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By Kurt Stock

The war caused a demand for enormous quantities of high-grade zinc, which were not available and could not be produced from pure ores in sufficient amounts and in the time required. Redistillation of virgin spelter on a large scale was practiced to supply this demand; this paper gives a full description of the process used by the Oklahoma smelters of the Bartlesville Zinc Co. As the redistillation of zinc has become of historical interest only, having been superseded by the electrolytic process, it was deemed advisable to give expression to this phase of the metallurgy of zinc that, in the past, had never gone beyond laboratory experimentation. THE grades of spelter demanded by the consuming industries were not definitely established until the American Society for Testing Materials undertook to fix specifications, based on the varying percentages of the common impurities (lead, iron, and cadmium) as follows: TOTAL, NOT LEAD, IRON, CADMIUM, OVER. PER PER CENT. PER CENT. PER CENT. CENT. A. High grade 0.07 0.03 0.05 0.10 B. Intermediate 0.20 0.03 0.50 0.50 C. Brass special 0.75 0.04 0.75 1.20 D. Prime western 1.50 0.08 The question which grade was the best for certain purposes and why was left unanswered. The conservatism of the zinc-smelting industry and the unwillingness of the spelter-consuming industries to engage in research work prevented the full benefits being obtained that such standardization promised. The custom smelters, producing spelter in pigs or plates, found it impossible to adhere closely to the established limits on account of the variety of ores treated; and the smelters with long-established and known brands, or those manufacturing their metal into marketable products, like sheet zinc, did not have to abide by the newly established grades based on chemical percentages.

Jan 7, 1924

By Jack L. Taylor

WITH the exception of the work of Vogel,&apos; and Rolla and Iandelli, very little information has appeared in the literature on titanium binary systems with the rare earth elements. Rare-earth additions to titanium alloys may possibly parallel the beneficial effects on the physical properties of certain steels. Having this in mind, some knowledge of solubility limits and intermediate phases, if any, would be useful. An investigation of the titanium-rich Ti-Ce system was started. Alloy Preparation The iodide titanium from the New Jersey Zinc Co. and the cerium metal from the Institute for Atomic Research Ames Laboratory used in this work were supplied with the typical analysis shown —iodide titanium: 0.0065 pct Mn, 0.0022 pct Fe, 0.0015 pct Cu, and 0.0042 pct Pb; cerium metal: <0.01 pct Fe, <0.03 pct Si, <0.05 pct Ta, <0.02 pct Pr, <0.03 pct Ca, <0.02 pct Mg, with no trace of Nd, La, or Th. The cerium metal, stored in oil, was washed and scraped just before weighing into capped cups machined from iodide titanium. The cold hearth helium-arc furnace described by Schramm et al3 was used for melting. The alloy buttons from the arc-melted cup were cut in two, mounted, and examined. Homogeneous alloys were demounted and rolled to approximately 1/4-in.sq bars. Sections l/8 in. thick were cut from the bar to provide samples. The Ti-Ce alloy buttons analyzed for cerium were of the following composition: 0.19, 0.36, 0.48, 0.61, 1.15, 2.52, 3.06, 3.70, 4.30, 9.20, 14.26, and 18.50 wt pct. Nominal

Jan 1, 1958

By J. Kucera, J. Vreštál

DIFFERENT authors1 &apos; have been engaged in meas-uring the vapor pressure of pure cobalt. The results of their measurements satisfy the expected temperature dependence of vapor pressure and are in mutual agreement, with the exception of the results by De Dyk Man and ~esmejanov.~ The latter authors, by using the effusion method, have achieved considerably higher values than other workers. By using the isotope exchange method they obtained much lower values than other authors. The determination of thermodynamic functions of the binary Ni-Co system was carried out, as far as we know, only by De Dyk Man and Nesmejanov.4 This determination was based on extremely low values of vapor pressure over pure cobalt obtained by the isotope exchange method. Therefore we considered it useful to repeat these measurements. Furthermore, the reliable values of thermodynamic functions should complement the migration characteristics, the inner magnetic field data obtained by Miissbauer effect measurements, specific heat data, and the K effect and positron annihilation characteristics that have been achieved for the Ni-Co system in the Institute of Metallurgy of the Czechoslovak Academy of Sciences in Brno.5-9 The measurements in this paper were performed by the isotope exchange method. In this method, as has been shown by analysis,10-&apos;3 the vaporization rate, w, can be calculated from the relation w = k/1oSw [1] i0Sw) [1] where L, is the activity per unit mass of the source, S is the area of evaporation, k is the tangent at the point t = 0 to the curve giving the radioactivity de-pendence of the target vs annealing time, t, and wis the probability for the tracer atom condensation on the target surface. The value for cc. can be obtained from the equation w = a + 2P(l-a) [2] where P is Clausing&apos;s coefficient and a is the condensation coefficient. In the present work the cylinder shaped containers for annealing the samples were used, characterized by the ratio 1:d = 1.06. Here 1 is the length and d the diameter of the container. For this ratio P = 0.514 and w =0.5, and w is independent of the condensation coefficient. The vaporization rate is related to the vapor pressure p by the relation where R is the gas constant, T is the absolute temperature, and M is the molecular weight of the component investigated. Measurements of the vapor pressure of the i component over the pure metal, p!, and the alloy, pi, at the given temperature and composition enable one to calculate the thermodynamic activity of this component from the equation ai=pi/pi [4] is and the activity coefficient ri=ai/xi [5] xi where xi is the molar fraction of the investigated alloy component. EXPERIMENTAL Evaporization rate measurements were carried out with pure cobalt and eight different Ni-Co alloys, which were kindly delivered by the Centre National de Recherches Me&apos;tallurgiques Liege, Belgium. The composition of the alloys is given in Table I. The cobalt used in these alloys contained the following impurities: 0.016 wt pct Fe, 0.014 wt pct Cu, 0.01 wt pct Mn. Other elements were present in much lower concentrations. From the melts, samples in the form of small cylinders of 12 mm in diam were ma-chined. The thickness of the targets and sources was 2.5 and 1.2 mm, respectively. The lower thickness of the sources was chosen to make their over-all ac-tivity as low as possible. Sources were activated in

