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By K. A. Jackson, J. D. Hunt

A new classification of eutectics is proposed, based on tlze entvopies of wzelting of the tuio eutectic phases. The clnssification was used to predict suitable tvansparent analogs of the metallic systems. Experimental confir?nation loas obtained for the theovetical shape of the lamellar solid-liquid interface, fov the fault mechanisms of lanzellar spacing changes, and for the development of low-energy solid-solid boundaries between the lamellae. An explanation is presented to account jov the irvegular and coinplex regular structures zrhich are found in some eritectic systems. FrOM experimental observations, single-phase materials can be divided into two groups according to their solidification characteristics, those that grow as faceted crystals and those that do not. acksonl' showed from thermodynamic reasoning that the type of growth depended on a factor a which was almost thg entropy of melting. Most nonmetals have high entropies of melting (a greater than 2) and grow with crystalline facets. Most metals have low entropies of melting (CY less than 2) and grow almost isotropically with no facets. The authors propose that eutectics may be classified in a similar manner. There are three groups of eutectics, those in which both phases have low entropies of melting, those in which one phase has a high and the other phase has a low entropy of melting, and those in which both phases have high entropies of melting. Lamellar or rodlike structures are formed in systems in which both phases have low entropies of melting. In these alloys dendrites of either phase may be formed, when the alloy is rich in the relevant component. Examples are Pb-Sn, Sn-Cd, Pb-Cd, Sn-Zn, Al-Zn. Irregular, Fig. 14((), or complex regular, Fig. 14(b), structures are formed in alloys in which one phase has a high entropy of melting and the other has a low entropy of melting. Examples are A1-Si, Zn-MgzZnll, Pb-Bi, Sn-Bi. When the alloys are rich in the low entropy of melting phase, dendrites are formed; when the alloys are rich in the high entropy of melting phase, faceted primary crystals are produced. These crystals are sometimes called hoppers or pseudodendrites. In this work the term dendrite will only be used to describe nonfaceted primary crystals. Dendrites are not formed during solidification in high entropy of melting single-phase materials. The third group of eutectics includes alloys in which both phases have high entropies of melting. Each phase grows with a faceted solid-liquid interface. Since most metals do not have high entropies of melting, metallic examples in this eutectic group are rare. However they may occur between some intermetallics and semiconductors or semimetals such as silicon, germanium, and bismuth. Attempts have been made to study eutectic solidification visually by watching the growth process.374 Since metals are not transparent, the observations had to be made on external surfaces. This difficulty can be overcome by using transparent analogs of the metallic systems. As was mentioned earlier, most single-phase compounds have entropies of melting greater than 2 and so grow as faceted crystals. Recently organic materials with entropies of melting less than 2 were investigated.' These materials grow in exactly the same way as the low entropy of melting metals. When the materials are pure, they grow with a solid-liquid interface parallel to an isotherm; when they are impure, cells or dendrites are formed. Since these materials are transparent, have low melting points, and even have cubic structures, they should be ideal for making up transparent analogs of the metallic eutectics. The purpose of the present work was to investigate these organic eutectics and to see whether this quite different series of eutectics could be classified in the same way as the metallic systems. The observations made on the organic alloys are also discussed with reference to the current theories of lamellar growth. Explanations are proposed to account for the structures formed in the other eutectic groups. EXPERIMENTAL Thin cells containing the organic alloys were uni-direction ally solidified on a specially constructed microscope stage.' Uniform growth rates were obtained by moving the cells, with a motor drive, through a fixed temperature gradient, so that the solid-liquid interface remained stationary with respect to the microscope objective lens. The cells were made by fusing two microscope cover slides 7/8 by 7/8 by 1/100 in. together on three sides, leaving a gap of 1 to 3 mils between the slides, and these were filled by surface tension. A preliminary investigation of the phase diagram between two components could be made very rapidly. One side of the cell was filled with component A and the other side with component B. Since only a small amount of mixing could occur every composition from pure A to pure B was present in the cell. When the cell was placed in the temperature gradient a pictorial representation of the phase diagram was obtained. Eutectics, peritectics, "interorganics", and solid -solid transformations could be readily detected. Fig. 1 shows part of a eutectic phase diagram. The Sample was first grown slowly then stopped. The two

Jan 1, 1967

By Howard N. Eavenson

An analysis of the bituminous coal situation by an authority who traces the production, mining, safety, markets and labor trends in comparison with other fuels.

Jan 2, 1950

By William D. Schwab

In the technical literature of 1965 and 1966, there were several papers about future power for mining and construction equipment. Most of these papers made the same predictions: •More power •Better reliability and durability •Ease of service and maintenance •Operating economy •The possibility of future environmental concern •The entrance of the gas turbine In the five years that have since passed, some of the 1965-66 predictions have at least partially come true, while others have not been fully realized. Actually the list still appears sound today. Priorities may have changed and details may be different, but the main points cover the requirements for future prime movers quite well.

Jan 1, 1971

By C. W. Vaupell

THE Huitzuco mines lie in north central Guerrero, Mexico; production has been about 90,000 flasks of quicksilver since 1873. Near-surface ores fill extinct mud geysers and the deep deposits are chambered veins, stock-works in brecciated blocks, and replacements in limestone. The epigenetic minerals livingstonite, stibnite and sulphur occur in limestone, gypsum and dolomite through a developed vertical range of 260 meters. The deepest workings expose an increased amount of stibnite, which probably indicates that the lower limit of mercury mineralization is being approached. A resurgence of heat and water formed geysers over an extended area after the period of mercury mineralization. Mud geysers, which are situated, in the outcrops, contain the secondary mercury minerals, cinnabar and barcenite in the gravel and mud filling the vents. A 150-ton flotation plant is in operation concentrating stope fills that assay 3.0 kg. of mercury per ton. In one open stope, which is more than one hectare in area and 60 m. high, 150,000 tons are available. INTRODUCTION The Huitzuco mercury mines are of interest because of the unusual occurrence of ore in extinct geyser vents and the presence of several rare mercury minerals. Some of the deposits have typical characteristics of the telethermal zone and there is a gradation towards typical epithermal mineralization in depth. Halse,1 Villarello,2 Mactear3 and Merrill4 have described the geology and the early operations in the district, and Barcena5 and Mallet6 have described the rare mercury minerals, livingstonite and barcenite, found at Huitzuco. LOCATION The village of Huitzuco lies in the north central part of the State of Guerrero, Mexico, 27 km. (16.7 miles) east of Iguala, which is the largest and most important town in the area. Iguala is served by the Mexican National Railways and also by the Mexico City-Acapulco highway. The highway is surfaced from Mexico City to Iguala, a distance of 200 km. (124 miles) by road, and there is a fairly good, level, dirt road from Iguala to Huitzuco. The elevation above sea level is about 1000 m. (3280 ft.). The climate is warm and very dry except during the rainy season, from June to

