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By L. P. Teas

The main facts brought out by the study of the blende-bearing ores examined are as follows: 1. Chalcopyrite as minute triangular or rectangular dots, or as

Jan 1, 1918

By J. S. Rinehart, W. C. Maurer

The mechanics of impact crater formation in rock, particularly sandstone, has been sutdied, the velocity range being approximately that normally associated with oilwell gun perforators. The bullets were small steel spheres having diameters of 3/16, 9/32 and 7/16 in; impact velocities ranged from 300 to 7,000 ft/sec. The craters have two distinct parts — a cylindrical hole (or burrow) with a diameter the same as that of the impacting sphere, and a wide-angle cup comprising most of the volume of the crater. The burrow is fornred as material in front of the projectile is crushed and pushed aside, forming a cylindrical hole surrounded by a high-density zone. The clip forms as fractures are initiated in front of the projectile and propagate along logarithmic spirals, approximaling maximum shear trajectories, to the free surface of the rock. A most significant observation (made for the first time) was that, below the base of the cup in one type of sandstone, there are a group of similar fractures, not extending to the surface, which are spaced uniformly a few millimeters apart. Each fracture follows roughly the contour of the base of the cup and appears to require a certain threshold impulse to initiate it. These fractures comprise a relatively high fraction of the total, newly exposed surface area. The volume of the material removed by crushing varies as the first power of the impact velocity and the volume removed by fracturing, as the second power of the impact velocity. Penetration varies linearly with the impact velocity and is inversely proportional to the specific acoustic resistance of the target material, the proportionality constant being dependent upon the shape of the projectile. INTRODUCTION Yield of oil from a producing well is frequently enhanced by firing bullets and shaped charges through the well casing into the oil-bearing rock, forming craters and fractures from which oil can flow more readily. The purpose of this investigation has been to develop a better understanding of the mechanics of impact crater formation in rock, particularly sandstone, the velocity range being approximately that normally associated with oilwell gun perforators. FORCES OPERATIVE DURING IMPACT When a projectile moving at considerable velocity strikes a- massive target such as oil-bearing sandstone, intense and complex transient stress situations develop within both the projectile and the rock or sandstone against which it is striking. Usually the struck rock fails, the missile or projectile penetrating into the rock to some depth where it comes to rest or is forcibly ejected from its burrow by expansion of a plug of target material compressed in front of it. When the impact velocity is very high, the projectile itself may fail, breaking apart or becoming distorted; this situation is not considered here, the discussion being limited to nondeforming projectiles. Many experimental studies'.' have been carried out to determine the nature of the mechanics of crater formation and the salient features of the forces coming into play, some of the earliest studies being the French Army experiments performed at Metz between 1835 and 1845.' The stratagem in most instances has been to make a post-mortem examination of the crater, measuring volume and depth of penetration and deducing force relationships from these observations rather than performing the more difficult (usually almost impossible) feat of measuring stresses during penetration. In many materials, the force acting during penetration of the projectile is found to be the sum of two components—(1) a constant force, independent of the velocity, representing some inherent strength of the target material; and (2) a component, proportional to the square of the velocity, representing inertial forces. For such materials, the average force per unit area acting on the projectile at any instant while it is in motion and being decelerated may be written F/A = a + bv2 . . . (1) where v is the velocity of the projectile at that instant, A is the cross-sectional area of the penetrating projectile taken normal to its trajectory, and a and b are constants which are dependent upon the target material and the shape of the projectile. It follows that the total penetration s is given by .........(2) where v, is the velocity of the projectile when it just strikes the target. Values of a and b for spherical projectiles impacting in a loose sand-gravel mixture and compacted earth were obtained in the Metz experiments. For sand-gravel, a and b are 620 psi and 0.0115 (psi) (ft/sec)', respectively; and for compacted earthworks, a and b are 432 psi and 0.0008 (psi) (ft/sec)'. Figs 1 and 2

By A. B. Cook

Gas cycling is generally considered a much less efficient oil recovery mechanism than water flooding. HOWever, recoveries from some fields have been exceptionally high as a result of gas cycling. Recovery from the Pick-ton field, for example, was calculated to be 73.5 perceni of the stock-tank oil originally in place. In evaluating pressure maintenance projects, determining how much of the recovery is due to displacement by gas and determining how much is due to vaporization of the imrnohile oil in the flow path of the cycled gas is very difficrilt. Even though most of the oil is recovered by displacetr~ent, the success of a project may depend on the amount of oil vaporized. A limited number of experiments have heen performed with a rotating model oil reservoir that simulates gas cycling operations and allows a separation of the oil from, tile free gas flowing into the laboratory wellbore at reservoir conditions, thus revealing which is displaced oil and which is vaporized oil. It Iras been determined that the amount of varporizatio'n is .significant if proper conditions exist These experiments show that oil vaporization depends on pressure, temperature, volatility of the oil and amount of gas cycled. Increases in each of these conditions increase the volume of oil vaporized. Data from six experiments affecting vaporization are presented to illustrate reservoir condition that range from favorable to unfavorable. 111 these eaperitnenis recovery by vaporization ranged from 73.6 to 15.3 percent of /he immobile oil (oil not produced by gas displacerrlt). INTRODUCTION Between 1930 and 1950, gas cycling was a popular. oil recovery practice. especially for the deeper reservoirs. Later, with many case history-type studies published for both gas cycling and waterflooding, it was generally believed that waterflooding was far superior to gas cycling, even when gas cycling was conducted as a primary production procedure by complete pressure maintenance. A good example illustrating the advantage of water-flooding over gas cycling is given in a paper by Matthews' on the South Burbank unit where gas injection was followed by waterflooding. The author concluded in part that "Early application of water injection, without the intervening period of gas injection, would have recovered as much total oil as ultimately will be recovered by waterflooding following the gas injection, and total operating life would have been shortened". This appears to be a logical conclusion. However, it should not be applied to all fields. Pressure maintenance with gas in the Pickton field, as reported by McGraw and Lohec;' will result in a much larger percentage of oil recovery than was obtained in the South Burbank unit. The great success in the Pickton field resulted partly from vaporization of the immobile oil in the flow path of the cycled gas. The amount of vaporization is related to the following conditions: volatility of the oil as reflected by the APT gravity of the stock-tank oil; reservoir temperature; reservoir pressure during gas cycling; and the amount of gas cycled. Therefore, the U. S. Bureau of Mines is investigating these effects on vaporization in a research project using a model oil reservoir. Three different stock-tank oils having 22, 35 and 45" API gravities are being used as base stock to synthesize reservoir oils. Experiments are being performcd to determine vaporization at 100, 175 and 250F and at 1,100, 2,600 and 4,100 psia. This is a progress report showing the results from six experiments. Other Bureau of Mines reports"- concerning vaporization are listed. LABORATORY EQUIPMENT AND PROCEDURES The equipment ' consists of an internally chromium-plated steel tube packed with finely sifted Wilcox sand. The tube is approximately 44 in. long and has an ID of 13/4 in. The sand section contains approximately 570 ml of voids, has a porosity of 32 percent, and a permeability to air of 4.3 darcies. A unique feature of the laboratory reservoir (Fig. 1) permits the tube part to rotate at 1 rpm while the outlet and inlet heads are held stationary. The outlet end contains diametrically opposed windows to permit observatlon of the flowing fluids, and two valves, one on the top and the other at the bottom. Oil and free gas. when being produced simultaneously, can be separated by manipulating the two valves to keep a gas-oil interface in view through the windows. Thus, only gas is produced through the top valve and only oil flows through the bottom valve. The laboratory equipment was designed to study vaporization. Therefore, a uniform reservoir was made using dry sifted sand as opposcd to using a consolidated sand core with interstitial water. Furthermore. the reservoir was tilted to minimize fingering of gas. This tilting also in-

