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By G. H. Bishop

The kinetics of the inter granular penetration and embrittlement of [100] tilt boundaries in 99.998 pct pure nickel upon exposure to bismuth-rich Ni-Bi liquids have been determined in the temperature range from 700° to 900°C. The kinetics of penetration are parabolic in time at constant temperature over most of the temperature range. In a series of 43-deg bicrystals the rate of penetration is anisotropic with respect to the direction of penetration into the grain boundaries. In lower-angle bicrystals the penetration rate is isotropic. The rate of penetration decreases with tilt angle at 700°C. The activation energy for penetration in the 43-deg bicrystals is 42 kcal per g-atom independent of direction. It is concluded that the intergranular penetration and embrittlement in the presence of the liquid proceeds by a grain boundary diffusion process and not by the intrusion of a liquid film. This was confirmed by a determination that the kinetics of penetration and embrittlement were the same in the 43-deg bicrystals upon exposure to bismuth vapor under conditions such that no bulk liquid phase would be thermodynamically stable. WhEN solid metals are exposed to a corrosive liquid-metal environment, the grain boundaries are sites of preferential attack. Depending on the temperature, the composition of the liquid, and the composition, structure, and state of stress of the solid, a number of modes of attack are possible. This paper reports a study of the kinetics of intergranular penetration and embrittlement of high-purity nickel bicrystals upon exposure to bismuth which, together with an earlier study by Cheney, Hochgraf, and Spencer,&apos; demonstrates that there are at least two modes of intergranular attack possible in the Ni-Bi system. In the study by Cheney et al., columnar-grain specimens of 99.5 pct pure nickel were exposed to liquid bismuth presaturated with nickel in the temperature range 670" to 1050°C. They found that the majority of the boundaries, which were predominantely high-angle boundaries, were penetrated by capillary liquid films, the attack proceeding by a process which will be termed grain boundary wetting. This process occurs in a stress-free solid when twice the liquid-solid surface tension is less than the surface tension of the grain boundary,* i.e., when 2yLs < YGB In this case the penetration of the grain boundary by the liquid occurs at a relatively rapid rate, resulting in the severe embrittlement of a polycrystalline solid. Grain boundary wetting is a common mode of intergranular attack in systems in which the lower melting component is relatively insoluble in the solid, but the solid has an appreciable solubility in the liquid, for example, the Ni-Bi system, Fig. 1. In systems of this type at temperatures above the range of stability of any intermetallic phases, once the liquid is saturated with respect to the solid so that no gross solution occurs, chemical gradients are small, and surface tensions become major driving forces for attack, provided the solid is stress-free. The results of Cheney et al. appear to be typical of those encountered when grain boundary wetting occurs.&apos; Capillary films were observed in the boundaries after quenching from the exposure temperature. The mean depth of penetration increased linearly with time, and the activation energy for the process was found to be 22 kcal per g-atom. In a study of the Cu-Bi system Yukawa and sinott4 found that the depth of penetration of bismuth into high-purity copper bicrystals of orientations from 22 to 63 deg of tilt about (100) at 649°C ranged from 0.05 to 0.25 in. after a 12-hr anneal. This corresponds to a linear rate of 6 to 15 X 10~6 cm per sec. At the same reduced temperature of 0.68 the rate for the Ni-Bi system&apos; was 7 x lo-&apos; cm per sec. In another study of the Cu-Bi system, Scheil and schess15 determined the kinetics of grain boundary wetting in hot-worked commercial rod. While there were several complicating factors present in this study, there is general agreement with the above results. The kinetics of penetration were linear, the activation energy was 20 kcal per g-atom, and at 650°C the rate of wetting was 2 to 5 x 10-6 cm per sec. The rate of wetting in the A1-Ga system6 is somewhat

