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By A. L. Marshall, F. J. Norton

The object of this investigation was to make a comprehensive study of the degassing of molybdenum in order to determine how rigorous a treatment was necessary to completely remove sorbed gases from molybdenum electrodes in vacuum tubes. Some work has also been done with tungsten, nickel, iron and carbon. As a logical development of this work it has been shown that the gas is present throughout the body of the metal and a study has been made of the solubility of nitrogen in molybdenum and tungsten and the rate, of diffusion of nitrogen through molybdenum has been calculated. Tests were made on molybdenum from all the commercial sources and no difference was discovered in the nature of the gases present, the amounts or the ease of removal. The reason for this was apparent when a study was made of the manner in which gases are absorbed by gas-free molybdenum. It is necessary to heat molybdenum to 1760°C. in a vacuum of the order of 0.001 micron for a time which varies lineally with the thickness, in order to obtain a condition in which no further gas is evolved by the sample. A sample so degassed can be handled and subsequently assembled in a tube and then degassed readily. The gases obtained from molybdenum are carbon monoxide and nitrogen, the nitrogen being the more difficult to remove. Apparatus and Technique The apparatus is shown in Figs. I and 2. It consisted of two units, a degassing system and an analytical system. Each had a bake-out oven, as shown surrounding the systems in the sketches. The system , will be traced, starting from the sample in the degassing system. A water-cooled quartz chamber surrounded the sample. The high-frequency coil, which heated the sample, extended only around this chamber and was cooled by an air blast. High-frequency power of 1800-meter wave length was obtained from a self-rectifying oscillator circuit with a maximum power input of 20 kw. A graded seal connected the quartz to the rest of the apparatus, which was of hard glass. The temperature of the molybdenum sample was observed by an optical pyrometer through an optical window about 40 cm. distant from the sample. Since the object viewed under these conditions was not a black body, true temperature was not observed, but the so-called "brightness temperature." The correction of this to true temperature is discussed in a later section. The apparatus was taken apart just above the graded seal; the quartz chamber was slipped off, washed with nitric acid, water and alcohol, and dried by an air stream. The old sample was removed by unscrewing the lower nut, and the new

Jan 1, 1944

By Fritz Wald, Martin Weinstein, Herbert E. Bates

ONE of the methods for preparing a fiber-reinforced composite is that of directional solidification of a eutectic melt. Its major drawback lies in the fact that the matrix in this case is a pure constituent (or a terminal solid solution of fixed concentration) and the ratio of fiber to matrix volume is fixed. Only very few, if any, pure metal matrices possess technically useful properties, and the necessity for alloying is the inevitable consequence of this fact. Nevertheless, structures similar to binary eutectic ones can be obtained in higher-order systems by pseudoeutectic reactions of a type where crystallites and a solid-solution matrix are simultaneously precipitated from a liquid.1"3 Trials to solidify such alloys directionally—the matrix consisting of a solid solution of chromium, nickel, and silicon and the reinforcing phase being Cr3C2— will be reported elsewhere.4 This note describes constitutional studies carried out primarily to determine -the position of the pseudoeutectic and further to insure that no undesirable reactions between the reinforcing phase and components of the matrix occur in the solid state at elevated temperatures. In the investigation it was specifically desired to reinforce a matrix which is as close as possible to the 80/20 Nichrome composition with Cr3C2 to insure good oxidation resistance and improve the strength at high temperatures. No konstitutional information on the quaternary C-Cr-Ni-Si svstem in the range of interest was found in the literature. Nevertheless, the two most important ternaries c-cr-Ni5 and have been completely investigated. On C-Cr-Si some investigations have been conducted,7"9 and C-Ni-Si was studied with a few alloys in the course of the present investination 9 Eight alloys were prepared to investigate the changes in the constitution of the ternary C-Cr3Ce-yNi eutectic5 with silicon contents up to 10 wt pct. Five alloys were made with varying chromium and carbon contents around compositions containing -60 to 70 wt pct Ni and 5 to 6 wt pct Si. The latter alloys were designed to locate the y(Ni-Cr-Si-C)-Cr3C2 pseudoeutectic reaction and to determine the maximum chromium content in solid solution compatible with a two-phase equilibrium between y and Cr3C2 only. The alloys were prepared from electrolyte nickel, semiconductor-grade silicon, high-purity chromium (99.999 pct pellets), and semiconductor-grade graphite. They were melted inductively in high-purity alumina crucibles under flowing argon. Twenty-gram charges were prepared and investigated by optical microscopy (including hot-stage investigations), X-ray powder methods, and electronmicroprobe analysis. The alloys were studied in the as-cast condition and also after a homogenization annealing treatment of 48 days at 900°C in evacuated quartz ampoules. The structures of all alloys based on the ternary eutectic plus silicon in the as-cast state consisted generally of an inhomogeneous solid solution and at least two other phases. Annealing of the alloys showed that the solid solution was homogenized but that an incomplete solid-state reaction had taken place in all alloys with silicon contents over 5 wt pct. This reaction is clearly visible in Fig. 1 around the large Cr3C2 crystals (gray areas). Below this concentration, the alloys consisted of a homogeneous matrix and precipitates of Cr3C2 plus graphite, Fig. 2. The Cr3C2 was entirely unreacted here. From these observations and subsequent X-ray and microprobe investigations, it was deduced that the