By S. J. McCarroll

Fig. 1—The belt shown at right carries filter cake to mixing station over calciner. Crude ore conveyors appear in right background. THE Three Kids mine, some six miles east of Henderson, Nev., is in a typical southwest desert area, with high dry summer heat and cool to cold winter seasons. The manganese deposit was located during World War I.' During this period 15,000 to 20,000 tons of ore assaying up to 41 pct manganese were shipped. Interest in the deposit was not revived until the middle thirties, when experiments on the ore were initiated. Test work indicated possible recovery of only 70 pct by flotation, but in 1941 additional work was done at the Boulder City pilot plant of the U. S. Bureau of Mines and also by M. A. Hanna Co. As a result, the Manganese Ore Co. was formed and a plant utilizing the SO2 process was constructed. Numerous operation difficulties ensued, and the plant. was closed when the manganese situation in the country eased. In 1949 Hewitt S. West initiated negotiations to acquire the plant. In 1951 Manganese, Inc., was formed and contract entered into with the General Services Administration to supply 27 million units of metallurgical grade manganese in the form of nodules to the national stockpile. A second contract was made to upgrade 285,000 tons of stockpile ore. Test work was undertaken by the Southwestern Engineering Co. and likewise by the Boulder City pilot plant at the U. S. Bureau of Mines. Results obtained indicated the commercial feasibility of the flotation process. Construction of the plant, which is shown in Figs. 1 and 2, was started in June 1951, and operations on a break-in basis began in September 1952. Apart from the usual starting difficulties two major disasters caused serious setbacks, one a kiln failure in February 1953, and the other a fire that destroyed the flotation building in June of the same year. The nodulizing section of the plant resumed operation in November, and the flotation section in January 1954. The ore minerals are chiefly wad,* with minor amounts of psilomelane, and occur in sedimentary beds of volcanic tuff. The ore is overlain with beds of gypsum which outcrop or may be covered with surface gravel. Intermediate beds of red and white tuff occur frequently with lenses of red and green jasper and stringers of gypsum and calcite. Small amounts of iron are present; lead content averages about 1.0 pct and minute amounts of copper and zinc are found. Barite, celestite, and bentonite are present. Since these are made up of minute asicular crystals, moisture content is very high, averaging about 18 pct. Ore reserves have been estimated at 3 million tons averaging 18 pct Mn2 and up to 5 million tons after grade is dropped to 10 pct Mn. A good part of the orebody was stripped of overburden by the previous operating company . Approximately 50 pct of the ore, representing more than 60 pct of the manganese, can be mined by open-cut methods. A system for underground min- . ing has not yet been decided on. Open-cut mining with benches of 20 ft has proved satisfactory. Although the ore is soft and appears dry and dusty it has a certain resilience, probably due to the porosity and moisture which makes drilling and fragmentation difficult. Wagon drills have been abandoned in favor of the Joy 225-A rotary drill which will put down a 43/4 -in. hole at the rate of 2 ft per min. Holes are spaced in a pattern with 8 to 9-ft centers. Forty percent powder has been used, but better breaking to 2-ft size is obtained with low velocity bag powder of 30 pct strength. Loading is done with one 21/2-yd shovel, and cleanup follows with one D-7 bulldozer. The ore is hauled with Euclid trucks about 1000 ft from the pit to a blending pile, where the daily mine production is spread in layers by bulldozing until approximately one month's mill feed is accumulated. A new pile is then started and mill feed is drawn from the first pile by one 13/4-yd shovel and Euclid trucks, with a haul of approximately 500 ft. Mining is performed by an independent contractor with engineering and supervision by the company staff. Early test work indicated that the manganese could be floated with soap, a wetting agent, and fuel oil to give a recovery of better than 75 pct with a grade of 43 pct Mn. The concentrate when nodulized with coke would upgrade to 46 pct Mn or over, and the lead volatilized to 0.6 pct residual.

