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By O. L. Culberson, J. J. McKetta

Experimental and smoothed data are presented for the solubility of methane in water for temperatures of 77, 100, 160. 220. 280, and 340°F at prejsures to 10.000 psia. The minimum solubility phenomenon exists within this temperature range to pressures of 10.000 psia. INTRODUCTION The study of hydrocarhon-water systems has been extended to the determination of the solubility of methane in water at pressures to 10.000 psia. The experimental apparatus, and the technique. are the same as that previously reported.' - In the determination of the solubility of methane in water, only two phases were present at temperatures between 100 and 340°F. these being the vapor phase and the water-rich. liquid phase. The determinations involved the agitation of methane and water in an equilibrium cell. withdrawal of a sample from the liquid phase, and the analysis of the sample. The experimental value; determined in this manner are pre9ented in Table I and in Fig. 1. Since experimental and analytical techniques have improved since the initial experiments with this equipment, it was decided to repeat the 77°F isotherm determinations.' Fig. I shows that the individual results for this isotherm are much

Jan 1, 1951

By J. J. McKetta, O. L. Culberson

Experimental and smoothed data are presented for the solubility of methane in water for temperatures of 77, 100, 160. 220. 280, and 340°F at prejsures to 10.000 psia. The minimum solubility phenomenon exists within this temperature range to pressures of 10.000 psia. INTRODUCTION The study of hydrocarhon-water systems has been extended to the determination of the solubility of methane in water at pressures to 10.000 psia. The experimental apparatus, and the technique. are the same as that previously reported.' - In the determination of the solubility of methane in water, only two phases were present at temperatures between 100 and 340°F. these being the vapor phase and the water-rich. liquid phase. The determinations involved the agitation of methane and water in an equilibrium cell. withdrawal of a sample from the liquid phase, and the analysis of the sample. The experimental value; determined in this manner are pre9ented in Table I and in Fig. 1. Since experimental and analytical techniques have improved since the initial experiments with this equipment, it was decided to repeat the 77°F isotherm determinations.' Fig. I shows that the individual results for this isotherm are much

Jan 1, 1951

By C. H. Brehaut, W. N. Taylor, R. S. Douglas, H. A. Shannon

The name for this new method of mining is derived from a composition of Horizontal, Radial, Diamond, and the drilling is from raises. This method, worked out at Copper Mountain, B.C., is believed to be distinct in many features from other known methods. Geology The ore deposits of copper Mountain are related to the copper Mountain stock, which is an ideal example of the magmatic in in that it grades from a basic gabbro at the border to an almost pure orthoclase-pegmatite core. The "contact" ore bodies lie along the contact of the gabbro and an older complex of volcanies and sediment termed the "Wolfe Creek" formation. These older rocks, collectively referred to as greenstone, had been fractured prior to the intrusion of the stock and were highly metamorphosed during the intrusion. The "outlying" ore bodies are somewhat different in character, though a similar structural pattern prevails. It is believed that a deep-seated magma of which the Copper Mountain stock is a part has given off solutions that caused a partial graniti-zation of some of the volcanies. Mining problems are caused further by the presence of a series of soft barren dikes intersecting a great many of the ore bodies, which are about 30 ft. wide, strike north-south, and dip at a high angle to the east; and are further increased by the presence of four major faults, with a great many minor faults running at acute angles from them. Fault zones average 8 ft. in width, and consist of gouge and breccia. They strike northeast and dip steeply to the northwest. The faults cut through the ore zones and the dikes, and continue on into the gabbro. The general mine structure with two types of Ore bodies, bounded by weak walls and intersected by several series of soft barren dikes and major faults, indicated that a method of mining should be devised that would remove the ore at low cost with the least disturbance of the waste walls and dikes. , Theoretical Estimate of Stoping with the Diamond Drill After consideration of various methods, the most suitable one appeared to be horizontal drilling to break the ore in a manner similar to shrinkage stoping Drilling vertical holes or rings from a bench and breaking to an open slot was eliminated because the weak walls of ore, dike or waste would not permit this type of opening. It was then decided to drill either horizontal radial holes from a raise or parallel holes from a slot cut across the ore body. After discussion, the latter method was believed unsuitable, for the following reasons:

Jan 1, 1946

By M. G. Gulley

The drilling for and production of crude oil in the Lima-Indiana and Michigan fields were directly and profoundly affected by the severe strain to which the petroleum industry was subjected during the year 1931. Serious and long-continued overproduction in the large flush areas of the western and southwestern fields, coupled with a nationwide decrease in the annual rate of consumption-increase, served to precipitate ‡ This curve is the Mid-Continent price for 38" gravity crude and hence. affords a basis for estlmating the influence of general factors upon the price structure m these fields. a mid-year economic depression which was functionally reflected in every producing area in the United States. A study of the curves of price changes in portions of the central west territory (Fig. 1) will demonstrate this relationship as well as the ensuing upward trend, which developed when pressure was artificially relieved, at least for the time being, in the producing areas in the southwestern states. All field activities in the Lima-Indiana and Michigan territory during 1931 follow the price curve closely: the mid-year depression was evident in drilling activities— both wildcat and within the proved limits of producing fields, in pipe line

