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By T. G. Digges, C. L. Vold, M. R. Achter

A study was made of the effect of the growth conditions on the perfection of single crystals of niobium (columbium). Dislocation densities, determined by means of double-crystal diffractometer measurements , were not greatly affected by the method of crystal preparation but could be reduced by annealing treatments. However, the size, sharpness, and tilt angles of the substructures, observed with X-ray reflection macrograph, were sensitive to variations in growth procedures as well as to subsequent thermal treatments. Although the dislocation density was the same in both types, there were more low-angle bound-aries in crystals grown by zone melting than in those prepared by strain anneal. Mechanisms to account for these observations are discussed in terms of dislocation movements. A planned study of the structure-sensitive properties of refractory metals required the use of single crystals of a high degree of structural perfection and, for ease of handling, of large cross section. It appeared that the strain-anneal technique could satisfy both of these requirements. First, crystals grown in the solid state have been reported to be more perfect than those obtained from the melt.' Second, the diameters of rods which may be produced by zone melting should have a theoretical limit determined by specific gravity, thermal conductivity, and surface tension, while the diameter of strain-annealed rods is limited only by practical considerations. Previously it was shown that niobium (columbium) single crystals of 1 in. diam2 may be grown by strain anneal, compared to the 0.5 in. maximum diameter achieved by zone melting, as reported for molybdenum by Belk.3 The current research was undertaken to investigate and optimize the effect of various process variables on the perfection of 1/4 and 1/2-in.-diam niobium single crystals grown by strain annealing and to compare their perfection to those grown by zone melting. Characterization of these crystals was more conveniently accomplished by means of X-ray than by metallo-graphic techniques. EXPERIMENTAL PROCEDURE Specimen Preparation. Zone-melted crystals of 1/4 in. diam were produced by the standard electron-beam zone-melting technique. The swaged and cleaned rods were outgassed, in the solid state at a temperature near its melting point, at a rate of 12 in. per hr, and single crystals were grown by making two molten passes at 2 in. per hr. By maintaining a zone length of 4 to % in., very uniform single crystals several inches long were obtained. For the strain-annealed crystals, an induction heater was used, in preference to other types of heating, to take advantage of the good penetration of large sections. A five-turn coil, 1 in. long, operating at 10 kc and powered by a motor generator, was contained in a vacuum chamber. The rod, suspended from the upper end, was raised through the coil for both recrystallization and crystal growth. In preliminary work single crystals of the same material were also grown with single and multiturn coils powered by a 450-kc generator. A vacuum of 2 X 10-6 Torr was maintained at temperatures up to 2400°C. Starting with electron-beam-melted ingots of 21/2 in. diam, the analysis for which is given in Table I, the material was cold-swaged to the desired cross section of 1/4 and 1/2 in. diam and then recrystallized. The rods were then strained in a tensile machine and converted to single crystals by passing through the induction coil. As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and smallman,4 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point in the poly crystalline portion. Finally, it is returned to the chamber and growth is continued "around the corner". This procedure has certain limitations. If the bending operation exceeds the critical strain, recrystallization may take place. Also, the amount of bending which can be imparted to the rod is limited by coil geometry, and up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. In preparation for X-ray examination, single crystals were sectioned and planed by means of the spark-erosion technique. To obtain the maximum reflected intensity, the (110) plane was exposed for examination. They were then etched 3 to 5 min in a mixture of con-

Jan 1, 1967

By P. E. Phillips

INTRODUCTION Rocky Mountain Energy is the mining subsidiary of the Union Pacific Corporation, and has been active m uranium exploration since 1966. Since 1970, RME's uranium activities have been funded 50% by Mono Power, the fuels supply division of Southern California Edision. RME and Mono recognized the need for development of new methods for recovering low grade uranium deposits, and contacted Halliburton Services in regard to in situ leaching, because of Halliburton oil industry experience. As a result, a joint venture between the three parties was formed in 1974. BEAR CREEK The first ISL test was at the Bear Creek deposit in the Powder River Basin of Wyoming, about 60 miles north of Douglas. The mineralized sand is the tertiary Wasatch formation, which is an arkosic sandstone. The sand typically contains about 10% clay. The predominant clay being montmorillonite with some kaolin and illite. The roll front type trends occur along the flanks of old stream channels. This deposit was being considered for exploitation as an open pit mine. Routine amenability testing indicated it was quite amenable to a conventional acid leach, consuming about 50 lbs. of sulfuric acid per ton of ore in an agitation leach, while recovering more than 95% of the uranium. Hydrology testing indicated a permeability of about 1 darcy. The groundwater has a pH of about 8. 0 and TDS of about 1200. Test Facility The Bear Creek test was a summer-only operation, with no effort towards weather-proofing. Uranium was removed from the recovered leach solution by fixed bed ion-exchange columns. Loaded resin was eluted with strong sulfuric acid. The recovery plant was designed for simplicity of operation, with little concern for the grade or form of the yellowcake product. The plant was constructed of PVC piping and valves, fiberglass reinforced tanks, and stainless steel pumps. All waste streams were directed toward a lined evaporation pond. Wellfield The test pattern was a 30 foot radius 5 spot, with wells fully penetrating the 30 foot ore sand to a total depth of about 165 feet. The injection wells were three-inch PVC with slotted casing, while the producer was eight-inch I. D. , with a stainless steel screen. The eight-inch well was necessary in order to accommodate a six-inch stainless steel pump. Wells were cemented using cement baskets, at the top of the sand, to contain a latex acid resistant cement. Leach Conditions The lixiviant generally contained from five to seven gpl sulfuric acid, and about 0. 5 gpl hydrogen peroxide. The pH was generally 1.4 and EMF was usually -550 millivolts. Injection rates were rather variable from well to well, with a total injection rate between 12 and 25 GPM. Production rate was set at 25 GPM, since the production pump could not be throttled more than that. Approximately two pore volumes of solution were injected during the three-month test. Leach Results Injectivity was quite variable, but was generally rather poor, because of poor completion techniques. The problem stemmed from injecting before the injection wells had been completely cleaned of drilling mud. Pregnant solutions averaged about 50 ppm U308, with groundwater dilution varying from 10 to 50%, depending on the injection rate. Injectivity did decline with time, probably as a result of contamination of the well faces. A total of 1000 lbs U308 had been recovered when the test was shut down. This probably represented about 10% of the mineral under leach.