Jan 1, 1955

Full sets of 149 Vols., including 4 Indexes, covering 1871-1940 incl. Indexes to Vols. 1-35, 36-55, 56-72, 73-117 (set of 4 Indexes)

Jan 1, 1940

By F. F. Schmidt, H. R. Ogden, E. S. Bartlett

Continuing tantalum alloy development studies have been concerned with a more detailed investigation of promising binary, ternary, and more complex tantalum alloys containing Groups IV-A, V-A, VI -A. VII-A, and VII-A metal additions. A primary objective of these studies was to improve the elevated temperature strength of tantalum with minimum degradation of fabricability and low-temperature ductility by alloying. Several alloys were found to exhibit hot tensile strengths in the excess of 25, 15, and 10 ksi at 2700°, 3000°, and 3500°F, respectively, combined with excellent cryogenic toughness and ductility. Particularly outstanding in this respect are alloys in the system Ta-Mo-W. Ternary parameter curves describing hot-strength, low-temperature ductility, recrystallization temperature, weld ductility, and fabricability are presented for the Ta-Cb-V, Ta-Hf-W, Ta-Mo-Hf, Ta-Mo-V, Ta-Mo-W, and Ta-V-W systems. At present, only four metals qualify for large scale structural applications at temperatures above about 1800°F. These are tungsten, tantalum, molybdenum, and columbium. Research and development work on these refractory metals has progressed to the point where efforts are now primarily directed toward the improvement of high- and low-temperature mechanical properties through alloying. High melting point combined with excellent low-temperature ductility, fabricability, toughness, weldability, and high solubility and tolerance for both substitutional and interstitial solutes are important attributes of tantalum. Conversely, its high density and relative scarcity compared with other refractory metals are the major deterrents to the use of tantalum. Early studies in the Battelle alloy development program established base line data on the mechanical and metallurgical properties of high-purity tantalum.' These studies were extended to include a preliminary investigation of the effects of various alloying elements on the established base properties.2,3 Recent studies involved a more detailed investigation of promising binary alloys containing Cb, Hf, Mo, Os, Re, Ru, and W, and ternary Ta-Cb-V, Ta-Hf-W, Ta-Mo-Hf, Ta-Mo-V, Ta-Mo-W, and Ta-V-W alloys. Results of major importance obtained are given in this article. EXPERIMENTAL PROCEDURES Electron-beam-melted tantalum (Wah Chang) and high-purity alloying elements were consolidated as 150-g ingots by multiple nonconsumable arc melting under a partial atmosphere of helium. Homogeneity of the button ingots was checked radiographically. Alloy buttons measured about 1-1/2 to 1-3/4 in. in diam by about 0.35 and 0.50 in. thick. Nominal alloy compositions were checked on each alloy button by weighing after arc melting. In most instances, weight losses were within 3 pct of the total weight charged. Subsequent chemical analyses on a number of selected alloys showed interstitial contents to range as shown below: Range of Interstitial Content, ppm 0 C N H 25-75 50-100 10-50 1-5 Metallic alloying additions were found to agree well with nominal compositions based on weight change data. Fabrication directly from the cast button to sheet was conducted at low (75° to 900°F), intermediate (1800° to 2000°F), or high (3000°F) temperatures, depending upon alloy content and hardness. Evacuated stainless steel or molybdenum packs were used for fabrication at intermediate and high temperatures, respectively. The temperature required to complete recrystal-lization in one hour was determined by hardness measurements and metallographic observations (longitudinal test sections) after vacuum annealing at 180°F intervals in the range 2010° to 2910°F. All mechanical property evaluations were conducted on recrystallized sheet, nominally 0.04 in. thick. Weldability of the various alloys was screened using manual TIG welding techniques. Bend ductility (bend axis perpendicular to weld axis) was the criterion used for evaluation. Tensile specimens employed 0.200 by 1 in. gage lengths, and bend test specimens measured about 1 by 1/4 in. Low-temperature tensile tests were conducted using a crosshead speed of 0.02 in. per min up to the point of yielding, and 0.05 in. per min to fracture. High-temperature tensile tests were conducted in vacuum using a crosshead speed of 0.01 in. per min

Jan 1, 1963

By James C. M. Li

The Petch relation between the flow stress and the gain size is derived from a consideration of gain boundary sources of dislocations without the need of dislocation Pile-ups. Three mechanisms for inierpreting the yield stress: the gain boundary strength, the unpinning of Frank-Read source near a grain boundary, and the generation of dislocations from the grain boundary are compared and the condition of their equivalence is shown. The effect of the average angle of misfit of pain boundaries is found to be sma11 and so is that of the average angle of misfit of subboundaries having impurities. The effect of impurities on the ledge density in the grain boundary is treated thermodynamically and a relatwn is proposed for the variation of Petch slope with impurity activity. The effect of temperature on the Petch slope is interpreted as due to the change of ledge structure in the grain boundary. It is indicated that the effect of annealing temperature may be more important than that of the test temperature and therefore should be studied. The effect of plastic strain on the Petch analysis is deduced from a work-hardening equation in which the generation of dislocations has first-order kinetics and the annihilation of dislocations has second-order kinetics. It is concluded that the Petch slope will decrease with plustic strain if the rate of annihilation of dislocations is sufficiently large. Critical experiments which may shed light on the mechanism for the Petch relation are suggested. THE relation between the yield or flow stress, 0, and the grain size, l, was first proposed by all' and later studied more extensively by Petch and co-workers, who also proposed a similar relation for the fracture stress and deduced from these a grain-size effect of the ductile-brittle transition temperature. The microscopic mechanism used by all' and petch2 involves a pile-up of dislocations of like sign generated from a Frank-Read source. The yielding or flow takes place when the pile-up exerts sufficient stress at the grain boundary so that the plastic deformation can propagate from one grain to another. If the average strength of the grain boundary is ai and the average length of the pileup is lp, the Petch slope, k, is given by" where p is the shear modulus, b the Burgers vector, and v the Poisson ratio. This slope will be independent of the grain size if l/lp is a constant. This is possible, since, if the Frank-Reed source is situated near the grain boundary, lp = 1, and if it is situated in the middle of the grain, Ip = 1/2. cottrell,12 also using the pile-up mechanism, proposed that the stress concentration at the grain boundary will initiate Frank-Read sources near the grain boundary and in this manner a Lüders band can propagate from one grain to another. Assuming that the average distance between the Frank-Read sources and the grain boundary is 1, and the unpinning stress of the Frank-Read sources is op, Cottrell obtained the following Petch slope: This slope will be independent of the grain size if ls is independent of the same, which is not as obvious as the condition, Ip = I for Eq. [2]. In addition to this assumption, the direct relation between the Petch slope k and the unpinning stress, up, was recently questioned by Johnsonon grounds that it is inconsistent with the following observations: the independence of k with temperature and strain rate, and the small k in columbium, which, like iron, has a sharp yield point. As pointed out by ohnson," the most important objection both to the Hall-Petch mechanism, in which the strength of the grain boundary plays the role in yielding, and to the Cottrell mechanism, in which the unpinning of Frank-Read sources plays the role in yielding, is the lack of direct observation of the pile-ups. The dislocation structure in deformed iron has been examined recently in the electron microsope.'-' Dislocations appear to be generated from grain boundaries or other interfaces; they form clusters and tangles within the grain at very early stages of deformation, even in the Lüders band, if the deformation is slow or at normal and elevated temperatures. Although it is still too early to interpret bulk properties from thin-film observations, it does seem worthwhile to look for a mechanism for the Petch relation which does not require dislocation pileup. SUBBOUNDARY SOURCES In order to show that a consideration of grain boundary sources can lead to the same Petch relation as does the consideration of the strength of the grain boundary, we shall first discuss the case of a simple tilt boundary whose elastic properties have been studied in detail.17 The strength of a partially