Jan 1, 1969

By D. H. Woodard

One of the principal uses of polarized light in metallurgy is to show the granular structure of metals by contrasting reflections. This use is confined largely to anisotropic metals, such as beryllium, tin, magnesium, and the like.1 Recently, Hone and Pearson2 have extended the use of polarized light to include the isotropic metal aluminum. This was made possible by the formation of an anodic film that was optically anisotropic and that had a fixed and reproducible structural relationship to the grains in the substrata. With their method, it was possible to indicate localized textures in annealed aluminum sheet. In the course of an investigation of plastic deformation at the National Bureau of Standards, it was found that the isotropic single phase alloy Monel could be made optically anisotropic by treatment with the usual Monel contrast etchant. Experiments soon showed that dif- , ferences in orientation could be detected easily. Previous investigations involving the use of polarized light have been restricted to annealed metals. In this paper it will be shown that inhomo-geneous plastic deformation which results in lattice bending and development of deformation bands, experienced by individual grains in polycrystalline Monel, is revealed in the microstruc-ture. This interpretation of the micro-structure was confirmed by a study of slip lines formed after prior plastic strain. Materials and Procedure The material used was Monel, the chemical composition of which was C—0.17 pet, Mn—1.28 pet, Fe—1.61 pet, S—0.009 pet, Si—0.17 pet, Cu— 30.70 pet, Ni—66.04 pet. The material was divided into 2 lots which were treated as follows: Lot A was heated at 1700°F for 3 hr to produce a fully annealed, coarse grained structure. Lot B was heated at 1400°F for 1 hr to produce a close approximation of a fully annealed structure without appreciable increase in the grain size of the original material. After each of these heat treatments the material was cooled in air. Samples for metallographic examination were cut from tensile and compression test specimens and were prepared by grinding on lead-tin laps, followed by electrolytic polishing, † Etching and the development of ridges were avoided by keeping the voltage above 3.8 and by preventing contamination of the polishing solution with water. Monel, when polished and treated with most etchants, is optically isotropic. However, when given a light etch for about 4 sec with the Monel contrast solution the surface of the metal becomes optically active. The microstructure when observed under crossed nicols* appears different from that viewed by ordinary light. This is shown by a comparison of micrographs made of the same area of a plastically deformed specimen using polarized light (Fig la) and white light (Fig 16). If Monel, which has been lightly treated with the contrast etchant, is slightly deformed by compression, rectangular figures are apparent over the specimen. However, within too short a period to be photographed, these rectangles become circular, probably because of surface tension effects within the etched film. The two observations,

Jan 1, 1950

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By M. R. J. Wyllie, H. W. Patnode