Jan 1, 1979

By J. B. Nau

A short time ago some interesting experiments concerning a new steel-making process in the open-hearth furnace were made by the writer at the Croton magnetic mine, N. Y.

Jan 1, 1892

By R. E. Anderson, R. S. Busk

The mechanical properties of many nonferrous alloys can be modified by heat-treatment. This is almost always effected by controlling the amount of alloy in solid solution and the amount and distribution of second-phase material. The latter often is accomplished through precipitation or age-hardening treatments. The procedure is to solution-heat-treat the metal to provide a supersaturated solid solution and then cause precipitation of the dissolved material at some temperature below the solvus for the alloy. The generally used magnesium sand-casting alloys arc based on the ternary alloy system Mg-Al-Zn. Solid diffusion reactions in the system are slow enough so that a substantially completely supersaturated solulion is maintained even though the metal is relatively slowly cooled from heat-treating temperatures. Consequently, it is general practice to air-cool magnesium-alloy castings from the heat-treatment temperature prior to aging at an elevated temperature. Since it is necessary with many other alloys to cool quite rapidly before aging if optimum benefit from the aging is to be obtained, this study was undertaken to determine the effects of quenching on magnesium alloys. The] alloys used are shown in Table I, being selected as typical of the presently used magnesium alloys. Cooling Rates Since quenching is a means of rapidly extracting heat, there are two factors of interest in its study: (I) the rates of cooling that can be obtained and (2) the effect of various rates on the as-cooled as well as subsequently aged metal. The cooling rates were measured by drilling a hole 1/16- in diameter longitudi~lally in the center of a cylinder % in. in diameter and 3 in. long. The drilling was stopped to place the end of the hole at the center of the long axis of the cylinder. An iron-constantan thermocouple was inserted in this hole and wedged in place. The temperature drop during rapid quenching was recorded by a special1y built General Electric potentiometer recorder capab1e of measuring ' 500°F. temperature drop in 1/10 sec. For the slower cooling rates in air or oil, the temperature drop was measured by a Leeds and Northrup potentiometer recorder with the chart speed increased to One inch per minute' The cylinder was heated to the desired temperature, quenched as desired, and the temperature-time curve recorded. The cooling rates in still air, in oil at 350°F., in water at 180°F. and in a cold, high-pressure water spray were determined in this manner. The results of this study are presented in Fig. I. There is a great difference between water quenching and either air or oil quenching. There is little difference between the hot water quench and the cold water spray. Cooling rates were also

Jan 1, 1945

By Henry A. Mather

While this device is not new in its inception, its peculiar advantages failed to be of practical utility until furnace-builders instituted the mechanical reform of supporting the upper and lower water-jackets by hanging them from an I-beam frame, independently upheld by iron columns, instead of resting the entire weight of structure on the bottom, as practice formerly prescribed. The Colorado Iron Works were among the first to build copper-furnaces of this description, and the device, illustrated herewith, has been installed by them in three recent plants,—two furnaces for the Westinghouse interests near Ely, Vermont, and one for the Grand Prize Copper Company, of Gila county, Arizona. The jack-screw supports (Figs. 1 and 2) and the familiar iron bottom of former practice are retained as integral parts of this new furnace-bottom. And, instead of resting inert on the tapfloor of the furnace-room, the jack-screws are supported on and bolted to two I-beams the length of the furnace, placed immediately beneath, and parallel to, its sides. These I-beams are bolted to, and supported by, three steel axles equipped with small flanged wheels, the whole constituting a carriage, which runs freely on a track. The entire apparatus is movable or rigid at will, for the wheels are easily braced, if the tension of the tightened jack-screws does not serve to hold the whole in position. The advantages of this design will be at once apparent to those who have had practical experience in barring furnaces provided with stationary iron bottoms. It is a well-known fact that the larger part of the time occupied in cleaning and preparing a frozen furnace for active service is necessitated by working in a confined place where the temperature is uncomfortable, and that in such case the débris must be removed from

