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By K. G. Wikle, J. G. Klein, W. W. Beaver

Consolidation of hydride process, electrolytic, calcium reduced, and comminuted thorium powder, as well as saw chips and lathe turnings, by vacuum hot pressing and by cold pressing-vacuum sintering was studied. The mechanical properties of the consolidated material in the extruded form are compared with those of wrought castings. AT present there little little industrial use for thorium metal, although it has some important though small scale applications in electronic equipment. Despite its high inelting point—about 1750°C —a low modulus of elasticity, 11.4xl0 si at 20°C;' relatively low mechanical properties coupled with a high density, 11.7 g per cu cm; and an unusually high chemical activity with normal atmospheres limit any structural applications. The metal is utilized as an alloying element principally in magnesium. Pure thorium finds utility as electrodes in gaseous discharge lamps such as the high intensity mercury lamp' because its low work function and high electron emissivity provide lower starting potentials and more uniform operating characteristics than other available materials. The metal is also found in photoelectric tubes used for the measurement of the ultraviolet spectrum." Thorium metal has been used in germicidal lamps of the cold cathode type as sputtered coatings on nickel in order to provide a low work function surface and a low starting voltage. Other applications have involved the radioactive properties of thorium for the production of ionized particles." The potential value of thorium is much greater than its present use pattern because of possible utility in the field of nuclear power. Th may be converted through nuclear reaction to a fissionable element U which should be capable of acting similarly to U in the g'eneration of atomic power. Thorium has been reported to be about three times as plentiful as uranium in the earth's crust, placing it in the order of abundance of lead and molybdenum." Thus, it is of interest in augmenting the potential supply of fissionable material for nuclear power. Because of its high melting point, thorium is usually produced as a powder through the calcium reduction of its oxide or thermal reduction of halides by sodium, magnesium, and calcium. It may also be produced in flake form by electrolysis of fused alkali or alkaline earth chloricles and fluorides. Therefore, powder metallurgy assumes importance in the fab- rication of thorium metal shapes. Furthermore, it is rather difficult to obtain pure thorium by melting, as the molten metal reacts readily with graphite as well as oxide, carbide, and nitride refractories. These contaminate the melt with oxides, carbides, and metallic impurities." The current investigation was undertaken to examine the fabrication of thorium by powder metallurgy methods which have been used for the commercial production of beryllium and other metals.' A sparcity of data concerning the comparative cold and hot compaction of thorium powders of different derivation existed. Therefore, all commercially available types were examined along with other experimentally produced thorium powders in order to round out the comparison of consolidated thorium powders with melted reguline metal. Review of the Literature By heating a mixture of ThC1, with potassium, Berzelius made the first thorium metal as an impure powder in 1828. Improvements in the basic process, increasing thorium assay to 99 pct, were made by several investigators including Arsem," Lely and Hamberger10 and Von Bolton." Calcium reduction of Tho, to make powders was investigated by Berger," Huppertz,'" Kroll," and Kuzel and Wedekind.'" A thorium powder produced by this method using a CaC1, fluxing agent assayed 99.7 pct, as reported by Marden and Rentschler.'" Compacted and sintered, this product was found to be ductile, and could be fabricated into wire and sheet. Improvements of the calcium reduction process were made later" wherein CaCl, was eliminated from the reaction, producing metal assaying 99.8 pct Th. Further work by Lilliendah118 howed that a coarser metal could be obtained by the substitution of ThC1, or ThOC1, for oxide with consequent advantage of stability to atmospheric reaction. Reports on the technology of thorium developed in Germany during World War II have been made by Espe."' Thorium powder of 99.5 pct Th was obtained by reduction of the oxide by calcium. Screening to —200 mesh, compacting with about 20 tsi, and sintering in vacuo at 1320" to 1360°C for 3 hr resulted in a porous sinter cake. The sinter cake was sufficiently ductile to be worked into bar, wire, and sheet which could be employed as electrode materials.