Jan 1, 1937

By J. W. Halley, T. S. Washburn

RIMMING steels derive their name from their action during solidification in the molds. As a result of incomplete deoxidation, gas is evolved during freezing, and the metal has a characteristic rolling action. The metal rises along the mold walls and descends in the center of the ingot. This action keeps the top of the ingot open and the advancing rim of solid metal can be seen. The rim grows until the rolling action is insufficient to prevent the top of the ingot from freezing or until the action is stopped by capping the ingot with a heavy plate. The violence of the reaction and its characteristics, such as growth or drop in the molds, are determined by the composition, the furnace practice, and the deoxidation in the ladle and in the molds. Though rimming steels represent a large proportion of the amount of plain carbon steel made, they have received comparatively little attention in the technical literature. The manufacture of rimming steels has been described by Hibbard, 1, 2 Fleming,3 Pierce4 and Jackson.5 The reactions occurring during rimming have been considered from the theoretical point of view by Chipman and Samarin.7 The structure of rimmed-steel ingots has been discussed by Nead and one of the present authors.6 Meyer,8 in studying segregation, investigated the distribution of carbon, sulphur and phosphorus in rimmed-steel ingots by analyzing the rim and core of blooms. In their studies of segregation, the Joint Committee of the Iron and Steel Institute and the British Iron and Steel Federations studied distribution in one billet and one ingot of rimmed steel.. A detailed study of the distribution throughout the ingot has not been published. The present investigation was undertaken to determine accurately the distribution of carbon, manganese and sulphur in normal rimmed ingots and the general distribution of other common elements present. The study included some work on the effect of pouring conditions and furnace practice on the distribution, though there is still much to be done in this direction. The structure of a rimmed ingot that has been split by dynamiting and a schematic diagram of the zones in the ingot are illustrated in Fig. 1.

Jan 1, 1938

By D. R. Shoemaker

BACKGROUND AND PROJECT DESCRIPTION A 16.5 kt per day underground molybdenum mine is being developed at Questa in northern New Mexico by Molycorp, Inc., a wholly-owned subsidiary of Union Oil Company of California. Small scale underground mining first began in 1920 and large scale open-pit mining was initiated in 1965, but because of the high stripping ratio, surface mining is being phased out. Construction of the underground mine began in 1979, and first production is scheduled for 1983. Full production of 9 Gg of molybdenum per year will be reached in 1984. Access to the mine will be through a service shaft, development shaft, and a conveyor decline. 'The service shaft, 7.3 m in diameter and 396 m deep, will be used for personnel, supplies, development muck, and fresh air intake. It will be equipped with a large, double-deck man and material cage. A double-drum hoist will be used for cage hoisting and will handle up to a 27-t load in balance with a counterweight. Development muck will be loaded into skips in balance and a single-drum auxiliary hoist will provide secondary access. The 396-m-deep, 4.3-m-diameter development shaft will be used for initial mine development, mine exhaust air, and a slick line pass for concrete entering the mine. The development shaft is located 400 m north of the service shaft. Run-of-mine ore will be transported from one of two 1.4-kt storage pockets by a 1.2-m-wide conveyor belt located in the 10°, 1980-m-long, 5.0-m-wide, and 4.6-m-high decline. The decline conveyor belt has a centerline length of 2229 m and a vertical rise of 363 m. It will be powered by four 448 kw motors driving a single drive pulley. There will be two 1.2 m transfer belts on the surface with centerline lengths of 322 m and 542 m. All three conveyor belts will be reinforced with steel cables. On the surface, in addition to the headframes and hoist houses for the two vertical shafts, a large maintenance shop, warehouse, compressor house, change house, main office building and timber framing building have been constructed.

Jan 1, 1981

By H. J. Wasson

At the close of 1927 Venezuela was producing at the rate of 205,000 bbl, per day, making it the third country in the world in point of present daily production. For the year, the total was close to 64,000,000 bbl., representing an increase of about 70 per cent. over the 37,000,000 bbl. in round numbers produced in 1926. All of the 1927 production canie from fields opened up before the beginning of the year. While no new fields were added to the list of shippers, the past 12 months' wildcatting yielded a fair quota of new discoveries which, in the light of prcsent results, may be considered likely sources of production in due time. Altogether three such promising finds were made Of first importance, at least for the immediate future, is the completion by the Lago Petroleum Corpn. of the San Matins well, 4 miles north of the present edge of the Lagunillas field. Although rated as only a 125. bbl. well, at 3217 ft., it indicates a probable extension of the field over the intervening 4 miles between the two. The two other wildcat discoveries of importance were the Los Manueles well in the District of Colon, which has in all probability opened up a new field about 7 miles north of the present Tarra oprations; and the Honibre Pintado well of the Standard Oil Co. of Venezuela,. in the State of Falcon, which is considered to be a promising clc~vc~lop~ncnt. Neither of these last mentioned two discoveries will apprcciably affect production during 1928, as the Manueles area must await the carrying out of a general plan for the exploitation of the District of Colon, a problem requiring time. The Hombre Pintado area is being tested further, but doubtless several wells will be put down before. anything definite will be done towards making the pipe line. arrangements that rnust necessarily precede the commercial exploitation of the field. The San Matias Well The San Matias well is a highly significant dcvelopment,. It is located along the trend of the La Rosa-Ilagunillas producing formations, and when drilling started, production in the Lagunillas field was 4 miles