Jan 1, 1969

By I. S. Levy, J. L. Brimhall, B. Mastel

Specimens of&apos; Hastelloy X-280, a low-cobalt version of the solid-solution- hardened nickel-base alloy Hastelloy X, were given a series of thermomechanical treatttzents. They were then Lensile-tested at room temperature and 1350°F. The Microstructures of the specimens tested at 1350°F were studied by electron Microscopy. Microscopy showed that dislocation tangling, caused by the cold working, mas still in evidence after aging-for 24 hr to temperatures as high as 1550oF. (Cr, Mo)23 C6, (Fe, Mo)6 C&apos;. as well us an unidentifiable phase precipitale due to the combination of the thermomechanical treatments and subsequent tensile strain. The room -temperature and 1350°F tensile properties show a general increase ill strength and decreccse in ductility with increusing cold-work level. This is due to the dislocation taangling-. PerLurbatiot~s to this general trend occur- due to solid-solution weakening at the higher cold-work levels as a direct result of the preciplitation reactions. THE requirements for corrosion resistance and high-temperature strength place nickel-base alloys among the more promising materials for advanced nuclear reactor applications. However, when these alloys are irradiated at service temperatures, they generally suffer severe embrittlement&apos;" and reduction in rupture life.3 Certain experimental treatments resulted in improvements in the tensile and stress-rupture properties of Hastelloy X-280, a solution-hardened nickel-base alloy.&apos; To provide a basis for understanding these improvements, unirradiated tensile specimens were examined by electron microscopy. The results are reported in this paper. EXPERIMENTAL DETAILS Material. Hastelloy X-280, a low-cobalt version of Hastelloy X, is a member of the solution-hardened class of nickel-base alloys. The Hastelloy X-280 was obtained from 4- and 1-in: thick plates in the mill -annealed condition. Table I gives the chemical composition of the material as reported by the National Spectrographic Laboratories. ~x~erimental Treatments. Plates of suitable size, 12 by 3 by 1 in., or by + in., were cut under a water jet from the stock material and examined ultrasonic -ally for homogeneity of grain size and absence of voids. The acceptable plates were solution-treated at 2150°Ffor 1 hr and air-cooled. These plates were then reduced in thickness by cold rolling 0, 10, 15: or 20 pct along the original rolling direction. The plates were machined into buttonhead tensile specimens with a gage diameter of 0.125 in., with a gage length of 1.125 in., and with their tensile axes parallel to the rolling direction. The specimens were examined for quality of finish with a penetrant dye, ultra son ically checked for voids, and finally given a dimensional tolerance check with an optical comparator. The acceptable specimens were aged for 24 hr at either 1000" or 1500 F and air-cooled. These specimens were then held at 540°F in a water loop for approximately 18 days to qualify as controls for similar specimens irradiated under the same conditions of time, temperature, water chemistry, and flow rate. Table U summarizes the treatments. These treatments were investigated to establish whether prior precipitation and stabilization of carbide phases at strain sites within the matrix could reduce the amount of carbides available for precipitation at grain boundaries during service. Tensile-Test Conditions. Specimens were tested to fracture at room temperature or 1350 F in air on an Instron tensile-testing machine at a crosshead speed of 0.05 in. per min. The time for the furnace to reach equilibrium at 1350°F was approximately 30 min; soak time prior to testing was 15 min; and test duration was approximately 5 min.

Jan 1, 1968

By George C. Branner

BAUXITE is produced in Arkansas from two mining districts in the central portion of the State. These are (1) the Fourche Mountain district, immediately south and southeast of Little Rock in Pulaski County, and (2) the Bauxite (town) district, about five miles east of Becton in the eastern part of Saline County. These two mining districts are about twelve miles apart, separated by territory which, so far, has produced a negligible amount of commercial ore. Mining was by open-pit methods exclusively until 1924, when underground methods came into use. From 1924 to 1930 about 40 per cent of all of the ore produced in Arkansas was mined by underground methods, mainly by retreating caving.

Jan 1, 1935

By Herbert Kilburn Scott

The information in this paper was collected by the author during a five years&apos; residence in the State of Minas Geraes. Outside the State itself, very little is known of the gold-field. Such accounts as have been published are antiquated and contained in publications mostly out of print. The increased attention now attracted to the natural resources of Brazil, and the probability that American capital will be, in the near future, largely invested there, will make an up-to-date account specially useful at this time. I. Historical and General. Soon after the Jesuits founded what is to-day the city of S?o Paulo, gold was discovered in the streams of the neighborhood; and this incited the natives, known as paulistas, to look for it farther afield. After many expeditions into the interior, gold was found in quantity in placer-deposits in the vicinity of Ouro Preto, in 1699, by a prospecting party headed by Antonio Dias. The name of Ouro Preto (black gold) was given because of the superficial dark coating of the gold, and the inhabitants of the district were known as mineiros (miners). Later on, the placers of Cuiaba, in the State of Matto Grosso, were discovered in 1718, and those of the State of Goyaz in 1724. All this territory was at the time a private colony, but on account of its increasing importance it was taken over by the Crown, and in 1739 a royal governor was appointed, with his nominal capital in S?o Paulo, though for a number of years the real capital was Ouro Preto. In 1711 Ouro Preto was raised to the rank of a city, with the name of Villa Rica de Ouro Preto (" rich city of black gold"); and in 1720, by reason of administrative difficulties, Minas Geraes was constituted a separate colony from S?o Paulo, with Villa Rica as its capital. The site of this city

Jan 1, 1903

By Craig R. Smith, Warren Pfefferle

Tests were conducted utilizing large flat jack devices placed in a vertical slot for high pressure loading of rock to measure in-situ properties of a rock mass. The high pressure flat jack devices were used as a site investigation tool to obtain rock mass properties. Tests were conducted before and after a 100 ton surface high explosive detonation test to assess explosive effects on the rock. It was conclusively demonstrated by these tests that meaningful flat jack tests could be successfully accomplished; also, a significantly different response of the rock medium was measured as larger areas of rock were loaded. Surface jointing was severely disturbed by the explosion.