Jan 1, 1903

By L. A. Dale, D. A. Dahlstrom

Closed-water circuits are justified today from two standpoints: economical operation and prevention of stream pollution. In today's modern preparation plant, it has been found very desirable to have the plant circulating water maintained at a relatively low solids concentration of around 3%. In so doing, bene-ficiation equipment can operate at a much higher efficiency. However, makeup water requirements would become excessive if the fines were to be removed from the preparation plant by bleeding a 3% solids concentration to a tailings pond. With the ever increasing percentage of —200 mesh coal, clay and slimes in the raw coal, coupled with the creation of these fines within the preparation plant, the need for water conservation for economy reasons becomes even more important. Because of stream pollution laws, tailings ponds have become very costly to operate and maintain, resulting in the necessity of employing an in-plant method of water recovery. Accordingly, the primary system employed in water recovery in the coal preparation plant today consists of a solids concentration device to thicken refuse solids while at the same time producing a sufficiently clarified effluent that can go back to the preparation plant for water reuse. The thickened product is then normally passed to a dewatering device that will produce a handleable solid that can be disposed of

Jan 1, 1965

By John Fritz

Gentlemen of the American Institute of Mining Engineers : I desire to thank you sincerely for the distinguished honor you have conferred upon me by electing me to the presidency of this society, a position which in the past has been filled by some of our most distinguished and ablest members, men eminently qualified by education, practical training and a business ability which has enabled them not only to fill the position with credit to themselves, but as well with honor to the society. In deference to a custom long established, by which the presidentelect is expected to read a paper on some subject with which he is more or less familiar, I have thought that a brief review of the methods employed in the manufacture of iron, as witnessed by myself, and reaching back to 1838, would interest some of our older members and give our younger ones a glimpse into the trials and difficulties encountered in those early days by the pioneers in this great industry. In 1840, 12 to 20 tons of pig-iron was the make of a furnace per week—at this time from 1200 to 2000 gross tons. In 1840, 3 to 4 tons No. 4 wire rods per turn. They have lately made 176 gross tons in 11 hours. In 1840 I have not the quantity of puddled iron made; but it was

Jan 1, 1895

PORPHYRY mining in the Bisbee district in Arizona did not begin until 1923, though Bisbee had been the scene of profitable copper-mining operations since 1880, and during the interval had contributed roughly 2,000,000,000 lb. of copper to the world's supply. At that time it ranked third among the copper districts of the United States, first place for total production going to Butte, Montana, and second to the district centering around Calumet, Michigan. Bisbee's production had come from the so-called "limestone" mines operated principally by the Phelps Dodge Corporation and the Calumet & Arizona Mining Co. Each of these companies had a large smelting plant at Douglas, 25 miles southeast of Bisbee on the Mexican border. The town of Douglas owed its existence primarily to the copper mines of Bisbee, the particular location having been determined, first, by the fact that water in adequate supply could be obtained by sinking wells; and, second, by its position about equally distant from Bisbee and the mines in Sonora, Mexico, of the Moctezuma Copper Co., a Phelps Dodge subsidiary. Three partners, Martin, Reilly, and Ballard, conducted the first operations of consequence at Bisbee about 1880; and in 1881 a smelting plant consisting of two 36 in. water-jacketed blast furnaces was erected near by. The ore came from open-cut workings on the later-to-be-famous Queen orebody. The furnace charge is said to have averaged 23 per cent copper-twice as rich as the concentrates from the mills and four times as rich as the smelting ore shipped from Bisbee in recent years. As early as 1881, disputes arose among owners of various claims, and groups of claims, over the ownership of orebodies under the law of apex and extra-lateral rights. This law gives a miner the right to follow his vein downward on its dip, even

Jan 1, 1933

By Henry J. Sandri

The use of economic models for forecasting purposes is an inexact yet necessary tool for mineral decision making. One method not commonly used is cyclical analysis because of its "non-scientific approach". However, under certain circumstances a modified cyclical approach can provide useful insight to mining companies. The current paper discusses mineral modeling, the type of economic models and the use of cyclical forecasting for mining firms (not speculators) involved in precious metals.

