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By R. A. Meussner, C. T. Fujii

Chromium solution in wustite depresses the oxygen activity in a nonideal manner and expands the lattice slightly. Gravimetric measurements of the equilibrium compositions of wustite containing 0.00 to 1.38 wt pct Cr define the oxygen potential (CO2-CO atm) and the limits of the phase field at 1000°C. These data extrapolate to a maximum solubility of 2 wt pct Cr. The lattice parameter data, room-temperature measurements of quenched samples, differ significantly from those in the literature. Both pure and chromium wus-tites contract at uniform and equal rates as the oxygen content (metal deficit) increases. The a. US metal deficit relationships are straight lines showing none of the curvature previously reported. At constant metal deficit, the a. expands by 0.002? on alloying with 0.4 to 0.5 wt pct Cr but is insensitive to further chromium additions: a small expansion rather than a marked contraction. These results require a modification of the accepted alloying mechanism. IN the high-temperature oxidation of Fe-Cr alloys in Ha-H,and CO2-CO atmospheres the vapor transfer of oxygen from the continuous wustite outer scale to the porous inner scale/alloy interface sustains the high oxidation rates.1"3 The driving force for this transport is the difference in the oxygen activity of the outer wustite and that at the inner scale/alloy interface. In pure CO2, as well as in CO2-CO atmospheres, carburization of the alloy accompanies this oxidation. Current efforts to evaluate the parameters controlling this carburization have shown that the process is not simple; i.e., the carbon concentration in the alloy initially increases rapidly, reaches a maximum, and then decreases slowly as the oxidation time is extended. This is the same pattern reported by McCoy for the more complex oxidation-carburization of stainless steels and an Fe-Cr alloy in CO2 at lower temperatures.4 These changes in the carburization process occur while the overall oxidation rate and the lattice parameters of the scale layers remain constant. If this invariance of the lattice parameter is assumed to indicate a constant scale composition and thus a constant oxygen potential, the carburization results are not easily explained. Electron microprobe traces across the thickness of these outer scales, however, have revealed distinct chromium gradients penetrating 10 to 50 µ from the inner surface where the chromium concentrations were estimated at a few tenths percent. The variation of the chromium cmcentration on the inner surface of the scale, and the resulting change of the oxygen activity, during the oxidation process is considered to be important in defining the carburization process. Thus, to gain an understanding of the complex oxidation-carburization proc- ess, it was necessary to measure the properties of wustite containing known amounts of chromium (chromium wustite). Although the general features of the Fe-Cr-0 equilibrium diagram between 900° and 1300°C have been fairly well established by Richards and white: Wood-house and White,6 Seybolt,7 and Katsura and Muan,8 there have been no detailed studies of the limits of the chromium wustite phase field or the properties of these alloyed wustites. The recent results of a limited study of chromium wustite by Levin and wagner9 indicate that more than 0.67 wt pct Cr is soluble in wustite above 850°C and that this alloying is accompanied by a substantial lattice contraction. This change in the lattice parameter was not evident in the X-ray diffraction patterns of wustite layers from the oxidation experiments;1,3 the lines were sharp even though a chromium gradient existed in the scale. The present paper describes gravimetric equilibrium experiments which delineate the boundaries of the chromium wustite single-phase field at 1000°C and define the changes in the oxygen activity and the lattice parameter of wustite as functions of chromium and oxygen contents. The lattice parameter data of chromium wustite obtained from these equilibrium and special quenching experiments differ considerably from those reported.9 Those for pure wustite show significant differences from the widely accepted data of Jette and Foote.10 Since the causes of these differences are not easily assignable, and since the literature contains many sets of data on wustite which if not in conflict are at best not in harmony, the experimental procedures are discussed in the present paper. EXPERIMENTAL Oxide Preparation. The specimens used in these studies were porous pellets compacted from high-purity (Fe,Cr)2O3 or Fe2O3 powders. These powders were prepared from electrolytic chromium (99.8 pct purity) and electrolytic iron purified by consumable-electrode, vacuum arc-melting processing (299.9 pct purity).11 The oxides were produced by standard analytical procedures: solution of the metals in acids (HC1, then HNO3 added), coprecipitation of the hydroxides (NHaOH), and filtering and washing these precipitates. Initial dehydration of the coprecipitated hydroxides was done in a porcelain evaporating dish heated by a Meker-type burner, final dehydration by firing in a recrystallized alumina crucible at 1000" to 1050°C for 20 hr in an electrically heated furnace. Spectrographic analysis detected the following impurities: silicon, 0.01 pct or less; aluminum, 0.001 pct to trace; manganese and copper, 0.0001 pct to none. Each of these levels is at least one order of magnitude lower than in commercially available CP grade ferric and chromic oxides. Fluorescence analy-