In the quantitative interpretation of electric log data it is essential to know the formation factor, defined as the ratio of the resistivity of the formation 100 per cent saturated with brine to the resistivity of the brine.' This concept implies that the formation factor for any given rock is constant irrespective of the resistivity of the brine or solution with which it is saturated. It is apparent that this can be true only when the rock matrix is wholly non-conductive. As reservoir rocks may contain clay or shale having an appreciable conductance one may expect these constituents to influence the determination of true formation factor. The formation factor may be theoretically derived from log data by dividing the resistivity of the mud filtrate invaded formation by the resistivity of the mud filtrate. Such a method of calculntion has implicit in it the assumption that the fluids in the invaded formation are wholly replaced by mud filtrate. that the solid matrix is non-conducting, and that the formation factor of the invaded zone is identical with the formation factor of the uninvaded zone. Since the validity of the first two basic assumptions regarding the insulating character of porous matrices and the displacement of the interstitial fluids in porous media do not appear to be fully established, the formation factors of a number of cores and clay slurries have been measured under conditions suitable for verifying the assumptions and the extent of any errors inherent in them. CORE STUDIES Apparatus and Procedure Resistivity measurements were made on short cylindrical permeable cores which had been previously mounted in lucite.2 The cores were clamped by means of insulated bolts between brass plates about 5 cm square and 1 cm in thickness. The plates were provided with a ring seal to prevent leakage between them and the core mount, and had a centrally located orifice so that fluids could be flowed through the mounted core. The brass mounting plates were used as electrodes and any current flow between them necessarily passed only through the constituents of the intervening core. Fluid saturation of the core, and fluid flow through the core, were effected by a centrifugal pump connected to the outflow end of the core, thus providing a differential pressure across the core of approximately one atmosphere. The procedure used was first to evacuate each core by means of the pump and then to saturate the core with an aqueous sodium chloride solution of known resistivity. The resistance of the core was measured and flow of the solution through the core continued for sufficient time to establish a constant resistance reading. After equilibrium had been reached with one solution, another sodium chloride solution of a different resistivity was flowed through the core and the flow continued until a constant resistance reading was again obtained. This procedure was continued until resistance measurements of the core had been made with a series of solutions within a salinity range from 1.0N NaCl to distilled water. The data obtained enabled the apparent formation factor of given porous rocks when saturated with fluids of different resistivity to be computed and also provided information regarding the ability of an invading fluid to displace interstitial water from a core. Results Berea Sandstone — The first core examined was a specimen of Berea sandstone." This core had been cut essentially parallel to the bedding for permeability studies. The core was clamped in the core holder and saturated with 1.0N NaCl solution and the resistance determined. It was subsequently flushed and the resistance measured when saturated in turn with 0.1N, 0.025N, 0.01N, .005N sodium chloride solutions and finally with distilled water. In flushing the core with each

Jan 1, 1950

By O. P. Quist, S. H. Carpenter

The internal friction of single-crystal LiF has been investigated as a function of crystal orientation, while simultaneously applying a static compressive load. Three different crystal orientations were used, these being samples with the (100), (110), and (111) directions along the sample length. Results show the internal friction measured to be similar in appearance but different in magnitude for the (100) and (110) samples. With both orientations, application of a static stress caused an increase in the amplitude-independent damping, which recovered with time. The amplitude-dependent damping was found to first decrease with load up to the yield stress and then increase rapidly. Samples of the (111) orientation were found to have no measurable internal friction even when loaded up to 3.0 kg per sq mm. These results are discussed in terms of current theories of internal friction in ionic crystals. This paper presents the results of an investigation of the dislocation mobility and dislocation motion in high-purity single-crystal LiF at applied stress levels up to the yield stress. Internal friction measurements of the dislocation damping while simultaneously applying a static compressive load was the experimental technique used. LiF crystals much prefer to slip on the (110) set of slip planes. However, with a suitable stress distribution they can be forced to slip on the {100} set of slip planes.' For both sets of slip planes the slip direction is the same, namely (110). The object of this investigation was to try and learn more about the dynamical properties of dislocations on the different slip systems in LiF crystals. EXPERIMENTAL PROCEDURE Dislocation damping was measured, in terms of the log decrement, using a five-component marx2 composite piezoelectric oscillator. The apparatus used allows one to measure the dislocation damping while simultaneously applying a static compressive load on the sample. A schematic of the apparatus used is shown in Fig. 1 and a complete discussion of its construction and operation is given elsewhere.3 All measurements were made at room temperature with a longitudinal resonant frequency of approximately 50 kc per sec. Damping measurements were made using longitudinal vibrations with strain amplitudes from up to 10. Static loads up to 3.0 kg per sq mm were applied to the sample while the damping was being measured. Samples used in this investigation were high-purity single crystals of LiF purchased from the Harshaw Chemical Co. All samples were approximately of an in. square and were hand-ground in length to one-half wavelength to match the resonant frequency of the driver and gage quartz crystals. Samples of three different crystallographic orientations were used, namely, crystals with the (loo), (110), and (111) direction parallel to their length. The magnitude of the damping is a direct measure of the area on the slip planes swept out by dislocations during a complete oscillatory cycle. With a sample of the (100) orientation the maximum applied shear stress, due to longitudinal vibrations, is on the (110) slip planes with zero shear stress on the (100) slip planes. Thus, damping measured from a (100) sample is due entirely to dislocation motion taking place on the (110) set of slip planes. Similarly, for a sample of the (111) orientation there is zero shear stress on the (110) set of slip planes and the damping measured from a sample of this orientation is due entirely to dislocation motion on the (100) set of slip planes. Samples of the (110) orientation will have a component of shear stress on both sets of slip planes and