Jan 1, 1928

By C. W. Vaupell

The Huitzuco mines lie in north central Guerrero, Mexico; production has been about 90,000 flasks of quicksilver since 1873. Near-surface ores fill extinct mud geysers and the deep deposits are chambered veins, stock-works in brecciated blocks, and replacements in limestone. The epigenetic minerals livingstonite, stibnite and sulphur occur in limestone, gypsum and dolomite through a developed vertical range of 260 meters. The deepest workings expose an increased amount of stibnite, which probably indicates that the lower limit of mercury mineralization is being approached. A resurgence of heat and water formed geysers over an extended area after the period of mercury mineralization. Mud geysers, which are situated, in the outcrops, contain the secondary mercury minerals, cinnabar and barccnite in the gravel and mud filling the vents. A 150-ton flotation plant is in operation concentrating stope fills that assay 3.0 kg. of mercury per ton. In one open stope, which is more than one hectare in area and 60 m. high, 150,000 tons are available. Introduction The Huitzuco mercury mines are of interest because of the unusual occurrence of ore in extinct geyser vents and the presence of several rare mercury minerals. Some of the deposits have typical characteristics of the telethermal zone and there is a gradation towards typical epithermal mineralization in depth. Halse,1 Villarel1o,2 Mactear3 and Merri114 have described the geology and the early operations in the district, and Bar-cena5 and Mallet6 have described the rare mercury minerals, livingstonite and barcenite, found at Huitzuco. Location The village of Huitzuco lies in the north central part of the State of (Guerrero, Mexico, 27 km. (16.7 miles) east of Iguala, which is the largest and most important town in the area. Iguala is served by the Mexican National Railways and also by the Mexico City-Acapulco highway. The highway is surfaced from Mexico City to Iguala, a distance of 200 km. (124 miles) by road, and there is a fairly good, level, dirt road from Iguala to Huitzuco. The elevation above sea level is about 1000 m. (3280 ft.). The climate is warm and very dry except during the rainy season, from June to

Jan 1, 1941

By C. W. Vaupell

The Huitzuco mines lie in north central Guerrero, Mexico; production has been about 90,000 flasks of quicksilver since 1873. Near-surface ores fill extinct mud geysers and the deep deposits are chambered veins, stock-works in brecciated blocks, and replacements in limestone. The epigenetic minerals livingstonite, stibnite and sulphur occur in limestone, gypsum and dolomite through a developed vertical range of 260 meters. The deepest workings expose an increased amount of stibnite, which probably indicates that the lower limit of mercury mineralization is being approached. A resurgence of heat and water formed geysers over an extended area after the period of mercury mineralization. Mud geysers, which are situated, in the outcrops, contain the secondary mercury minerals, cinnabar and barccnite in the gravel and mud filling the vents. A 150-ton flotation plant is in operation concentrating stope fills that assay 3.0 kg. of mercury per ton. In one open stope, which is more than one hectare in area and 60 m. high, 150,000 tons are available. Introduction The Huitzuco mercury mines are of interest because of the unusual occurrence of ore in extinct geyser vents and the presence of several rare mercury minerals. Some of the deposits have typical characteristics of the telethermal zone and there is a gradation towards typical epithermal mineralization in depth. Halse,1 Villarel1o,2 Mactear3 and Merri114 have described the geology and the early operations in the district, and Bar-cena5 and Mallet6 have described the rare mercury minerals, livingstonite and barcenite, found at Huitzuco. Location The village of Huitzuco lies in the north central part of the State of (Guerrero, Mexico, 27 km. (16.7 miles) east of Iguala, which is the largest and most important town in the area. Iguala is served by the Mexican National Railways and also by the Mexico City-Acapulco highway. The highway is surfaced from Mexico City to Iguala, a distance of 200 km. (124 miles) by road, and there is a fairly good, level, dirt road from Iguala to Huitzuco. The elevation above sea level is about 1000 m. (3280 ft.). The climate is warm and very dry except during the rainy season, from June to

Jan 1, 1941

By Charles Baker

THE district of Catorce, San Luis Potosi, ranks among the first half-dozen silver-producing camps f Mexico. Mining has been more or less continuous there for 150 years. The large producing mines, Mapum, Mazapil, Palomas, Musquiz, Minas Virjas, now for the most part idle or abandoned, are grouped around the head of two valleys: one, which drains to the west, falls 2000 ft. (609.6 m.) in 4 1/2 mi. (7.2 km.) between the main Catorce and the western foot of the range and is characterized by steep canon walls; the other, east of the main town of Catorce from which it is separated by a high divide, heads in a number of steep tributaries above the basin in which lies the town of Potrero and flows nearly north for 10 mi. (16 km.) to the northern base of the range; below Potrero, it has for the most part gently sloping valley walls and a broad valley floor. The Sierra Catorce is the highest range of the region, the summits reaching altitudes of over 11,000 ft. With the exception of a few cliffs of the erosion escarpment of the lower limestone and the canon walls below the main town of Catorce, which is the highest town in Mexico, the gently rounded slopes are characteristic of a maturely eroded mountain range composed of folded sedimentary rocks. As is usual in desert regions, the heavy-bedded limestones are the most resistant to erosive forces. Folded into anticlines, they form the mountain ranges; and the intermontane valleys and basins, originally carved out of less resistant shales, clays, marls and sandstones, are covered by debris forming a mantle with surface gradually rising upwards toward the hills. In time, the debris buries, in deposits formed from their own ruins, all but the highest summits of the original mountains; some f this region has already nearly reached this stage. Most of the debris is firmly cemented by calcium carbonate (caliche). Solution f the limestone by meteoric waters afforded the supply of lime carbonate, which has been redeposited upon evaporation of the waters as a cement binding the boulders, pebbles, and finer detritus.