Jan 1, 1969

By Charles Hart

THE-report of the advisory committee to the U. S. Bureau of Mines, on the use of oxygen in metallurgy, brings to the art of steelmaking a radical change in the method of operation of the many processes of this widely diversified industry. When completed, the improvements suggested by the use of oxygen will be far-reaching and revolutionary. As to its effect upon the iron blast furnace, the use of oxygen should be as important as any of the improvements in the art of iron smelting and should take its place beside the German "Hochofen" which was the first attempt to use a shaft for preheating the stock, and beside the hot-blast stove which heated the blast before entering the furnace. The former initially produced molten iron and the latter made unbelievable economies in fuel consumption. It would seem that a discussion of this paper would be best served by following the conclusions on page 17 of the report and analyzing them seriatim. 1. (a) A decrease in costs, due to higher smelting heats is only attainable by taking full advantage of these heat units. This is affected by, adding additional ore to the burden which in turn increases production and yields a larger tonnage upon which to figure costs. These economies appear in decreased cost per ton of iron for coke and limestone consumed, and a proportionate reduction in all items entering the cost above materials. We can take no exception to these. premises. It is a well-known fact that silicon in the iron and sulfur removed" are the result of hearth temperature, other matters remaining constant. To a practical furnaceman the most satisfactory manner of controlling a furnace is by increasing the burden. It is not necessary, therefore, to consider the question of refractories, for this discussion presupposes that the temperatures in the furnaces will be kept practically where they now stand for making the various grades of iron. The same situation obtains in regard to the height of the furnace, which, as intimated, was one of the great strides forward in this art, and its abandonment at this time, is inconceivable. The shaft prepares the stock so that at each succeeding step we have exactly the proper conditions. All the stock entering the furnace is dried and preheated. The limestone is calcined by sensible heat practically at no cost, for this is sensible heat which otherwise would pass from the top with the gases. Under normal conditions, external calcination has been attempted without tangible results. Under normal average furnace operation, limestone requires about 760 B.t.u. for calcination and the loss of sensible

Jan 11, 1924

By George R. Ensminger, E. Heaton Hemingway

During the past year, the Watertown Arsenal has been interested in the occluded gas and oxide content of certain ordnance steels in order to determine, if possible, whether some of the peculiar failures in their physical properties might not be traced to these causes. For the purpose of best accomplishing a study of this nature, it was decided to heat the various samples of steel in a vacuum for definite periods of time at high temperatures and carefully examine the quantity and composition of the gases evolved. By the use of a fused quartz tube fitted with a water-cooled, ground-glass stopper, it was possible to maintain a vacuum at a temperature of 1000" C. for 10 hr. without perceptible leakage being evidenced as measured by a McLeod gage. The silica tube was connected with an evacuating system so constructed that the volatilized gases could be removed from time to time and a low vacuum of 0.0002 to 0.0010 mm. of mercury continuously maintained. At no time during the period of heating or in the removal of the gases did the evacuated system come in contact with rubber stoppers or any rubber connections, making contamination from such a source, impossible. In other words, the only volatile products that could be: obtained must necessarily have come from the steel itself or from the glass and fused quartz system or from the mercury used as a sealing agent. In the carlier experiments, the steel treated was in the form of turnings, but this practice was discarded because the weight's of the turnings before and after being heated were widely inconsistent,, even when taken from the same piece of steel. This discrepancy developed largely through variation in the amount of metal volatilized with the gases; this metal could always be seen in the form of a ring where it condensed in the cooler portion of the tube in either the amorphous or crystalline condition. Because of the frequency in occurrence and the variation in the manner of deposition, this material was roughly analyzed and found to consist for the most part of iron. At the same time two samples of steel that had been

Jan 1, 1922

By E. Heaton Hemingway, George R. Ensminger

During the past year, the Watertown Arsenal has been interested in the occluded gas and oxide content of certain ordnance steels in order to determine, if possible, whether some of the peculiar failures in their physical properties might not be traced to these causes. For the purpose of best accomplishing a study of this nature, it was decided to heat the various samples of steel in a vacuum for definite periods of time at high temperatures and carefully examine the quantity and composition of the gases evolved. By the use of a fused quartz tube fitted with a water-cooled, ground-glass stopper, it was possible to maintain a vacuum at a temperature of 1000" C. for 10 hr. without perceptible leakage being evidenced as measured by a McLeod gage. The silica tube was connected with an evacuating system so constructed that the volatilized gases could be removed from time to time and a low vacuum of 0.0002 to 0.0010 mm. of mercury continuously maintained. At no time during the period of heating or in the removal of the gases did the evacuated system come in contact with rubber stoppers or any rubber connections, making contamination from such a source, impossible. In other words, the only volatile products that could be: obtained must necessarily have come from the steel itself or from the glass and fused quartz system or from the mercury used as a sealing agent. In the carlier experiments, the steel treated was in the form of turnings, but this practice was discarded because the weight's of the turnings before and after being heated were widely inconsistent,, even when taken from the same piece of steel. This discrepancy developed largely through variation in the amount of metal volatilized with the gases; this metal could always be seen in the form of a ring where it condensed in the cooler portion of the tube in either the amorphous or crystalline condition. Because of the frequency in occurrence and the variation in the manner of deposition, this material was roughly analyzed and found to consist for the most part of iron. At the same time two samples of steel that had been