Jan 1, 1984

By C. C. Wright, R. J. Day

ALTHOUGH data on the exact tonnage of recoverable coal silt are not known, the quantity produced in 1943 was estimated to be over five million tons for the anthracite region of Pennsylvania alone. Since that time the recovery of the No. 5 buck- wheat size previously included in silt estimates has increased greatly thus reducing the total silt tonnage. As a compensating factor, however, the methods of recovering silt previously escaping into the rivers and streams have been markedly improved so that the net figure may not have changed materially. Comparable estimates for bituminous coal are lacking, but undoubtedly the silt represents a significant tonnage. With the trend toward increased wet cleaning of the smaller sizes of bituminous coal, it is to be expected that even greater quantities of silt will be available in the future. The raw silt from anthracite collieries usually contains a high mineral matter content, but technological developments in fine coal cleaning have been making rapid advances and it appears probable that more extensive use of these methods will be employed in the near future. Bituminous coal silt in many instances contains a similar high mineral matter content. As with anthracite silt, however, the cleaning of this material, where necessary, appears both technologically and economically feasible. With a view to upgrading the size and value of silt, considerable laboratory and pilot plant work has been conducted by a number of organizations on what is commonly known as pelletization. Actually the process is one of extrusion in which the moist silt is extruded from a die in the form of rods, which usually break into relatively short lengths-a few inches long-as they fall from the die. Fig I is a photograph of some extruded 3/8-in. diam pellets and of the anthracite silt from which they were produced. This technique of producing larger sized material from fines is by no means new, having been used extensively by the industrial carbon and clay industries for years.' The application of the process to coal silt appears, however, to be relatively new. The first major program of investigation dates back only to July 1945, when a group of engineers representing the Anthracite Institute, The Pennsylvania State College and the J. F. Pritchard and Co. conducted preliminary tests on the extrusion of anthracite silt at the Floridin Co. plant at Warren, Pa. Since that time these three organizations-individually, together, and in co- operation with other interested groups- have actively pursued work on various phases of the problem. Much of the early history and details of the laboratory and pilot plant work by the Anthracite Institute, has been reported by Mulcey and Eckerd.2 It is the purpose of this paper to report additional information on the process, especially with respect to the factors influencing the quality and use properties of the product, and the current develop

Jan 1, 1948

By G. A. Moore

A brief review is given of methods designed to produce metallic iron of high purity, and typical results are listed. A recent method, utilized at the National Bureau of Standards, consists of the extraction of ferric chloride by ether, reduction of this ferric chloride to ferrous chloride, further purification of this chloride, and the subsequent electrolytic deposition of metallic iron. iron produced by this procedure apparently is softer than, and otherwise different in properties from, any iron previously prepared and contains appreciably smaller amounts of impurities. THE history of attempts to produce "pure" iron reaches to antiquity and it may be presumed that each ancient armorer who succeeded in making a better steel concluded, correctly, that he had done a better job of removing the "base metals," and incorrectly, that he now at last had a "pure" metal. Early metallurgical papers mentioned use of "pure iron" in making alloys—this "pure" iron in most cases being inferior to some commercial stocks of the present time. Improvement has been continuous, and usually at a sufficient rate to convince each succeeding group of workers that they, at last, were using the really pure metal (until the analysts also improved their techniques to again discover the impurities). These adventures were reviewed in some detail by Cleaves and Thompson.' Although the ores of a metal may be abundant, difficulties in extracting it may make the pure metal very rare. When impurities are restricted to a total of a few parts per million, nearly all pure metals become rarities. Lead, copper, gold, mercury, silver, zinc, aluminum, bismuth, and the six platinum metals are claimed to be available with total impurities ranging from 2 to 50 ppm. The present small and scattered world supply of so-called "pure" iron holds an unimpressive place in another group of 16 metals having approximately 100 ppm of foreign material. Of about 20 less rare metals, only the platinum metals are more costly to prepare. While the production of such rare varieties of iron may appear insignificant in the presence of thousand-ton operations with 95 to 99 pct metal, it must be emphasized that all researches on commercially interesting irons and steels are in fact studies of the modifications of the properties of iron by additional materials. Until the properties of high purity iron are directly measured, all ferrous research must operate without known base values. Traces of impurities may affect the properties of a metal in many ways. Infinitesimal traces of solutes, by disturbing the electronic configuration, greatly change the electrical properties of transistors and semiconductors2-3 and slightly larger traces might alter these quantities in iron. Soluble impurities which disturb the perfection of lattice arrangement not only may alter the magnetic constants and electric properties, but by their close association with dislocation phenomena probably control the very existence of the "yield point"; determine the value of yield stress; and perhaps control the selection of slip and cleavage planes. It has been speculated that impurities might even cause the allotropic transformation in iron, but in any case their rearrangement must contribute to the unreliability of heat capacity and other thermodynamic measurements. Impurities which do not remain in solution may cause even greater effects on the properties. Microscopically visible amounts of phases other than ferrite can be found in all high purity irons which have come to my attention. It can be calculated that from 50 to as little as 2 ppm of an insoluble material might be sufficient to completely film all grain boundaries in irons having grain sizes from ASTM Nos. 10 to 1. Should this occur, such films, even though invisible, may be very important in fracture problems, especially at extremes of temperature:' Studies of grain growth and diffusion normally imply consideration of a single-phase system, hence, in the presence of insoluble impurities they can be expected to give ambiguous data." High purity iron is also in demand for use as chemical and spectro-chemical standards; for work in classifying the lines of the iron spectrum; for biological work in nutrition; and for work in nuclear physics. where the presence of some sensitive