Jan 9, 1921

By Alfred H. Bell

The year 1937 has been outstanding in the history of the Illinois oil industry. During the course of the year the state's daily production has been trebled, increasing from 12,000 bbl. per day at the beginning to 37,000 bbl. per day at the end, and the year's total, 7,426,000 bbl. is 66 per cent above the previous year's production of 4,475,000 bbl. The production in January was 368,000 bbl.; in December it was 1,085,000. Production from the old fields increased slightly. Most of the new production is from fields in the central part of the Illinois Basin, an area that for many years was considered unfavorable to the occurrence of oil and gas. The principal producing horizon of the new fields is the McClosky "sand," an oolitic limestone in the Ste. Genevieve formation of lower Mississippian age. Although development has not yet gone far enough to permit accurate estimates of oil reserves in the new fields, it is believed that they are of the order of 100,000,000 barrels. The following are the oil fields discovered in 1937 listed in order of amount of daily production at the end of the year; Noble (Richland County), Clay City, including Southeast Clay City (Clay and Wayne counties), Patoka (Marion County), New Centralia (Clinton County), Olney (Richland County), Cisne (Wayne County),.Beecher City (Fayette County), and Rinard (Wayne County). One gas field, the Russellville, in Lawrence County, was discovered in 1937. For locations of the new fields see Fig. 1. A generalized geologic column for Illinois, showing producing horizons in the new fields, is given in Fig. 2. The total productive area of the new fields at the end of 1937 was 1712 acres, in which 230 wells were producing. Thisrty-five dry holes were drilled within 1/4 mile of producing wells. At the end of the year there were 19 drilling wells, 28 rigs standing, 18 rigging up and 4 new locations in these fields. In the whole state 447 wells were completed, of which 284 were oil producers and three gas producers. Total initial daily production of

Jan 1, 1938

The 140th meeting* of the American Institute of Mining and Metallurgical Engineers was held in New York, Feb. 16 to 19, 1931. It consisted of the annual business session, twenty-six technical sessions at which 149 papers were presented, two round table discussions, two meetings of the Board of Directors, three meetings of Section Delegates, two formal lectures, four group dinners and 11 group luncheons, luncheon daily for members and guests, 20 committee meetings and conferences, the annual reception and dinner dance, an informal dance, a smoker-dinner, two meetings of the Woman's Auxiliary and a special program of entertainment for the ladies. Former members of the Rocky Mountain Club and friends lunched together at the Engineers Club on Tuesday. The proceedings of the Iron and Steel Division included four general technical sessions, an Iron Ore Round Table, the Howe Memorial Lecture, the Division luncheon at the Engineers Club Wednesday noon, a session each of the Executive Committee and the Committee on Nondestructive Testing, a luncheon each of the Committee on the Manufacture of Alloy Steel and the Blast-furnace Conference Group, and a dinner of the Committee on Physical Chemistry of Steelmaking. Dr. F. F. Lucas delivered the Howe Lecture, the title of which was "On the Art of Metallography." The Institute of Metals Division held three general sessions, its annual lecture, which was delivered by Dr. Arne Westgren and entitled "X-ray Determination of Alloy Equilibrium Diagrams," and a Division dinner at the Hotel New Yorker Thursday evening, at which Dr. G. W. Thompson was the principal speaker. The Executive Committee assembled at a luncheon on Thursday. A round table on Coal Land Valuations, a general technical session and a Division luncheon were held by the Coal Division. C. E. Bockus, President of the National Coal Association, made an informal talk at the luncheon which was held at the Engineers Club Monday noon. The Petroleum Division held six general sessions, including its annual production symposium. The annual dinner was held at the Engineers Club Thursday evening. A Gold Supply Symposium was the feature of the proceedings of the Committee on Mining Geology. This Committee also held a general session and a luncheon meeting. Sessions were held by other Technical Committees as follows: Mining Methods, 2; Mine Ventilation, 1 (besides which the Committee on Mine Ventilation Code held a meeting); Ground Movement and Subsidence, 1; Milling Methods, 1; Nonferrous Metallurgy, 1; Engineering Education, 1 (also a Committee luncheon); Non-metallic Minerals, 1, and Geophysical Prospecting, 2.

Jan 1, 1931

By L. F. Bryant, J. P. Hirth, R. Speiser

The surface, gain boundary, and twin boundary energies, as well as the surface diffusion coefficient, of cobalt were determined from tests at 1354°C in pure hydrogen. A value of 1970 ergs per sq cm was calculated for the surface energy, using the zero creep method. It was possible to measure the creep strains at room temperature because the phase transformation was accompanied by negligible irreversible strain and no kinking. Established techniques based on interference microscopy were used to obtain values for the other three properties. The gain boundary and twin boundary energies were 650 ad 12.7 ergs per sq cm, respectively, while a value of 2.75 x l0 sq cm per sec was determined for the surface dufusion coefficient. In the course of a general study of cobalt and cobalt-base alloys, information was required about the surface energy of cobalt. Hence, the present program was undertaken to measure the interfacial free energy, or, briefly, the surface energy, of the solid-vapor interface of cobalt. The microcreep method was selected for this measurement because other surface properties could also be determined from the accompanying thermal grooving at grain boundaries and twin boundaries. A brief summary of the methods for determining the various surface properties follows. At very high temperatures and under applied stresses too small to initiate slip, small-diameter wires will change in length by the process of diffu-sional creep described by Herring.1 The wires acquire the familiar bamboo structure and increase or decrease in length in direct proportion to the net force on the specimen. For a specimen experiencing a zero creep rate, the applied load, wo, necessary to offset the effects of the surface energy, y,, and grain boundary energy, y b, is given by the relation: where r is the wire radius and n is the number of grains per unit length of wire. The first results obtained from wire specimens were reported by Udin, Shaler, and Wulff.' udin3 later corrected these results for the effect of grain boundary energy. The grain boundary energy is determined from measurements of the dihedral angle 8 of the groove which develops by thermal etching at the grain boundary-free surface junction. For an equilibrium configuration: Measurements of the angle 8 can be made on the creep specimens4'5 or on sheet material, as was done in this investigation by a method employing interference microscopy.= If the vapor pressure is low, the rate at which grain boundary grooves widen is determined primarily by surface diffusion and, to a lesser extent, by bulk diffusion. The surface diffusion coefficient, D,, is obtained from interferometric measurements of the groove width as a function of the annealing time, t. As predicted by Mullins~ and verified by experiment, the distance, w,, between the maxima of the humps formed on either side of the grain boundary increases in proportion to if grooving proceeds by surface diffusion alone. For this case: where fl is the atomic volume and n is the number of atoms per square centimeter of surface. When volume diffusion also contributes to the widening, the surface diffusion contribution can be extracted from the data by the method described by Mullins and shewmon.8 Where a pair of twin boundaries intersects a free surface, a groove with an included angle of A + B (using the groove figure and notations of Robertson and shewmong) forms by thermal etching at one twin boundary-free surface junction. If the "torque terms", i.e., the terms in the Herring10 equations describing the orientation dependence of the surface energy, are sufficiently large, an "inverted groove" with an included angle of 360 deg-A'-B' develops at the other intersection. The angles A + B and A' + B' are measured interferometrically. When the angle, , between the twinning plane and the macroscopic surface plane is near 90 deg, the twin boundary energy is calculated from the relation: 1) EXPERIMENTAL TECHNIQUES Five-mil-diam wire containing 56 parts per million impurities was used for making ten creep specimens. These specimens had about 15 mm gage lengths with appended loops of wire and carried loads (the specimen weight below the midpoint of the gage length) ranging from 3.7 to 149.8 mg. The wires were hung inside a can made from 99.6 pct pure cobalt sheet. Beneath the wires were placed small specimens of 20-mil-thick, 99.9982 pct pure cobalt sheet from which the relative twin boundary and grain boundary energies and the surface diffusion coefficient were measured. All the specimens were annealed at a temperature of 1354" i 3°C which is 92 pct of the absolute melting point of cobalt. The furnace atmosphere was 99.9 pct pure hydrogen that was purified further by a Deoxo catalytic unit, magnesium perchlorate, and a liquid-nitrogen cold trap. As a precautionary measure the gas was then passed through titanium alloy turnings which were heated to 280" to 420°C and replaced after every test period. The hydrogen was maintained at a