Jan 1, 1922

By P. J. Jacquard, C. Jain

Interpreting pressure measurements is one of the fundamental problems in the operation of oil reservoirs. The principal methods and means of study zuhich are currently used are reviewed. Emphasis is placed on the necessity of improving the quality of the information to turn it to the best possible account. One of the important aspects of the problem is the development of a system of automatic interpretation of the pressure measurements. The proposed method aims at this objective: starting from the relation which exists between a local perturbation of permeability and its effect on the velocity potentials in the wells, we determine by successive approximation the modifications to be made to the permeability map by fitting the least squares between the measured pressures and the pressures indicated by the mathematical model. The method has already been successfully employed in the case of heterogeneous reservoirs of radial- circular symmetry. Its application is extended here to the two-dimensional case, and is illustrated by two examples, for which the results are presented. The conditions required for the method to become fully operational are likewise analyzed. I — INTRODUCTION One of the basic problems of production and recovery from oil fields is interpreting pressure measurements made in wells in the single-fluid-phase regime. Simplifying assumptions, for example supposing the reservoir to be homogeneous, make it possible to use more or less simple methods which permit the estimation, from these pressure measurements, of a mean value of the permeability around the wells. Considering the actual heterogeneity of the majority of reservoirs, and the phenomena of interference between wells, these methods are only indicative. Much has been published on the studies of different cases of comparatively simple heterogeneity: some have discussed the radial heterogeneity around a single wel1,l or vertical heterogeneity.2 The results of these works have shown the influence of variations of permeability on the pressure, but unfortunately they are not very useful in practice because they all are concerned with the phenomena around a single well, without interference between wells, and they correspond to relatively simple and theoretical schemes. These studies of reservoirs or parts of reservoirs on a larger scale are made by the electric analyzer or digital model. We define a permeability map and a porosity map, then reproduce the production history of the wells on the wells of the model, and note the corresponding pressures. These pressures are then compared with actuality, and the discrepancies observed are analyzed. From this analysis we deduce the modifications to be made to the maps of permeability and porosity, and repeat until the coincidence between the pressures indicated by the model and the actually observed pressures is considered adequate. We have adjusted the model. Obviously, in this method of investigation, everything depends on the formula which permits the modification of the permeability to approach the adjustment. Considering the complicated nature of the problem, some oversimplified formulas are poorly adapted to reaching a good adjustment. For example, we have shown that the elementary operation of increasing the permeability not far from a producing well to compensate for too low pressures in the well can, in certain cases, express itself by an effect exactly opposite. 3 The project described here is for a system where we begin with the pressure measurements and the several known parameters of the reservoir, and develop the most probable permeability map, taking account of the measurements available and a subdivision of the reservoir fixed a priori. Ideally, this system is conceived as one in which no manual intervention would be necessary. The model simulating the reservoir is only one part of the whole system, and it is neither the longest nor the most complex part. The need to integrate the model into an aggregate of much more extensive processes has led to the adoption of the digital solution, even though a solution combining the digital and the analog is perfectly conceivable. The simulating model is in that case no more

Jan 1, 1966

By Henry A. Wriedt, John Chipman

Equilibrium in the reaction of hydrogen gas with oxygen in liquid nickel, iron, and their alloys has been studied at temperatures of 1500° to 1700°C. The equilibrium con^stant, 0/p, [% O], is greater in nickel then in iron by a factor of 45 at 1594 C. In the alloy steel range, the activity coefficient of oxygen is slightly increased by the presence of nickel. NICKEL is more resistant to oxidation than is iron, in both the solid and the liquid state. The solubility of oxygen,' however, is greater in nickel than in iron. The two metals and their liquid alloys constitute an interesting series of solvents in which the chemical behavior of oxygen can be studied by methods similar to those used for liquid iron.' Experimental Method The furnace assembly, including the tube for preheating the entrant gas, was the same as that described by Gokcen and Chipman. " controlled mixture of water vapor, hydrogen, and argon preheated to approximately the melt temperature impinged upon the surface of the liquid metal. The charge, weighing about 35 g, was held in an alumina crucible at constant temperature in the gas stream for a prolonged period, then quenched in a stream of cold helium, sampled, and analyzed for oxygen by the vacuum fusion method. The temperature of the liquid metal was measured by a Leeds and Northrup optical pyrometer which had been checked against a similar instrument certified by the National Bureau of Standards. The freezing point of electrolytic iron in hydrogen, taken as 153j°C, was used for frequent checks. This point and the emissivity determined by Dastur and Gokcen" established the transmissivity of the optical system. The emissivities of Fe-Ni alloys at 1535" are known from the experiments of Smith and Chipman,h nd it was assumed that the variation with temperature is parallel with that of iron. Recorded temperatures are probably accurate within k5"C. Preparation of Gas Mixtures—Since the ratio H,O:H, had to be much higher for nickel than for iron, it was found convenient to construct two separate systems for gas preparation. In both cases, the ratio of argon to the sum of the other two gases was at least 4, the proportion of hydrogen and water vapor being varied to produce H,O:H, ratios from 0.2 to 70. The primary purpose of the argon was to diminish the errors caused by thermal separation' in the gas phase. In addition, its presence lowered the saturation temperature required for a given H,O:H, ratio and minimized the difficulty of preventing condensation. Both systems were modifications of the one used by Dastur and Chipman.' For H,O:HI ratios greater than 2, welding-grade argon purified by passage over magnesium chips at 620°C was mixed with hydrogen produced in the electrolytic cell shown in Fig. 1. The design was based on a cell used by Bodenstein and Pohl," the important features of which area nickel wire cathode and sodium hydroxide solution as the electrolyte. The rate of hydrogen evolution was controlled by a calibrated ammeter and a rheostat in the circuit, the current efficiency being taken as 100 pct. Precise control of the argon flow rate at about 300 ml per min was achieved by means of a capillary flowmeter having a controlled pressure drop. The molar flow rate was measured volumetrically before each run, and a constant flowmeter setting was maintained thereafter. The A-H, mixture passed through a water saturator of the type previously described," the saturation temperature being maintained automatically with a fluctuation of k0.04"C. The tube between saturator and furnace was heated by a resistance winding. The system was of all Pyrex construction with the exception of the stainless steel tube containing magnesium chips. This was connected with the glass tubing at the upstream end by

Jan 1, 1957

By E. T. Knight, John D. Gill

IN ITS capacity for service to the public the oil industry is truly gargantuan. But it is only in this respect that the industry is the voracious, many-headed, many-armed and many-handed creature it has been so often painted by those who know it not too intimately and only from the outside. Contrasted sharply with the immensity of the service rendered is the relatively modest share of the national income which has gone to those who provided the tools and the mental and manual labor with which the service was performed. No doubt the relative meagreness of the re- ward was the result of a combination of fortuitous circumstances respecting the nature and accessibility of the industry's raw material and the extensive development and application of the most advanced technology, spurred by an intense competition.