Jan 1, 1970

By Charles A. Stetefeldt

This treatise is the sequel of a paper on "Russell&apos;s Improved Process for the Lixiviation of Silver-ores," etc., read at the Chicago meeting, in May, 1884, and published in the Transactions, vol. xiii., page 47. The facts it presents are principally compiled from Mr. Russell&apos;s notes on his practical experience gained in various places where the Russell process has been introduced. For a complete understanding of this paper a perusal of my former one is desirable, as can be seen from the frequent references here made to it. All silver-ores that do not carry a large percentage of lead or copper can be treated by Russell&apos;s process with success and economy. I do not mean to create the impression that from ores containing considerable quantities of lead and copper a high percentage of the silver cannot be extracted by this process. Such ores, however, will, in many localities, be reduced to better advantage by smelting. In case lead-bearing silver-ores are suitable for concentration, it may be profitable to concentrate the ore by Krom&apos;s dry system, obtaining a smelting-product high in lead, and to lixiviate the tailings and the dust. This plan has been adopted in a mill recently erected in Cortez District, Nevada. The dry system of concentration deserves the preference because it delivers the tailings and the dust in a condition ready for chloridizing-roasting. In wet concentration the drying of the tail ings would be expensive, and there would be a considerable loss of silver in slimes. Oxidized ores, containing silver chloride and lead minerals, may be lixiviated after crushing, and the tailings may be concentrated for lead. In this case wet concentration would be most suitable. This has been done at the Old Telegraph Mine, Utah. I would give, however, the preference to dry concentration in all cases which, of course, requires that concentration should precede lixiviation. The Russell process is also adapted to the treatment of tailings resulting from ores which have been worked either by the old

Jan 1, 1887

By Charles W. Frey

SUCCESSFUL mining today means proper mechanization. Before any mine can begin production on a paying scale, some machinery must be installed. There must be pumps to remove water, fans and blowers to provide proper ventilation, elevators and hoists to raise materials, and a source of power to turn the countless wheels on which the world&apos;s mineral supply rolls from its earthhound source to the market. Only the prospector with his burro and the anthracite "bootlegger" continue to mine without mechanical aid, and with the recent years even these can be discounted, for the burro has given way to the Model T, and the "independent" coal miner must have a truck to haul his coal away. The few types of machinery mentioned above are but a beginning. The

Jan 1, 1938

The following is an incomplete list of members and guests who called at Institute headquarters during the period July 10, 1919, to Aug. 10, 1919. Howard C. Arnold, Washington, Pa. J. S. Lane, New York City, N. Y. L. M. Banks, Denver, Colo. H. W. Lawrie, Washington, D. C. George S. Blair, Pittsburgh, Pa. J. L. McAllen, Latouche, Alaska. Richard H. Catlett, Newark, N. J. David F. McFarland, Urbana, Ill. George L. Clark, Council Bluffs, Iowa. James F. Magee, Lancaster, Pa. Capt. Frederick S. Cook, Portland, Ore. A. G. McGregor, Warren, Ariz. John J. Croston, Atlanta, Ga. Emory M. Marshall, Santa Fe, N. M. Thomas Davis, Seattle, Wash. Benjamin L. Miller, Bethlehem, Pa. J. C. Dick, Salt Lake Cite, Utah. 2d Lieut. C. 0. Noble, U. S. Army. Chris. G. Dobson, Vancouver, B. C. Irving Perrine, Hutchinson, Kans. H. S. Emlaw, Grand Rapids, Mich. Fred S. Porter, Seattle, Washington. F. A. Fahrenwald, Cleveland, Ohio. Capt. H. R. Robbins, Peking, China Lieut. James L. Head, St. Louis, Mo. Joseph P. Ruth, Jr., Denver, Colo. A. A. Holland, Napanu, Canada. William A. Simkins, San Francisco, Calif. W. E. Hopper, Washington, D. C. T .V. Smirnoff, Siberia. Harry Hotchkin, Chicago, Ill. Harrison Souder, Cornwall, Pa. L. L. Hutchison, Tulsa., Okla. F. J. Sur, Denver, Colo. Paul S. King, Wilmington, Del. Harry Wolf, Denver, Colo. George K. Anderson, Jr., lies accepted a position as manager for Wight & Co., producers of air-cooled blast-furnace slag, at Longdale, Va. J. M. Armstrong, with the Caribbean Petroleum Co., has been transferred from Philadelphia to Maracaibo, Venezuela. Fred Sherman Baker, who has been with the Oriental Consolidated Mining Co., at Unsankinko, Chosen, Korea, is now at Columbia City, Ind. Ray J. Barber has removed from Roxbury, Mass., to New York City, and is now consulting engineer for the Roxbury Cold Mines, Inc.