Jan 1, 1969

By W. F. Flanagan, D. H. Polonis, S. D. Dahlgren

Rotation diffraction patterns of Cu-4.84 wt pct Si polymystalline samples were taken during the course of isothel-ma1 affing of the suPersaturated a phase, a diffraction spots were obserzled to streak during the initial stages of aging, and this streaking was similar to the streaking of a spots observed earlier by Barvett with deformed super saturated samples of the same composition. Although it was suggested that stacking faults were the sole cause of styeaking in the deformed samples, the present study has shown that plates with one small crystallite dimension can also contribute to the streaking when there is lattice coherency across close-packed planes. THE decomposition of the supersaturated a phase in Cu-Si alloys has been reported to occur by means of both thermal and stress activation.1-4 According to the Cu-Si phase diagram,3 Fig. 1, the supersaturated a phase (fcc) is expected to transform during aging by the precipitation of the y phase. The results of earlier studies2,4 have indicated that metastable k phase (hcp with nearly ideal close packing) forms initially at temperatures below the eutectoid temperature, after which the k transforms to the a and y phases. Hof-mann et al.4 have proposed a metastable version of the phase diagram, showing the approximate boundaries for k formation below the eutectoid temperature. In view of the close-packed nature of both the a and k phases, it is essential to consider the role assumed by stacking faults in the transformation. Streaking effects have been reported by Barrett 1 in the rotating crystal X-ray patterns of strained Cu-Si alloys and were attributed to stacking faults rather than particle size effects. This deduction was based on the observation that streaks in the diffraction patterns did not occur tangent to the 220fee Debye ring. It is known that the atom movements involved in faulting leave some X-ray reflections unaffected while others are broadened,' and, in particular, it has been shown that faulting will not cause streaking of 220fee reflections tangent to the 220fee Debye ring as would be expected if all the reflections were broadened.' The formation

Jan 1, 1967

By H. R. Barnhurst

It would be a difficult matter to trace from the beginning the very few improvements made in the burning of fuels prior to 1860. Donbtless the crossing of the sticks of wood in building a mood fire early appealed to our savage ancestry as a means of expediting its effectiveness for their crude culinary purposes. Stones and andirons came later in assisting the admission of air to the under part of the fuel bed, while beacons and cressets, utilized metal bars as supports for the same purpose. It is probable that Tuba1 Cain owed his success to the use of bellows making possible the use of mixed fuel and charge upon a hearth. With the development of working in cast iron, grate bars came in, and they are still with us doing duty in every household and almost every art where heat is a factor. Little was done beyond these crude methods prior to 1860. With the advancement of knowledge came the fuel-gas producer, a natural child of the retorts employed in supplying illuminating gas. It is only within the last 15 years that the conclusion became general that complicated systems for saving heat would not remedy deli-. ciencies in its primary development, and within that time there has been great advancement in the means of producing initially a fire of high effciency, so that to-day we are moving rapidly toward both high development and high absorption, with the resultant of high efficiencies. In studying the subject of the availability of pulverized coal as a fuel, it may occur to ask, why has this not come up earlier? This, question would be naturally prompted by recalling the fact that Thomas Crompton's English patents upon his methods were issued to him nearly 40 years ago. A conclusive answer to this, however, is that Crompton at that time had very crude facilities for making what was at best a very imperfect pulverization of the coal, arid the expense of preparation mas very great. He does not seem to have been aware of the advantage of a thorough drying of the coal in the

Jan 1, 1914

By E. A. Stevens

It has been ascertained in recent years that certain rocktypes, geological formations and structural conditions may be used as fairly reliable guides, when prospecting in recognized mineral belts or milling districts, with a reasonable certainty of discovering "pay-ore;" and that such is considered as a practically established conclusion may be inferred from a perusal of the recent reports of the U. S. Geological Survey and the literature of the several scientific societies discussing mining, geology, and kindred subjects. Cripple Creek is no exception to this conclusion, and the

