Search Documents

By Chu-Phay Yap

This is the second of a series of theoretical papers on the iron-carbon system. The solidus lines obtained as a result of the different methods of investigation fall naturally into three classes; namely, (1) a straight solidus originally suggested by Roozeboom and supported in the main by the work of Carpenter and Keeling, Andrew and Binnie, et al., using the thermal analysis method; (2) a slightly curved solidus obtained by Honda and his associates, using the magnetic and resistance methods: and (3) Gutowsky's solidus obtained by the Heycock and Neville method of quenching at successively higher temperatures. Although the thermodynamic method as shown in the first paper indicates that the straight solidus line is correct, no explanation has ever been advanced to account adequately for the disagreement in the shape and position of the solidus lines obtained. The nature of the solute in austenit.e is theoretically discussed. On the basis of such discussions, the data obtained by Honda and Endo on the change of magnetic susceptibility of steels with respect to temperature were critically subjected to a graphical analysis, which is shown to yield a rational explanation of the curved solidus lines.

Jan 1, 1931

Steel Tape The new Lufkin Royal Ni-Clad steel tape, made in 25, 50, 75, and 100-ft sizes, is stated to cost less than any other steel tape on the market. Figures and graduations are an integral part of the steel and the nickel plated surface is rust and corrosion resistant. Circle No. 1 Lift A manually operated and propelled hydraulic lift marketed by Century Products Co. weighs only [ ] 150 lb, but the 23x24 in. platform will raise 1000 lb from floor level to 4 ft height. Circle No. 2 Scintillation Counter The Scintillator from Precision Radiation Instruments, stated to have 100 times the sensitivity of the Geiger counter, is suitable for prospecting and may be operated from plane or moving vehicle. The instrument is contained in a 2-lb probe and the belt mounted battery box weighs less than 4 lb. Circle No. 3 Generators Wincharger Corp. announces development of a Speedy-Shift wheel-barrow base type attachment for model 700, 1800 and 5000 engine-generator sets. Portability of the engine-generator sets themselves has been improved by belted construction for higher operating speed and maximum weight reduction. Circle No. 4

Jan 1, 1952

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 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

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 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 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

By R. M. Jorda

The mechanism of parafin deposition and prevention has been studied in the laboratory using an apparatus which provides a quantitative means of studying parafin deposition on metal and plastic surfaces. The amount, hardness, adhesion, per cent wax and mean molecular weight of parafin deposits appear to be governed by surface roughness alone, all other conditions being constant. Tests of various plastic coatings indicate that most smooth, nonparafinic plastics are capable of reducing parafin deposits in oil wells, but flexible, highly polar, nonparafinic plastics are more suitable for providing long term resistance to parafin deposition in oil wells if the flow stream contains abrasive materials. INTRODUCTION The problem of paraffin deposition is one of long standing in the oil industry.' Crude oils often contain paraffins which precipitate and adhere to the liner, tubing, sucker rods and surface equipment as the temperature of the producing stream decreases in the normal course of flowing, gas lifting or pumping. Heavy paraffin deposits are undesirable because they reduce the effective size of the flow conduits and restrict the production rate from the well. Where severe paraffin deposition occurs, removal of the deposits by mechanical, thermal or other means is required, resulting in costly down time and increased operating costs. The troublesome paraffins are normal hydrocarbons ranging from approximately C15H38 to C38H78 mixed with small amounts of branched paraffins, monocyclic paraffins, polycyclic paraffins and aromatics.' The amount of paraffins found in crude oils varies from less than 1 to more than 30 per cent. Many publications are available which deal with this problem, and perhaps the most significant findings in recent literature are contained in a publication by Hunt3 ho developed the "cold spot tester", a really useful means of investigating paraffin deposition. Hunt's observations led to many generalized conclusions concerning the effect of surface roughness on paraffin deposits. He ascertained that there was an observable qualitative correlation between the severity of paraffin deposition and the roughness of the surfaces which he tested (cold rolled steel, stainless steel and several plastics). Because of the number of meaningful observations made by Hunt, his cold spot tester was modified somewhat and extensive tests were per- formed to study the quantitative relationship between surface roughness and the physical and chemical nature of paraffin deposits. LABORATORY TEST PROCEDURES The cold spot test apparatus consists of a flat circular plate mounted on a curved tube and positioned in a vessel containing a wax-oil solution (Fig. 1). The apparatus is arranged so that the temperature of the central portion of the circular plate can be varied by means of a circulating liquid stream; the test equipment includes provisions for maintaining a constant wax-oil solution temperature and stirring speed. In the paraffin deposition studies, the modified cold spot tester was used as follows. The cold spot probe consisted of a flat circular plat 2 in. in diameter and 1/8-in. thick positioned in the wax-oil solution kept at constant temperature. As in Hunt's earlier experiments," a cold liquid was circulated through a tube connected to the circular plate so that the liquid impinged on one side of the plate cooling the plate from the center outward, causing paraffin to deposit on the side of the plate exposed to the wax-oil solution.