Jan 1, 1954

AT the meeting of the Board of Directors on Jan. 28, 1927, the tentative budget of this Institute for next year was discussed, and in connection with the evident necessity for a larger income to meet increasing demands for service, the advisability of in- creasing the dues of members, was brought up. W. Spen- cer Hutchinson advocated an upward revision of the dues "believing it necessary that the Institute have a larger income, in order that it may carry on necessary work and render adequate service to its membership." Since this is a matter that directly affects every member, .President Taylor was directed to appoint a committee, which he did, consisting of George D. Barron, W. H. Bassett, and R. H. Sweetser, with T. T. Read as secre- tary, to bring in a tentative outline of the main factors in the problem for discussion at the annual meeting, on Feb. 15, and to prepare, after they have had the benefit of the discussion at that meeting, a report for the board. The amount of the annual dues is fixed by the con- stitution and can only be changed by proposing an amendment to the constitution. This amendment would have to be submitted to the members by letter ballot at the time of the election of officers for 1928, so that no change can be made in the dues for 1927 in any case. WHY THE INSTITUTE NEEDS MONEY At the annual meeting past-president Reynders, as chairman of the executive committee made the follow-ing report, which since it admirably sets forth the rea-sons why an increase in the dues has been suggested, is included here. "The report of the president has covered the situation so fully that little is left for me to say. However, a word in regard to the functions of the executive com-mittee may not be out of place.

Jan 3, 1927

By Gilbert E. Doan, William C. Schulte

An extensive program of investigation is being carried out at Lehigh University in the study of arcs and arc welds of high-purity iron1, sponsored by the Engineering Foundation. The part of that program reported in the present paper deals with welds made of high-purity iron in an argon atmosphere and for comparison with them welds made of the same iron in ordinary air. Welds of commercial steel also were made in argon and in air. The primary purpose of the study is to discover the basic physical constants of iron welds when not contaminated either by impurities in the iron or by the action of oxygen and nitrogen of the air during welding. Upon these constants can be founded such future studies as will determine what effects the various impurities and alloy elements present in steel have upon its welding characteristics, and what influence is exerted by the action of oxygen and nitrogen. The welding of steel involves such a multitude of variables, both of composition and of procedure, that development in the fabrication of this most important metal has necessarily been slow, wasteful, and in many instances discouraging. In the present investigation, the simplest possible condition has been selected; namely, iron practically free from contamination and a nonparticipating atmosphere, the inert gas argon. This simplification reduces the number of variables to a point where more rigid control of the system is possible. Although this study is significant for the contributions it makes to the science of steel fabrication, yet it is hoped that it will not be without value also in increasing knowledge of the. nature and behavior of iron and steel in general. From the standpoint of open-hearth practice, and to some extent from the standpoint of electric-furnace practice also, the conditions of melting and casting iron in this investigation are extraordinary. The casting temperature is high, the mean temperature of the metal probably reaching 2000' C. (3600' F.)? The rate of chilling of

Jan 1, 1936

By William C. Schulte, Gilbert E. Doan

An extensive program of investigation is being carried out at Lehigh University in the study of arcs and arc welds of high-purity iron1, sponsored by the Engineering Foundation. The part of that program reported in the present paper deals with welds made of high-purity iron in an argon atmosphere and for comparison with them welds made of the same iron in ordinary air. Welds of commercial steel also were made in argon and in air. The primary purpose of the study is to discover the basic physical constants of iron welds when not contaminated either by impurities in the iron or by the action of oxygen and nitrogen of the air during welding. Upon these constants can be founded such future studies as will determine what effects the various impurities and alloy elements present in steel have upon its welding characteristics, and what influence is exerted by the action of oxygen and nitrogen. The welding of steel involves such a multitude of variables, both of composition and of procedure, that development in the fabrication of this most important metal has necessarily been slow, wasteful, and in many instances discouraging. In the present investigation, the simplest possible condition has been selected; namely, iron practically free from contamination and a nonparticipating atmosphere, the inert gas argon. This simplification reduces the number of variables to a point where more rigid control of the system is possible. Although this study is significant for the contributions it makes to the science of steel fabrication, yet it is hoped that it will not be without value also in increasing knowledge of the. nature and behavior of iron and steel in general. From the standpoint of open-hearth practice, and to some extent from the standpoint of electric-furnace practice also, the conditions of melting and casting iron in this investigation are extraordinary. The casting temperature is high, the mean temperature of the metal probably reaching 2000' C. (3600' F.)? The rate of chilling of