Jan 1, 1957

By R. W. Raymond

CLARENCE King born January 6,1842, at Newport, R. I. His ancestors on both sides mere New Englanders, of English blood, and among them not a few distinguished themselves in art, science, politics or commerce. His grandfather, Samuel Vernon King (partner in 1803 in the house of Talbot, O1yphant & King, later known as King $ Co.), was a pioneer in the China trade, and four of his sons succeeded him in the business. Three of the four died in the far East; and one of

Jan 1, 1903

By B. H. Caudle, L. H. Silberberg

Reservoir depletion by natural water drive is typified by the movement of water from an aquifer into the adjacent oil-bearing formation. Prior studies of this type 01 water movement have generally neglected the resistance to flow in the aquifer and its effect on the movement of water into the oil bearing zone. A method for designing and operating scaled models of such reservoir systems is presented. Experimental data on a model of an edge-water-drive reservoir are shown and discussed. INTRODUCTION Most petroleum reservoirs derive at least a part of their productive capacity from water influx. This water may be injected from the surface or it may come from an aquifer adjacent to the oil zone. In either case, the reservoir engineer must be able to estimate the advance of the water as a function of either the elapsed time or the fluid produced. This paper describes a type of fluid flow model which includes the effect of viscous and gravitational forces in the reservoir and the surrounding aquifer. Natural water influx can be divided into three general (but widely overlapping) categories according to the direction of flow in the aquifer. These are shown schematically in Fig. 1. Fig. l(a) illustrates an edge-water-drive mechanism. In this case, water advances updip along the stratum but the movement of water is essentially horizontal and very little of the oil is actually underlain by water. The bottom-water drive (Fig. l(b)) is characterized by a thick aquifer underlying the oil zone. The water movement is generally vertical in the aquifer. The third category is illustrated in l(c). Referred to as the "thin oil column", this type of oil accumulation consists of oil over water in a relatively thin stratum. Fluid movement is horizontal in both the oil and water zones, except close to the producing well. One characteristic which all three of these types have in common is that part of the water flow takes place in the water invaded region of the oil reservoir while the remainder of the water flow occurs in the aquifer. The resistance to the flow of water usually will not be the same in these two regions. This occurs because the porous rock normally contains only water in the aquifer, while the water-invaded region always contains microscopic globules of bypassed oil (residual oil) which interfere with the flow of water through the rock. The production history of any type of a water-drive system is a function of two phenomena — where the water goes, and how it displaces the oil in the area invaded by the water. It is usually impractical to study these two phenomena at the same time. In most cases one type of analysis is used to predict the gross movement of water in the reservoir, while a different type of analysis is employed to determine the amount of oil to be recovered from the gross volume contacted by the water. The portion of the oil reservoir which is invaded by water is mainly a function of the resistances to fluid flow in the several parts of the flow system. This gross water influx in the three types of natural water drive typically results in water cusping to the production wells either from the side or from below (water coning). In 1747, Muskat described a greatly simplified mathematical model for predicting the area invaded by water in a bottom-water-drive reservoir.1 This model used the Laplace equation and suitable boundary conditions to describe the isopotentials and streamlines in the flow system. The use of this model assumes that (1) the reservoir rock is homogeneous in nature, (2) the oil and water mobilities are equal, (3) there is no oil flowing in the water invaded region, and (4) external forces — such as gravity — do not affect the flow. This method has been used for both natural water drives and water injection projects. In this, as in most models, the method of images is used to reduce the size of the model necessary to describe the reservoir. The assumption of equal viscosities and permea-

Jan 1, 1966

By R. L. Wilcox, M. L. Fuller

Most commercial alloys undergo changes in phase composition after casting. This is a natural result of the fact that the alloys are not in a state of phase equilibrium as cast and phase changes will therefore take place, with more or less rapidity, in an attempt to attain equilibrium. The practical aspect of aging in zinc-Alloy die castings concerns the changes in physical properties and in dimensions that may accompany aging phase changes. Harmful alterations have been reduced to a minimum and zinc-alloy die castings are being produced today that are so stable with respect to dimensions and physical properties that they are entirely suitable for most practical purposes1. In the first paper2 of this series, and in this paper, aging phase changes of zinc-alloy die castings have been investigated and the possible influence of these changes on dimensional changes of the castings has been evaluated and compared with the dimensional changes actually experienced. The change of dimensions has been selected for practical comparison in these papers because the effect of phase changes on the dimensions of a casting is directly calculable from X-ray crystal-analysis data of the phase structure. The die-casting alloys considered contain, in addition to zinc, 4 per cent of aluminum, about 0.03 per cent magnesium, and from 0 to 3 per cent of copper. It was shown in the former paper that the eutectoidal decomposition of the beta aluminum-zinc phase, while intrinsically capable of causing a considerable shrinkage, can have very little effect on the observed shrinkage of die castings because it takes place within a few days of aging, whereas the observed shrinkage continues for five weeks. It was therefore concluded that the other existing phase change, namely, the segregation of secondary phase from the zinc-base solid solution, must account for the major portion of the shrinkage.