Jan 1, 1967

By T. J. Whalen, S. M. Kaufman

Surface-tension measurements for liquid Fe-C-Co and Fe-C-Ni alloys were performed by the sesszle-drop technique at 1350o and 1425°C. Cobalt was shown to he more effective than nickel in lowering the surface tension of Fe-C alloys A minimum value for surface tension of 1640 dynes per cm was found in the Fe-C-Co system at a concentration of 1.5 pet C and 12pet Co. Analysis of these measurements in terms of adsorption and desorption behavior indicated that cobalt and nickel lower surface tension in Fe-C alloys by replacing carbon at the liquid-vapor interface. Comparison of results to date for Fe-C liquid alloys has shown that most substitutional-type elements having about the same atomic diameter as iron also have relatively the same influence on surface tension when present in dilute amounts. It has been shown previously that surface-adsorption behavior in liquid Fe-C ternary alloys is related to the manner in which the ternary addition affects the activity of carbon in the bulk solution.' Certain ternary additions, such as chromium, tending to decrease carbon activity cause adsorption of carbon and chromium to the liquid-vapor interface. Additions, such as silicon, increase the carbon activity, resulting in a desorption of carbon and an adsorption of silicon. Both cases were shown to cause a decrease in surface tension due to adsorption. It is the object of this paper, as part of the writers' continuing interest in the effect of alloying additions on the surface tension of Fe-C alloys, to present and discuss surface-tension data on solutions in the ternary systems Fe-C-Co and Fe-C-Ni. Available activity measurements for these systems in the solid state indicate a strong increase in carbon activity when either nickel or cobalt is added to Fe-C alloys.2, 3 EXPERIMENTAL PROCEDURE The alloy compositions used are shown in Table I. These alloys were prepared by vacuum melting in stabilized zirconia crucibles and then vacuum casting into cold-steel molds. The nominal analyses for the alloys used in this investigation are given in Table I. Surface tensions and densities were measured by the sessile-drop method4,5 in conjunction with the tables of Bashforth and bdams.' Specimens were prepared by slicing 1/4-in. cubes from the center of the vacuum-cast ingots and grinding the edges of these cubes until their shapes approximated spheres with flat bottoms. Proper handling techniques, including an acetone rinse immediately before use, assured minimum contamination from sources extraneous to the actual melting. For each experimental run a sample was placed on a BeO plaque and positioned and leveled inside a vacuum induction heating apparatus. The sample and plaque arrangement sat inside a molybdenum tube which acted as the susceptor. Diagrams of this apparatus may be found in the literature.= After heating to temperatures just above the liquidus at pressures of the order of 10-4 to 10- 5 mm Hg, photographs of the drop profile were made using its natural thermal radiation as a light source. Some measurements were made with partial pressures (-1 cm Hg) of a mixture of H2 and He gases. The H2-He atmospheres proved to be necessary at higher nickel contents to retard excessive vaporization losses. Chemical analysis for carbon and the ternary addition was performed for each alloy sample after completion of the experimental run.