Jan 1, 1936

By N. J. Grant, B. C. Giessen, M. Morris

The slvuclures of alloys in the system In-Bi have been investigated after (levy vapid queuching from the mell (splat cooling) to -190°C. Tuo-phase fields could be suppressed over most of the tota1 concentvalion range; five melastable phases a1, a2, ?, ?1. and ß exisl, of which four have simple elementtike structures. For example, ß has the A5 struclure of white till. Crystal-tographic data and coordination numbers for these phases aye given, as well as addilional information on the equilibrium diagram, where a new phase In5Bi3 teas found. THE phase diagrams of binary combinations of B elements from the groups B2, B3, B4, and B5 are usually of a simple type and show considerably fewer intermediate phases than combinations of these elements with A metals, transition metals, or the B1 noble metals. Aside from phases such as the typical B3-B5 compounds with the ZnS-B3 structure type, few stoichiometric phases are known; among them are In2Bi and 1nBi.l Nonstoichiometric phases include ß (In-Sn), a1, (In-Pb), and the tin-rich ? phases in the In-Sn, Cd-Sn, and Hg-Sn systems.' The first two phases have a close relationship to indium, while the latter group are known to be structurally related to a Sn. Thus, there are generally no immediate experimental data for the correlation of the crystal structures of B metals and B metal combinations with certain monotonously varying parameters, such as the valence electron concentration (VEC), or the average atomic size. Such parameters have been recognized as structure determining, e.g., for the transition 4 Sn — y phase,2,3 where nonintegral valence electron concentrations are encountered. It should be possible to extend such correlations to other binary systems, if nonequilibrium single-phase alloys could be produced over broad valence electron concentration ranges, and if their crystal structures could be regarded as being imposed by their electronic states. It has been shown in the case of the tin-rich 7 phases3 that alloy phases with typical crystal structures can be produced in B metal alloys rapidly quenched from the liquid to -190°C by the splat cooling technique due to Duwez,3-8 and reviewed in Refs. 5 and 6. The In-Bi system was selected because it extends over a valence electron concentration range in which several metastable, nonstoichiometrir phases could be expected to occur. Further, the low melting points of the known intermediate phases, In2Bi and InBi, Fig. 1(a), indicated low binding energies and thus possibly low driving forces for the formation Of the equilibrium structures. EXPERIMENTAL TECHNIQUES AND RESULTS The preparation of the quenched foils followed the practice described in Ref. 3. Master alloys were produced by melting of indium (99.97+) and bismuth (99.99+) in evacuated Vycor capsules or in an inert gas arc furnace; quantities of 20 mg were splat-cooled onto copper and silver substrates held at - 190°C; and crystal structures and lattice parameters were determined on a GE XRD-5 diffractometer using Cu Ka, radiation at -190°C and at room temperature. The duplication of each run with both substrates permitted the elimination of overlap of the substrate diffraction pattern and that of the investigated substance. The XRD patterns were usually taken from sin2 " = 0.03 to 0.35; the substrate was used as a means of internal calibration. The fractional accuracy of the lattice parameters of metastable phases is approximately 10-3 In the following, all percentages are in atomic percent. The stable and metastable phases found after rapid quenching to -190°C are listed in Table I, together with estimated concentration ranges and crystallographic data. The investigated alloys and phases present in them are given in Table 11. Except for the region between indium with 33 and 50 pct Bi, where a revision of the equilibrium phase diagram became necessary to include a new stoichiometric phase In5Bi3, the diffraction patterns taken after heating to room temperature agreed with those expected from the phase diagram, Fig. l(a). This suggests that the new nonstoichiometric phases are not stable at room temperature, thus following the observations made for the y phases based on tin.3 Results concerning the equilibrium phases In2Bi and In5Bi3 and the revision of the equilibrium phase diagram which is made necessary by the inclusion of In5Bi3 will be treated first. The Crystal Structure of In2Bi. Makarov7 had identified In2Bi as belonging to the AlB2-C32 type ; however, in a later paper the structure was revised.8 In2Bio was found to be of the Ni21n-B8ß type,21 with a = 5.496A, c = 6.57.9A, and N = 6 atoms per unit cell.9 This crystal structure was confirmed in the present work; definite evidence for the doubling of the c axis, as compared to the A1B2-C32 type, and for the proposed order structure, was found in the powder pattern. The observed lattice parameters agree well with those of Ref. 8; those measured at -190°C are given- in Table I. The Crystal Structure of In5Bi3. A new, equilibrium, intermediate phase was identified in slow-cooled, as-cast alloys; it was identified as In5Bi3. The structure has been worked out by Giessen and Grant;" lattice parameters at -190°C are given in Table I. This phase is probably identical with "In3Bi2", produced by vapor deposition techniques, but not recognized as an equilibrium phase by Palatnik et a1.11 After completion of the present work, the existence of In5Bi3 has also been demonstrated by superconductivity measurements on In-Bi alloys.20