Jan 1, 1963

By Carl A Zapffe, George A. Moore

In a previous publication from this laboratory1 the conclusion was drawn that the embrittling effect of occluded hydrogen on iron and steel must result from the precipitation of the gas within small openings through the crystal structure. A review of the literature then published indicated the real existence of crystal substructures of the mosaic type and gave presumptive evidence that the "rift openings" associated with hydrogen occlusion are the same as the L'disjunctions" of the mosaic theory. Inasmuch as no clear conception of the actual nature of the crystal fragments and openings inherent in these theories has been established, it was considered desirable to obtain direct micrographic evidence of their true configuration. In this direction the standard methods of metallographic attack have proved useless. Recourse was had, therefore, to the direct examination of the surfaces upon which failure by cleavage had resulted from the presence of hydrogen. It was expected that such a surface, unaffected by chemical attack and undis-torted by polishing, would reveal the fine openings penetrated by the gas and thus indicate the real nature of the substructures. Materials Studied In commercial steels, defects caused by hydrogen take various external forms according to such factors as structure and purity, and to the extent to which hydrogen either occludes or produces chemical changes. The present work relates only to the well-known transcrystalline hydrogen embrittlement—-"pickling brittleness "—in which elemental hydrogen occluded within the grain develops cleavage characteristics. For example, hydrogen embrittlement resulting from hydrogen reaction products is excluded from detailed study. It was also desirable, as far as possible, to have the study uncomplicated by other elements which themselves cause brittleness. Three types of iron were used. These included ingot iron, decarburized free-machining steel, and a specially prepared, aluminum-killed, electrolytic iron. This choice allowed a comprehensive selection of unavoidable minor impurities and inclusions, which could subsequently be shown to have no specific effects on the structures within the grains. Carbon, and any other impurities free to react with hydrogen, were first removed by a preliminary annealing treatment in hydrogen. Subsequent treatment in vacuo extracted much of this hydrogen and its gaseous reaction products. The resultant ductile iron was then embrittled either by a second anneal in hydrogen, followed by rapid cooling, or by cathodic electrolysis. Group 1: Prepared from Armco Ingot Iron As shown in Table 1, the principal impurity in this iron was oxygen, which survived the purifying treatment to a large extent. Two series were prepared. The first (Nos. SIO-24) was purified only one day in hydrogen and dehydrogenized one day in nitrogen. Containing both hydrogen and its

Jan 1, 1943

By Carl A. Zapffe, George A. Moore

In a previous publication from this laboratory1 the conclusion was drawn that the embrittling effect of occluded hydrogen on iron and steel must result from the precipitation of the gas within small openings through the crystal structure. A review of the literature then published indicated the real existence of crystal substructures of the mosaic type and gave presumptive evidence that the "rift openings" associated with hydrogen occlusion are the same as the L'disjunctions" of the mosaic theory. Inasmuch as no clear conception of the actual nature of the crystal fragments and openings inherent in these theories has been established, it was considered desirable to obtain direct micrographic evidence of their true configuration. In this direction the standard methods of metallographic attack have proved useless. Recourse was had, therefore, to the direct examination of the surfaces upon which failure by cleavage had resulted from the presence of hydrogen. It was expected that such a surface, unaffected by chemical attack and undis-torted by polishing, would reveal the fine openings penetrated by the gas and thus indicate the real nature of the substructures. Materials Studied In commercial steels, defects caused by hydrogen take various external forms according to such factors as structure and purity, and to the extent to which hydrogen either occludes or produces chemical changes. The present work relates only to the well-known transcrystalline hydrogen embrittlement—-"pickling brittleness "—in which elemental hydrogen occluded within the grain develops cleavage characteristics. For example, hydrogen embrittlement resulting from hydrogen reaction products is excluded from detailed study. It was also desirable, as far as possible, to have the study uncomplicated by other elements which themselves cause brittleness. Three types of iron were used. These included ingot iron, decarburized free-machining steel, and a specially prepared, aluminum-killed, electrolytic iron. This choice allowed a comprehensive selection of unavoidable minor impurities and inclusions, which could subsequently be shown to have no specific effects on the structures within the grains. Carbon, and any other impurities free to react with hydrogen, were first removed by a preliminary annealing treatment in hydrogen. Subsequent treatment in vacuo extracted much of this hydrogen and its gaseous reaction products. The resultant ductile iron was then embrittled either by a second anneal in hydrogen, followed by rapid cooling, or by cathodic electrolysis. Group 1: Prepared from Armco Ingot Iron As shown in Table 1, the principal impurity in this iron was oxygen, which survived the purifying treatment to a large extent. Two series were prepared. The first (Nos. SIO-24) was purified only one day in hydrogen and dehydrogenized one day in nitrogen. Containing both hydrogen and its