Jan 1, 1971

By Frank H. Macpherson

When it became apparent early in 1941 that the United States might be drawn into the war, studies were made of the bauxite situation in Arkansas, principally because 9.5 pct of the known bauxite reserves of the country were located in that State. Bauxite mining was then geared for maximum production to supply ore to meet this country&apos;s war requirements and, if necessary, to supply the needs of Canada as well. In view of the comparatively small bauxite reserves, Congress appropriated funds for an extensive exploratory drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. An alumina plant was erected near Bauxite and an aluminum plant near Hot Springs, Ark., by the Defence Plant Corp. The Metals Reserve Co. established a schedule of prices, arranged for stockpile sites and a buying agency. Operators cooperated to step up production and new ones came into the field. Production Record Prior to 1941, the greatest annual production in Arkansas was 562,892 long tons, dry basis in 1918. During the single month of August 1943, 693,596 long tons were mined—130,704 tons more than for the entire year of 1918. In general the Arkansas bauxite deposits are relatively small, irregular in thickness, somewhat scattered and, compared to coal, iron or open-pit copper deposits, are ill-adapted to an expansion in output. Commercial deposits range in horizontal extent from less than an acre to about 40 acres and are usually very irregular in outline. The average thickness of all known workable deposits is between 12 and 15 ft. with a maximum of about 60 ft. The ore bodies are usually somewhat undulating and nearly horizontal although locally some deposits dip as much as IS°. Types of Bauxite Three physical types of bauxite may be recognized: pisolitic, granitic and amorphous. Pisolitic ore is the most common type. It consists of small pebble-like nodules, ranging from the size of a pin head up to several inches in diameter, all set in a fine grained matrix. Transported bauxite is usually- pisolitic. Most residual bauxite is granitic. It is believed not to have moved appreciably from the location where it originally was formed. This is indicated by the fact that it appears to grade into unaltered nephelite syenite, which it overlies. Amorphous ore is the least abundant. It is nonpisolitic and resembles clay, has no characteristic texture, and can be identified definitely only by chemical analysis. Uses of Bauxite Bauxite is chiefly used for, and at the present time is substantially the only

Jan 1, 1948

By Frank H. Macpherson

When it became apparent early in 1941 that the United States might be drawn into the war, studies were made of the bauxite situation in Arkansas, principally because 9.5 pct of the known bauxite reserves of the country were located in that State. Bauxite mining was then geared for maximum production to supply ore to meet this country&apos;s war requirements and, if necessary, to supply the needs of Canada as well. In view of the comparatively small bauxite reserves, Congress appropriated funds for an extensive exploratory drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. An alumina plant was erected near Bauxite and an aluminum plant near Hot Springs, Ark., by the Defence Plant Corp. The Metals Reserve Co. established a schedule of prices, arranged for stockpile sites and a buying agency. Operators cooperated to step up production and new ones came into the field. Production Record Prior to 1941, the greatest annual production in Arkansas was 562,892 long tons, dry basis in 1918. During the single month of August 1943, 693,596 long tons were mined—130,704 tons more than for the entire year of 1918. In general the Arkansas bauxite deposits are relatively small, irregular in thickness, somewhat scattered and, compared to coal, iron or open-pit copper deposits, are ill-adapted to an expansion in output. Commercial deposits range in horizontal extent from less than an acre to about 40 acres and are usually very irregular in outline. The average thickness of all known workable deposits is between 12 and 15 ft. with a maximum of about 60 ft. The ore bodies are usually somewhat undulating and nearly horizontal although locally some deposits dip as much as IS°. Types of Bauxite Three physical types of bauxite may be recognized: pisolitic, granitic and amorphous. Pisolitic ore is the most common type. It consists of small pebble-like nodules, ranging from the size of a pin head up to several inches in diameter, all set in a fine grained matrix. Transported bauxite is usually- pisolitic. Most residual bauxite is granitic. It is believed not to have moved appreciably from the location where it originally was formed. This is indicated by the fact that it appears to grade into unaltered nephelite syenite, which it overlies. Amorphous ore is the least abundant. It is nonpisolitic and resembles clay, has no characteristic texture, and can be identified definitely only by chemical analysis. Uses of Bauxite Bauxite is chiefly used for, and at the present time is substantially the only

Jan 1, 1948

SMELTING is a thing essential to the end for which ores are sought, for without it every ore is a useless stone. This art is especially needed by those who, drawn on by hope, have mined ores in large quantities with great expense and effort. For this reason it is worth while to use one&apos;s wits and, if ordinary ways should not suffice, to consider how to find new ways of smelting the ores in order to extract the metals and to purge them of their earthiness. For this reason I shall now tell you of blast and other furnaces, and I shall also tell you, in order that you may be warned, that whoever wishes to do this well must first look at the nature and quality of the ore. You will already have had enlightenment on this from the experiments on assaying and with this as guiding star it is necessary to make ingenious structures and to provide for-the other needs as necessary, for one ore requires iron and another lead. Since I have already spoken of these in their own places on their ores, it is not necessary at present that I repeat, but here I wish to speak only of copper ore as a companion of silver and gold, and of where art is most required and where difficulties chiefly appear. For these things a machine must be built that is convenient to a good water supply in order to continue the work more easily. Its wheels should be large and easily moved, constructed in such a way that the force of the water lifts the bellows that are placed at the tuyère to direct the blast inside the furnaces that are to smelt the ores. For this, attention must first be given to the site of the machine, the quantity of water, and its fall; then to the wood for building the machine and for making charcoal; then to the stones that are used for the blast furnaces; then to the provision of good bellows that are wide, long, and full in their sides and made of cloth, for the better these are, the more they quicken the power of the charcoal

