction heating under argon. EXPERIMENTAL WORK Chemical analyses of rods used are given in Table I. Chromium rods were prepared from iodide-process crystals which had been are-melted, hot-extruded, warm-swaged, and centerless-ground.'

Jan 1, 1964

By T. A. Rickard

The earlier paper (Trans., xx., 463) describing this Victorian mining district, to which the present is supplementary, was mainly confined to the consideration of the "saddle-reefs," as scientifically the most interesting and economically the most important of the

Jan 1, 1893

By Howard Reiss, C. S. Fuller

A theoretical and experimental study has been made of those interactions between holes and electrons which influence the solubilities of donors and acceptors in semiconductors. The major portion of the work concerns the solubility of lithium in silicon doped to varying degrees with boron. This solubility increases with increasing boron content in a manner predicted by theory and exhibits the expected temperature dependence. A qualitative experiment in germanium is described which demonstrates, in accordance with theory, that doping with a donor decreases the solubility of another donor. SEVERAL authors have discussed the possibility that holes and electrons behave like chemical entities and influence the solubilities of ionized impurities, Wagner was the first to invoke this concept in connection with his studies on nonstoichio-metric oxides. He used it again in explaining the solubility of hydrogen in molten binary alloys. In a theoretical paper,' Reiss drew attention to the fact that solutions of impurities in semiconductors

Jan 1, 1957

By M. C. Lavine, H. C. Gatos, R. S. Mroczkowski

The structure of GaAs-Ge heterojunctions prepared by a back-melting process was studied by X-rav diffraction, melallographic, and electron-micro-analyzer techniques. The boundary region between the GaAs and the germanium was found to consist of a four-layered band. A discontinuity between the two inner bands was brought about by solidification occurring simultaneously from the GaAs and the germanium side. The junction material OH either side of the central discotinuity was found to have grown as a single Crystal with the orientation of the parent substrate. It was found essential to determine the GaAs-Ge phase diagram. This was accomplished by a series of alloys containing 0 to 40 wt pet GaAs. Over this range the diagram is a simple eutectic with the eutectic point at 74 wt pet Ge and 845 C. The limiting- solubility of Coils in germanium was found to bc less than 5 wt pet. The Kossel divergent-beam X-ray technique was used to study orientation relationships across the boundary lager. A great deal of effort has been recently expended on the electrical properties of heterojunctions. Little attention, however, has been given to the metallurgical variables which may be of importance in the formation of the junctions. The present work was undertaken to investigate some of the more pertinent metallurgical aspects of interface-alloyed GaAs-Ge heterojunctions. Such parameters as solidification processes, composition gradients, orientation effects, and the accommodation of crystal structures have been the objects of study in this program. EXPERIMENTAL PROCEDURES Phase Diagram. The phase diagram of the GaAs-Ge pseudobinary system was determined by means of cooling curves. A Bridgeman furnace was employed with the center section maintained at 1200°C and the upper section at 800°C. Melts varying from 0 to 40 at. pct in GaAs content were used. Each charge was incapsulated under a two-thirds atmosphere of argon in a carbon-coated quartz tube. Five min in the furnace hot zone provided rapid melting and homogenization. The capsule was then removed to the cooler portion of the furnace. Cooling times were of the order of 3 min. The resulting homogeneous microstructure indicated that equilibrium conditions were obtained by this procedure. Formation of Heterojunctions. Rectangular parallelepiped single-crystal samples were cut with the large faces of either the (l00), (110), or (111) orientation. The remaining four surfaces were also cut to specific orientations to permit accurate relative orientation of the GaAs-Ge pairs. The

Jan 1, 1965

By William P. Blake

In another paper I have described in general the close association of zinc-blende and iron pyrites in the ore-deposits of southwest Wis consin. These two minerals generally occur together at the same horizon, a sheet of one being overlain by a sheet of the other; and also the pyrites is disseminated through the blende to such a degree that the latter is rendered comparatively worthless for the produc tion of spelter. Ordinarily the pyrites, which is mostly the trimetric marcasite variety, occurs in about equal quantity with the blende and is separated by hand-culliug and chipping; but there are large de posits where the ores are so closely mixed that they can neither be separated by culling nor by any mechanical method. The specific gravity of the two minerals is so nearly the same that attempts often made to effect even a partial separation by jigging have proved un. successful. The smelters of zinc-ores in the Mississippi valley will not take ores which carry more than 7 per cent. of iron; and it is therefore necessary to cull the massive ('jack" with great care and at consid erable expense, in order to bring it up to the market-standard of purity. The results of trials to effect a separation of blende and pyrites in other regions have been equally unsatisfactory. The literature of this branch of metallurgy abounds in examples. In Wisconsin efforts have been made in the past to " burn " the mixed ores in heaps, in order to soften or destroy the pyrites, and facilitate its separation from the massive blende. The same method has also been resorted to when galenite is mixed through the substance of the blende, for the purpose of disintegrating the ore, so that it could be separated by jigging. The custom was to pile the ore and the fuel together. As might have been expected, the results were far from satisfactory. As is usual in heap-roast ing, some portions of the ore were overheated and decomposed; zinc was lost by volatilization; the galenite in some portions was

Jan 1, 1894

By R. G. Davies

Above 500°C, where dislocation climb is rate controlling, it is observed that the activation energy for creep is independent of the apblied stress, although it varies from 62 kcal per mol at 15 pct A1 to 73 kcals per mol at 20 pctA1 due to the change in short-range ovdw with composition. Below 500°C, when the nonconservative motion of jogs upon dislocations is thought to be rate controlling, the activation energy is stress dependent. A sudden increase in the creep rate, for which no explanation is availab2e, occurs at the highest stress at all temperatures. CREEP has been the subject of numerous research publications during the past decade with most of the attention focused upon high temperature steady state creep, i.e., above 0.5 TM, where TM is the absolute melting temperature, as it is the most amenable to theory. Many of the proposed theories involve the climb of dislocations out of their slip plane, which allows them to circumvent obstacles or to annihilate dislocations of opposite sign on other slip planes.' For pure metals it is observed that the activation energy for this creep is equal to the activation energy for self diffusion.' The position is much more complicated in alloys as there are many possible microcreep mehanisms, as well as dislocation climb, which could be rate controlling. There has been little systematic investi- gation of alloys, but Weertman (lead and indium base alloys)3 and Lawley, Coll, and Cahn (Fe-A1 alloys)4 suggest a microcreep process as the controlling factor. A Cottrell-Jaswon atmosphere mechanism is proposed for the lead and indium alloys, and a mechanism involving crystallographic order for the Fe-A1 alloys. Lawley et al. showed that the formation of a super-lattice, either of the FeAl or Fe3A1 type. decreased the rate and increased the activation energy for creep. From the measurements of lattice parameters,= resistivity,' magnetic properties,7'8 internal friction: and dilatometry10 the ordered region is thought to commence at -19 at. pct Al. However, a recent investigation by the author indicates a value

Jan 1, 1963