Jan 1, 1943

By M. J. Pool, P. J. Spencer, J. R. Guadagno

THE present work was carried out as part of a general program to study the magnitude and concentration dependence of exothermic heats of solution of various metals in liquid tin. Thermodynamic data for the Te-Sn system are very limited, particularly for dilute alloys. Indeed, apart from the prior heat of solution determinations of Pool,1 the only other published values are those of McAteer and seltz2 who carried out electromotive force measurements on solid alloys of compositions from 75 to 95 at. pct Te at temperatures between 543° and 668° K, of Colin and Dro-wart3 who made mass-spectrometric studies of the vapor in equilibrium with solid SnTe, and of Robinson and Bever4 who determined the heat of formation of SnTe by solution calorimetry. The present work thus provides further thermodynamic information for this system, specifically in a temperature range where the solubility of tellurium is very limited. The liquid metal solution calorimeter used in this investigation has been described previously.' No further discussion of its design or operation will therefore be given here. For each series of measurements a tin bath consisting of approximately 70 g of 99.99 pct pure Sn was carefully weighed out and inserted in the calorimeter which was maintained at the desired temperature to within ± 1/4°c. Tellurium, of 99.999 pct purity, was supplied by Atomergic Chemetals Co., a division of Gallard-Schlesinger Chemical Manufacturing Corp. Approximately 0.0006 to 0.001 g-atom specimens of tellurium were used for each experimental run and these were added to the calorimeter from a temperature of 273" K. Heat of solution values were calculated by analysis of a strip-chart recorder plot of the heat effect accompanying the solution of each sample in the tin bath. The heat capacity of the latter was determined at regular intervals during a series of tellurium drops by using pure tin or tungsten calibration samples, the heat contents of which were obtained from the standard compilation of Hultgren et al5 The composition of the bath was calculated after each drop from a knowledge of the weights of tin and tellurium added. Values of the heat of solution of tellurium at 725" and 775° K are listed in Table I together with the corresponding tellurium contents of the alloys. The data are also plotted as a function of tellurium concentration in Fig. 1, which includes the equivalent data obtained by pool' at 750° K. It can be seen that the heat of solution remains

Jan 1, 1969

By F. Kurata, P. C. Davis, T. L. Gore

An experimental method and apparatus for the study of the low-temperature phase and volumetric behavior of volatile mixtures are described. The phase diagrams, including the critical points, and the volumetric behavior of a natural gas and a mixture of the natural gas with methane at temperatures from -40°F to -200°F and pressures to 1.200 11si are givrn. INTRODUCTION Knowledge of the phase and volumetric behavior of mixtures of the light hydrocarbons at low temperatures is becoming increasingly important as interest in low-temperature separation processes increases. Distillation at low-lemperatures has been used for some time to recover ethane and ethylene from natural gas and refinery gas for petrochemical uses. Removal of excess nitrogen from natural gas by distillation has been proposed as a means of increasing the capacity of gas transmission lines and of improving the marketability of the gas.1,2 Evaluation of the latter process has been hampered, however, by the scarcity of data from which the phase behavior of natural gases at low temperatures might be predicted. While existing correlations of vaporization equilibrium constants may be used to predict the behavior of such mixtures at lower pressures, high-pressure computations often require knowledge of the location of the critical point of the system involved. Although correlations have been developed for the prediction of the critical temperature and pressure of certain types of hydrocar-bon systems, they do not apply to very volatile systems such as nitrogen-bear-ing natural gases. This paper describes the initial stages of an investigation of the low-temperature behavior of a numher of natural gases and other gases of commercial interest. The experimental method and apparatus are described. and the phase and volumetric behavior of a natural gas and a mixture of the natural gas with methane are presented. PREVIOUS WORK The published low-temperature vapor-liquid equilibrium data for hydrocarbons and mixtures of hydrocarbons with nitrogen and helium are listed in Table I. Most of these data are for binary systems, and the data of Stutz-man and Brown" at 100 psi are the only data on a natural gas. The data of Bloomer and Parent3 on the methafie-nitrogen system, which have been phblished since this study was completed, are a valuable addition to the knowledge in this field. Prior to the publication of these data the only published critical point data on systems having critical temperatures below the ice point were those of Ruhemann.1 on the methane-

Jan 1, 1952

By Wilbert G. McBride

Two Also 3 1/2-ton motor trucks were used by Young Bros. while operating at the Mammoth Collins mine at Shultz, Ariz. One was equipped with an oil tank holding 1,075 gal. and was used for the transportation of "tops." The other was fitted with a stake body and used to carry machinery, wood, rails, pipe and all classes of miscellaneous supplies. The bodies were made of oak with maple flooring and were attached to the frame of the chassis by U-bolts, to avoid drilling the main members of the frame. Most of the hauling was done from Tucson, a distance of 47 1/2 miles. During the first 3 months, part of the road was in very bad condition and the tire cost was excessive. After this part was repaired the road was in fair condition, but never good. There were no excessive grades or bad sand, but wagon ruts, too narrow for the truck wheels and of a different gage, caused heavy tire loss; while chuck holes, sharp curves and stones, both imbedded and loose, were objectionable features. During wet weather the trucks could not get sufficient traction to climb some of the hills and were likely to stick in the mud in certain places, so that no attempt was made to run them unless they were on the' road when the rain started. This lost time amounted to about 5 per cent. of the total, but, whenever possible, it was utilized in making minor repairs. The price of gasoline was from 17 to 21 c. per gal. Rubber tires were used throughout. Drivers were said $4.50 to $5 per shift, and a return trip to Tucson was counted as two shifts even when made in one day. Drivers were provided with a room in Tucson and were paid for a11 time lost due to causes beyond their control. Trucks were loaded one way only. Speedometers were placed on both trucks but the excessive vibration soon caused them to fail. For this reason, and because no account was taken of the distance covered in picking up a miscellaneous load or in other minor ways, the mileage given is under the actual distance traveled. Some of the weights had to be estimated, but care was taken to have the number of ton-miles low rather than high, to avoid underestimating the costs. The cost of hauling from Tucson to the mines was $12 per ton