Jan 1, 1969

By A. J. Shaler, H. Udin, J. Wulff

In the study of the sintering of meta powders, we have come to the conclusion in this laboratory that further progress requires a more basic understanding of the operating mechanisms. This is emphasized in detail by Shaler. He has shown that a knowledge of the exact value of the surface tension is imperative for a solution of the kinetics of sintering. This force plays a principal role in causing the density of compacts to increase.2 Furthermore, a knowledge of the surface tension of solids is also applicable to other aspects of physical metallurgy. C. S. Smith3 points out the relation between surface and interfacial tension and their function in determining the microstructure and resulting properties of polycrystal-line and polyphase alloys. This paper describes one group of results of an experimental program designed for the study of the surface tension in solid metals. As a by-product of this work, considerable information has been obtained on the rate and nature of the flow of a metal at temperatures approaching the melting point and under extremely low stresses, a field of mechanical behavior heretofore scarcely touched by metallurgists. The importance of this additional information to students of powder metallurgy need not be stressed. Theoretical Considerations Interfacial tension arises from the condition that an excess of energy exists at the interface between two phases. Gibbs proves that this energy is a partial function of the interfacial area; thus: ?F/?s = ? where ?F/?s is the rate of change of free energy of the system with changing surface area, at constant temperature, pressure and composition, and ? is the interfacial tension, or interfacial free energy per unit area. If one of the phases is the pure liquid or solid, and the other the vapor of the substance, ? may properly be termed "surface tension," and is a characteristic of the solid or liquid. The attempt of a body to lower its free energy by decreasing its surface gives rise to a force in the surface which is numerically equal in terms of unit length to the free energy per unit area of the surface. Thus ? may be expressed either in erg-cm-² or in dyne-cm-1. Similarly, surface tension may be determined either by a thermo-dynamic measurement of the surface energy or by a mechanical measurement of the surface force. We have chosen the latter approach. Tammann and Boehme4 determined the surface tension of gold by measuring the amount of shrinkage or extension of thin weighted foil at various temperatures and interpolating to zero strain. The method is of questionable accuracy because of the tendency of foil to form minute tears when heated under tension. Their assumption of F = 2W?, where W is the width of the foil, is unsound, as the foil can decrease its surface area by transverse as well as by longitudinal shrinkage. Although their experimentation was meticulous, the paper does not include details of the sample configuration required for recalculating ? on a correct basis, even if such a calculation were possible. In the experimental procedure chosen here, a series of small weights of increasing magnitude are suspended from a series of line copper wires of uniform cross-section. This array is brought to a temperature at which creep is appreciable under extremely small stress. If the weight overbalances the contracting force of surface tension, the wire stretches; otherwise, it shrinks. The magnitude of the strain is determined by the amount of unbalance, so a plot of strain vs. load should cross the zero strain axis at w = F?. If balance is visualized as a thermodynamic equilibrium, the critical load is readily calculated. At constant temperature, an infinitesimal change in surface energy should be equal to the work done on or by the weight: ds = wdl [A] For a cylinder, s = 2pr2 + 2prl [2] If the volume remains constant, r = vV/pl [31 s = 2vpl+2V/l [4] ds = vpv/l - 2V/l²) dl [5] Substituting [5] into [I] gives for the equilibrium load, w = ?(z/rV- 2V/12) [6] and, again expressing V in terms of r and l, w = pr?(1 - 2r/l [7] Here the end-effect term, 2r/l, is neglected for thin wires in subsequent work. Eq 7 can be confirmed by means of a stress analysis. If the x-axis is chosen along the wire, then the stress is 2pr? - w pr² pr2 [8] A cylinder of diameter dis equivalent to a sphere of radius r, insofar as radial surface tension effects are concerned.³ Thus xv = 2?/d = ?/r = sz [9] For the case of zero strain in the x direction, the strain will also be zero in the y and z directions. Since the wire is under hydrostatic stress, Eq 8 and 9 are