Jan 1, 1903

I. C. WHITE, Morgantown, W. Va. (written discussion *).-The writer's conclusions with reference to the possibility of finding commercial deposits of petroleum in Brazil were published in 1908 in the Final Report of the Coal Commission of Brazil.1 Since this volume is not generally accessible, and the author has nothing to acid thereto, the following quotation found on pages 243-7 may prove of interest: The Possibility of Petroleum Deposits in Brazil "The writer has often been asked to express an opinion as to the possibility of finding petroleum in commercial quantity in Brazil. "The question is one that does not admit of an adequate answer except for the regions visited by the writer, which as already stated, include only, a portion of that great territory, and only the southern portion of Brazil; namely, the states of Rio Grande do Sul, Santa Catharina, Paraná, and a few rapid excursions across São Paulo, and Minas Geraes, as well as the brief visit to Marahú in Bahia. "That the sedimentary beds of the Brazilian Permian once held some petroleum is attested by the evidence of the Iraty black shale which gives off the characteristic odor of this substance from São Paulo to Rio Grande do Sul.

Jan 1, 1918

EUGENE WESLEY SHAW,* Washington, D. C. (written discussion ?).-Studies of the probable future production of oil wells and fields-particularly those in the nature of the recent work by Lewis and Beal, having the object of increasing the percentage of recovery-rank, in both practical and theoretic value, very high, if indeed they do not outrank all other petroleum investigations except structural surveys. Even such surveys, although saving untold millions that might have been spent in prospecting unpromising territory, may have less ultimate value than generally supposed, for it may perhaps be argued that much if not most of the condemned territory will sooner or later be tested-some is already productive-and the most that can be rightly claimed is the recovery of cream first; also that the consumption of the richest portions first cannot be extenuated, as it might with some resources, on the ground that if the best is not taken now it will deteriorate.

Jan 5, 1918

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem' has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.' show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967

W. L. Saunders, New York, N. Y. (communication to the Secretary*):—The Laramie tunnel, though a small one, compares very favorably in the speed of driving with the great Alpine tunnels which have the record so far. I think it safe to say that, taking all things into consideration, the record made at Laramie is the best American record, though it still falls short of the long-tunnel records abroad. In discussing tunnel-records it must always be borne in mind that there are conditions peculiar to each individual tunnel job, so that no comparisons are complete, fair and conclusive. At Laramie there is one point which stands out prominently, and which distinguishes this from any of the recently-built Alpine tunnels, and that is that here we have great progress in an American driven tunnel without the use of a carriage for mounting the drills. At the Arlberg and Loetschberg tunnels, the carriage was an essential condition for progress. All the heading-drills were mounted upon a bar which rested upon a small carriage. This carriage was withdrawn after the drilling and run into the heading after the blast without much disturbance of the drills, and with very little adjustment except that required in jacking the horizontal bar across the tunnel. The carriage was so small in its track-area that it required little mucking to run it in to the face; and as the rock-drills used were heavy machines 38 in. in diameter, progress in setting up and drilling was very much accelerated by the use of the carriage. At the Laramie tunnel hammer-drills were used instead of piston-drills, and here we have an important distinction which