Jan 1, 1932

By E. G. De Coriolis

The development of huge production facilities and of new or improved processes for manufacturing magnesium from its raw sources has been an outstanding achievement of this war. Furthermore, at least one new method has reached a stage of pilot production that offers promise. Its potentialities seem to indicate that a reduction in cost and simplification or elimination of problems incident to the use of at least one of the present processes are quite within the realm of possibility. Although magnesium of very high purity (99.9 per cent and higher) is obtained, and the rate of recovery reasonable (60 to 70 per cent). the ferrosilicon reduction process is open to a serious objection, which at the time its use was proposed was thought to be sufficient to raise some doubts as to its success, at least on a high production basis. The temperature range at which the reaction is carried out—namely, 2100" to 2150°F.—is very close to the failure temperature of the material of which the retort is made. It is so close that for a time it was assumed it might make commercial use of the process an impossibility. However, at the time under discussion, the demand for magnesium was so great that it was felt by those who had to go ahead and produce this essential metal that the emergency warranted their taking a chance on this process. Subsequent developments have fully justified the soundness of their decision. Fortunately for the war effort, when the plants were put into operation it was discovered that although the retorts did collapse in rather short periods of time, as predicted, they could be blown back into operable shape by application of high-pressure air. This practical method of operation so relieved the situation that the problem disappeared. Nevertheless, if the process had not been successful, or the production of magnesium by the electrolytic process had not been able to keep pace with demands, our war program would have been seriously impaired. Fireless Cooker'' Process For this reason a program was set up and assigned for the development of a new method that had been suggested to the War Production Board in 1941. It is believed justifiable in terming the method "new" for several reasons: (I) while utilizing the same (ferrosilicon) process as the Pidgeon, hence involving similar reactions, the type of retort or furnace is essentially different, (2) the method of operation, reaction temperatures, etc., differ materially, and, most important of all, (3) the problems to be overcome in making the process successful were not and could not have been anticipated by anything previously known about the Pidgcon process. As will be shown later, the briquetting process, the condenser, the furnace lining

Jan 1, 1949

By W. M. Mobley

The coal industry in Alabama, centered in Birmingham, has pioneered coal-bene-ficiation practice in the United States. The nature of the coal seams and mining methods employed have necessitated use of equipment and methods best adapted to the local conditions. Although all of the 30 or more coal seams now being mined in the state receive beneficiation, only the three most important producers of coking coals, the Pratt, Mary Lee and Black Creek, are discussed in detail. Nature of the seams, washability characteristics and equipment used are given as examples of the extent of work and progress in this field. The coal seams in Alabama are relatively thin and pitching, making mining difficult and expensive. Most of them are characterized by thin partings of rock or shale in the seam itself, as well as laminations of bone and rash. Mechanical mining methods have increased the occlusions from roof and floor to such an extent that nearly all the coal mined in the state must receive some treatment before it can be put on the market. During the year ending Sept. 30, 1943,' 18,129,792 tons of coal were mined in the state and 14,364,177 tons, or 79.2 per cent, received treatment. Excluding from the total the 1,223,014 tons produced by small wagon mines and the hand-picked lump coal, the amount re- ceiving beneficiation would be more than 90.00 per cent. This is, by far, greater than in any other coal-producing state. The earliest record of coal beneficiation in Alabama was the installation in 1890 of an experimental Lurig washer by Alexander Cunningham, for the Sloss Iron and Steel Co. at its blast furnace in Birmingham.2 In 1894 the Jeffrey Manufacturing Co. introduced the English Robinson washer, a combination of a hydraulic classifier and centrifugal machine. Erskine Ramsay, who has contributed so much to the coal industry, saw its possibilities as well as its mechanical defects and soon had his inventive mind at work. He added a sludge tank of his own design, and many Robinson-Ramsay washers were installed in Alabama and other states. The Stewart jig appeared in 1900, followed by the Montgomery jig in 1910 and both have found extensive use. Increased interest in this field led to new designs, such as the American, Elmore, Burke and Faust. The first Baum-type Norton jig was operated in 1930 and within the last five years six large installations of this type have been made by the McNally-Pitts-burg, Jeffrey and Link-Belt Companies. Wet-washing tables were introduced in 1922 but not extensively used until recently. The two most popular types are the Deister-Overstrom and Deister Plat-O. The coal-cleaning equipment used in Alabama has been relatively simple, yet efficient, but as the amount of impurities in the raw coal has been increased by mechanical mining and labor costs have become higher, much interest has been shown in sand cones, froth flotation and