Jan 1, 1942

By R. Havens, K. C. Dean, H. Dolezal

Mine, mill, and smelter wastes aggregating billions of tons are scattered across the country as unattractive barren piles that mar the natural beauty of the land. As the population of the United States increases and the demand for land intensifies, populous centers are slowly encroaching on these formerly isolated wastes. Encroachment sharply intensifies the importance of controlling the air and water pollution derived from natural weathering of such wastes. Use or stabilization of these wastes comprises the only viable means for minimizing pollution. Utilization is preferable to stabilization, because full use would both eliminate the waste and broaden the mineral resource base. However, the wastes typically comprise immense tonnages of materials discarded by selective mining or after recovering the significant mineral values by milling and/or smelting. Only rarely can such low-grade material be reprocessed to extract additional minerals at a profit. Some mineral wastes are suitable for disposal as mine fill, railroad and highway road ballast, and land fill. Similarly, some mineral wastes can be utilized as raw materials for making brick, rock wool, concrete, and ceramic products. Several means exist for stabilization of relatively fine-sized wastes, which constitute the chief sources of air and water pollution. These include physical, chemical, and vegetative stabilization, and combinations thereof. Massive coverings of coarse slag, concrete, and soil may be used to prevent erosion of waste piles. A variety of chemicals can be used to bond the particles of fine-size waste into a relatively inert mass. However, the most promising method of producing an esthetically appealing storage site is vegetative stabilization. Numerous species of plants can germinate, grow, and reseed in waste materials which have been adequately prepared to support plant life.

Jan 3, 1969

By M. E. Wadsworth, T. L. MacKay

Sintered UO, samples were leached in sulfuric acid solutions of various concentrations. A pressurized system was used so that it was possible to investigate the kinetics of the reaction to 270°C with oxygen overpressures as high as 900 psi. The rate was observed to be a function of the concentration of hydrogen ions and directly proportional to the partial pressure of oxygen. Evidences are presented which indicate that a UO2 surface site reacts with a molecule of water to form a hydroxyl complex which in turn can dissociate with the characteristics of a weak acid. A rate determining step has been proposed which involves the reaction between an oxygen molecule and the hydroxyl complex on the surface of UO,. ThE 2 principal methods for uranium dissolution are carbonate and acid leaching. The sulfuric acid leach is the more popular and is used for the treatment of the majority of the ores of Africa, Canada, and the United States. Low recoveries in basic leach circuits led investigators at the University of British columbia1 to study leaching of uranium ores in pressurized vessels. Early in the study of dissolution of uranium it was found that only uranium in the hexava-lent state could be leached in acid or basic circuits. Therefore, the use of oxygen over-pressure in an autoclave offered an interesting approach to solving the low recovery problems of carbonate leaching. UO, was used in this study because it could be obtained in high purity and also because it is representative of the most refractory of the primary uranium minerals. A pressurized system was used to provide a means whereby important temperature and pressure parameters could be varied for the evaluation of the kinetic processes. The mechanism for the dissolution of UO2 should be similar for any of the uraninite type minerals. At the present all of the kinetic studies that have been conducted have been in carbonate media. Peters and Halpern2 carried out a kinetic study of the leaching of pitchblende. Their specimens were pitchblende ores selected on the basis of high grade and homogeneity. Pearson and wadsworth3 conducted a kinetic study of the dissolution of UO2 in carbonate solutions with results very similar to those obtained by Peters and Halpern. EXPERIMENTAL The UO2 as received* was found by spectroscopic *Mallinckrodt reagent, supplied by the Atomic Energy Commission. analysis to have a purity of 99.94 pct 0.03. It was ground in a mechanical agate mortar and screened through a 400-mesh sieve. Thin flat disks of UO2 were prepared by pressing the sized powder in a specially constructed die at a total pressure of approximately 25 tons per sq in. The pressed disks were approximately 0.25 cm thick, 1.6 cm diam, and 3.5 g in weight. As pressed, the samples were approximately 65 pct of theoretical density. It was essential that a binder such as poly-vinyl alcohol be added before pressing to prevent formation of cracks when fired. It was found by trial and error that pressed disks sintered close to 1870°C in a hydrogen atmosphere, reach densities between 91 and 91.5 pct of the theoretical density. At this density the samples had no measurable porosity based upon a 2-hr emersion in boiling water. An X-ray examination of these sintered UO2 disks showed them to be identical with the original UO2 received. Reaction of UO2 with the alundum furnace core was prevented by placing molybdenum between the samples and the core according to the method of Corwin and Eyerly.4 Leaching studies were carried out in a specially designed autoclave, the details of which have been presented e1sewhere.6 The main features of the equipment as applied to a kinetic study are: 1) solution samples may be removed during the course of a single run; and 2) temperature and agitation are carefully controlled. Two-ml samples removed from the autoclave during the course of a run were analyzed for U3O8 content with a Beckman model DK-2 spectrophotometer by the method of