Jan 1, 1968

By A. Raman

The Nb-Co system was nuestigated in the range 10 to SO at. pct Co with X-rays. A pt phase with the W6Fe.r-type structure occurs in the system between 46 and 52 at, pct Co. Its unit-cell dimensions are nearly identical to those of the p Phases found in the Nb-Fe and Nb-Ni systems. Two Laves phases, one having the MgZnz-type structure and the other the MgCuz-type structure, already t-eported in the literature, are found to exist in the system. The ,l.IgZnz-type phase occurs between 62 and 64 at. pct Co. A MgNi2-type Laves phase, reported in the literature, is no! obtained. A binalry phase is found to exist belozv I000C around 82 at. pct Co. THE cobalt-rich side of the system Nb-Co has been repeatedly investigated by previous inestiators" and the following intermediate phases are known to occur: NbCo, which crystallizes in the MgCu2-type structure and Nbc03,' reported originally by Wall-bam, which has the MgNiz-type structre. Jordan and uwez' as well as lliott' were unable to find the MgNiz-type phase. Two phases, designated as x and y, were reported by Saito and eck.' The phase x was inferred to have a narrow composition range near 77 at. pct Co. No published work is known to the author which reports the investigations in the niobium-rich portions of the system. This paper presents the results of an investigation in the Nb-Co system between 10 and 80 at. pct Co. EXPERIMENTAL PROCEDURE Two or three grams of the alloys under investigation were prepared using niobium (99.9 pct +) and cobalt (98.8 pct + with 0.14 pct Fe and and 0.03 pct C) in a tungsten-electrode arc furnace under commercial argon atmosphere. They were then wrapped in molybdenum sheets and annealed for a period between 5 days and 1 week at 1300°C in high vacuum (10-" orr) or in evacuated quartz amules for 2 weeks at 1000°C. Powders of -325 mesh size were prepared for X-ray work by crushing and grinding the specimens. Subsequent reannealing of the powders was not undertaken since most of the alloys were brittle and broke easily. X-ray powder patterns of the as-cast and annealed samples were prepared in a Siemens cylindrical camera (57.3 mm radius) with Cr-K, radiation. A Siemens diffrac to meter was used to get the X-ray patterns of some new phases. Metal log raphic examination of the alloys supplemented the X-ray findings. RESULTS The results of the X-ray and microstructural analysis Of the alloys are in in Table I. The lattice parameters of the phases are listed in Table 11 for quick reference. A set of micro photographs in Fig. l(n) to (j) show the microstructures of some alloys. A probable equilibrium diagram is drawn in Fig. 2

Jan 1, 1967

By George S. Rice

Those who for the first time see, at a mine, a great hole caused by subsidence; or, going underground, see an extensive fall of roof or hanging wall are apt to regard such an occurrence as an accident and not a normal condition of exhaustive mining. Moreover, the public is inclined to believe that a cave or subsidence of the surface is the result of carelcssness in mining or the rapacity of the mine operators in "robbing pillars," a tern too loosely used in descriptions of coal mining. This belief is fostered by the common-law requirement that an owner of the surface or of surface improvements is entitled to full support of the surface. Court decisions have upheld this law even when that owner has sold or leased the underlying mineral, unless a clause in the sale or lease contract exempts the mining company from paying the owner of the surface for damages that may result from mining. Another reason for this belief is the earlier practice (which is still extensively followed in this country) of leaving all coal pillars unmined, except as they have been thinned by so-called robbing; by not extracting the pillars, the surface may be supported by them for years, perhaps for generations. Inasmuch as the practice of leaving permanently in the mines from one-third to one-half of the mineral is wrong, with respect to conservation of a national resource, it behooves the mining engineers to assemble data and disseminate information on the subject, pointing out that subsidence must follow complete extraction, unless expensive methods of back-filling are employed, such as are used in Germany and France. These methods inevitably increase the cost of mining and the price of the mineral produced. It is popular to speak of "waste in mining" without a realization that much so-called wasting is unavoidable unless subsidence is accepted and provision made therefor where the surface is valuable, or else the only present known alternative of hydraulically placing sand or crushed stone filling in the excavations, at an increased cost of the mineral product to the consumer.

Jan 1, 1923

By George S. Rice

Those who for the first time see, at a mine, a great hole caused by subsidence; or, going underground, see an extensive fall of roof or hanging wall are apt to regard such an occurrence as an accident and not a normal condition of exhaustive mining. Moreover, the public is inclined to believe that a cave or subsidence of the surface is the result of carelcssness in mining or the rapacity of the mine operators in "robbing pillars," a tern too loosely used in descriptions of coal mining. This belief is fostered by the common-law requirement that an owner of the surface or of surface improvements is entitled to full support of the surface. Court decisions have upheld this law even when that owner has sold or leased the underlying mineral, unless a clause in the sale or lease contract exempts the mining company from paying the owner of the surface for damages that may result from mining. Another reason for this belief is the earlier practice (which is still extensively followed in this country) of leaving all coal pillars unmined, except as they have been thinned by so-called robbing; by not extracting the pillars, the surface may be supported by them for years, perhaps for generations. Inasmuch as the practice of leaving permanently in the mines from one-third to one-half of the mineral is wrong, with respect to conservation of a national resource, it behooves the mining engineers to assemble data and disseminate information on the subject, pointing out that subsidence must follow complete extraction, unless expensive methods of back-filling are employed, such as are used in Germany and France. These methods inevitably increase the cost of mining and the price of the mineral produced. It is popular to speak of "waste in mining" without a realization that much so-called wasting is unavoidable unless subsidence is accepted and provision made therefor where the surface is valuable, or else the only present known alternative of hydraulically placing sand or crushed stone filling in the excavations, at an increased cost of the mineral product to the consumer.