Jan 1, 1940

Through the generosity of Sir Robert Hadfield, Honorary Member, the Directors of the American Institute of Mining Engineers are enabled to announce the Hadfield Research Prize of $1,000 for the best contribution to the publications of the Institute upon the general subject of The Different Forms and Combinations of Carbon with Iron, including those in Iron Alloys. The prize will be awarded at the Annual Meeting of the Institute in February, 1916, to the best paper upon this subject which is presented to the Institute before Nov. 1, 1915, provided such paper is deemed worthy by the Institute's Iron and Steel Committee. The following suggestions are also added for the guidance of those who may take part in this research. While' it is not desired to define closely the exact lines or scope of the proposed research, as it is advisable to make these as broad as possible, the object in mind maybe said to be generally as follows: To elaborate and find out the best methods of determining the forms of carbon in steel or iron, including those in iron alloys. A portion of the work would probably be a continuation of the researches which have in the past been carried out by Jullien, Abel, Muller, Ledebur, T. Sterry Hunt, Akerman, Arnold, Stead, E. D. Campbell, Hogg, Parry, Upton, and others. In a generic way, metallurgists now speak of carbides, sub-carbides, double carbides, special carbides, and other combinations. It is very desirable that these should be accurately defined and understood. It is also desirable to know whether there are other or new forms; if so, can these be separated and their characteristics obtained. It may be interesting to point out that the carbon compounds now definitely known are stated to number over 80,000. It is very probable, therefore, that there is room for much valuable and useful research to be carried out with the object of increasing our knowledge of the various combinations of carbon with iron, as probably some of these are still unknown

Jan 5, 1914

By L. W. Legerwood

During the past three decades, the oil industry has expended increasing eflorts seeking improved drilling tools or systems to reduce drilling costs. The total cost of these efforts is unknown, but it certainly amounts 10 tens of millions of dollars. Most of the "new" system that past and present investigators have sought to develop actually are old public information. In seeking to implement new-systern concepts, investigators have tested the following: impact at frequencies ranging from 6 to 300 cycles per second; electrical, mechanical and hydraulic meam of actuating percussors; bit rotary speeds up to 2,000 rpm; electric and hydraulic bottom-hole means of rotating bits; bottom-hole machines with power outputs up to 400 hp; shock waves; explosives; high-velocity pellets; flame; arc; grinding wheels; abrasive jets; erosion by high-velocity gases; chemical attack; electric current; magnetic waves; retractable rock bits; reelable drill pipe; continuous coring with reverse circulation; and automation of drilling rigs. Table I shows how these investigations are grouped for discussion purposes in this paper. In spite of these efforts to discover new and improved systems, rotary drilling main;aim its economic leadership. Undoubtedly, rotary drilling costs will continue to be reduced by rigid application of the best available technology and by development of new rotary technology. In view of the extensive past development programs, however, significant long-range improvement appears to be a research, not a development problem. Research must postulate and prove theories and principles governing variour subsurface rock-failure processes pertinent to both rotary and new systems. Ah, research must produce physical and engineering data relative to these processes. When such information is available, earth boring will graduate from an art to a science. Major improvements in rotary drilling can then be expected, and the systematic evolution of an improved drilling method can be initiated—with a strong probability for success. Development of drilling methods other than rotary drilling has been one approach investigated by the industry as a means for reducing drilling costs. Major cost-reduction efforts, however, have been centered on engineering development work aimed at incremental improvements in rotary drilling. A relatively minor effort has been expended to establish basic physical principles and engineering data pertaining to the earth-boring process which can serve as a foundation for the development of cost-cutting drilling hardware. Current oil-industry economic trends have added impetus to the need for effective programs to reduce drilling costs. However, areas for expanded future efforts should be selected only after careful study of past investigations. It is the purpose of this paper to review past and Dresent industry efforts to develop new drilling tools or systems and to suggest areas where additional science is needed. Past reviews of drilling methods have been limited to a few processes prominent at the time the reviews were made. This paper seeks to present a concise, well organized review of all methods that have received actual development or test work. The preparation of a paper seeking to review all past developments is fraught with many difficulties, not the least of which are errors in or obsolesence of printed matter used as source material and the lack of data on industry developments which have not been published. Since de-