Jan 1, 1959

By C. R. Johnson, R. A. Greenkorn, R. E. Haring

Three confined five-spot miscible displacements at unity, favorable, and unfavorable mobility ratios were conducted in a shallow, water-saturated sandstone of Pennsylvan-ian age near Chandler, Okla. These studies, plus associated laboratory experiments, were designed to measure miscible displacement performance in a controlled natural system, using known scaling criteria to develop an approach to modeling the heterogeneous field system. We have concluded from these studies that: (I) displacement efficiency in the field is a pronounced function of mobility ratio, indicating that miscible fingering observed in simple laboratory models occurs in the field: (2) field displacements can be quantitatively predicted by scaled laboratory models if the degree and location of field permeability variations are preserved in the models: and (3) arbitrary simplifications of heterogeneity will not necessarily predict observed displacement efficiency, and the simpler the model, the more optimistic the prediction. INTRODUCTION Many processes to achieve miscible displacement of reservoir oil by injected fluids have been conceived and field tested by the oil industry. Among the better known are high-pressure gas, enriched gas, and LPG banks. The simplest form of miscible displacement—one fluid miscibly displacing another fluid of different viscosity but the same density—has been studied extensively in homogeneous laboratory models. Observations of unstable fingering have been made which explain the significant decrease in displacement efficiency as the mobility ratio (ratio of displacing fluid mobility to displaced fluid mobility) increases. General industry experience with field tests of miscible displacement projects, mostly LPG banks, has been premature solvent breakthrough and lower than predicted production rate increases. These results have been attributed to either unstable fingering, unusual or unexpected permeability stratification, or both. Miscible displacement data in a controlled natural system have never been reported, however. Also, it has not been shown that properly designed and constructed laboratory models quantitatively predict field-scale behavior. The purpose of the combined field and laboratory ex- periments reported in this paper is twofold. The first was to measure miscible displacement performance at different mobility ratios in natural rock approaching field size under precise, controlled conditions. The second purpose was to utilize known scaling criteria plus several approaches to heterogeneity to model the field. Comparison of model and actual field results should then determine whether or not the laboratory phenomena (manifested by miscible displacement efficiency) are exhibited in large, natural rock systems. We carried out our program by first locating a shallow, water-saturated reservoir whose rock properties were representative of oil-bearing reservoirs. Detailed reservoir description by core analysis and interference testing showed the field site to be heterogeneous. A sequence of controlled, aqueous-phase miscible displacements was conducted at unity, favorable and unfavorable mobility ratios. A central, confined pattern was used to obtain the displacement data. A laboratory program using sand-packed models was conducted to determine the modeling criteria necessary to simulate field behavior of miscible displacement in a heterogeneous system. SCALING THEORY The detailed derivations and descriptions of the scaling laws that apply to laboratory models of reservoirs are adequately described elsewhere, so the following discussion will be restricted to facets of importance in this study. For a displacement in which one liquid miscibly displaces another, the following dimensionless groups are required to have the same numerical value in the model as in the field: The model also must be geometrically similar to the field, be spatially oriented the same as the field (same dip angle), and have the same initial and boundary conditions as the field (same initial fluid saturations and same injection-production well arrangement). When these conditions are satisfied, the theory predicts that at dny dimensionless time (pore volumes of produced fluids) the dimen-sionless flow potential and dimensionless fluid concentrations will be identical at all dimensionless spatial locations within the model and the field. If this prediction is correct, then the local dimensionless velocities must be identical, thus the instantaneous fraction of displaced fluid produced and the cumulative recovery expressed as fraction of original fluids in place must be identical at all dimensionless times. The theory outlined above has been obtained by either dimensional analysis or inspectional analysis of differential

Jan 1, 1966

By AIME AIME

The Bulletin. As already announced in the January Bulletin, this publication will be issued during the coming year monthly instead of bi-monthly as heretofore. Among other reasons for this change, it is desired to effect thereby the earlier transmission to members of important papers, lists of candidates for membership, and other items of timely information. The New Haven Meeting. As already announced in special circular, the XCVIth meeting of the Institute for the reading and discussion of papers will be held at New Haven, Conn., beginning Feb. 23, 1909. The Secretary of the Local Committee is Prof. J. D. Irving, Box D, Yale Station, New Haven. The program embraces visits to many interesting works in New Haven, Ansonia, Bridgeport, etc. The leading topics for discussion at the sessions will be: The Conservation of Natural Resources; A Sea-Level Canal at Panama; and The Technical Education of Mining Engineers. But papers on other subjects also are announced. A supplementary session of this meeting will be held in New York City, at some time during March, 1909, as a joint session with other national engineering societies, for the further discussion of the subject of The Conservation of Natural Resources. A Pacific Coast Meeting. The XCVIIth meeting will be held on the Pacific Coast, including a visit to the Exposition at Seattle, and various other points en route going or coming, depending upon the route and program finally adopted. More definite information will be announced at the New Haven Meeting, or at the earliest possible date thereafter.