Jan 1, 1950

By William F. Harris, Joseph Easha

FOR many years basic control of refinery operations depended on visual observation of small chill specimens poured at various intervals during processing. The oseto of these samples was related to the physical and chemical properties of the metal. Since the =setn is dependent on many factors other than oxygen content, this method, while giving a general indication of the condition of the copper, does not accurately measure the oxygen content. For the last 3 years a modified vacuum fusion procedure which enables the operator to determine the oxygen content of the copper within 1 5 min of sampling has been in use at the Westinghouse Copper Mill. For use with this apparatus a sampling technique has been developed which gives oxygen values representative of the oxygen content of the wire bar. The sampling technique is based on a statistical study, which compared the oxygen content of the laboratory sample of copper poured at the same time a wire bar was being poured, with the oxygen content of the wire bar. The apparatus used for the determination of oxygen in copper is shown in Fig. 1 and is essentially the same as previously described but with one important modification. A very porous fritted glass disc has been inserted in the tubing between the manom- eter and 40/50 ground glass joint. The fritted disc retains the copper vapor and copper particles in the furnace section and prevents contamination of the mercury in the manometer. Without the disc the manometer became difficult to read after a few weeks of operation. In earlier work1 it had been established that the simplified vacuum fusion apparatus used at the Copper Mill gave essentially the same results as a con-vential vacuum fusion apparatus. However, for this study it was necessary to determine the difference, if any, between the oxygen content of the wire bar and the oxygen content of the small chill sample used for the oxygen analysis. This correlation was established by taking a chill sample at the same time wire bars were being poured. The wire bar being poured at the time the chill sample was taken was marked and removed for further analysis. The copper is sampled at various times during refining and cast into laboratory size samples with the mold shown in Fig. 2. The mold is made of cold rolled steel and is 2 in. high and 2 1/2 in. in diam. The large upper portion of the cast sample is used for measurement of the conductivity of the copper, The lower portion which is a rod about 1/4 in. diam by 3/4 in. long is used for determination of the oxygen content. This portion of the sample weighs about 5 g which is approximately the size sample used for the analysis. The only preparation neces-

Jan 1, 1962

By Joseph Fry, Ralph H. Espach

In the spring of 1943, when it was evident that the Tensleep bandstone in the Elk Basin Field, Wyoming and Montana, held a large reserve of petroleum, Bureau of Mines engineers obtained samples of oil from the bottom of nine wells and analyzed them for such physical characteristics as the volumes. of gas in solution. saturation pressures or bubble points, shrinkage in volume caused by the release of gas from solution, expansion of the oil with decrease in pressure, and other related properties. The composition of the gas in solution in the oil was studied. The pressures and temperatures existing in the reservoir and the productivity characteristics of the oil wells were determined. The data obtained indicate that the oil in the Tensleep Reservoir of the Elk Basin Field has unusually varying physiral characteristics, such as a saturation pressure of 1,250 psia and 490 cu ft of gas in solultion in a barrel of oil at the crest of the structure and a saturation pressure of 530 psia and 134 cu ft of gas in solution in a barrel of oil low on the flanks. The hydrogen sulfide content of the gas in solution in the oil varies from 18 per cent for oil on the crest to 5 per cent for oil low on the flanks of the structure. Of even greater significance is the fact that these and other variable characteristics of the reservoir oil are related to the position of the oil in the structure. Many geologists and petroleum engineers have considered that all the oil in a petroleum reservoir has rather uniform physical characteristics and that equilibrium conditions prevailed in all underground accumulations of oil and gas; that such is not always so is borne out by the results of the study by the writers. INTRODUCTION The Rocky Mountain region is one in which may be found striking examples of the unusual in oil and gas accumulations, as is evident from the following: The high helium content (7.6 per cent) of the gas in the Ouray-Leadville limestone sequence in the Rattlesnake Field, New Mexico, and gases of similar helium content in other fields; 50" to 55' API gravity distillate in solution in carbon dioxide gas and recoverable through retrograde condensation, in the North McCallum Field, Colorado; the occurrence of gas, oil, or both in closely related structures contrary to the usual concepts of gravimetric segregation: the accumulation of gas and/or oil in structures closely related to other structures that apparently are more favorable but do not contain oil or gas accumulations; the high hydrogen sulfide content (as high as 42 per cent) of the gas associated with oil in some fields in the Big Horn Basin, Wyoming; and the wide range of fluid chararteristics found in the Elk Basin reservoir. Elk Basin, an interesting old oil field that has been producing oil from the Frontier formation since 1915, is situated in a highly eroded basin resulting from the erosion of the crest of an anticline and some of the underlying softer shales. The field came back into national prominence during 1943 when it became known that it was the largest single reserve of new oil discovered in the United States that year. The Tensleep sandstone was found to contain oil in November. 1942, when a well drilled to a depth of 4,538 ft (44 ft into the Tensleep sandstone) flowed oil at the rate of 2,500 B/D. By the end of 1949, 137 oil-producing wells and five dry holes had been drilled, and approximately 32 million bbl of oil had been produced. Approximately 6,000 acres may be considered productive of oil in the Tensleep Reservoir, and estimates of the oil that will be produced average 200 million bbl. The Tensleep Reservoir has further interest because it ha-greater closure than any oil field in the Rocky Mountain region; the closure of the Elk Basin anticline is variously estimated at 5.000 to 10,000 ft. of which the top 2.00 ft of the structure contained oil. SUBSURFACE OIL SAMPLING Fig. 1 is a structural map of the Elk Basin Tensleep Reservoir, on which the nine wells used in this study and the numbers correvponding to the well designations hereafter referred to are shown. Wells 1. 2, 3, 4, and 8 were tested and sampled during October and November. 1943. and Wells 5, 6. 7, and 9 during June and July, 1944. An electromagnetic type sampler developed by the Bureau of Mines and described by Grandone and Cook' was used in obtaining the subsurface oil samples. As the wells were tubed nearly to bottom, the sampler was run as far as possible in the tubing hut never below the top perforations. The following procedure was used in testing and sampling the wells: A well was shut in for at least three days, after