Jan 1, 1936

By Michael B. Bever, Carl F. Floe

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By Carl F. Floe, Michael B. Bever

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By T. W. Guy

DURING recent years, tremendous strides have been made in the economical use of coal. This has resulted in, and to some extent has been a result of, making the fuel specifications more and more rigid. For this reason, all producers have found it necessary to improve their preparation materially, both as to sizing and the elimination of impurities, either by more effective preparation underground or at the tipple and cleaning plant, or both. This cause and its effect in all producing fields seem likely to continue for several years-at least. The splendid inherent qualities of the Pocahontas and New River coals are known all over the world, but their good reputation is only partly due to inherent qualities, and to natural conditions which generally favor loading coal comparatively free from impurities; it is due in large measure to the care and skill used, either with or without the aid of mechanical devices, to ship products consistently low in ash. The first coal from the West Virginia smokeless fields was mined and shipped near Quinnimont, on New River, in 1871, while the first shipments from the Pocahontas field were in 1883. The development of both fields progressed rapidly. At first activities followed the main lines of the Chesapeake & Ohio and Norfolk & Western railroads, and were extended later as branch lines were built from these roads. The Virginian R. R., about 1907, opened up the Winding Gulf territory, which has since become a large producer of smokeless coals from the Pocahontas and the New River measures.

Jan 1, 1931

By D. S. Greig

There was a decline in the Italian oil production in 1933 and also in the footage drilled. A total of about 194,500 bbl. of crude oil was produced in the Emilia district of northern Italy from the same fields in production as in 1932. New drilling to the extent of 80,700 ft. failed to find new production to compensate for the decline in old wells, and no new fields were discovered in spite of an active exploration campaign by the government-owned company A.G.I.P., which has just completed the first year of a five-year exploration program. This company drilled a total of about 33,000 ft. The majority of its tests were drilled in the Po Valley upon locations selected by geophysical methods. This company is changing over to the rotary system for all future wells. It produced about 16,600 bbl. of oil from wells near Salsomaggiore and in the Po Valley. The Petroli d'Italia, which operates the old fields of Montechino, Valleja and Gratera south of Piacenza, has been doing normal development drilling in the endeavor to extend its present fields. Also it was drilling two exploration wells in the Torino district. It drilled a total of about 13,930 ft. and produced approximately 12,645 bbl. of very high-grade oil (specific gravity about 0.765). The Societa Petrolifera Italiana was occupied chiefly in exploratory drilling in the endeavor to extend its producing fields at Salsomaggiore and at Vallezza, south of Parma. It was also drilling one exploration well at Rile dell7Olio near Voghera on the line Milan-Genoa. It drilled a total of 33,849 ft. and obtained a production from its two fields of 165,273 bbl. It also produced 123,220 gal. of casinghead gasoline from Vallezza field absorption plant.

Jan 1, 1934

By H. Reginald Hardy, Gary L. Mowrey

Field studies were conducted over a longwall coal mining operation to investigate the feasibility of using microseismic techniques to detect and to locate any areas of instability in the vicinity of the longwall. An array of geophones buried at depths of 3 to 8 m from surface were positioned approximately 130 m above the active area of the longwall panel. A mobile microseismic monitoring facility amplified, filtered, and recorded the microseismic activity sensed by the geophones. Microseismic events were detected at depths of at least 130 m and at horizontal distances in excess of 250 m from the source. Most events, which resembled decaying sinusoidal transients, had frequencies of 10 to 100 Hz, and particle velocities of 1 to 8 pm/s. Source locations for the 150 largest events were computed using a least-square travel-time-difference method. Both isotropic and unique wave propagation velocity models were considered when evaluating the source locations. Most of the events were computed to be within ± 30 m vertically of the coal seam and ± 15 m horizontally of the longwall face, when the unique velocity model was employed.