Jan 9, 1919

By A. Aly Selim

A computer model was developed to calculate the fragmentation cost for in situ leaching operations as a function of the blast design and deposit parameters. The model is based on blasting an ore zone only or an ore zone plus overburden by either a coyote blast or a vertical blasthole system. The model calculates the blast design parameters and the fragmentation cost based either on a user input powder factor value or on a powder factor calculated by the model as a function of the overburden height and the ore zone thickness. Examples of blast design parameters calculated by the model are the number and spacing of blastholes for a vertical blasthole system and the number and spacing of crosscuts for a coyote system. The model also calculates the total amount of explosives, the detonating cord length, and the number of primers. The cost of blasthole drilling can be calculated by the model based either on purchasing and operating a drill or on a user input value of the contracted cost of drilling. Application of the model to an example ore deposit showed that the vertical blasthole systems were more economical than the coyote system when there was no overburden and the deposit had an average ore thickness less than 45 meters. With no overburden and ore thickness greater than 45 meters, the vertical blasthole system was either more or less expensive than the coyote system depending on the number of levels used in the coyote system. With overburden, the coyote system was less expensive than the vertical blasthole system for blasting either the ore only or the ore plus the overburden. A coyote blast will usually produce larger particle sizes than a vertical blasthole system. Larger particle sizes can result in lower copper recoveries so that a less expensive coyote blast may not improve the overall economics of an in situ leaching operation. Blasting the ore zone only was generally less expensive than blasting the ore plus the overburden by either blasting system. Also, for the example considered, the coyote system costs were less sensitive to changes in overburden thickness and powder factor while the vertical blasthole system costs were less sensitive to changes in ore thickness.

Jan 1, 1977

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 Carl J. McHargue

Mechanical twins were produced in electron-beam melted columbium by high-speed impact at room temperature and by slow or fast compression at -196°C. The composition plane of the twins was { 112} and the shear direction was <111>. Notches in the twin bands often corresponded to traces of {110) of the matrix and appeared to be untwinned regions. Markings within the twin bands were interpreted as resulting from {110} slip in the twins. THERE has been much work in recent years concerning plastic deformation by glide, and the dislocation theory relating to glide has reached a relatively high degree of development. On the other hand, there have been fewer studies of deformation by mechanical twinning, and understanding of this process is far from satisfactory. This method of deformation is of interest for at least two reasons. First, it provides a mechanism in addition to glide for the relief of stresses, and, in the bcc and hexagonal close-packed metals may result in significant amounts of plastic flow. Secondly, there is the possibility that twins may act as barriers for dislocation movement, resulting in pile-ups which could nucleate cracks. As might be expected, the bulk of the literature on mechanical twinning in the bcc metals is concerned with iron. A good summary of the work done prior to 1954 is contained in the book by all.&apos; Recently the refractory bcc metals have become increasingly important. Limited studies have shown that tantalum,2,3 molybdenum,4,5 vanadium,6,7 tungsten,&apos; and columbium9-11 deform by mechanical twinning under some conditions. Alloys of molybdenum with rhenium and tungsten with rhenium show extensive deformation by twinning at room temperature.I2-l4 Most of these studies have dealt primarily with mechanical properties at low temperatures or have shown the existence of twins, and there is only a small amount of information concerning the conditions under which they form. The subject of the present paper is the formation of twins under stress in columbium with a consideration of their morphology. EXPERIMENTAL PROCEDURE The material used for these studies was taken from an ingot of columbium which had been melted twice by the electron-be am-method. The analysis of the ingot was (in ppm): B < 1, C = 10, Fe < 100, The cast ingot contained very large grains, and it was possible to obtain single-crystal prisms which measured from ¼ to 3/4 in. on a side. A few experiments were conducted on polycrystalline plate which was prepared by rolling material from the same ingot at room temperature and annealing at 1000 in a dynamic vacuum of 10-6 mm Hg. This gave a plate in which the grains had an average diameter of 3 mm. After the specimens were cut from the ingot, the six faces were metallographically polished and elec-tropolished to remove all traces of cold work. Most of the observations were made on the surfaces of the deformed specirllens without further treatment. Occasionally, etching after deformation was desirable. In these cases, an etchant of the composition 50 parts H2O, 5 parts HNO3 25 parts HF, and 10 parts H2SO4 was found to delineate the twins very well. Unless considerable care was taken to ensure the removal of all disturbed metal left by the mechanical polishing, etching failed to reveal many of the features discussed in this; paper. The specimen&apos;s were deformed either by impact or slow compression at 77°K (liquid-nitrogen coolant), 198°K (dry ice and acetone coolant), and 298°K. The impact load was delivered by a hammer except in one case where the load was delivered by a bullet. Slow compression was carried out on a hydraulic testing machine equipped with a chamber to hold the coolant. EXPERIMENTAL RESULTS It has been generally believed that the conditions favoring the formation of deformation twins are large grains, low temperature, and impact loading. In fact, Barrett and Bakish2 found twins in tantalum only after impact deformation at 77°K, and Adams, Roberts, and Smallman10 observed twins in columbium only at 20 For these reasons, the initial experiments of this study used impact loading. Hammer blows caused many bands resembling twins in single crystals a.t 77" but not at 198°K. Only a few slip lines were observed on any of the single-crystal specimens of this study—essentially all the deformation occurred by twinning. The appearance of the twins on the as-deformed surface is shown in Fig. 1. Although both Figs. 1(a) and l(b) are photomicrographs of twins taken at the same magnification and from the same crystal, they are startlingly different in appearance. Fig. 1(a) was taken from the crystal face approximately perpendicular to the shear direction, whereas Fig. 1(b) was taken from