Feb 1, 1909

By D. F. Kaufman, V. V. Damiano, G. J. London, L. R. Aronin

Beryllium bicrystals were Prepared by a seeding and floating zone-melting technique from high-purity beryllium single-crystal material. The starting material was given six floating zone purification passes prior to producing the bicrystals. Symmetric, asymmetric, and antisymmetric bicrystals were tested in tension. Included were bicrystals with boundaries both parallel and perpendicular to the tension axis. Modified symmetric bicrystals were also examined in detail. In these cases, the angles made by the slip planes with the boundary were not equal. Failure by (0001) cleavage, (1180) cleavage, and boundary separation were all observed depending on the orientation of these cleavage planes and the boundary with respect to the tension axis. Failure occurred on whichever system experienced the greatest normal stress. The origin of the fractures observed and the operative dislocation mechanisms were investigated by frac-tography and transmission electron microscopy. The results indicate that low-angle boundaries form in close proximity to the bicrystal boundary and act as sites for crack nucleation. It has been concluded that, although macroscopic compatibility was satisfied in many of the bicrystals examined, the bicrysta1 boundary was effective in Producing "early" failure by local bend plane formation as plastic deformation proceeded, followed by cleavage initiation and crack propagation. SINGLE crystals of high-purity beryllium oriented with the basal plane inclined 45 deg to the tension axis exhibit a critical resolved shear stress of about 300 psi and 200 pct extension by slipping only on the basal plane before failure by cleavage on that plane. Single crystals, oriented with the basal plane parallel to the tension axis, deform by prism slip at a critical resolved shear stress of 9000 psi and exhibit an extension of over 100 pct before failure in a ductile manner.&apos; In contrast to the behavior of single crystals, poly-crystalline beryllium deformed in tension or bending exhibits little or no ductility at room temperature. Beryllium&apos;s lack of ductility at room temperature has been attributed to its lack of a sufficient number of independent slip systems. Beryllium has only four independent slip modes at room temperature and according to the Taylor2 and von Mises3 criteria at least five independent shear modes are necessary to completely satisfy the strain compatibility conditions at all the boundaries in a random polycrystalline sample. Studies of beryllium bicrystals thus appear to provide a convenient way in which to determine whether the condition of strain compatibility is a necessary and sufficient condition to prevent failure and whether obviously incompatible boundary conditions result in boundary separation. Bicrystal studies, although not providing all of the constraints encountered in polycrystalline samples, do allow one to select very specific orientation relation-

Jan 1, 1969

By A. P. Herring, S. F. Ravitz

Manganese dioxide reacts with sulfur dioxide solution in the absence of oxygen to form manganous ion and dithionate ion, together with a small amount of sulfate ion. The effects of SO, concentration, hydrogen ion concentration, stirring speed, and temperature on the rate of the reaction were studied. If it is assumed that undissociated SO2 molecules react rapidly with MnO, at active surface sites and that bisulfite ions react slowly, an equation can be derived that satisfactorily represents the observed reaction rates. For solutions in which the reaction with undissociated SO2 predominates, reaction rates and activation energies estimated from diffusion theory agree well with those found experimentally. Manganese dioxide dissolves readily in aqueous solutions of sulfur dioxide. The nature of the dissolution reaction was first investigated by Gay-Lussac and welter1 in 1819; they identified a new oxysulfur radical, the dithionate ion, S2O6, as one of the reaction products. Since then, the reaction has become a standard method of preparing dithionates in the laboratory and one of the more promising methods of leaching manganese from low-grade ores. In the "dithionate process" developed by the U.S. Bureau of Mines2,3, manganese-dioxide ore is suspended in a solution of calcium dithionate and leached with gas containing sulfur dioxide. The manganese is dissolved and the sulfur dioxide is oxidized according to the reactions:

Jan 1, 1965

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of-the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication.1-5 In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators. of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating and distillation in-the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char.6 Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking. qualities by inspection of chemical analyses of coals.7 A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: Coking index =[ a+b+c+d 5] a equals 22/oxygen content on ash and moisture- free basis, . b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/1.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above 1.1 indicate good coking tendencies. Although generally usable, this formula is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct.8,9 Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1952