Jan 1, 1913

By H. Buttner, F. H. Udin, J. Wulff

GRAIN boundaries, the interface between adjacent crystals differing only in respective orientation, have been the object of much experimental and moderate theoretical attention for many years. The earlier experimental work was primarily concerned with the effect that grain boundaries have on the physical behavior of metals, while the basic nature of the boundaries themselves drew only secondary attention. A complete turnabout has been witnessed in more recent years, however, as researchers are now undertaking investigations bearing as directly as possible on the character and physical properties of the grain boundary. Quite comprehensive reviews of the past literature on the subject of grain boundaries have been reported on numerous occasions by various authors, and together these references represent a thorough coverage.'-? It becomes evident in these reviews and other papers"" that the properties of grain boundaries can be explained by regarding a grain boundary as a crystalline region of transition between two unmatched grains. Studies show that grain boundaries have a definite interfacial energy. By measuring the geometry about a point where three interfaces meet in equilibrium, the energy of any two boundaries can be measured with respect to the third. If the absolute interfacial energy of one boundary is known, the absolute energy of the other two boundaries can be calculated. This apparently holds true for any system of phases and interfaces.""25 Most studies have been carried out on solid-solid or liquid-solid systems, or systems of both. However, if about the point of intersection one phase is vapor and the other two are disoriented grains, then two interfaces are surfaces, and one is a grain boundary. Investigations leading to relative grain boundary energy for this particular system have been made by Fullman,23 Greenough and King," and Bailey and Watkins." Herring" treats the system mathematically and arrives at an equation, which appears as Eq. 1, in a form consistent with the reference angles indicated in Fig. 1, ( d?1 ?n = x sina + cosa ( ------- 2 ?2 Sinß da + C0Sß (d?2/d As the system of interfaces comes to equilibrium, a groove of angle appears at the intersection of the grain boundary with the surface, an effect first observed by Rosenhain and Humfrey." Eq. 1 is essentially a summation of the vertical components in Fig. 1 set equal to zero, where ?1 and ?2 are surface tension vectors lying along the side of the groove at point 0 in the groove root. The differential vectors represent the forces tending to rotate the surface into a position that will expose a crystal cleavage surface of lowest energy. Chalmers, King, and Shuttleworth- simplify Eq. 1 by assuming the differential vectors equal to zero, ?1 = ?2= ?Surface and arrive at the following equation: ?B = 2?s cos [2] Greenough and King24 use Eq. 2 for determining the grain boundary energy of silver using prepared bi-crystals of known orientation. Bailey and Watkins25 have done the same for copper, as did Chalmers and others on lead. These authors report the grain boundary values as ratios relative to the surface energy. In the above work, the orientation of grains forming the grain boundary in all cases was controlled so

Jan 1, 1954

By A. E. Dwight, A. F. Berndt

Binary and ternary alloys of uranium with transition metals were prepared with U2X stoichiometry. The compounds U2Tc, U2Rh, U2Os, and U2lr were formed by peritectic or peritectoid transformations, and were shown to be isostructural with U2Ru. The lattice constants are presented. Miscibility relationships obtained from the study of ternary alloys are graphically summarized in terms of an area-of-stability plot. The compound U2Re is not isostructural with either U2Ru or U2Mo. A series of compounds with stoichiometry U2X has been prepared in which X is technetium, rhodium, rhenium, osmium, or iridium. The only other U2X compounds, for which X is related to the above transition metals by proximity in the periodic table, are U2Mo and U2Ru. The structure of U2Mo is the tetragonal C11b type (MoSi2 type)1 and U2Ru is monoclinic, with a new structure type.' This investigation was undertaken to determine if any of the above compounds are isostructural with either U2Ru or U2Mo and to find the range of occurrence of these phases. EXPERIMENTAL Alloys were prepared from stoichiometric amounts of electrolytic uranium (99.99 pet pure) and transition metals of 99.5 pet purity (98+ pet pure Tc), by arc melting on a water-cooled copper hearth under an Ar-He atmosphere. Weight losses were negligible. The buttons were homogenized at temperatures between 700o and 800°C (900°C for U2Tc) in evacuated capsules and air-cooled. The X-ray powder specimens were annealed briefly at the temperature of homogenization. Except in the case of the technetium alloy, metallographic examination was used to determine the number of phases present. The radiation hazard involved in handling technetium precluded the use of metallography to examine U2Tc. The temperature and mode of formation of the U2X phases were determined by heating the metallographic specimens to successively higher temperatures, until examination indicated the presence of chilled liquid or a peritectoid transformation. RESULTS The U2X compounds investigated were found to be formed under the following conditions: UzTc unknown U2Ru peritectic 897o ± 3°C U2Rh peritectoid 755o ± 5°C U2Re peritectoid3 below 750°C Uas peritectic4 920°C U2Ir peritectoid 775o ± 5oC Debye-Scherrer patterns for the above U2X phases were made with CuKa radiation (nickel filter). The similarities in the positions and intensities of the strongest lines in the front-reflection region strongly suggested that U2Tc, U2Ru, U2Rh, U2Os, and U21r are isostructural with only minor differences in the unit-cell dimensions. The known lattice constants and intensities of the Debye-Scherrer rings for U2RU2 were used as a guide in order to index the low-angle X-ray reflections of the U2TC, U2Rh, U2Os, and U2Ir powder patterns. Approximate lattice constants for these compounds were thus obtained and were used along with the intensities observed for U2Ru to index the strongest lines in the back-reflection regions. A sin2 2? correction term was included and the lattice constants were refined and standard deviations estimated by least squares. Comparison of observed and calculated values of Q(= 4 sin2?/?2) used in these calculations are given in Table I. In each case when the positions of lines could not be resolved on the films they were not measured. The final lattice constants, with their standard deviations, are given in Table 11, along with the unit-cell volume and X-ray density. The values of the atomic volume5 of the transition ele-