Jan 1, 1962

By Axel Sahlin

Jan 1, 1898

By D. B. Jugle, J. B. Darby

The equilibrium solubility limits of the transition elements Ti, V, Cr, Fe, and Co in liquid tin were determined in the temperature range from 827" to 1211°K. Since the equilibrium concentration of Ti, V, or Cr in liquid tin is moderately dilute in the temperature range investigated, the solubility data were employed to estimate the partial molar enthalpy and the partial molar excess entropy of solution for the three solutes in liquid tin. The reference state s for titanium or vanadium were selected relative to the solute in an intermetallic compound. The thermodynamic quantities for chromium were calculated relative to pure chromium. RECENT experiments1 have shown that the rate of solution of several transition elements in liquid aluminum can be qualitatively predicted from a knowledge of the temperature dependence of the solvent-rich liquidus. In order to extend the analysis to binary tin systems,&apos; it was necessary to know the equilibrium solubility of several of the first-long-period transition elements in liquid tin. Since solubility data for the tin-rich portion of binary systems are meager, the present investigation was undertaken to determine the equilibrium solubility limit of Ti, V, Cr, Fe, and Co in liquid tin in the temperature range from 850" to 1200°K. EXPERIMENTAL PROCEDURE A useful technique3 to determine the equilibrium solubility of a solute in a liquid-metal solvent consists essentially of placing a pure solute in contact with a pure solvent and allowing sufficient time for equilibrium to be attained at the temperature of interest. Subsequently, the solvent is removed and the equilibrium solute concentration in the solvent is determined by an appropriate analytical procedure. The technique can be applied very successfully to relatively simple systems such as the copper-germanium system.3 However, in many binary systems of transition elements with tin, several intermediate phases are known to exist and precipitation of the phases from solution, in solubility experiments, can lead to an erroneously large solubility. The difficulty was avoided in the present work by equilibration of the most solvent-rich intermediate phase with the pure solvent over a range of temperatures. The compounds employed in this investigation, and the temperature range over which each compound is in equilibrium with liquid tin are listed in Table I. No stable intermediate phases are reported in the chromium-tin system4 and, therefore, pure chromium was utilized as the solute. The stoichiometric compounds were prepared by arc-melting on a water-cooled copper hearth in a helium-argon atmosphere. The elemental tin employed in.this investigation was 99.998 pct pure, and typical lot analyses of the transition elements were reported elsewhere.&apos; A sample of an appropriate solute, in the form of a button and in sufficient quantity to exceed the equilibrium solubility, and the pure tin solvent were placed in a high-purity recrystallized-alumina crucible. The crucible and contents were placed in a horizontal furnace under a high vacuum (10-6 torr) and held at temperature for periods varying between 24 and 72 hr. A water-cooled quench tank, partially filled with diffusion-pump oil, was attached close to one end of the

Jan 1, 1970

By D. F. Kaufman, E. D. Levine, L. R. Aronin

ThE primary slip plane in hcp metal crystals can usually be inferred from the c/a ratio. Basal slip is the primary system at room temperature for zinc, cadmium, magnesium, cobalt, and rhenium, all of which have a c/a ratio greater than 1.60. Zirconium and titanium, on the other hand, each with a c/a ratio of 1.59, deform primarily by (1010) [ll20] prismatic slip. The increasing tendency toward prismatic slip in these materials is generally thought to be associated with the increase in atomic density on (10i0) as c/a is reduced. Beryllium, with a c/a ratio of 1.57, would, according to the above scheme, be expected to exhibit prismatic slip. However, in beryllium of commercial purity, the primary deformation mode at room temperature is basal slip.&apos; The ratio of critical shear stress for prismatic to that for basal slip at room temperature is approximately 5:l. The critical shear stress for prismatic slip decreases quite rapidly with increasing temperature, however, and at 500°C the ratio is approximately unity. The apparently anomalous behavior of beryllium has led to speculation that prismatic slip in this material may be restricted by an anisotropic effect of impurities,&apos; and that, if beryllium could be purified to a sufficient extent, prismatic slip might predominate at room temperature. In such a case, the conditions under which basal cleavage can occur would be suppressed, and enhanced low-temperature ductility might result. With the advent of the floating-zone method for purification of beryllium,3 it has become possible to determine experimentally the effects of purification on basal and prismatic slip. Tensile tests were performed at room temperature on single crystals oriented favorably either for basal or prismatic slip. The crystals had been purified to various extents by zone-refining, employing procedures that have been described elsewhere.4 Relative purities of the crystals were estimated by measuring the ratio of electrical resistance at 4.2"K to that at 298°K. Typical values ranged from 0.40 for commercial-purity material to 7.7 X 10"4 for crystals prepared from vacuum-distilled beryllium and subjected to six zone-refining passes. The purity dependence of the critical shear stresses for basal and prismatic slip is shown in Fig. 1. In the purity range studied, the critical shear stress for basal slip is decreased from 1.4 to 0.14 kg per sq mm. The critical shear stress for prismatic slip is decreased from 6.7 to 5.3 kg per sq mm. The decreases in critical shear stress for each deformation mode, therefore, are approximately equivalent. No purification anisotropy is observed. Because of the absolute magnitudes of the critical stresses, the ratio of the critical shear stress for prismatic slip to that for basal slip actually increases from 5:l to 38:l at the highest purity level studied. It is evident, therefore, that basal slip is the primary deformation mode in high-purity beryllium. This fact must be accounted for in any rationalization of the deformation behavior of hcp metals. This work was performed at Nuclear Metals, Inc., under the sponsorship of the U.S. Atomic Energy Commission.