By D. J. Schmatz, H. I. Aaronson, H. A. Domian

Diffusion kinetics in disordered hcp Cd-Mg alloys have been investigated by means of the Kirkendall effect and concentration-penetration curves determined with an electron-microprobe analyzer. Self-diffusion coefficients of both species were determined at the three marker compositions obtained, averaging 27.6, 46. 7, and 78.1 at. pct Mg, by means of the Darken analysis. These coefficients were then corrected for the unequal and concentration-dependent partial molar volumes of the two elements with the Balluffi analysis, and for the vacancy flux effect by the Manning analysis. The latter correction reduced the Balluffi correction produced larger changes in the self-diffusiv-ities; neither, however, produced statistically significant changes in the Do&apos;s or the H&apos;S. The most striking result of this investigation is that at all three compositions and at all temperatures studied both the uncorrected and corrected self-difjusivities of magnesium are higher than those of cadmium. The Cd-Mg system is the first one found in which the higher melting, lower vapor pressure element diffuses more rapidly. Both an empirical correlation due to Toth and Searcy and considerations of the atomic mechanism of diffusion indicate that this anomaly is probably due to a comparatively low value of the activation energy required for a magnesium atom and a vacancy to exchange sites, perhaps occasioned by the higher compressibility of magnesium atoms. KIRKENDALL effect studies have been previously reported for only two hcp solid solutions: the E phase of the Zn-Cu system1 and the a phase of the Cd-Hg system.&apos; In neither investigation were the marker-movement studies supplemented with the concentration-penetration curve determinations necessary to evaluate self-diffusivities by means of the atano and the Darken analyses. The present program was undertaken to obtain both types of data on a hexagonal solid solution in order to provide more detailed information relevant to the mechanism of diffusion in this type of lattice. The Cd-Mg system was chosen for this study because the disordered solid solution extends across the entire phase diagram at temperatures above 253"c5 and the substantial difference in the melting points of the component pure metals promised that marker movements would occur at reasonably rapid rates should the diffusivities of the two species be as unequal as might be anticipated. The experimental convenience of the relatively low melting points of cad-miun and magnesium and the availability of extensive and accurate activity data6 (required for application of the Darken analysis) were additional reasons for selecting this alloy system. Since the anisotropy of diffusion is not large in either pure cadmium7 or pure magnesium,&apos; the diffusion couples were prepared from polycrystalline components. The presence of a well-defined texture in the couples—the c axis of individual crystals tended to be normal to the diffusion direction— however, provides a fair degree of crystallographic definition to the data obtained. The principal (and entirely unexpected) finding of this investigation, that magnesium, the high-melting low-vapor pressure element, diffuses more rapidly than cadmium, in contradiction to a broad range of results in fcc and bcc alloys, as well as in the previously studied hcp alloys,172 makes the self-diffusivity determinations of immediate interest in understanding the origin of this anomalous result. EXPERIMENTAL PROCEDURE The cadmium (Belmont Smelting and Refining Co.) and magnesium (Dow Chemical Co.) used in this study were both of 99.99 pct purity. Alloys containing 51.0 and 65.6 at. pct Mg were prepared from these materials by melting under a MgC12-base flux in a high-purity graphite crucible. These alloys were subsequently hot-worked and then homogenized in a helium atmosphere at temperatures close to their solidus points. Sandwich-type diffusion couples of the type g/d/g were prepared from the pure metals by solid-state diffusion. Two-piece alloy couples of Mg/65.5 at. pct Mg (Mg/gCd) and Cd/51.0 at. pct Mg (Cd/CdMg) were welded by a liquation technique. The individual components of both types of couple were initially cylinders 1.27 cm in diam and in length; the ends of these cylinders were machined accurately flat and parallel. For both welding techniques, the pure cadmium cylinders and the alloys were chemically polished in a mixture of 40 pct ethyl alcohol, 40 pct hydrogen peroxide (30 pct conc), and 20 pct nitric acid,g while those of pure magnesium were polished in a solution of 10 pct nitric acid in ethyl alcohol.&apos; Immediately afterwards, both metals were rinsed in freshly distilled acetone, and then in similarly purified methanol.&apos; The Mg/Cd/g couples were assembled in a carefully cleaned stainless-steel welding fixture, in which a screw operating through a self-centering arrangement permitted a controlled pressure to be exerted upon a couple prior to welding.&apos;&apos; Tungsten marker wires 0.005 cm in diam were placed at the d:g interfaces of some of these couples, and imbedded in the couples during the application of pressure. As soon as a couple had been assembled, the welding fixture was inserted into a Pyrex capsule containing a packet of zirconium chips at each end. The capsule