Jan 1, 1965

By John F. Slonaker, Joseph W. Leonard

This note is a review of current research intended to increase the utilization of coal ash. Due to the magnitude of the fly-ash research program, some projects may be inadvertently omitted. Field research on fly-ash for use as an agricultural fertilizer is being monitored at Virginia Polytechnic Institute and State University. This research is directed at determining the plant nutrients that are available in fly ash as well as the quantities of fly ash that can be applied to agricultural soil.

Jan 1, 1975

By W. L. Korbee, P. Hazebroek, M. Prats, E. E. Allen, C. A. 225-000-000-017 Verbraak, H. C. van Elst

In a recent paper,' one of us has presented some experimental evidence on the relationship between twinning and brittle fracture in steel. From metallographic examinations of brittle fracture it could be derived that mechanical twins and microcracks are formed already in front of a running brittle fracture. A tentative explanation based on the evaluation of the statistical distribution of mechanical twins vs various angles to the fracture was given in the above mentioned paper. It was suggested that these twins are caused by stress waves emitted by a running brittle fracture. With the aid of high-speed photography and the use of photo-stress sheet we are now able to study in more detail the propagation of a brittle fracture and the emittance of stress waves connected with fracture. A typical example is given in Fig. 1. In this figure a running brittle fracture in an ordinary Thomas steel is shown. The experiment was performed on a Robertson apparatus and the stress waves caused by the fracture were made visible with photo-stress

Jan 1, 1962

By Ronald C. Koo

THE effect of grain size on the mechanical properties of the bcc metals has been a subject of intensive theoretical and experimental study.'-l5 Quantitative relationships have been established experimentally between yield stress and grain size and between the ductile-brittle transition temperature and grain size in a number of metals.6"15 Much significance has therefore been attached theoretically to the grain size dependence. In all these experiments, different grain sizes were always achieved by annealing specimens at various temperatures. The implicit assumption was that any change in the dislocation substructure or in the distribution of impurities which might occur simultaneously with the production of various grain sizes had only a negligible effect on the mechanical properties. The validity of this assumption, however, is questionable. transformation in iron-nickel alloys is actually an extraneous phenomenon due to inadvertent compositional changes in the martensite if the heating rate is not sufficiently rapid. This complication can be avoided by up-quenching for the reversal treatment,5 and then the stabilization does not appear. Clearly, the lattice imperfections and strengthening produced by the reverse transformation are not responsible for the marked stabilization which has been observed by other investigators in these alloys. Data will be presented in this note to show that, at least in recrystallized tungsten of commercial purity, the difference in the ductile-brittle transition temperature of specimens annealed at various temperatures is more a result of a variation in the distribution of impurities rather than of the difference in grain size produced by the anneal. Ductile-brittle transition temperatures in tension were determined on powder-metallurgy tungsten specimens recrystallized at various temperatures. Tensile specimens having a gage length of 1.50 in. and gage diam of 0.18 in. were recrystallized at 1450°, 2000°, 2350°, 2550°, 2750°, or 2800" for 30 min in a vacuum furnace at a pressure of 1 x 10"5 mm of Hg and then tested at a constant extension rate of 8 x 10 per sec in an argon atmosphere from 100" to 800". Typical quantitative analyses of impurities are given in the Table. These results show that, within the precision of the analyses, see Table, annealing did not result in any detectable change in the impurity contents of the specimens, nor was there any detectable difference in purity between specimens having large differences in grain size annealed at the same temperatures . The results of the tensile tests yielded three distinct ductile-brittle transition curves approximately 225' apart. As shown in Fig. 1, data of specimens annealed at 1450°C and those of specimens annealed at 2000°C (O) fell on Curve A. Data of specimens annealed at 2350" and 2550°C fell on Curve B, and those of specimens annealed at 2750" and 2800°C fell on Curve C. The decrease in ductility with increase in annealing temperature became so pronounced that one third of the specimens annealed at 2750" and two thirds of the specimens