Jan 1, 1964

By L. Thomassen, N. Spooner, J. M. Thomas

NI-CR and some Ni-Cr-Fc alloys, when used as electrical resistance heating elements in reducing atmospheres, at times suffer rapid breakdowns due to so-called "green rot." These reducing atmospheres are most frequently used in bright annealing and heat-treating furnaces which are kept for long periods of time at 1500&apos; to 1800°F. The green rot is a preferential oxidation of the chromium in the alloy to such an extent that the remaining metal frequently becomes ferromagnetic. The Curie point (magnetic transition point) at room temperature for a pure Ni-Cr alloy is known to be at about 7 pct Cr.¹ This represents a severe loss in chromium for one popular grade of resistance alloy, which is nominally 80 pct Ni-20 pct Cr. The formation of oxides along the grain boundaries makes the ribbon brittle and gives the fracture a green, earthy appearance—hence the name. The authors have studied this phenomenon, simulating the industrial conditions by heating resistance ribbons in various reducing atmospheres, such as moist hydrogen or the atmosphere specified in the ASTM test.² This atmosphere contains 16 pct H2, 10 pct CO, 4 pct C02, 1 pct CH1, 1.5 to 2.5 pct H2O, balance N2. Little success was had in producing severe corrosion with the commercial 80 pct Ni-20 pct Cr alloys. It had been noticed, however, that 90 pct Ni-10 pct Cr alloy wires deteriorated very rapidly when placed in the bottom of narrow thermocouple protection tubes. The bottoms of the tubes with the wires were heated in air. This took place both in porcelain tubes and in Inconel* tubes either with the cold end open or loosely stoppered with asbestos. On examination the wires showed microstructures which would be classified as green-rot corrosion. Subsequent investigations with various alloy wires confirmed the observation that corrosion occurred in some wires, including 80 pct Ni-20 pct Cr alloys, much more rapidly in such tubes than had occurred previously in test atmospheres mentioned above. When 90 pct Ni-10 pct Cr alloys are oxidized with an abundant air supply, the oxide coat consists of both nickel and chromium oxides. In this case thermodynamic equilibrium between the oxides is not established. However, when oxidized 90 pct Ni-10 pct Cr alloy specimens were heated to 1500" to 1800°F inside small diameter tubes, the oxide coat transformed to a bright metallic outer layer of nickel or nickel-rich alloy, beneath which appeared a green oxide, followed by intergranularly attacked metal. The obvious explanation is that in the narrow tubes, thermodynamic equilibrium is being established according to the equation NiO + Cr (in alloy) ? Ni + Cr2O3 This reaction is favored due to the fact that the oxygen pressure over nickel oxide is more than 10"&apos; times the oxygen pressure over the green chromium oxide. The initial oxygen in the tubes is depleted very rapidly by oxidation of the wire and of the tube, if it is metallic. A confirmation of the occurrence of the reaction, reduction of NiO by the chromium in the alloy, was obtained by putting oxidized nickel foil into an evacuated quartz tube along with a piece of bright 90 pct Ni-10 pct Cr alloy ribbon, and heating the tube at 1820°F for a number of hours. The nickel oxide on the foil was completely reduced to pure nickel, leaving a bright foil. The 90 pct Ni-10 pct Cr alloy became strongly magnetic and showed the typical green-rot structure. Weights of the samples before and after testing showed the weight loss of the foil to approximately equal the weight gain of the ribbon. Evidently the bottom of long, narrow protection tubes, stoppered or not, may under certain conditions act just as the sealed quartz tubes in respect to being a confined space in which oxygen is not freely replenished. This condition of oxygen depletion can be prevented by introducing a small amount of air into the bottom of the tube. Many conditions becloud the green-rot phenomenon, such as carburization, sulphidization, and the presence of other corrosive agents. However, these experiments have shown that the basic reaction is a case of internal oxidation which can occur simply by adjusting the oxygen pressure to a low enough level so that the atmosphere will leave the nickel intact and oxidize the chromium. The action of the other agents in commercial atmospheres can then be taken up as individual cases. From these and numerous other tests completed to date or still in progress, it is believed that a more critical evaluation of electrical resistance alloys for their resistance to green-rot corrosion can be made. A much better understanding of the mechanism for this type of corrosion should also result. A more complete report on these experiments will be published later. In the May 1953 issue: TP 35213 Discussion: Solubility of Carbon and Oxygen in Molybdenum by W. E. Few and G. K. Manning, discussion by N. A. Gokcen: p. 747, first column, the fifth, sixth, and seventh lines should be the first, second, and third lines, followed by the present first, second, third, fourth, eighth, ninth, and tenth lines.