Jan 1, 1967

The Pinto Valley, Arizona, plant of Cities Service Company is one of the newest copper producers in the United States, having started production in 1975. It is located a few miles west of Miami, Arizona, on the site of the Castle Dome Mine, a World War II operation which was shut down and its mill later moved and renamed the Copper Cities plant. The Pinto Valley concentrator uses six 18 ft (5. 5 m) diameter by 21 ft (6.4 m) long, 4000 hp, single-stage ball mills, taking crushed ore from four 7 ft (2. 13 m) standard and eight 7 ft shorthead crushers. It has a design capacity of 40,000 stpd but has higher tonnage capability for an expanded concentrator. The copper porphyry-ore is mined by two 15 yd and one 20 yd shovels (11.5 and 15.3 cu m) and is transported to the primary crusher by 150-ton trucks. The dump pocket is relatively shallow (14 ft or 4. 27 m deep); and because of the width necessary for the 150-ton trucks, it was designed to use the ore itself instead of manganese steel as an abrasion- resistant lining, although a heavy steel cap protects the dump pocket top edge. The pocket has a capacity of 300 tons of ore. Water sprays under the dumping positions direct a fog toward the truck being dumped for excellent dust control. Breaking of oversize is done by a hydraulic impact breaker mounted on a hydraulically operated articulated arm situated at the side of the dump pocket. Again because of the shallow pocket, no splitter is used to protect the spider of the 60 in. by 89 in. Traylor gyratory crusher, which is equipped with a hydroset mechanism. Crushed ore at 8 in. (203 mm) drops into the 360 st surge chamber lined with AR plate and then is fed directly to the 60 in. (1.52 m) stock- pile conveyor by an 84 in. by 20 ft (2. 13 m by 6.1 m) four-speed apron feeder at a rate of up to 4000 stph. Early in 1977, Cities Service will replace the four -speed electric drive with a hydraulic pump and motor with infinitely variable speed. They are also studying the replacement of the apron feeder with an 8 ft wide (2.44 m) belt feeder similar to those at Similkameen and Palabora. Peak crushing capacity would then be increased to 5000 stph. The AR plate in the crushed ore pocket was installed in large, rectangular sheets which required much less embedded metal to hold it in place than would the more conventional, smaller arid square pieces of cast manganese steel. For duty in the crushed ore pocket, where wear is not severe, the AR plate is a satisfactory material. The new Palabora Figure-8 crusher also uses this design.

Jan 1, 1978

By Bezalel C. Haimson

Anna, Ohio, at the junction of Cincinnati, Findlay and Kankakee arches, has been the site of repeated and sometimes damaging earthquakes. As part of a seismicity investigation near-surface (0.15-1 m depth) overcoring strain measurements were conducted in four limestone and dolomite quarries surrounding Anna, the results of which suggest a complicated regional stress pattern, with changes in the maximum horizontal stress direction from N45ºE to N15ºW. Since such abrupt stress fluctuations are rather atypical in the Midwest and since the reliability of near-surface tests in defining regional stress had not been established, we decided to remeasure the stresses at the same locations but at greater depths (0-200 m) using the hydrofracturing method. Owing to the weak horizontal bedding planes of the Silurian shaly limestones and shaly dolomites and the relatively shallow depths, many of the tests yielded horizontal fractures, providing information only on the vertical principal stress (-0.029 MPa/m depth). However, sufficient tests in each of three testholes resulted in vertical hydrofractures to enable the calculation of all three principal stresses. Within 50-170 m depth the horizontal stresses in all three quarries appear to belong to a uniform regional Stress field defined by the following relations: [&apos;]Hmin = 5.1 + 0.014 D; [0] Hmax = 10.1 + 0.014 D, where D is depth in meters. The direction of [O]Hmax within 50-170 m depth is uniform at N70°E (±15º). The hydro- fracturing results obtained at Anna, Ohio are in agreement with the prevailing stress regime in the midcontinent both with respect to magnitudes and directions. The results suggest a possible thrust mechanism for a proposed NW-SE fault along which most of the earthquake epicenters have been located, and a left lateral strike-slip at greater depths. The focal mechanism solution of a recent major earthquake near Sharpsburg, Kentucky, some 200 km south of Anna, also indicates strike-

Jan 1, 1982

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.&apos; At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir&apos;s work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.&apos; Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By Robert Schorr

A Discussion of the Paper by Robert Schorr, read at the Atlantic City meeting, February, 1904. (Washington Meeting, May, 1905.) E. T. DUMBLE, Houston, Texas (communication to the Secretary*) :-In addition to the list of publications mentioned by Mr. Schorr and those by Prof. Hofman, I call attention to the following references : Studi sulle Lignite, by Capacci. Turin (1890). (An excellent work.) Report of Brown Coal Industry in Germany. J. Cosmo Newberry. Department of Mines, Victoria (1892). Second Report of the Royal Commission. on Coal Supply. Vol. II. London (1904). Peat Fuel: Its Manufacture and Use. Report of the Bureau of Mines of Ontario, 1903. Mr. Schorr says : " Brown coal and peat are briquetted as a rule without binder," but this statement is entirely true only so far as raw peat is concerned, and it is but partly true of brown coal. With regard to raw peat, briquetting without bond is carried on successfully both in Europe and America, and the development of the industry in Canada is fully described in the Bureau of Mines report for 1903, mentioned above. While there is still room for improvement in the efficiency of some of the arrangements for drying the peat previous to briquetting, a very satisfactory fuel is made at a price which enables it to compete with coal. During the late strike in the anthracite regions of Pennsylvania, the manufacture of peat: briquettes received a considerable impetus, and possibly the attention directed to it on this account may result in a. considerable increase in the output. In Canada. the peat when it is first excavated from the ground

Mar 1, 1905