Jan 1, 1980

GENERAL GEOLOGIC DESCRIPTION The Escalante silver deposit located in southwestern Utah is an epithermal vein system consisting of a hanging wall and footwall vein, straight along strike and dipping about 1.2 rad (70°). The veins consist of banded quartz and calcite fissure fillings between volcanic wall rock that are silicified for some distance outward from the vein. The walls of the veins are sharp and the silver values are irratically distributed through the various bands within the vein. Only very low grade values are to be found in the wall rock on either side. The portion of the veins above the water table have been somewhat leached, with some secondary enrichment below. The mineralogical zonation is variable due to a fluctuating water table through geologic time. SAMPLE MANAGEMENT AND COMPOSITE ASSAYS Sample data for the deposit was obtained from over 50 diamond drill holes, from channel samples cut at intervals across a drift, and from scattered surface trenches along the out- crop of the hanging wall vein. Fig. 13-1 is a surface plan map showing the vein outcrop and some diamond drill locations. Two cross sections through the vein are shown in Figs. 1 3-2 and 13-3. Nearly all of the diamond drill core of vein material was assayed in 0.3-m (I-ft) lengths, from which weighted composite assays were manually calculated for the horizontal thickness of the vein. The centers of the composited samples were plotted in north and east coordinates and by elevation, and locations and assay

Jan 1, 1980

By M. E. Wadsworth, K. J. Richards

The oxidation rates of tantalum in various partial pressures of carbon dioxide in the temperature range 700°to 950°C were measured with a thermo-gravimetric balance. Oxidation involved a surface -controlled reaction associated with the formation of a nonprotective layer of Ta2O5. Below about 720°C, there was a change in the rate-determining mechanism, and above 830°C the linear rate was preceded by a complex region of nonlinear oxidation behavior. The linear oxidation of tantalum has been explained quantitatively in terms of carbon dioxide adsorption, followed by a rate-controlling surface reaction. The initial adsorption has been expressed both as an equilibrium process and as a steady-state reaction. The enthalpy for chemisorption of CO, was determined to be -17.3 kcal per mole. The surface-controlled reaction had an activation enthalpy of 40.4 kcal per mole. A considerable amount of interest has been shown in recent years in the oxidation of tantalum and the nature of the oxide film produced. This interest is associated with the increasing demand in our technology for structural materials to withstand high temperatures and corrosive atmospheres. The low oxidation resistance of tantalum has severely restricted its application as a high-strength, high-temperature material. As a fundamental approach to the realization of the full poten- tials of this metal, the kinetics of the oxidation of tantalum in oxygen and air have been extensively studied; however, very little work has been reported on the effect of other gases, including carbon dioxide. According to Miller,' the only reported study of the reaction between tantalum and dry carbon dioxide is a restricted observation by O'Driscoll et al.2 at 8 atm absolute pressure and 500°C. Therefore, this study was made to investigate the reaction of tantalum with carbon dioxide. EXPERIMENTAL MATERIALS AND METHODS The vacuum-annealed tantalum used in this study was obtained from Fansteel Metallurgical Corp. as 0.025-mm-thick sheet stock. This material had less than 0.1 pct total impurities, and the maximum individual impurity concentrations were

Jan 1, 1964

By Willard S. Morse

The purpose of this paper is to record the results obtained in the use of the Russell process at Aspen, Colo., covering a period of fourteen months, from November, 1891, to December, 1892, during which time over 30,000 tons of ore, purchased outright, on sample and assay, were treated. No explanation of results will be attempted, nor will the chemistry of the process be discussed. The plant was designed by C. A. Stetefeldt, of San Francisco, and built by the owners by day-labor. The entire plant is run by water-power, supplied by a flume 3600 feet long, and a pipe-line 2200 feet long, with a head of 170 feet. A Pelton water-wheel, 8 feet in diameter, is used, from which power is transmitted by wire-rope to the main counter-shaft in the mill, a distance of about 250 feet. From the mill to the samplingworks, about 150 feet, power is also transmitted by a wirerope. A Pelton water-wheel, 3 feet in diameter, supplies power to the dynamo for lighting the plant. The works are located adjoining the Santa Fe railroad tracks, and all ore and supplies are unloaded directly from the cars to the works. The sampling-works are provided with crushers and rolls, the latter being used only on samples, and not on the entire ore. The Cornish hand-quartering method is used in sampling ore for purchase. After crushing and sampling, the ore goes to the bedding-floor, where it is made up into mixtures suitable for the mill. The drying-plant consists of four Stetefeldt double shelfdryers, six shelves high, and is provided with dust-chambers and a stack 65 feet high for draft. These dryers are fired with gas