Jan 1, 1954

By Yves Dardel

THE literature concerning the remelting of aluminum and its alloys is very rich. Unfortunately the greater part of the papers about this subject have no scientific value, for the theories or explanations are too often in opposition to the laws of physical chemistry. Furthermore only a few of the methods of purification1,2 are considered in the literature. Hence it has seemed necessary to the author to sketch a general theory of the purification of secondary aluminum. The purpose of the purification is to eliminate the impurities that the charges and the atmosphere of the furnaces bring into the bath during the successive remeltings. Indeed scrap as well as metal can be used when soiled with oil, greases, water, .. , if it has been sufficiently dried and contains oxides. At the melting point of the metal, the oils and greases are decomposed into their constituent elements H2, 02, H2O, C02, CO, CH4, and others. These gases are added to the corresponding gases in the atmosphere of the furnace. The impurities introduced into the metal during the remelting will accordingly be the products resulting from the action of these gases on the liquid bath. The quantity of hydrogen that is soluble in aluminum and its alloys is given by the relation of Sieverts3 as a function of its partial pressure PH2 in the atmosphere [m = K _%/PH, [I]] where K is a constant, which depends only upon the temperature and increases with it. The experiments of Röntgen and Braun4, Röntgen and Möller5, Bircumshaw6 and Winterhager7 have rendered it possible to determine the value of K, when the temperature is inferior to 1.000°K. One obtains: [log K = - 4,702.5 + 0.238 [2]] Besides its usual signification, the term PH2 represents also the internal pressure of dissolved hydrogen, since in the equilibrium, that is, when no gas exchange occurs between the two phases, the pressures of hydrogen in the metal and in the atmosphere must be equal. Eq I shows that when the partial pressure of H2 increases the amount of dissolved hydrogen in equilibrium increases, and that, if the contrary occurs, the quantity of H2 should diminish. However, if for any reason the diffusion of hydrogen is hindered and the total amount of dissolved gas remains constant while the temperature lowers, the internal pressure of H2 increases until it reaches the value of the hydrostatic pressure. At this point, bubbles of hydrogen appear in the bath and escape out of it. The amount of hydrogen in the metal is then limited by a maximum depending on the hydrostatic pressure, which is practically equal to one atmosphere. Indeed hydrogen does not accumulate in the form of a hydride appearing as a separate solid phase. However, even the mechanism of the solubility is not yet elucidated. One does not know exactly as yet, whether the

Jan 1, 1947

By M. C. Flemings, R. Mehrabian, G. E. Nereo

Analytical expressions derived previously are used to describe quantitatively effects on macrosegregation of some solidification and mold design variables. Al-4.5 pct Cu alloy is used as example. It is shown that abrupt changes in heat transfer rate result in solute-rich or solute-poor "bands". Severe solute-rich bands accowzpany "reheating" that can result, for example, from abrupt formation of an air gap at a mold-metal interface. With planar isotherms, solute-poor regions also result from reduction in cross section through which fluid flow to feed shrinkage takes place. It is suggested that the negative "cone" of segregation often found at the base of large ingots results from this reduction in cross section for feeding. Consideration is given to the positive and negative segregation to be expected in laboratory ingots in association with changes in ingot cross section. Under-riser positive segregation is considered and it is concluded this segregation results when vertical temperature gradient is low in the region of the riser; the segregation is accentuated by the temperature gradient reversal which can occur in inadequately insulated risers ("&apos;hot tops"). Finally it is shown for Al-4.5 pct Cu alloy that the assumption of constant k and p in analytic solutions gives calculated results close to those obtained for the case of ziariable k and 0. A basic "local solute redistribution equation" was derived earlier&apos; for calculation of macrosegregation resulting from flow of solute-rich liquid to feed solidification shrinkage, thermal contraction, and/or other contractions occurring during solidification. This expression relates fraction liquid, g~, to liquid composition, CL, at a given position x, y, z, in a solidifying Eq. [I] is for the general case of three-dimensional heat and fluid flow assuming constant solid (but not necessarily liquid) density during solidification, negligible net solute change from diffusion, and no pore formation. In this paper we first demonstrate application of this equation for calculation of macrosegregation in several examples involving one-dimensional heat and fluid flow. Specifically considered are examples in which segregation results from sudden changes in heat flow conditions. Next, Eq. [I] is used to describe segregation in examples where isotherms remain planar but where fluid flow is no longer one-dimensional. Application of this expression illustrates the type of segregation to be expected in unidirectionally solidified ingots of gradually or abruptly varying cross section. For segregation calculations, A1-4.5 pct Cu alloy is employed with constant k and p Vz = 0.172, 4 = 0.055), eutectic composition (CE = 33 pct Cu). In all examples, fraction eutectic is neglected in velocity calculations; this was previously shown to introduce little error.&apos; A linear distribution of fraction liquid in the liquid-solid zone is assumed. In a concluding section it is shown that the assumption employed of constant k and /3 gives results close to those obtained when the actual (variable) values of k and 0 are employed.