Jan 1, 1964

By R. F. Domagala, M. Hansen, D. J. McPherson

On the basis of metallographic analysis, incipient melting data, thermal analysis work, and X-ray diffraction, phase relationships in the 0 to 50 atomic pct Cr region were carefully resolved. Phase relationships in the 50 to 100 atomic pct region were outlined. A single intermediate phase, ZrCr,, was established in the system. A eutectic and a eutectoid were found in the zirconium-rich region of the system, while a eutectic was located in the chromium-rich region. Limited solubility of chromium in both a and a zirconium was observed. THIS is another in a series of papers on zirconium-base binary phase diagrams based on a program sponsored by the Atomic Energy Commission. The Zr-Sn,' Zr-Si,' and Zr-Mo and Zr-W" systems have already been published. Previous work on the Zr-Cr system includes a partial diagram by Hayes, Roberson, and Davies' and a complete diagram by McQuillan." The phase relationships reported by these authors were determined with magnesium-reduced zirconium, whereas those reported herein are based on iodide metal. Some X-ray work on the intermediate phase in this system was also reported by Hayes et al., as well as by Wallbaum.' Comparisons with these data are made in the appropriate sections. Thermal analysis, metallographic and incipient melting techniques were employed to accurately resolve phase relationships in the 0 to 50 atomic pct Cr region, while the remainder of the diagram is outlined on a basis of cast structures and thermal analysis. A description and analyses of the metals used in the preparation of alloys for this study are included in Table I. A "low-hafnium" zirconium crystal bar (Westinghouse "Grade 3") was used. This material was produced by the decomposition of a volatile iodide onto a hot zirconium filament. The as-received crystal bar was coated with corrosion product from a standard autoclave test by which its grade designation is determined. A sand-blasting and subsequent HF-HNO, pickling treatment was employed to remove this contamination. The bars were cold-rolled to approximately 1/32-in. sheet, pickled again, sheared to 1/4-in. squares, washed with acetone, and stored for use. Ingot chromium metal from National Research Corp. and electrolytic chromium flakes from Johnson, Matthey and Co., Ltd., were available as alloy additions. The ingot chromium was received in granular form. The large granules were sized by crushing, treated for iron removal, rinsed with acetone, and stored. The flakes were broken to approximately 1/8 in. with mortar and pestle, cleaned with acetone, and stored for charging. Experimental Procedure A nonconsumable electrode arc furnace identical to that described by Hansen, Kessler, and McPher-son,' was used in this work. A 400 amp dc welding generator was the source of power. To insure homogeneity, ingots were melted in a water-cooled spun copper crucible, a total of four times without opening the furnace. No difficulties were encountered in the preparation of these binary alloys. Analyzed chromium contents were found to agree very well with the intended content. Melts of pure zirconium were interspersed in the course of preparing the alloys and their hardness was measured to keep a constant check on the melting technique. Vycor and quartz bulbs were used to contain the samples for isothermal annealing treatments. Vycor bulbs were employed for temperatures up to 110O°C, while quartz was used above this temperature. For treatments up to 950°C the bulbs were evacuated before sealing, but for higher temperatures a partial pressure of argon was admitted to the

Jan 1, 1954

By H. S. Wang, Y. P. Gupta

Diffusion of zinc and germanium in liquid silver is measured in the temperature range 975" to 1400°C by use of the capillary-reservoir technique. The ex-perinzental results are discussed in terms of the fluctuation and the "hole" theories of liquid diffusion, assunzing the solute as a point charge equal to the difference in the valences of the solute and solvent atoms. The additional coulombic interaction term due to the excess solute charge is evaluated in terms of the Thomas-Fenni approximation. The theoretical and experimental results agree with both the fluctuation and "hole" theories of liquid diffusion. No perceptible effect on solute diffusion in liquid silver of the size difference between the solute and solvent atoms/ions is apparent. DIFFUSION in liquid silver of electropositive solutes indium, tin, antimony, and homovalent gold has been previously reported by Leak and Swalin1 and Gupta,' respectively. These solutes have nearly the same atomic size but differ principally from one another in excess valence (+2, +3, +4, respectively). The observed differences in the temperature dependence and the rate of solute diffusion were explained in terms of an added coulombic interaction between the solute and the solvent atoms. In the case of diffusion of gold in liquid silver, the data were found to be consistent with an effective valence for gold of -0.85, as proposed by Le Claire.3 Recently, Wang and Gupta4 have reported a study of diffusion of ruthenium, iron, and cobalt in liquid silver. The results of diffusion of these solutes and their temperature dependence were found consistent with the hole theories and the fluctuation theories of liquid diffusion, if ruthenium, iron, and cobalt were diffusing in liquid silver with relative valences -2, -1.3, and -0.5, respectively, instead of -3, -3, and -2 as suggested by the relative position of these elements in the Periodic Table of Elements. Furthermore, the predicted valences for these solutes were observed to be consistent with the sparsely available information on the magnetic properties of some of the dilute alloys of copper and silver with these solutes. In theoretical calculations of solute diffusivity, the solute was assumed as a point excess charge equal to the difference in the valences of the solute and solvent atoms. Both the assumption of a point excess solute charge and the use of the Thomas-Fermi approximation to calculate the potential of a solute charge are less precise for the case of electronegative solutes. Therefore, it was not possible to infer from the data on ruthenium, iron, and cobalt an effect, if any, on solute diffusion of the relative differences in either the Period or the size of the solute and solvent atoms or the solute atoms themselves. A study of the diffusion of Period 4 elements, specifically zinc and germanium was, therefore, undertaken since zinc and germanium, respectively, have relative valences of +1 and +3 in liquid silver and the data obtained on diffusion of these solutes could be compared with the available data on diffusion of Period 5 electropositive solutes, indium, tin, and antimony in liquid silver. From such a comparison, it was hoped to learn something about the effect, if any, of the ion size or the structure of the ion core on impurity diffusion in liquid silver. EXPERIMENT The diffusion of tracer zinc and germanium in liquid silver was studied by the capillary reservoir technique, modified adequately for use at high temperatures. In principle, capillaries containing liquid silver