Jan 1, 1896

By L. C. Brown, J. S. Kirkaldy

Measurements have been made of carbon diffuswn in the five ternary austenites Fe-C-Si, Fe-C-Ni, Fe-C-Co, Fe-C-Mn, and Fe-C-Cr in which the carbon (component 1) diffuses through interstitial sites and the ternary addition (component 2) diffuses substitutionally. Values of the diffusion-coefficient ratio, D12/D11 were determined for each system with finite couples using the transient equilibrium method. The effect of temperature and of concentrations of both the carbon and substitutional component upon D12/D was examined and was found to agree with the theoretical predictions. It is concluded that within an experimental uncertainty of 10 to 15 pct, it is possible to calculate the ratio D12/D11 from purely thermody-namic data. Difficulties of measuring the other off-diagonal coefficient, 4,, are discussed. Any quantitative attack on the fundamentals of the hardenability problem in steel must begin with the multicomponent diffusion formalism and with the accumulation of data pertaining thereto. In a recent paper Kirkaldy and purdy 1 employed the formalism derived from irreversible thermodynamics to treat the problem of diffusion in ternary austenites. In the latter solutions, carbon diffuses through interstitial sites and the substitutional component diffuses through the lattice. Examples were given of diffusion in the systems Fe-Mn-C and Fe-Si-C. In the present paper, we present new results on and discuss their agreement with the thermody-namic theory. Since the theory has been slightly modified from the original presentation of Kirkaldy and Purdy, their results on Fe-Si-C and Fe-Mn-C have been recalculated and are presented here for completeness. The flux of the interstitial component with respect to a fixed lattice framework can be written as a linear expansion in the independent concentration gradients, where X1 and X2 are the independent thermody-namic forces in the lattice fixed frame of reference. These forces can be obtained from the general statement for forces in a volume fixed frame2 if the partial molar volume of carbon atoms is set equal to zero and that of the substitutional component 2 is set equal to unity, viz where the are the chemical potentials and the N's are mole fractions. Introducing into [3] and [4] the function If, as suggested by statistical arguments, the off-diagonal interaction L12 is sufficiently small, [6] reduces to i.e., the coefficient ratio becomes purely thermo-dynamic. The activity of components 1 and 2 in a dilute ternary system (standard state at infinite dilution) may be represented by the expansion3

Jan 1, 1964

By Ervin E. Underwood

IT has been recognized for many years that dis-persed particles have great value in raising the creep resistance of metallic alloys. In fact, some of the most successful high-temperature alloys owe their superiority to this factor above all others. A recent observation by Glen1," indicates that even better high-temperature resistance to deformation results in alloys capable of two successive precipitation reactions. The ramifications of this finding are of great interest. Unfortunately, our understanding of the reasons for such notable improvements has not kept pace with technical developments. In an effort to uncover some of the basic facts governing strengthening by particles, a program was initiated at the Battelle Memorial Institute with the primary goal of comparing creep strengths in single-phase and two-phase (precipitating) alloys. The effects of precipitation from solid solution on the creep properties of alloys are generally such that the resistance to creep is increased. However, if alloys are heat treated to different degrees of hardness before creep testing, it is often found that those possessing the maximum hardness initially do not necessarily have the maximum creep resistance. Depending on the stresses and temperatures involved other structures may prove more desirable. Considerations of the above nature indicate the importance of defining the initial state of the alloy. Here, it was decided to start with quenched single- phase alloys in which precipitation and creep deformation proceed concurrently. Equipment and Experimental Procedures Preparation of the Specimens—Four 25 lb ingots were prepared from 99.999 pct Cu and 99.996 pct Al to compositions of 1, 2, 3, and 4 wt pct Cu. Spec-trographic and chemical analyses are listed in Table I. After heat treatments and intermediate reductions, the alloys were cold rolled to 1/8 in. thick sheet. The final cold reductions amounted to 50, 40, 20, and 10 pct for the 1, 2, 3, and 4 pct Cu alloys, respectively. The specimens for creep testing were machined into tensile flats 7 in. long, 3/4 in. wide (at the shoulders), and 1/8 in. thick. The reduced sections were 1/4 in. wide and 21/2 in. long. After heat treatments at 540°C to an ASTM grain size of 1 1, the specimens were quenched into water at room temperature, then electropolished in a glacial acetic acid and perchloric acid solution. The gage marks were Knoop impressions placed 2 in. apart on the reduced sections. Blanks of 1 x 1 in, were cut from the same sheets for the age hardening runs and were given the same grain size heat treatments. The specimens and blanks were stored in a refrigerator at —40°C until needed for testing. Creep Measurements—Creep tests were conducted in a constant temperature room which was maintained at 26° ±1°C. A split-type, hinged, vertical-tube furnace was mounted on a horizontal track so that the specimen could be enclosed suddenly. Thus, it took about 15 min for the specimen to come within 5°C of the test temperature. The temperature variation along the specimen was controlled to about