Jan 1, 1951

By Joseph Fry, Ralph H. Espach

In the spring of 1943, when it was evident that the Tensleep bandstone in the Elk Basin Field, Wyoming and Montana, held a large reserve of petroleum, Bureau of Mines engineers obtained samples of oil from the bottom of nine wells and analyzed them for such physical characteristics as the volumes. of gas in solution. saturation pressures or bubble points, shrinkage in volume caused by the release of gas from solution, expansion of the oil with decrease in pressure, and other related properties. The composition of the gas in solution in the oil was studied. The pressures and temperatures existing in the reservoir and the productivity characteristics of the oil wells were determined. The data obtained indicate that the oil in the Tensleep Reservoir of the Elk Basin Field has unusually varying physiral characteristics, such as a saturation pressure of 1,250 psia and 490 cu ft of gas in solultion in a barrel of oil at the crest of the structure and a saturation pressure of 530 psia and 134 cu ft of gas in solution in a barrel of oil low on the flanks. The hydrogen sulfide content of the gas in solution in the oil varies from 18 per cent for oil on the crest to 5 per cent for oil low on the flanks of the structure. Of even greater significance is the fact that these and other variable characteristics of the reservoir oil are related to the position of the oil in the structure. Many geologists and petroleum engineers have considered that all the oil in a petroleum reservoir has rather uniform physical characteristics and that equilibrium conditions prevailed in all underground accumulations of oil and gas; that such is not always so is borne out by the results of the study by the writers. INTRODUCTION The Rocky Mountain region is one in which may be found striking examples of the unusual in oil and gas accumulations, as is evident from the following: The high helium content (7.6 per cent) of the gas in the Ouray-Leadville limestone sequence in the Rattlesnake Field, New Mexico, and gases of similar helium content in other fields; 50" to 55' API gravity distillate in solution in carbon dioxide gas and recoverable through retrograde condensation, in the North McCallum Field, Colorado; the occurrence of gas, oil, or both in closely related structures contrary to the usual concepts of gravimetric segregation: the accumulation of gas and/or oil in structures closely related to other structures that apparently are more favorable but do not contain oil or gas accumulations; the high hydrogen sulfide content (as high as 42 per cent) of the gas associated with oil in some fields in the Big Horn Basin, Wyoming; and the wide range of fluid chararteristics found in the Elk Basin reservoir. Elk Basin, an interesting old oil field that has been producing oil from the Frontier formation since 1915, is situated in a highly eroded basin resulting from the erosion of the crest of an anticline and some of the underlying softer shales. The field came back into national prominence during 1943 when it became known that it was the largest single reserve of new oil discovered in the United States that year. The Tensleep sandstone was found to contain oil in November. 1942, when a well drilled to a depth of 4,538 ft (44 ft into the Tensleep sandstone) flowed oil at the rate of 2,500 B/D. By the end of 1949, 137 oil-producing wells and five dry holes had been drilled, and approximately 32 million bbl of oil had been produced. Approximately 6,000 acres may be considered productive of oil in the Tensleep Reservoir, and estimates of the oil that will be produced average 200 million bbl. The Tensleep Reservoir has further interest because it ha-greater closure than any oil field in the Rocky Mountain region; the closure of the Elk Basin anticline is variously estimated at 5.000 to 10,000 ft. of which the top 2.00 ft of the structure contained oil. SUBSURFACE OIL SAMPLING Fig. 1 is a structural map of the Elk Basin Tensleep Reservoir, on which the nine wells used in this study and the numbers correvponding to the well designations hereafter referred to are shown. Wells 1. 2, 3, 4, and 8 were tested and sampled during October and November. 1943. and Wells 5, 6. 7, and 9 during June and July, 1944. An electromagnetic type sampler developed by the Bureau of Mines and described by Grandone and Cook' was used in obtaining the subsurface oil samples. As the wells were tubed nearly to bottom, the sampler was run as far as possible in the tubing hut never below the top perforations. The following procedure was used in testing and sampling the wells: A well was shut in for at least three days, after

Jan 1, 1951

Some Things We Don't Know about the Creep of Metals. By H. W. Gillett (T.P. 1087) Reduction of Iron Ores under Pressure by Hydrogen. By Michael Tenenbaum and T. L. Joseph (T.P. loll, with discussion) Induction Furnaces for Rotating Liquid Crucibles. By E. P. Barrett, W. F. Hol- bRook and C. E. Wood (T.P. 986, with discussion) Mechanism of Solidification and Segregation in a Low-carbon Rimming-steel Ingot,. By Anson Hayes and John Chipman (T.P. 988, with discussion) Solidification of Rimming-steel Ingots. By A. HultGRen and G. PhRagmen. (Contribution 112) Dendritic Structure of Some Alloy Steels. By Daniel .I. Martin and James L. Martin (T.P. 1066, with discussion) Occlusion and Evolution of Hydrogen by Pure Iron. By George A. Moore and Donald P. Smith (T.P. 1065, with discussion) Structure of Iron after Con~pression. Hy Charles S. Barrett (T.P. 977, with discussion) Structure of Iron after Drawing, Swaging, and Elongating in Tension. Ry Charles S. Barrett and L. H. LevensoN (T.P. 1038, with discussion) Magnetic Torque Studies of the Texture of Cold-rolled and of Recrystallized Iron-silicon Alloys. By Leo P. TaraSovJ(T.P. 1012, with discussion) Influence of Atmosphere and Pressure on Structure of Iron-carbon-silicon Alloys. By Alfred Boyles (T.P. 1046) Kinetics of the Decomposition of Austenite at Constant Temperature. By J. H. Austin and R. L. Rickett (T.P. 964, with discussion) Reaction Kinctics in Processes of Nucleation and Growth. By William A. Johnson and Robert F. Mehl (T.P. 1089, with discussion) Phase Changes in 3.5 Per Cent Nickel Steel in the Acl Region. By I. N. Bavarine (T.P. 1031, with discussion) Chromium in Structural Steel. By Walter Crafts (T.P. 1055) Surface Allotropic Transformation in Stainless Steel Induced by Polishing. By J. T. BuHwell and J. WUlff (T.P. 1032, with discussion) Nature of :Passivity in Stainless Steels and Other Alloys, I and 11. Ry H. H. Uhlig and John WUlff (T.P. 1050, with discussion) Thermal Expansion of Nickel-iron Alloys (Nickel from 30 to 70 Per Cent). Ry J. M. Lohr and Charles H. Hopkins (T.P. 987, with discussion) Low-temperature Transformation in Iron-nickel-cobalt Alloys. By L. L. Wy~Ian (T.P. 1013, with discussion) Fracture of Steels at Elevated Temperatures after Prolonged Loading. By R. H. Thielemann and E. R. Parker (T.P. 1034, with discussion)