Jan 1, 1970

By G. S. Upadhyaya, A. D. McQuillan

HERE would appear to be a simple relationship between the group number in the periodic table of the early transition metals and the maximum amount of hydrogen which they can absorb.' Thus group IIIA metals (Sc, Y, and La) yield a trihydride in which the metal atoms are on a fcc lattice and the hydrogen atoms occupy both tetrahedral and octahedral interstices. Group IVA metals (Ti, Zr, Hf) form dihy-drides in which the metal atoms are on either a fct or cubic lattice, but in which only the tetrahedral interstices are occupied by hydrogen atoms. In group VA (V, Nb, Ta) the hydrogen-saturated metal attains a composition slightly below that of a monohydride under normal conditions. Finally the metals of group VIA (Cr, Mo, W) do not dissolve appreciable quantities of hydrogen. The manner in which hydrogen solubility disappears on alloying a group VA metal with one from group VIA has previously been investigated.2 It is necessary, in order to obtain a general picture of the reactions of alloys of the early transition metals with hydrogen, to examine a system containing metals from groups IVA and VA in which there must be a change from a fcc to a bee hydride phase. The system chosen for investigation was the pseudobinary system between titanium hydride and niobium hydride. Metallic alloys were prepared by melting iodide-prepared titanium with zone-refined niobium in an argon-atmosphere are-furnace. To ensure homogeneity each alloy was cold-swaged and then heated at 1250°C in a high-vacuum furnace until metallo-graphic examination confirmed its complete homogeneity. Small weighed specimens of the alloys were charged with hydrogen using gaseous hydrogen generated by heating titanium hydride. The apparatus has been described elsewhere.3 Throughout the charging process the hydrogen pressure was kept at about 1 atm while the specimen, initially at 800 °C, was slowly cooled to 150°C over a period of days. The total amount of hydrogen absorbed by each specimen and the room-temperature crystal structure of the hydride powders were determined. The X-ray investigation indicates that the fee hydride phase arises from alloys extending in composition from titanium to 67 at. pct Nb. After a two-phase field lying between 67 and 74 at. pct Nb in which the fee and bee hydrides coexist, all alloys richer in niobium yield a distorted bee hydride. Data derived from parameter measurements are presented in Fig. 1. The atomic volume per metal atom has been plotted against the composition of the initial metallic alloy in order to facilitate comparison of the effects of hydrogen addition in the two phases of different crystal structure. The amount of hydrogen absorbed by each alloy at saturation in terms of the hydrogen to metal ratio and alloy composition is given in Fig. 2. Over the whole range of the fee hydride phase the hydrogen content remains constant, while in the distorted body-centred hydride phase, the hydrogen content increases with increasing titanium content reaching a hydrogen/metal ratio of 1.4 at the boundary of the two-phase region. It seems likely, therefore, that the maximum hydrogen content of the fee hydrides is limited to a hydrogen/metal ratio of 2 because hydrogen atoms

Jan 1, 1962

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