The following is an incomplete list of members and guests who called at Institute headquarters during the period Dec. 10, 1918 to Jan. 10, 1919. P. G. Bandy, Mexico City. Wm. B. McKinley, Yonkers, N. Y. Bennett R. Bates, Berkeley, Cal. Captain C. E. McQuigg, Conn. William T. Bates, Mascot, Tenn. Lt. H. G. Mathews, Cal. Lt. Don C. Billick, Alturas, Cal. Lt. M. S. Mazany, Mich. L. E. Booth, Watertown, Mass. Ralph A. Meyer, Hill City, S. D. J. T. Boyd, Denver, Colo. C. F. Moore, Boston, Mass. J. R. Buchanan, Pasadena, Cal. H. W. Nichols, Chicago, Ill. Ensign G. M. Burke. R. B. Olsen, Mays Landing, N. J. Captain E. H. Clausen. M. L. O'Neale, Gouverneur, N. Y. F. L. Cole, Manila; P. I. F. W. Osborn, New York, N. Y. Joules Cousin. Lt. Fred S. Porter, Alaska. A. Faison Dixon, Washington, D. C. G. M. Richards, Palmerton, Pa. James T. Dixon, London, England. T. C. Roberts, E. Orange, N. J. Everett Drennen, Elkins, W. Va. W. E. Ruder, Schenectady, N. Y. F. Eichelberger, Helena, Mont. Ensign W. A. RuKeyser, Boston. R. B. Eldredge, Colorado Springs, Colo. A. H. Sawyer, Boston, Mass W. F. Ferrier, Ottawa. Lt. D. F. Schindler, New York. Martin Fishback, Benson, Ariz. L. G. Sparks, Greenshurg, Kan. T. E. Fisher, Dover, N. J. W. H. Staver, New York N. Y. D. C. Gilbert, Ft. Wayne, Ind. Douglas B. Sterrett, St. Cyr, Canada. Lt. Lauriston B. Herr, Cuba. Warren D. Thompson. G. S. Holmquist, Washington, D. C. Enrique Touceda, Albany, N. Y. Lt. E. Ross Housholder, Ohio. Mathew van Siclen. Hugh C. Ingle, Santa Rosa, Cal. Flying Cadet Christian Vrang, Cal. Lt. M. W. Kishman, Ariz. L. G. Weeks, Bisbee, Ariz. Hugo E. Koch, Watertown, Mass. C. E. Wheelock, Mogollon, N. M. H. M. LaFollette, LaFollette, Tenn. Major A. E. White, Washington, D. C. Clinton R. Lewis, Dawson, Y. T. Lt. J. L. White, Humboldt, Ariz. The Secretary of the Institute has received with sincere appreciation a Christmas card extending the season's greetings from the officers' mess of the 3d Tunnelling Company, Canadian Engineers, B. E. F., France, and takes this means of reciprocating to these officers and men of the company the best wishes of the members of the Board of Directors. Charles E. Addams has removed from Ray, Ariz., to Phoenix, Ariz., where he is chairman and director of the Arizona State Council of Defense.

Jan 2, 1919

By Arnold S. Epstein

Tlze green electroluminescence occurring at liquid-nitvogen temperature in epitaxial gallium phosphide diodes is exarnined using the donor dopants silicon and sulfur. Zinc is used as the p-type diffusant. Two tt~ain peaks are found, namely til 0.56 and 0.535 p. The intensity of the gYeen peak occurring at 0.56 is found to oary as -4"' wlzere Jf is the forward current density and to first order appears to be dependent on the concet~tvation of ionized donovs. Tile vadintive lifetinze fov this process is -10-'sec. The intensity of the 0.56-p lu~ninescence is nt least several ovdevs of magnitude greate,, at liquid-nitvogen temperature than that noted jor the 0.538 radiation for current densities up to about 35 amp per sq cm. The variation oj- the intensity of. the 0.538-p peak with current density caries according to the donor dopant. With sulfur as the donor one has a J12 dependence, whereas when silicon is the donov a J1.5 dependence is noted. Tl~e above can be fitted to a In molecular process (in first order) such as a band to band recombination. The constant B fir band to band vecombination) is found from our experitt~etlt to be of the order of 2 CZI cm per sec, zcl~ereas for tlze impurity vecombination peak (0.56 p]) tile A cotzstor~t is of the order of. 7 x 10-' cu cm per sec. The structuve o/. the diodes at liquid-nitvog-en tett~peruture is oj tlze double injection type, and by carefi~lly selecting. the thickness of the structure one can regulate the onset of the 0.538-p radiation. The diode clzavaclevistics follow an I-Vx laiv where x is >1. Llregatiue resistance in these structures con be correlated with saturation of tlze 0.56- peak. ThE development of high-purity, large single crystals of epitaxially grown gallium phosphide is the ultimate aim of the studies to be reported. While a number of papers and reviews' have been presented on properties of gallium phosphide grown from gallium solution and from the melt, less attention has been paid to the properties of epitaxial gallium phosphide grown from the vapor. In the studies to be reported we have examined the effects of shallow donor impurities, primarily silicon and sulfur, at liquid-nitrogen temperature, on both the electrical and green electroluminescent properties of carefully characterized single-crystal epitaxial Gap. I) EXPERIMENTAL PROCEDURES A) Material Preparation and Properties. The samules used in this investigation were single-crystal n-type epitaxial gallium phosphide. he single crystals were synthesized from the elements by vapor transport and epitaxial deposition on single-crystal gallium arsenide substrates. Typical transport agents used were chlorides. The growth procedures are described in more detail in Ref. 2. The samples were grown in the (111) orientation and had thicknesses up to 480 . Following the growth, the GaAs substrate was removed from the epitaxial Gap by etching in nitric acid. The Hall effect and resistivity of these n-type samples were measured as a function of temperature and analyzed for impurity content and compared with spectroscopic emission analysis. The results are given in greater detail in Ref. 3 but a summary is noted in Table I. In Table I, AED denotes the donor ionization energy, Nd is the donor impurity concentration, lvA is the acceptor impurity concentration, NI is the total impurity concentration, Rip vs temperature is the measured Hall mobility-temperature relationship from liquid nitrogen to about 400"K, n(77"K) is the measured carrier concentration at liquid nitrogen, and R/p(77'~) is the measured Hall mobility at liquid nitrogen. Good agreement is noted between electrical and emission analysis for the major donor impurity, silicon, in the two materials where it is a major constituent. In the case of the two samples SC90-6 and AP138-3(111) B which were sulfur-doped the ionization energy found from the electrical data is in good agreement with that reported for sulfur.4 The acceptor impurities are not known, although from the presence of magnesium in the samples as indicated by emission analysis and its known role as an acceptor in GaP,4 magnesium could be present as an acceptor. Similarly, since silicon is known to be an amphoteric impurity4 it may also be present as an acceptor in the Gap.* The *A small band has been noted at 0.625 11 in samples SC90-6, SC76-4, and SC77-4, suggesting according to Ref. 5 that sillcon could be present as an acceptor In these samples since these authors have found this peak to represent a donor-silicon emission. presence of calcium deduced from emission analysis is not correlatable with the electrical analysis and its presence as an electrically active impurity should be questioned. B) Sample Preparation and Diode Fabrication. The original slices were of the order of 2 sq cm in area witi the (111)B face up. The material was cleaved and sectioned and the best pieces selected (i.e., those which visually appeared to have the least strain and defects). The samples were polished, lightly etched, and cleaned in trichloroethylene. Zinc was diffused in a closed tube at 800°C to form a p-n junction. Diodes were made from these samples. The depth of junction varied, but did not exceed 10 p depth. The back side of the slice was lapped back and a low-resistance n-type contact was formed (at 600°C in forming gas) to an Au-Mo tab with a hole in the middle for