Jan 1, 1939

Some Things We Don't Know about the Creep of Metals. By H. W. Gillett (T.P. 1087) Reduction of Iron Ores under Pressure by Hydrogen. By Michael Tenenbaum and T. L. Joseph (T.P. loll, with discussion) Induction Furnaces for Rotating Liquid Crucibles. By E. P. Barrett, W. F. Hol- bRook and C. E. Wood (T.P. 986, with discussion) Mechanism of Solidification and Segregation in a Low-carbon Rimming-steel Ingot,. By Anson Hayes and John Chipman (T.P. 988, with discussion) Solidification of Rimming-steel Ingots. By A. HultGRen and G. PhRagmen. (Contribution 112) Dendritic Structure of Some Alloy Steels. By Daniel .I. Martin and James L. Martin (T.P. 1066, with discussion) Occlusion and Evolution of Hydrogen by Pure Iron. By George A. Moore and Donald P. Smith (T.P. 1065, with discussion) Structure of Iron after Con~pression. Hy Charles S. Barrett (T.P. 977, with discussion) Structure of Iron after Drawing, Swaging, and Elongating in Tension. Ry Charles S. Barrett and L. H. LevensoN (T.P. 1038, with discussion) Magnetic Torque Studies of the Texture of Cold-rolled and of Recrystallized Iron-silicon Alloys. By Leo P. TaraSovJ(T.P. 1012, with discussion) Influence of Atmosphere and Pressure on Structure of Iron-carbon-silicon Alloys. By Alfred Boyles (T.P. 1046) Kinetics of the Decomposition of Austenite at Constant Temperature. By J. H. Austin and R. L. Rickett (T.P. 964, with discussion) Reaction Kinctics in Processes of Nucleation and Growth. By William A. Johnson and Robert F. Mehl (T.P. 1089, with discussion) Phase Changes in 3.5 Per Cent Nickel Steel in the Acl Region. By I. N. Bavarine (T.P. 1031, with discussion) Chromium in Structural Steel. By Walter Crafts (T.P. 1055) Surface Allotropic Transformation in Stainless Steel Induced by Polishing. By J. T. BuHwell and J. WUlff (T.P. 1032, with discussion) Nature of :Passivity in Stainless Steels and Other Alloys, I and 11. Ry H. H. Uhlig and John WUlff (T.P. 1050, with discussion) Thermal Expansion of Nickel-iron Alloys (Nickel from 30 to 70 Per Cent). Ry J. M. Lohr and Charles H. Hopkins (T.P. 987, with discussion) Low-temperature Transformation in Iron-nickel-cobalt Alloys. By L. L. Wy~Ian (T.P. 1013, with discussion) Fracture of Steels at Elevated Temperatures after Prolonged Loading. By R. H. Thielemann and E. R. Parker (T.P. 1034, with discussion)

Jan 1, 1939

By H. W. Knott, M. H. Mueller

The crystal structures of Ti2Cu, Ti2Ni, Ti4Ni2O, and Ti4Cu20 have been determined using powder specimens examined by X-ray and neutron diffraction. Lattice constants have been determined for all four phases using X-ray powder diffraction films. Atom positional parameters of all four phases have been determined from observed neutron intensities. X-ray diffraction calculated intensity data have been presented also for the phase Ti2Cu to point out the particular suitability of neutron diffraction in this case. Interatomic distances have been determined using the positional parameters obtained from neutron diffraction. ALTHOUGH some investigations of the crystal structures have been made of these four compounds previously,'-13 it was the purpose of the present investigation to expand the previous work in order to locate the various atoms, determine their coordinates, and to confirm or to correct some of the previous work. It was convenient to group these four compounds together since they are related chemicallv and/or structurally. The compound Ti2Cu is tetragonil; and Ti2Ni, Ti4Ni2O, and Ti4CU2O are all large fees of the same space group. Ti2Cu has been previously reported as a fee phase by Laves and Wallbaum;1 and Rostoker2 which was possibly the oxide phase, Ti4Cu20. Joukainen, Grant, and Floe;3 and Trzebiatowski, Berak, and Ramotow-ski4 have also reported a phase of this composition. karlsson5 has reported a small fct phase of the composition Ti3Cu which may be the presently discussed Ti2Cu phase. More recently Ence and Margolin6 have reported a small fct phase for Ti2Cu and the present authors7 together with Nevitt8 have briefly reported it to be a bet related to the fct with a co three times the length of the co of the fct and have also reported that this phase has a very limited composition. Further refinements will be reported which have varied some of the parameters of this bct structure slightly. Ti2Ni has been reported as a fee phase by Laves and wallbaum;1 Duwez and taylor;9 Rostoker;2 Poole and Hume-Rothery;10 and Yurko, Barton, and parr.11 In a later paper Yurko, Barton, and parr12 have given the complete structure of this phase based on an X-ray diffraction study which was independently confirmed with neutron diffraction by Mueller and knott.7 Additional crystal structure information will be given. Ti4Ti2O, Ti4Cu2O, and a number of other compounds including Ti4Fe2O have been reported as fcc phases by Rostoker,2 and more recently Nevitt13 has confirmed the Ti4Ti2O phase. Rostoker,2 however has reported diffraction lines for Ti4Fe2O which do not have all odd or all even indices. These lines, therefore, cannot be observed if this compound has a fee structure. This same error has crept into the diffraction results reported for TiNi2O and Ti4Cu20 in the ASTM powder data which has been credited from Rostoker's data. Complete crystal structures of these two phases will be presented. Although all four of these structures have large unit cells and hence do not lend themselves for completely resolved neutron powder patterns, a sufficient number of individual reflections was observed for solving the structure. They also serve as good examples of some of the advantages to be gained by using both neutron and X-ray diffraction techniques. EXPERIMENTAL PROCEDURE All of the alloys were prepared by arc melting. The starting metals had the following purity: Cu 99.999 pct, Ni 99.83 pct, and Ti 99.92 pct. Oxygen was introduced into the two oxide phases as chemically pure TiO2, with the remainder of the titanium coming from the above mentioned metal. All of the sample buttons were annealed in evacuated Vycor tubes, the two binary phases for 5 days at 700°C and the two oxide phases for 3 days at 900°C. Oxygen analyses were performed on all four phases by two independent laboratories with the following amounts of oxygen present in atomic percent; Ti2Cu-0.06, Ti2Ni-1.03, Ti4Ni2O-13.95, and Ti4Cu20-13.87. The stoichiometric amount for the oxide phases is 14.29 at. pct. Since all of the samples were very brittle they were easily reduced to a powder for diffraction measurements. The lattice constants given in Table I were determined for the four compounds from X-ray diffraction patterns of powder samples exposed to filtered copper radiation using a 114.59 mm diam Debye-Scherrer type camera using the Straumanis loading. None of the patterns showed a detectable amount of a second phase. The lattice constants were obtained from an IBM 704 computer program employing a least squares treatment with systematic correction terms as previously reported.14

Jan 1, 1963