Jan 1, 1963

By A. T. Beckwith

The Lehigh Navigation Coal Company Inc. operates steep-pitch, relatively deep mines in the Panther Creek Valley, at the eastern end of the southern anthracite coal field. Commercially minable coal beds are the Mammoth,† Primrose, Orchard, and Buck Mountain;‡ their respective thicknesses average 50, 15, 10 and 12 ft. Sand slates immediately overlie and underlie these beds, though in some locations sandstone or conglomerate beds occur. Underground operations extend to a depth of 1200 ft. below the surface, and comprise a bulk of virgin work on the lower levels, and a small amount of remining on the upper levels. With increase in depth, ventilation has become a more important factor. Development In early days slopes or drifts were driven in the outcropping coal on the hillsides. Subsequent development was by water-level tunnels, with portals above high water in Panther Creek. These tunnels have been maintained because they intercept and drain much water that enters the mined-out portion of the bed and otherwise would follow down to the deep workings+ Below these tunnels, the coal was customarily developed by slopes. Muleways, which are zigzag chutes easy to travel, were also driven to connect lower openings with the water levels. When it became necessary to go still deeper, the slopes were abandoned, and vertical multicompartment shafts were sunk from the surface. Levels have been at vertical intervals of from 175 to 250 ft. Recent practice has been toward the latter spacing, splitting the total lift, however, by starting to mine from chutes extending halfway up to the level above. Chutes customarily are spaced at 50, 60 or 70-ft. centers along the gangways. At some mines, additional shafts have been sunk from the surface to the level containing the main pumping station, and these carry the discharge lines from the pumps. As the mines are ventilated by the exhausting system, both the hoisting and so-called water shafts serve as intakes. The main fan is always on the surface, and is connected with the return airways from the various levels by an air hole or a vertical shaft. For economy, when the present deepest levels were developed, and return-air shafts or air holes were not extended to the new level, but connections were made from the new level to that above by two or more holes. It is doubtful that this method will be continued, as complications in the system, increased resistance to flow, and other difficulties undoubtedly will counterbalance any economies this provision may afford. During the early years of mining, when operations were at no great depth, all development headings were driven in the coal bed. As mining progressed downward, increased ground pressures slowed develop

Jan 1, 1942

By A. T. Beckwith

The Lehigh Navigation Coal Company Inc. operates steep-pitch, relatively deep mines in the Panther Creek Valley, at the eastern end of the southern anthracite coal field. Commercially minable coal beds are the Mammoth,† Primrose, Orchard, and Buck Mountain;‡ their respective thicknesses average 50, 15, 10 and 12 ft. Sand slates immediately overlie and underlie these beds, though in some locations sandstone or conglomerate beds occur. Underground operations extend to a depth of 1200 ft. below the surface, and comprise a bulk of virgin work on the lower levels, and a small amount of remining on the upper levels. With increase in depth, ventilation has become a more important factor. Development In early days slopes or drifts were driven in the outcropping coal on the hillsides. Subsequent development was by water-level tunnels, with portals above high water in Panther Creek. These tunnels have been maintained because they intercept and drain much water that enters the mined-out portion of the bed and otherwise would follow down to the deep workings+ Below these tunnels, the coal was customarily developed by slopes. Muleways, which are zigzag chutes easy to travel, were also driven to connect lower openings with the water levels. When it became necessary to go still deeper, the slopes were abandoned, and vertical multicompartment shafts were sunk from the surface. Levels have been at vertical intervals of from 175 to 250 ft. Recent practice has been toward the latter spacing, splitting the total lift, however, by starting to mine from chutes extending halfway up to the level above. Chutes customarily are spaced at 50, 60 or 70-ft. centers along the gangways. At some mines, additional shafts have been sunk from the surface to the level containing the main pumping station, and these carry the discharge lines from the pumps. As the mines are ventilated by the exhausting system, both the hoisting and so-called water shafts serve as intakes. The main fan is always on the surface, and is connected with the return airways from the various levels by an air hole or a vertical shaft. For economy, when the present deepest levels were developed, and return-air shafts or air holes were not extended to the new level, but connections were made from the new level to that above by two or more holes. It is doubtful that this method will be continued, as complications in the system, increased resistance to flow, and other difficulties undoubtedly will counterbalance any economies this provision may afford. During the early years of mining, when operations were at no great depth, all development headings were driven in the coal bed. As mining progressed downward, increased ground pressures slowed develop

Jan 1, 1942