Jan 1, 1968

By A. N. Holden, J. H. Hollomon

A. H. COTTRELL* and A. T. * Dept. of Metallurgy, Birmingham Univ., England. CHURCHMAN*—We have been making some experiments recently very similar to those reported by Messrs. Holden and Holloman. Wires of Armco iron, 0.077 in. diam. were decarburized in wet hydrogen until the yield point was removed; they were then extended 31/4 pct and annealed at 880°C for 120 hr in dry hydrogen. This process produced large crystals which extended through the cross-section and were about 3/4 in. in length. Since the length of each crystal

Jan 1, 1950

By G. S. Cole, G. F. Bolling

A series of Al-Cu alloys has been cast from constant superheat to solidify either with a hot top or with a free liquid/air interface. All the other variables which affect relative fluid motions were kept constant except the imposition of slow rotations m oscillations of the mold. Depending upon the exact circumstances, evi-dence could be found for the nucleation of equiaxed grains from dendrite bits detached from the columnar zone, or from the free surface, or from solid bits induced at pouring; a special experiment showed the solute buildup during ingot solidification and by inference the reality of constitutional supercooling. All methods of grain nucleation are thus supported. When solidification is arranged in a static mold the columnar- to-equiaxed transition occurs by one of these nucleation paths, subject to the natural decay of temperature gradients which promotes nucleation or the survival of nuclei. But when solidification is forced under special fluid flows it may display odd transitions. In one of these the equiaxed zone is synihesized from. dendrite bits detached from the solid/liquid interface. These survive under the concurrent lowering of temperature gradients and eventually cause transition by impeding columnar growth. GRAIN structure control is desired because real experience shows that specific properties are associated with specific cast grain structures. But since control is thus a matter of need and does not require understanding, much of casting remains art. For example, the manipulation of relative fluid motions in simple ingots provides a control of grain structure development,1-4 but theoretical insight is not required in order to broaden its potential applicability. Fortunately, however, once a variable like fluid flow is recognized it can also provide paths toward new insight. New observations using this variable have provided an insight which is curious. All the theories or descriptions of the columnar-to-equiaxed transition (CET) seem to be supported as long as the appropriate experiment is carried out. In order to develop this idea, let us ignore segregation, the chill zone (until a later section of this paper), and the origin and development of the columnar zone.= The details of questioning how equiaxed material forms in a casting may be divided in two. The first part is simply a questioning of the origin for equi-axed grains: are there fresh nuclei from heterogeneous nucleation, or dendrite bits broken off or melted from the columnar zone or elsewhere,6 or other solid bits surviving from the outset of freezing? The second is more complex, a questioning of the CET: does columnar growth slow down and allow the dominance of equiaxed grains, however they are formed, or do equi-axed grains take over and force columnar growth to stop? This "chicken-or-the-egg" second question can be quite useful, especially because it allows us to delineate the ordinary or NATURAL EQUIAXED ZONE and the induced or SYNTHETIC EQUIAXED ZONE. A natural equiaxed zone occurs if solidification proceeds in the absence of disturbances or extraneous forces such as ultrasonics, stirrings, and so forth. Both the CET theory proposed by Winegard and Chal-mers, 7requiring constitutional supercooling, and the CET theory suggested by Chalmers,8 requiring nuclea-tion only on pouring, pertain to the natural equiaxed zone. The best collating evidence to date for both these theories is contained in the work by Biloni and Chal-mers;9,10 the former theory7 is supported by special versions of the unidirectional growth experiment performed by Plaskett and winegardl1 and the latter theory' is supported in detail for the solidification of small ingots. An equiaxed zone can be synthesized when disturbances caused by forced fluid flows2-4 or other artificial means9,10 break off or melt off dendrite tips from an advancing solid/liquid interface,* if (and only if) temperature gradients in the melt are (forcibly) reduced enough to ensure the survival of these bits of dendrites, 2'3 Willful disturbances even so trivial as those produced by rapping a mold might be included here; as will be shown for example, this follows Southin's suggestion that the free liquid/air interface

Jan 1, 1970

By J. H. Anderson, G. A. Parks, B. K. Jindal, H. Leslie Bullock

H. Leslie Bullock (Engineering Consultant, Oak Park, 111.) — In reading over the paper, I find that I have no quarrel with the thoroughness of investigation of the points studied, but I am forced to question the selection of oxides from oxides as the subject of the investigation, the inclusion of silica gel as an example, and to question the validity of some of the conclusions. Separation of oxides from oxide, in minerals where the liberation of values is possible by grinding, are comparatively rare. Most oxides are only slightly soluble and the action of carbon dioxide or other acid forming ingredient in the air must be added to humidity to produce surface action. Silica gel is a very special synthetic substance in which the adsorption is determined by total surface, pore dimensions and temperature. Quartz is our most prevalent oxide and its action in electrostatic separation is far more sensitive to its three thermal transition points than to humidity.