Jan 1, 1958

By C. F. Floe, M. Cohen, M. B. Bever, V. G. Paranjpe

NITROGEN is becoming recognized as one of the important elements in ferrous physical metallurgy. Several investigations indicate that nitrogen plays a significant part in such phenomena as strain aging and temper brittleness. Nitrogen is known to be a powerful austenite stabilizer and may be a useful alloying element in stainless steels. The hard-enability of steels has been found to be increased by nitrogen. The nitriding and carbonitriding pro- cesses are examples of successful industrial application of nitrogen in ferrous materials. For a complete understanding of the various roles played by nitrogen in ferrous metallurgy a knowledge of the phase relations in the binary iron-nitrogen system is essential. The literature contains a variety of iron-nitrogen phase diagrams. Those suggested by Fry, Sawyer,² Epstein and his coworkers,³,4 Lehrer,5 Eisenhut and Kaupp, and Hägg7,8 differ significantly from one another. Moreover, the most recent of these investigations dates back about twenty years. A re-determination of the entire diagram, therefore, appeared desirable. In addition to the published phase diagrams, investigations have been carried out on portions of the iron-nitrogen system. Bramley and Haywood determined the composition and temperature of the iron-iron nitride eutectoid. The maximum solubility of nitrogen in a iron was investigated by Portevin and Seferian10 and by Diikstra. 11 Several investigators have determined the crystal structure of the various iron-nitrogen phases. In fact, Eisenhut and Kaupp6 and Hägg7 based their entire phase diagrams on the results of such studies. Epstein' and Emmett12 reported lattice-parameter measurements on the E (hexagonal close-packed) phase. Osawa and Iwaisumi13 also studied the change in lattice parameters of the a, ? and E phases with nitrogen content. Brill" and Hägg7 showed that the y' phase has an ordered structure, and Hendricks and Kostingsl5 suggested a structural relation between the E and phases. In a recent investigation Jackl6 arefully studied the super-lattice reflections from the y' and phases. Experimental Procedure A large variety of experimental methods has been used by previous investigators in studying the iron-nitrogen system. These methods include thermal analysis, microscopic examination, X ray diffraction, magnetic measurements, dilatometric analysis and anelastic experiments. Thermal analysis is of low accuracy in determining changes in the solid state. This accuracy is further decreased for iron-nitrogen alloys since composition changes will occur during heating or cooling unless extreme care is taken to use a proper atmosphere. Metallographic methods are of small value . because homogeneous iron-nitrogen alloys of sufficient size can be produced only with great difficulty. The dilatometric method is open to the same objections as thermal analysis in that changes in composition may occur during heating and cooling. Lattice parameter measurements by X ray diffraction can be used satisfactorily for determining phase boundaries if cooling is fast enough to prevent structural changes. In view of the limitations of the various other techniques two methods only were adopted in this investigation, (1) X ray diffraction measurements, and (2) a controlled nitrogenizing method. The second method is an innovation for investigating the iron-nitrogen system, and will be described at length. Materials: All iron-nitrogen alloys were prepared from carbonyl iron powder of the analysis shown in table I. The average particle size was about 20