Jan 1, 1917

By J. A. Lund, A. M. Lawson

THE structures of quenched eutectoid and hypereu-tectoid Fe-Cu alloys have been examined by X-ray diffraction and by optical and electron microscopy. The relevant portion of the Fe-Cu phase diagram is given in Fig. 1. Several values have been reported for the solubility of copper in a Fe at the eutectoid temperature, including 1.4 wt pct by orton' and 2.13 wt pct by Wreidt and Darken.2 Alloys containing 4.8 and 7.5 wt pct Cu have been prepared from two batches of Ferrovac E iron (0.005C and 0.013C) and electrolytic tough pitch copper (99.90 Cu). Specimens of dimensions 0.8 by 0.8 by 0.1 in. were cut from hot-rolled material, austenitized, and quenched into brine at 25°C. Similar specimens were also cooled in the furnace, after a short soaking treatment at 1100°C, at a rate estimated to be 10°C per min in the temperature range of 900" to 500°C. X-ray diffractometry was performed on quenched and on furnace-cooled bulk specimens using iron radiation. Only a bcc phase could be detected in all samples. Lattice parameters were calculated from measurements on four lines, made up of two resolved high-angle doublets. Comparisons were made against a silicon standard. Results are shown in Table I. Based on X-ray diffraction studies of a series of alloys of lower copper concentrations, orton' estimated that the tattice constant of a Fe at 25°C increases 0.0014A per wt pct Cu in solution. Extrapolating Norton's data, it may be concluded that all copper was retained in solution in the brine-quenched 4.8 pct Cu alloy, and that approximately 5 pct Cu was also held in solution on quenching the 7.5 pct Cu alloy. Typical microstructures of brine-quenched specimens, as observed by optical microscopy, are shown in Figs. 2 and 3. Precipitation of the E phase (copper-rich) occurred along the y grain boundaries on quenching the 7.5 pct Cu alloy, rendering them readily detectable in the microstructure, Fig. 3. The original boundaries in the 4.8 pct Cu specimens were gener- ally not discernible, however. This indicates that the z phase which was seen in the higher-copper alloy was probably of proeutectoid origin. Thin foils for transmission electron microscopy were obtained from bulk specimens by spark machining to 0.006 in. thickness, followed by electrolytic polishing. Typical transmission electron micrographs

Jan 1, 1967

By Oliver Bowles

Slate is a fine-grained rock that has a more or less perfect natural cleavage, permitting it to be split readily into thin, smooth sheets. According to a definition established by the American Society for Testing Materials, slate is "a microgranular crystalline rock derived from argillaceous sediments by regional metamorphism and characterized by a perfect cleavage entirely independent of original bedding, which cleavage has been induced by pressure within the earth." Origin and Character Slates have originated from sedimentary deposits consisting largely of clay. Such materials were carried by streams and deposited in seas or lakes in successive horizontal beds. Other materials such as calcium carbonate, sand, or gravel may have been deposited over the clays, and the pressure of these superimposed materials gradually consolidated the materials below into bedded deposits of shale. Shale is a stratified rock formed by recrystallization of the clay plus adsorbed potash into the mica, sericite. Shale has neither the strength nor the splitting properties of slate since the mica is fine and the flakes unoriented, and the quartz grains do not interlock. Many shales, however, have been subjected to intense metamorphism. Mountain-building forces ever at work in the earth's crust may crumple, squeeze, and fold the shales. At the same time, accompanying high pressures and temperatures changed the original minerals into mica, interlocking quartz, or chlorite. Both mica and chlorite consist of minute tabular sheets or flakes with perfect cleavage. The intense pressure and movement tend to orient these flakes in parallel positions normal to the direction of pressure. The parallelism of the flakes results in the tendency to split with ease in one direction, which has been termed "slaty cleavage," and which is the outstanding characteristic of slate. Actually, the cleavage is through the cleavages of the individual micaceous plates. The original bedding of the slate is often folded and contorted, and the slaty cleavage commonly cuts across it at sharp angles. Composition MINERALOGICAL COMPOSITION The most abundant mineral in most slates is white mica (sericite), a hydrous silicate of potash and aluminum. It is present in very small flakes recognizable only with a microscope. Small grains of quartz (silicon dioxide) are also abundant and are regularly distributed among the mica flakes. The mica-like mineral, chlorite, is usually present in considerable quantities. Chlorites are of several kinds, the more common being hydrous silicates of aluminum and iron or magnesium. Other common minerals present in small quantities are rutile, clay, hematite, pyrite, carbonaceous matter, feldspar, zircon, tourmaline, calcite, dolomite, and siderite. The general range of the chief constituents is about as follows: Sericite, 38 to 40; quartz, 31 to 45; chlorite, 6 to 18; hematite, 3 to 6; and rutile, 1 to 1 ½ pct. CHEMICAL COMPOSITION Results of many analyses indicate that clays, shales, and slates differ little in chemical composition. The changes that take place during metamorphism are confined largely to rearrangement of the elements into new minerals with accompanying changes in physical properties such as hardness and cleavage. The general

Jan 1, 1960

By B. F. Oliver

A levitation zone melter is described which has the necessary characteristics for processing metals of controlled purity. No crucible is required; control of the solidification variables is stable; the environment of the charge is chenzically controlled. Rotation of the solidifying interface and mixing in the liquid by the magnetohydrodynamic stirring produce an eight-fold increase in freezing velocity over former melting units with better resulting solute redistributions. The smooth appearance of processed specimens, resistivity ratios as a hnction of position, as well as a segregation curve, are presented as evidence of smooth continuous solute fransport over distances in excess of ten zone lengths. THE difficulties of the floating zone-purification of higher density metals in large quantities under conditions of lowered surface tension are well known and have hindered fundamental research programs for some time. The inordinate amount of time required to obtain a small reproducible yield of high-quality metal has excluded the use of such material for many important material research programs. However, with the use of controllable induction levitation forces' to accomplish stable liquid zones with nearly flat solidifying interfaces, and with good physical and chemical control of the processes involved, these difficulties can be overcome. A zone melter that is to be used for both high-purity and controlled composition work in metal systems must have the following three characteristics: 1) The process must avoid the use of containers. 2) Physical control of the solid-liquid interface and of the mixing within the liquid phase must be stable. 3) The chemical environment of the melt chamber must be controllable. A description of an apparatus that accomplishes these objectives follows.* APPARATUS One of the basic features that is necessary for good process control of large sections is that the charge, the coil, and the motion mechanisms be within the same chamber. This arrangement permits a close coupling between the work coil and the load, which then provides a good flexibility for adjustments of coil dimensions, for controlling the amount of levitation needed for stable operation at a given power level. An overall view of the melter is shown, with the melt-chamber door open, in Fig. 1. The radiation shields surrounding the single-turn induction coil are of water-cooled copper. The chamber is stainless steel, as are most of the components within the chamber. The control panel for the scanner is located at the immediate lower right of the melt chamber. This panel controls the operation of the scanner. The operations controlled are the interface rotation rate, the stretch-squeeze or diameter control, the up and down scanning speeds, and the induction power. All of the drive motors are constant-torque variable-speed motors. The scanning speeds are set with precision helipots and continuously observed with the voltmeter on the control panel and checked with a mechanical indicator within the melt chamber. The rotation rate is also set with a precision helipot. The up-scanning speeds are 2 to 300 in. per hr.