Jan 1, 1968

By John Birkinbine

Four meetings of the Institute have been held in the anthracite coal-fields of Pennsylvania, and excursioris into the district, in connection with meetings elsewhere, have familiarized our members with

Jan 1, 1892

By D. E. Wolfson, D. A. Reynolds, F. W. Smith

IN 1948 the U. S. Bureau of Mines began a three-phase program to evaluate the extent and quality of U. S. coking coal: 1) a factual appraisal of known recoverable reserves in beds of mineable thickness, 2) a study of preparation characteristics, and 3) a study of carbonization properties. A previous paper presented the methods used in assessing reserves.' Although this investigation is only partly completed, data on coking properties of the Pittsburgh district coals are now available. The results are presented in this article. When coals are selected for manufacture of metallurgical coke more factors must be considered than for any other major use, as no basic industry requires coal of such high quality and uniformity. This is particularly true in the Pittsburgh district, where blast furnace practice is based on use of cokes from high quality coals. Although it is true that inferior coals are carbonized in other industrial areas, both here and abroad, the Pittsburgh coals are the best economically obtainable in the required tonnages, even though they are not the most desirable for metallurgical use. In the general evaluation of suitability of coals for coke making, particular attention is given to: 1) reserve, 2) ash and sulfur content, 3) inherent properties of forming strong, well fused coke, 4) expanding characteristics, and 5) blending properties. Items 1 and 2 are covered in detail in the first two phases of the survey, and coking behavior is considered in items 3 through 5. Problems is Coal Evaluation: Although not all coal beds of immediate or potential use to the coking industry in the Pittsburgh area have been tested for their coking properties, enough tests have been made to permit certain generalized statements. Virtually all the coals that will be used in this district are from the Appalachian region, and except for high oxygen coals from outcrops or stripping operations, they are coking coals. Hence the evaluation problem is not so much that of distinguishing between coking and noncoking coals as attempting to measure quantitatively differences in the coking and expanding properties of the better coking coals. Quantitative differentiation between good coking coals, is complex, since differences in their coking abilities are frequently of about the same magnitude as the precision of the test. Small-scale tests are generally unsuitable for measuring these slight differences, and there has been gradual acceptance of pilot-scale tests. Test Methods Employed: All the data reported here were obtained in two units known as the Bureau of Mines-American Gas Association (BM-AGA) carbonization apparatus and the sole-heated expansion oven. The BM-AGA unit, which consists essentially of a cylindrical steel retort about 18 in. diam and 26 in. high, carbonizes enough coal (180 lb) to allow evaluation of the coke by standard methods of the American Society for Testing Materials. The BM-AGA carbonization procedure and methods of testing the gas, liquid, and solid products have been described.' Expanding characteristics of the coals were determined in the sole-heated expansion oven," wherein the coal charge, heated from the bottom only, is carbonized under a constant applied force and the linear expansion or contraction is measured. Although results in this oven have never been quantitatively correlated with the expansion behavior of coals in conventional slot ovens, they are useful in assessing expansion behavior. In this report discussion will be confined to results obtained from these pilot-scale units, although the following data are available for most coals: proximate and ultimate analyses, free swelling index, agglutinating value, and plasticity. Sources of Coals Tested: In selection of coals for coke manufacture, economic considerations are as important as quality, and each coke plant balances these two factors to meet requirements of the most satisfactory coke at lowest price. Although these economic factors may in some instances outbalance small differences in coke quality, they are usually specific to each coke plant and cannot be given in any general statement. Recognizing that coal and plant operating costs are beyond the scope of the survey, the USBM evaluates the coking quality of various coals without regard to their competitive economic status. For the purpose of this article, coals of interest to the Pittsburgh district are arbitrarily defined as