Jan 1, 1923

By Edgar T. Wherry

EDGAR .T. WHERRY,* Washington, D. C. (communication to the Secretary ?).-Dr. Pogue's presentation of the facts concerning the emerald deposits is very clear and convincing, and the only addition that I can suggest is a summary of previous theories of origin. He makes it evident that the pegmatite theory is the only one capable of explaining the existing relations, but upon certain details there may be some difference of opinion. If I understand the term pneumatolytic, it does not imply that all the elements concerned in a given deposit were transported as gases, but rather that the crystallization of these elements into the various minerals was favored by the presence of certain gaseous substances, notably H20, C02 and HF. It is highly improbable that the oxides of glucinum, aluminum, chromium, and silicon, which enter into the composition of the mineral emerald could have been transported in the gaseous form. The same is true of the metallic constituents of the parisite and other associated minerals. The explanation suggested, that solutions separated into liquid and gaseous portions, the latter ascending and forming the emerald in the upper portions of the rock only, therefore, seems to me untenable. When two formations exist side by side and one, A, is mineralized while the other, B, is barren, the possible explanations may he classed as (1) chemical, and (2) physical. 1. Some chemical feature of A not found in B might have caused crystallization of certain minerals in the former, which did not appear in the latter. In the present instance both rocks appear to be so similar chemically that no such effect can be looked for. Pogue mentions carbon as a possible precipitating agent, but describes both formations as carbonaceous, so that the difference in the minerals of the two can not be thus explained.

Jan 10, 1916

By E. Buehler, J. E. Kunzler

High-pu.1-ity molybdenum has been heat treated, melted, and zone refined and the physical and chemical changes that are produced by these processes have been studied by making resistance ratio measurements. Pronounced effects are observed that are associated with recrystalliza-tion at about 1200°C and with melting. Melting alone is found to result in a substantial purification by the evaporation of impurities such as iron. Zone refining is found to be reasonably effective with four passes producing a three-fold decrease in resistance ratio and a minimum ratio of 0.0003. With the aid of low temperature measurenzents, it has been shown that the build-up of a deposit of the material being zone refined on the radio frequency coil used for heating can lead to contamination of the sample. CONSIDERABLE interest in high-purity refractory metals for the study of mechanical properties has developed during recent years. Also the need for highly pure metals in certain fundamental studies, such as electronic band structure, has become quite widely appreciated. Molybdenum can now be produced with sufficiently high purity to make it attractive for such investigations. The most suitable measure of chemical purity of metals used for many of these studies is its resistance ratio, R,.,o,/Ro, During the purification of molybdenum by zone refining and its subsequent evaluation by this technique, a number of informative observations were made. These observations concern the effectiveness of zone refining, the volatilization of impurities at the melting point, and the recrystallization of molybdenum and appear to be pertinent to other refractory metals. Also, the usefulness of low-temperature resistance measurements as an analytical tool for evaluating the presence of chemical impurities and physical defects in metals is again illustrated. Samples of high-purity molybdenum of known mechanical history were heated to various temperatures between 800°c and their melting point. Resistance ratios of the samples were measured after they had been given a specified treatment. The data were used, along with mass spectrographic analysis, as an aid in interpreting the nature of the processes that occurred in conjunction with each treatment. Changes in the concentrations of chemical impurities and physical defects are typical of things that effect the low-temperature resistivity. SAMPLES The starting material was obtained from Westing-house Corp., Bloomfield, N.J. It was in the form of molybdenum rods, usually 1/8 or 3/16 in. in diameter. These had been previously processed from bars, 5/8 in, in diameter, originally reduced from 4 in. diam arc-cast ingots, by hot swaging at about 1300°c. In the final step, the temperature was lowered to about l lOO°C which resulted in the production of elongated grains. Typical grains were about 0.03 mm thick and 0.6 mm long. The molybdenum was quite pure as is indicated by the results of mass spectro-scopic analysis1 given in Column 2 of Table I. Other nongaseous elements not listed in the table were not detected. ZONE REFINING AND THERMAL TREATMENT OF SAMPLES Several sample rods, 8 to 10 in. long, were zone refined or were heat treated at several temperatures. Both types of operations were performed using 3 me-

Jan 1, 1962