Jan 1, 1963

By Avnulf Muan, Egil Aukrust

Activity-composition curves jor cobalt oxide and manganese oxide in solid solutions with spinel-type structure have been determined by studying the equilibrium between the spinel phase and a coexisting solid-solution phase in the tewzperature range 1100" to 1400"C. Within limits of experimental error, the system displays the behavior of a regular solution. The excess integral free energy of mixing is represented by the equation . The standard free energy of formation of cobalt manganite, CoMn,O,, from the oxide components COO mzd Mn2OS at 1200°C is calculated to be -8.6 kcal. AMONG the technologically and theoretically most important oxide phases are those which crystallize with the same structure type as the mineral MgO . A120,. Although the name spinel originally was used only for this mineral, the term is generally used today to designate the whole group of oxide phases with this same structure type. It is in this wider meaning that the term is being used in the present paper. The previous literature on spinels is very extensive. There are two aspects of spinels which have attracted particular attention: the structure, including the nature and distribution of the cations present, and the physical properties (electric, magnetic). The status of knowledge in these fields has been well-summarized in recent review articles.1'2 By contrast, thermodynamic properties of spinels are virtually unknown. Delineation of the activity-composition curve over the whole composition range of a solid-solution series with spinel-type structure is the objective of the present work. The system at elevated temperatures (>1000"C) constitutes such a series. The activity-composition curves for this system can be calculated from a study of the equilibrium between the above spinel solid solution and a solid solution (Co,Mn)O with sodium chloride-type structure. Data for the latter solid solution have become available recently.3 The system, in contact with metallic CO at 1200°C, obeys Raoult's law. The determination of the activity-composition curve for the spinel phase is based on the following relations. Consider the reduction-oxidation equilibrium for cobalt ions according to the equation: Because it is impossible in practice to measure single activities of electrically charged constituents, we will treat the equilibria in terms of electrically neutral components. Eq. [I] can then formally be written as follows: where and the activities of cobalt oxide in the (Co,Mn)O and the spinel solid-solution phases, respectively, K is a constant at constant temperature, and Pa is the oxygen pressure of the gas phase. The numerical value of K can be determined from a determination of the oxygen pressure P& for the equilibrium coexistence of Cos04 and COO in the binary system Co-0. Under these circumstances be set equal to 1, and hence K = [Po Eq. [3] can therefore be written

Jan 1, 1964

By E. D. Hummer, J. A. Younkins. J. P. Proctor

Comparatively little has been published relating practical experience with the control of the solid content of washery water systems that must be "closed." A "closed" system is one that for some reason may not be cleaned by the emission Of any effluent Of high ''lid 'content to be rep1aced by 'lean water in Order to hold the solid content of the waste water within reasonable bounds for efficient washing. It is the Purpose of this Paper to describe practical experience with such a water system and to present data that it is hoped may be of some use to those who are faced with a similar problem. The washery clarification system described comprises three thickeners and three filters, and although it is admitted that each of the fields of water settling and thickening and filtration offers a wide scope for investigation, the authors are not attempting to present the answers to these problems but to set down the results of some experience along these lines, making no claims as to the ultimate solution of the problems in hand. The subject of water clarification has vast ramifications; for example, the science of flocculation as applied to water settlillg and filtering opens up fields of wide possibilities of which as yet little is known. A comparatively recent entry into the field of water treatment, which may offer possibilities of practical application, is the use of "wetting" agents such as "Aerosol." General Arrangement of Water System So that the reader may obtain a comprehensive picture of the factors concerned in the control of a closed water system, it is necessary to give a brief description of the washing plant that is serviced by the water system to be described in the following pages. As we are not primarily concerned with the washing plant in detail, only a brief description of the flow of coal as it relates to the water system will be given here. For a more detailed account of this type of washer, the reader is referred to earlier papers,1,2 The washer, which handles o to 4-in, raw coal (750 tons per hour) is an American Rheolaveur plant of two complements; the coarse coal or sealed discharge plant and the fine coal or free discharge plant. The sealed discharge plant (Fig. I) consists of twin 48.in. primary launders, each having two washing boxes, supplemented by one 32-in. rewash launder, which also has two washing boxes. "Push" water for washing and conveying coal in these launders is supplied from a constant-head tank under pressure head of 10½ ft. at the point of introduction at the feed end of the launder. This tank also supplies water for upward or vertical currents used in the Rheolaveur or washing boxes. Each box discharges into a sealed boot elevator (Fig. I).

Jan 1, 1942

By J. A. Younkins. J. P. Proctor, E. D. Hummer

Comparatively little has been published relating practical experience with the control of the solid content of washery water systems that must be "closed." A "closed" system is one that for some reason may not be cleaned by the emission Of any effluent Of high ''lid 'content to be rep1aced by 'lean water in Order to hold the solid content of the waste water within reasonable bounds for efficient washing. It is the Purpose of this Paper to describe practical experience with such a water system and to present data that it is hoped may be of some use to those who are faced with a similar problem. The washery clarification system described comprises three thickeners and three filters, and although it is admitted that each of the fields of water settling and thickening and filtration offers a wide scope for investigation, the authors are not attempting to present the answers to these problems but to set down the results of some experience along these lines, making no claims as to the ultimate solution of the problems in hand. The subject of water clarification has vast ramifications; for example, the science of flocculation as applied to water settlillg and filtering opens up fields of wide possibilities of which as yet little is known. A comparatively recent entry into the field of water treatment, which may offer possibilities of practical application, is the use of "wetting" agents such as "Aerosol." General Arrangement of Water System So that the reader may obtain a comprehensive picture of the factors concerned in the control of a closed water system, it is necessary to give a brief description of the washing plant that is serviced by the water system to be described in the following pages. As we are not primarily concerned with the washing plant in detail, only a brief description of the flow of coal as it relates to the water system will be given here. For a more detailed account of this type of washer, the reader is referred to earlier papers,1,2 The washer, which handles o to 4-in, raw coal (750 tons per hour) is an American Rheolaveur plant of two complements; the coarse coal or sealed discharge plant and the fine coal or free discharge plant. The sealed discharge plant (Fig. I) consists of twin 48.in. primary launders, each having two washing boxes, supplemented by one 32-in. rewash launder, which also has two washing boxes. "Push" water for washing and conveying coal in these launders is supplied from a constant-head tank under pressure head of 10½ ft. at the point of introduction at the feed end of the launder. This tank also supplies water for upward or vertical currents used in the Rheolaveur or washing boxes. Each box discharges into a sealed boot elevator (Fig. I).