Jan 1, 1958

By B. Wilshire, W. J. Evans

W. J. Evans and 8. Wilshire SEVERAL recent investigations1-6 have shown that the strain, c, during transient and steady-state creep is well-represented by the expression: € = e0 + et(l - e-mt) + Esl [l] where Eo is the instantaneous strain on loading, ET the total transient strain, C, the steady creep rate! and m a constant relating to the rate of exhaustion of transient creep. However, it has been noted6 that deviations from this equation occur over the first 10 to 15 pct of the transient stage, when the creep rate, (. decreases more rapidly than is predicted by this equation. This rapid decrease has been attributed to a large change in work-hardening coefficient. It 1s widely accepted that steady-state creep results from a balance between the rate of strain hardcning h and the rate of recovery r (=-s(st) as: dE/dt = Es = r/h [2] Comparison of values obtained for h at the end of the initial extension and during steady creep suggests that h increases several fold during the transient stage. which has the effect of reducing the creep rate proportionally.7 To examine the dependence, on r and h, of the deformation behavior during transient and steady-state creep. a series of constant-stress creep tests was carried out at 413°C at 6000 psi using 70-30 a brass. Prelinlinary investigation showed that. with this material. the transient stage constituted a significant portion of the total creep life (-0.4tf. where tf is the time to fracture). The alloy. obtained from Metals Research Limited. was made from high-purity copper, 99.999 pct. and zinc. 99.99 pct. Heat treatment at 675°C for 4 1/2 gave a uniform grain size of 5 mm-1. Details of specimen preparation and creep testing procedures have been given previously.6 Values of h (?s/?E) were determined by measuring the instantaneous strain. ?E. which occurred on increasing the stress during creep by a small amount. ?s. Similarly. v (= -?s/ ?t) was derived from the incubation period. At, after a small decrease in stress.' Several values of v and h were obtained throughout duplicate creep tests. using different stress increments in the range 300 to 800 psi. The accuracy with which Eq. [I] represents the present creep curves was established by determining the best value of the constants Es, Et, m , and 6, using a digital computer program based essentially on the graphical solution for this equation devised by Conway and Mullikan.9 About 40 strain/time readings were taken during transient and steady-state creep. Over most of the creep curve, the average difference between the measured reading and the calculated strain at the appropriate time was less than 0.0001. However.

Jan 1, 1969

Each spring most secondary schools select their best student science exhibits, prepared during the preceding academic year, and send them to regional "Science Fairs", which now number over 220. Winner-finalists of these regional contests are then sent to the annual National Science Fair, conducted by Science Service, a non- profit institution for the popularization of science, for final judging. (The Fair is now known as the "National Science Fair-International" because of participation by finalists from Japan, Thailand, Germany, France, Sweden and Canada.) For the first time since the Fair was started in 1950, AIME participated in the awards presentation. Held this year in Baltimore, Md., from May 5 to 9, five members of AIME's Washington, D.C., Section consented to represent the Institute as judges. They were: Marlin J. Ankeny-Director, Bureau of Mines, U.S. Department of the Interior. Kenneth N. Weaver-Director, Maryland Department of Geology, Mines, and Water Resources. William Harper-American Petroleum Institute. Vice-Chairman, Washington Section, AIME.

Jan 7, 1964

By H. E. Wheeler

The work described was carried out during 1917 and 1918 at the testing laboratory of Watertown Arsenal at the instigation of the Nitrate Division and later with the concurrence of the Cannon Section of the Ordnance Department, U. 8. A. The experiments follow three principal lines of work: First, the effect of nitrogen under pressure on steel containers of various compositions at a red heat; second, the effect of decomposing ammonia on various alloy steels, iron, and non-ferrous alloys; third, a new theory of the erosion of guns in respect to the effect of nitrogen in steel. Part I In the Haber process for the manufacture of ammonia from its elcnlents, it is necessary to have nitrogen and hydrogen of 1500 lb. per sq. in. (105.5 kg. per sq. cm.) at a temperature of 500 to 600' C. The steel containers for these gases gave trouble by failing without apparent cause. When the General Chemical Co. began to develop its method for the production of ammonia, it experienced the same difficulty and, knowing that the Haber process had solved the difficulty by the use of alloy steels, it made several small steel bottles of different compositions and kept them filled with these gases at this pressure and temperature until they failed. The time of service varied from a few days, for the plain steel casting, to two years for a chrome-vanadium forging. Four of these steel bottles were sent to this laboratory for investigation; they were a plain carbon-steel forging, a nickel-stee1 forging, a chrome-vanadium steel forging, and a chrome-steel forging. The time of service was as follows: plain carbon steel, 4 mo.; nickel steel, 6 mo.; chrome-vanadium steel, over 2 yr.; chrome steel, 4 mo. When these containers were cut open and the cross-section surface polished, they showed an inside zone with a different luster from the rest of the metal. Upon etching, this zone was almost unaffected while the rest of the steel etched normally.

Jan 1, 1922

By H. E. Wheeler

The work described was carried out during 1917 and 1918 at the testing laboratory of Watertown Arsenal at the instigation of the Nitrate Division and later with the concurrence of the Cannon Section of the Ordnance Department, U. 8. A. The experiments follow three principal lines of work: First, the effect of nitrogen under pressure on steel containers of various compositions at a red heat; second, the effect of decomposing ammonia on various alloy steels, iron, and non-ferrous alloys; third, a new theory of the erosion of guns in respect to the effect of nitrogen in steel. Part I In the Haber process for the manufacture of ammonia from its elcnlents, it is necessary to have nitrogen and hydrogen of 1500 lb. per sq. in. (105.5 kg. per sq. cm.) at a temperature of 500 to 600' C. The steel containers for these gases gave trouble by failing without apparent cause. When the General Chemical Co. began to develop its method for the production of ammonia, it experienced the same difficulty and, knowing that the Haber process had solved the difficulty by the use of alloy steels, it made several small steel bottles of different compositions and kept them filled with these gases at this pressure and temperature until they failed. The time of service varied from a few days, for the plain steel casting, to two years for a chrome-vanadium forging. Four of these steel bottles were sent to this laboratory for investigation; they were a plain carbon-steel forging, a nickel-stee1 forging, a chrome-vanadium steel forging, and a chrome-steel forging. The time of service was as follows: plain carbon steel, 4 mo.; nickel steel, 6 mo.; chrome-vanadium steel, over 2 yr.; chrome steel, 4 mo. When these containers were cut open and the cross-section surface polished, they showed an inside zone with a different luster from the rest of the metal. Upon etching, this zone was almost unaffected while the rest of the steel etched normally.

Jan 1, 1922