Jan 1, 1951

By F. H. Spedding

CONSIDERABLE confusion exists in the literature concerning the phase transformations exhibited by the lighter rare earth metals; namely, lanthanum,1-8 cerium,1,3,5,8,9-15 praseodymium,8 and neodymium.1,8,16,10 To obtain further information

Jan 1, 1958

By F. N. Rhines

Sintering may be defined as the process by which powders bond themselves into coherent bodies, usually, although not necessarily, under the influence of pressure and elevated temperature. For the sake of clarity and simplicity, the present survey will exclude from consideration the sintering of mixed or alloyed powders, with attendant complications, but at the risk of overlooking information of general applicability. Sintering in the presence of a liquid phase is thus automatically eliminated. The sintering of alloys involves much additional subject matter and deserves separate consideration. Since the literature of the subject is extensive and widely scattered, it will not be feasible to consider the contributions individually. Instead, the subject matter will be classified according to experimental observations and theory, and will be presented in summary form. It should be noted that the appended list of references does not constitute a complete bibliography; it includes only those works quoted below. More extensive bibliographies are included in several of the references; see particularly references 7, 9, 28, 34, 38, 50, 52, 54, a "Bibliography on Powder Metallurgy" published by the Library of Congress and a pamphlet published by the Metals Disintegrating Co. entitled "The Field of Powder Metallurgy and Bibliography." 11. Summary of Experimental Observations The following classified list is composed of general statements of established fact derived from the experimental results reported in the published literature. A few contested observations are included, because of their potential importance; these are labeled as such. Any satisfactory and complete theory must be capable of explaining all of the uncontested facts. Obviously, some important facts may be missing from this list and these may hold the key to the correct explanation of the sintering process, but the possible lack of such material should not deter attempts to understand the subject on the basis of what is available here. A, The Initial Bond at Room Temperature a. To a limited extent uncompressed powders and massive metals adhere at room temperature. Clean tin powder forms a weak "cake" on standing at room temperature, the strength increasing with time. Clean gold surfaces adhere on light con-tact, as do those of many other substances, including nickel.27 b. Upon compression the strength of the bond- is increased progres-ivelv. There is a limit of pressure

Jan 1, 1946

By F. N. Rhines

Sintering may be defined as the process by which powders bond themselves into coherent bodies, usually, although not necessarily, under the influence of pressure and elevated temperature. For the sake of clarity and simplicity, the present survey will exclude from consideration the sintering of mixed or alloyed powders, with attendant complications, but at the risk of overlooking information of general applicability. Sintering in the presence of a liquid phase is thus automatically eliminated. The sintering of alloys involves much additional subject matter and deserves separate consideration. Since the literature of the subject is extensive and widely scattered, it will not be feasible to consider the contributions individually. Instead, the subject matter will be classified according to experimental observations and theory, and will be presented in summary form. It should be noted that the appended list of references does not constitute a complete bibliography; it includes only those works quoted below. More extensive bibliographies are included in several of the references; see particularly references 7, 9, 28, 34, 38, 50, 52, 54, a "Bibliography on Powder Metallurgy" published by the Library of Congress and a pamphlet published by the Metals Disintegrating Co. entitled "The Field of Powder Metallurgy and Bibliography." 11. Summary of Experimental Observations The following classified list is composed of general statements of established fact derived from the experimental results reported in the published literature. A few contested observations are included, because of their potential importance; these are labeled as such. Any satisfactory and complete theory must be capable of explaining all of the uncontested facts. Obviously, some important facts may be missing from this list and these may hold the key to the correct explanation of the sintering process, but the possible lack of such material should not deter attempts to understand the subject on the basis of what is available here. A, The Initial Bond at Room Temperature a. To a limited extent uncompressed powders and massive metals adhere at room temperature. Clean tin powder forms a weak "cake" on standing at room temperature, the strength increasing with time. Clean gold surfaces adhere on light con-tact, as do those of many other substances, including nickel.27 b. Upon compression the strength of the bond- is increased progres-ivelv. There is a limit of pressure