Jan 1, 1969

By Arnulf Muan, R. E. Johnson

Equilibrium CO2 /CO ratios of a gas phase coexisting with selected oxide phase assemblages of the system CaO-"Fe0"-SiOz and vnetallic iron have been determined at 1080°C. The data obtained are used to calculate activity-conzposition relations for metasili-cute, orthosilicate, and CaO- "FeO" solid solutions, and to determine a new value for the free energy of formation of C&S&0,. The metasilicate solution is practically ideal, whereas large deviations from ideality exist in the othe,r two solid solutions. BECAUSE of the geochemical and metallurgical importance of the oxides CaO, "FeO", and SiOz, the system CaO-"FeO"-SiO2 has been the subject of several experimental studies during the past 30 years. Following the delineation of phase relations at liquidus temperatures by a group of investigators at the Geophysical Laboratory of the Carnegie Institution of Washington in 1933,1 Chipman and associates in the early forties2,3 determined activities of FeO in liquids of this system. Since that time, many attempts have been made to interpret the data of Chipman et al. in terms of the constitution of the silicate liquids and the interaction parameters among the various constituents of the system (see for instance papers by Richardson4 and by Flood and coworkers5). One of the assumptions made in some of these interpretations4 is that the binary silicate systems CaSiO3-FeSiO3 and CazSi04-Fe2SiO4 mix ideally in the solid state. The objective of the present study is to provide experimental data on activity-com position relations in solid solutions of the system CaO-"FeO"-SiO2. Such data will contribute toward an understanding of the thermodynamics of silicate solid-solution phases in general, and will serve specifically to confirm or refute some of the assumptions made in interpreting liquid slag behavior. PREVIOUS WORK Phase relations in the system CaO-"FeO"-SiO2 in contact with metallic iron were determined by Bowen, Schairer, and Posnjak,1 and additional phase-equilibrium data for this system have been presented by Allen and snow.&apos; A reproduction of the most up-to-date phase diagram for this system is shown in Fig. 1.7&apos;8 Of particular interest in the present investigation are the relations among the various crystalline phases slightly below the lowest solidus temperature in the system, as shown in Fig. 2. The present work will be concerned primarily with some of the composition

Jan 1, 1968

By G. P. Marino

The "conductivity ", Kr, of a spherical void in a linear temperature gradient due to radiation is calculated by integration of the general expression for diffuse radiation between two gray surfaces of arbitrary orientation. The spherical geometry allows an exact evaluation of the phenomenon without resorting to up-proximate expressions for the radiant heat flux. The resulting expression for Kr is three quarters of the approximate value obtained by Loeb. IN the determination of the thermal conductivity of porous materials such as sintered UO2 and ThO2 fuel pellets, the magnitude of the thermal conductivity in the pores due to radiative heat transfer across the pore, Kr, may be important in assessing the total conductivity of the pellets. Loeb&apos; has calculated Kr for various pore geometries by approximating the net flux of heat between two surfaces of temperature difference AT as 4eT~AT and obtained: K,=4yoet3odp [1] where a is the Stefan-Boltzmann constant, E is the emissivity of the radiating surface, To is the average absolute temperature of the region across which radiation occurs, dp is the largest dimension of the gap in the direction of heat flow, and y is a geometric factor. That is: y = 1 for laminar pores and cylindrical pores with axes parallel to the heat flow direction, y = 2/3 for spherical pores, y = /4 for cylindrical pores with axes perpendicular to heat flow direction. It was the purpose of this work to obtain an exact expression for K, in spherical pores by integration of the general expression for the net heat transfer between two incremental areas on the surface of a spherical pore. This procedure yields a value of Kr 3/4 of that obtained by Loeb. I) CALCULATION OF Kr Fig. 1 illustrates the general geometry which defines the problem. The total emissive power for a gray body is given by: E = EoT4 [2] where E is the radiated energy per unit area of the radiation surface per unit time, T is the absolute temperature, o is the Stefan-Boltzmann constant (o = 5.67 X lo- &apos;&apos; watt per sq cm-"K1), and E is the emissivity of the surface. Although Eq. [2] gives the exact expression for the total emissive power of any gray body, all practical problems involve the net exchange of thermal radiation between a body and surrounding bodies. The two major considerations in the solution of such problems are a) shape and relative position of the surfaces and b) the emissivities of the surfaces. In this work it shall be assumed that all incremental areas on a pore have the same emissivity and, further, that little or no reflection occurs (i.e., the radiation hitting a surface is either absorbed or transmitted). Thus, the solution of the stated problem requires only that consideration a be satisfied. Consider two incremental surface areas dA 1 and dA2 of the same material in a general orientation to one another. Let dAl be at temperature TI and dAz be at T2. Fig. 2 illustrates the geometrical parameters involved. That is, 71, is the normal of dA, n2 the normal of dA2, r the line connecting the centers of each area, 81 the angle between nl and r, and Q2 the angle between 7,2 and r. Using Eq. [2] and the Lambert cosine law of diffuse radiation it is easily shown that:293 WdAf- dA, = ecr T*------^fpi------" dAidA2 [ 3a 1 and