Jan 1, 1942

By T. J. Fabiniak, R. A. Dodd, R. Balow

ALTHOUGH the (111) slip direction in pure bcc metals is well established, the information on operative slip planes is less unambiguously interpreted. So far, (110) {112), and (123) slip planes have been identified, but it is not certain whether glide on (112) and (123) really occurs or if it is composite slip on non-parallel (110) planes. The second of these possibilities is supported by the work of Chen and Maddin on niobium and molybdenum, and a subsequent analysis by these same workers of slip in bcc metals generally.3 The alternative possibility is exemplified by the work of Opinsky and smoluchowsky4 who concluded that slip in Fe-Si crystals can occur on any one of the systems {110}(111), {112}(111), and {123)(111), depending on which system the resolved shear stress is highest. Allen et alS5 also found that glide in ar iron could occur on any of these three systems, the operative system being determined principally by orientation. By an analysis of crystal rotation, slip lines, and X-ray asterism Harris6 concluded that niobium also deforms on these same systems, but if one of these glide planes does not coincide with the plane of maximum resolved shear stress, composite slip on nonparallel (110) planes may occur giving a macroscopic high indices slip plane. Earlier work on iron by Vogel and Brick reached the same conclusion.7 The analysis of slip in bcc metals is made more difficult by the fact that the slip lines may be quite wavy. In fact, the generality of wavy slip lines suggests that screw dislocations slip readily from one plane to another in the (111) zone ("pencil glide") although, as noted, it is not certain whether planes other than (110) really contribute to the slip. If planes of higher indices than {110} do operate, there is a possibility they may do so more readily at higher temperature Argon and Maloof9 observed {100}{211}(111) slip in tungsten single crystals plastically strained at low temperatures, but the results were interpreted in terms of an orientation-dependence rather than temperature-dependence. Therefore, at the present time corroborative evidence for the operation of higher indices slip planes at higher temperatures is lacking. The present results were obtained during the course of an investigation into the effect of cathode and anode surface crystallography on the prebreakdown currents of vacuum insulated devices. In the experiment of particular interest, the 1/8-in.-diam anode and the in.-diam cathode were tungsten crystals (total impurities -230 ppm) with (110) and (100) faces respectively. The faces were electrolytically planed and examined for initial perfection by plastic/carbon replicas and a study of Kikuchi lines in reflection electron diffraction patterns. They were aligned precisely parallel in an insulating holder incorporated into the electron microscope, the measured microscope vacuum being 2 x 10-5 torr, and the electrode spacing 0.01524 cm. The anode structure shown in Fig. 1 was obtained

Jan 1, 1970

By G. R. Speich, Morris Cohen

The growth rate of bainite has been determined by hot-stage metallography in five hypereutectoid high-purity iron-carbon, iron-carbon-chromium, and iron-carbon-nickel alloys. The studies have been confined essentially to lower bainite. The growth rate is independent of time at constant temperature, but both the edgewise and sidewise growth rates increase with increasing temperature. Increasing the carbon content, or adding chromium or nickel, decreases the growth rate without greatly affecting the temperature dependence. The results lead to separate diffusion-controlled models for the edgewise and sidewise growth rates. ALTHOUGH bainite has been subject of many detailed investigations,1,2 the growth mechanism of this intermediate transformation product of steel remains unclear. One difficulty has been that practically all the kinetic measurements have been restricted to studies of the overall reaction rate. Only a limited amount of information3, 4-6 is available on the growth process itself. The purpose of the present work was to investigate the effect of time, temperature and composition on the growth rate of bainite using hot-stage metallography. This method makes it possible to observe continuously the isothermal growth of individual bainitic units because of the surface upheavals accompanying their formation.3 This information is needed to test the existing growth models and to obtain a better understanding of the factors controlling the bainitic transformation. EXPERIMENTAL PROCEDURE Alloys—The compositions of the alloys used in the present work are shown in Table I. The five alloys were vacuum-melted and cast, and were prepared from high-purity materials. The three iron-carbon alloys were available from the work of Roberts et al.7 in the form of 3/8-in. diam rods.* To facilitate machining, the rods were ing. The rods were then tempered for 3 hr at 650°C to allow machining. The iron-carbon alloys in Table I were selected for investigating the effect of carbon on the bainitic growth rate. Due to the rapidity of the transformations involved, it was not feasible to measure the growth rates in iron-carbon alloys having carbon contents much less than 0.9 pct C. The iron-carbon-chromium and iron-carbon-nickel alloys were selected to study the influence of chromium and nickel on the growth rate at a carbon level of about 1.1 pct C, since this carbon content was intermediate among the iron-carbon alloys. The concentrations of chromium and nickel were chosen to match isothermal trans formation diagrams in the literature.8'9 Hot-Stage—Since the iron-carbon alloys had such low hardenabilities, it was necessary to quench the hot-stage specimens drastically from the austentiz-ing temperature to the isothermal transformation temperature to prevent the formation of pearlite or proeutectoid constituents. A rapid-quenching metal-lographic hot-stage was built for this purpose. A maximum temperature of about 1100°C and quenching rates up to 500°C per sec could be attained with this equipment. The details of the apparatus are described in a recent publication. After being polished and mounted on the hot-stage, the specimen (0.020 in. thick) was protected from oxidation and decarburization during austenitizing by a vacuum of 10-4 to 10-5 mm. The quench to the reaction temperature was accomplished with a helium blast, and the isothermal run at this temperature was conducted in a helium atmosphere. A fine-wire thermocouple spot-welded to the sample and a high-speed

Jan 1, 1961