Jan 1, 1946

With the inauguration of Petroleum Technology this year, and approval by the Board to add an Assistant Secretary to the New York staff to serve the Petroleum and Coal Divisions, the Petroleum Division looks forward to greater opportunities and responsibilities. An improved medium of publication offers further incentive to engineers and investigators in the oil industry to make contributions. The authorization by the Board of Directors of a new Assistant Secretary is an appreciation of the splendid contributions made to the industry by the open forum of the Petroleum Division. It is also a recognition of the possibilities of greater service to the membership along the lines established ten to fifteen years ago by DeGolyer, Fohs, Ambrose and Lovejoy, to mention a few leaders. It isexpected that the new officer will spend a substantial part of his time in the field, visiting the student sections, the respective Divisions, helping in the arrangement of papers and Section meetings and intensifying interest in the Institute. The Petroleum Division will hold three meetings this year. The Fall Meetings will be held on Oct. 6 and 7 in San Antonio and on Oct. 20 and 21 in Los Angeles. The programs for these meetings will deal chiefly with engineering research and production engineering problems. Papers on production statistics and general economics of the industry are reserved for the Annual Meeting in New York. The annual production symposium and statistics are accepted as standard for the industry. With continuously deeper penetration into the earth in search for and exploitation of petroleum, it is necessary to have a better understanding of reservoir conditions and to place more phases of the operation under engineering control. Among the subjects relating to reservoir conditions tha thave been proposed for the fall meeting programs are phase equilibria at high pressures, interfacial tension between oil and water, the flow of oil and water through sands, the chemistry of films and underground temperatures. Investigations relating to control of operations include methods of continuously logging while drilling both visually and electrically, methods of studying drilling samples, properties of drilling fluids, improved cementing practices for isolating thin sands under high-temperature conditions and gas conservation, particularly production from high-pressure reservoirs. Additional suggestions of general themes or individual subjects will be welcomed, since it is desirable to build a backlog of material for Petroleum Technology. 9

Jan 1, 1938

By W. A. Koehler, M. E. Hinkle

THE oxidation of pyrites and marcasite in coal-mine strata to produce discolored acid mine drainage has long been explained by chemical reactions occurring in three stages: 1. The iron sulphide minerals are oxidized by air in the presence of water to produce a nearly colorless solution of ferrous (iron) sulphate and some sulphuric acid. 2, The ferrous sulphate and part of the sulphuric acid combine with additional oxygen to form ferric (iron) sulphate. 3. The ferric sulphate hydrolyzes to form a reddish-brown precipitate and additional sulphuric acid. Nevertheless, chemical data alone are not sufficient to explain all observed facts. The first stage seems to proceed more slowly in the chemical laboratory than in nature. The second and third stages normally occur to a marked extent within a few days with raw mine water. However, the visible discoloration that characterizes these latter stages will not develop for months if the mine water is sterilized. By means of bacteriological techniques, two organisms have been isolated from acid coal-mine drainage. These are believed to have a part in promoting the chemical reactions summarized above. One organism is considered to be Thio-6aciZZus thiooxidans, which is known to be able to convert elementary sulphur or sodium thiosulphate to sulphuric acid. Its relation to the formation of acid mine drainage has not Yet been established. Apparently it does not Promote the oxidation of ferrous iron compounds in mine drainage to the ferric state. The second organism has not been identified by name but is described as " Gram negative, non-spore-forming rods approximately 0.4 micron wide by 0.8 to 1.0 micron long." A pure culture of this when added to sterile mine water will cause the latter to become amber and develop the typical rusty precipitate. However, it has not been found to convert sulphur compounds to sulphuric acid. Further research is planned to determine whether or not these microorganisms play a significant part in the first stage of oxidation whereby pyrites and marcasite minerals go into solution. Some of the conditions found in abandoned sections of coal mines, such as a reduced Percentage of Oxygen and increased percentage of carboll 'dioxide in the air, as well as the existing temperature and acidity ranges, will be tolerated by and may even be favorable to these organisms. Acid Coal Mine Drainage Acid coal mine drainage has been the concern of coal mine operators, industrialists, sportsmen and public officials for many years. The amount of acid flowing into our streams in the coal-producing areas varies considerably from mine to mine and from

Jan 1, 1949