Jan 1, 1970

By M. E. Wadsworth, R. C. Peterson, W. M. Fassell

The temperature and pressure dependence of the reaction of tantalum in oxygen were investigated from 500° to 1000°C at pressures from 10 mm Hg to 600 psi total oxygen pressure. Tantalum was found to oxidize linearly under the above conditions. Three distinct regions of temperature dependence were found with different energies of activation. From 500° to 600°C the rate of oxidation of tantalum was found to be essentially independent of the oxygen pressure at the pressure investigated. The oxidation rate increases rapidly with an increase in pressure from 600&apos; to 800°C. The dependence of the oxidation rate on the bulk concentration may be expressed by V = k&apos;?, where k&apos; is the specific rate constant and ?=k1Co2/(l + K1Co2), where k, is the equilibrium constant for the adsorption of oxygen on tantalum. ONLY a limited amount of data has been presented in the literature on the oxidation behavior of tantalum metal. Some values of its oxidation rate were reported in the Corroston Handbook&apos; and by McAdams and Geil.&apos; The first extensive investigation of tantalum was the work of Gulbransen and Andrews." They determined the reaction rates of tantalum in O2 and N2. Their results indicate that this metal follows the parabolic law in the temperature range of 250" to 450°C in O2 at pressures of 7.6 cm Hg with an activation energy of 27,400 cal per mol. In nitrogen, the metal follows the parabolic law from 500" to 800°C at 7.6 cm pressure. All experimental determinations were of 2 hr or less duration and deviations from the parabolic rate conceivably could occur at longer times. A spectrophotometric study of the oxidation of tantalum by Waber, Sturdy, Wise, and Tipton&apos; indicated good agreement between this method and the microbalance technique. The experiments were conducted in air from 220" to 350°C. The metal was found to follow the logarithmic law up to 320°C and the parabolic law at higher temperatures. The activation energies in the logarithmic region were reported as 12.57 kcal per mol and 12.0 kcal per mol, respectively, for the microgravimetric and spectrophotometric methods. In the parabolic region the activation energy was found to be 27.2 kcal per mol, in good agreement with the value of Gulbransen and Andrews." The present paper is concerned with the behavior of tantalum from 500" to 1000°C in oxygen at pressures ranging from 1/2 to 40.8 atm pressure. Earlier preliminary data by McKewan5,6 indicated the following facts concerning the behavior of tantalum: 1—At temperatures from 500" to 600°C, the metal followed the linear law. 2—At 575°C the rate of oxidation was found to increase with O2 pressure. 3—The Arrhenius plot in this temperature region was nonlinear. The nonlinearity of the Arrhenius plot was indicative of a more complex behavior than originally suspected for this metal.

Jan 1, 1955

&apos;T. C. MERRIMAN, New Haven, Conn. (written discussion *).-This most interesting paper gives much carefully obtained and valuable data. However, there are two points in connection with the commercial application of such data that might possibly be a source of trouble and mis-understanding. In the first place, the examination of thin sections of annealed brass, subjected to standard Brinell test.(500 kg. on a 10-mm. diameter ball) at thicknesses from 0.075 to 0.150 in. (1.9 to 3.8 mm.) indicates that cold work has been performed on the specimen during the application of the load sufficient to extend way through the section, and have the hardness of the metal affected by the backing. If the usual steel support is used, this effect is very evident. If a piece of soft brass is used as a support, there is an indentation in the surface of the support accompanied by a bulge on the under side of the tested specimen opposite the impression made by the 10-mm. ball. The result is that Brinell specifications (governmental or otherwise) on stock for a certain purpose may not be fair in all cases, since manufacturers, owing to differences in equipment, etc., may not all use precisely the thickness and conditions of stock on which the Brinell specifications were based. This would mean that the government Brinell specification might not give them the temper of stock best suited for their manufacturing methods. The concluding paragraph of this paper, stating that "the hardness of cartridge brass may be determined with greater accuracy by the Brinell hardness measurement than by attempting to judge it from the grain size" appears to be in line with the movement of the last year or so among brass manufacturers toward substitution of the Brinell test for microscopic examination as an acceptance test on cartridge brass. The statement may he strictly true that the Brinell test is the best test for hardness, but it is not, as the statement might readily be construed, a sufficient test of suitable condition. For instance, some cartridge brass might accidentally have been overheated to a point where it would be distinctly unsafe to use for the manufacture of small arms cases and then be so rolled (reduction 3 to 5 per cent.) as to pass perfectly proper Brinell specifications. Under such conditions the microscope would reveal its unsuitability where the Brinell test had failed so to do.

Jan 4, 1919

By William G. Pariseau

The flexure of geologic strata, a phenomenon of interest to geologists and mining engineers alike, is examined as a sheet bending problem in Coulomb plasticity. Fonnulae for the distribution of stress, strain, and displacement increments; volume change; change in the length of the central surface; and power of dissipation, as well as for the neutral surface shift are given. Strains of any magnitude are considered. The analysis shows that deeply buried strata may bend and develop "tensile" cracks under generally compressive states of stress. It is also shown that bed separation and high capacity props are desirable in mechanized longwall mining, a result in keeping with operating experience. Although speculative at this time, the analysis provides a rational working hypothesis as regards the problem of strata flexure and control. | he purpose of this paper is to present an analysis of the flexure of geologic strata as a problem in the bending of a sheet of material failing in accordance with a Mohr-Coulomb criterion. The flexure of strata has an obvious academic interest to the geologist concerned with the mechanics of folding. It is of interest to the economic geologist as it relates to the structural control of certain types of ore deposits. It has an intimate association with mine subsidence phenomena, and is of concern to the mining engineer. Strata flexure is also the dominant feature of roof behavior about longwall workings. An improved understanding of strata flexure through a rational mechanical analysis thus appears desirable not only from the academic view but from the economic one as well. In the field, the most commonly observed feature of folding, subsidence, and longwall roof behavior is the permanent and therefore inelastic nature of the strata movement. Fig. 1 illustrates the physical disposition of strata in the vicinity of a longwall face. Inasmuch as most rocks (with the possible exception of certain evaporites) do not exhibit significant viscoelastic behavior, at least not over time spans of engineering interest, a plastic analysis is indicated. The analysis is meant to apply to strata whose deformation is dominantly that of bending such as might be expected in the remote roof about a longwall face.

Jan 1, 1970