Jan 1, 1947

By W. M. Mobley

The coal industry in Alabama, centered in Birmingham, has pioneered coal-bene-ficiation practice in the United States. The nature of the coal seams and mining methods employed have necessitated use of equipment and methods best adapted to the local conditions. Although all of the 30 or more coal seams now being mined in the state receive beneficiation, only the three most important producers of coking coals, the Pratt, Mary Lee and Black Creek, are discussed in detail. Nature of the seams, washability characteristics and equipment used are given as examples of the extent of work and progress in this field. The coal seams in Alabama are relatively thin and pitching, making mining difficult and expensive. Most of them are characterized by thin partings of rock or shale in the seam itself, as well as laminations of bone and rash. Mechanical mining methods have increased the occlusions from roof and floor to such an extent that nearly all the coal mined in the state must receive some treatment before it can be put on the market. During the year ending Sept. 30, 1943,' 18,129,792 tons of coal were mined in the state and 14,364,177 tons, or 79.2 per cent, received treatment. Excluding from the total the 1,223,014 tons produced by small wagon mines and the hand-picked lump coal, the amount re- ceiving beneficiation would be more than 90.00 per cent. This is, by far, greater than in any other coal-producing state. The earliest record of coal beneficiation in Alabama was the installation in 1890 of an experimental Lurig washer by Alexander Cunningham, for the Sloss Iron and Steel Co. at its blast furnace in Birmingham.2 In 1894 the Jeffrey Manufacturing Co. introduced the English Robinson washer, a combination of a hydraulic classifier and centrifugal machine. Erskine Ramsay, who has contributed so much to the coal industry, saw its possibilities as well as its mechanical defects and soon had his inventive mind at work. He added a sludge tank of his own design, and many Robinson-Ramsay washers were installed in Alabama and other states. The Stewart jig appeared in 1900, followed by the Montgomery jig in 1910 and both have found extensive use. Increased interest in this field led to new designs, such as the American, Elmore, Burke and Faust. The first Baum-type Norton jig was operated in 1930 and within the last five years six large installations of this type have been made by the McNally-Pitts-burg, Jeffrey and Link-Belt Companies. Wet-washing tables were introduced in 1922 but not extensively used until recently. The two most popular types are the Deister-Overstrom and Deister Plat-O. The coal-cleaning equipment used in Alabama has been relatively simple, yet efficient, but as the amount of impurities in the raw coal has been increased by mechanical mining and labor costs have become higher, much interest has been shown in sand cones, froth flotation and

Jan 1, 1947

By J. Alfred Berger, O. M. Katz

The Zv-Hf-H ternary system was studied between 500° and 900°C at pressures less than 1 atm of hydrogen gas between 1 and 60 at. pct H. A new and unique microgravimentric apparatus was used. Cizanges of slope on pressure-hydrogen composition isothernis delineated phase boundaries. These boundaries separatecl the three regions, a, 0, and y—so designated to correspond to the regions of the Zr-H binary system—from the multiphased areas between them. A eutectoidal decomposition was found with the ß region phase or phases decornposing into a lamellar product on quenching to rool ter,zperatuve. Reproducible decomposition-pressure hysteresis occilrved lnainly at lower hydrogen cornpositions and at lower temperatures across multiplzase vegions between a and 0 and a and y. Tire effects of hqfniur7z on the hydriding charactevistics of zirconiurrz weYe as follows: 1) stabilization of the a and y vegions while destabilizing the 0 region; 2) a/?preciable elevation of the decomposition pressrkres in the multiphase region between the a and /3 field; 3) ~nouenzent of the eutectoid reaction to high te~nperatures; 4) reduction in the total qiiantity of hydrogen absorbed under one atmospheve of Hz p7-essure; and 5) introduction of a split deconzposilion at the eiitectoiclal poinl in pa?? of the ternavy. Assuru~ptions based on an ir-2terstitial vandonl-solulion rtioclel 0.f hydrogen in metals slzowed that the bindit~g energy between solute sites prednnzinatecl at low /i?!dvogen concentrations. However, at high hydrogen contents the entropy was the predorninatlt factor in determining the stability of the Zr-Hf-H al1o.s. This was interpreted to mean a scarcity of filrtlzer itltevslilinl solute sites caused by hydrogen-hydvogen intet-actions in the metal lattice. INTEREST in the reaction of hydrogen with metals has increased in the past few years for the following reasons: 1) the formation or use of high hydrogen potential environments in nuclear reactors; 2) the reaction of hydrogen with alloys in nuclear reactors with the accompanying deleterious effects on the mechanical and corrosion properties; 3) the theoretical implications of thermodynamic data on the theory and rules of alloy formation in the metal-hydrogen systems; 4) the use of hydrogen-containing fuels in rocket engines; 5) the need for a process of making fine metal powders of high-melting reactive metals; and 6) the beneficial impregnation of superconducting alloys with hydrogen. In nuclear pressurized-water reactors, the problem exists of limiting the hydrogen pickup of zirconium alloys which are utilized as fuel cladding, heat shields, and support members. In general, zirconium alloys have good mechanical and corrosion-resistant properties in high-temperature water. However, hydrogen is absorbed from the corrosion reaction between metal and water, greatly accelerating the formation of the corrosion product ZrOz as well as mechanically embrittling the underlying metal. In addition, recent observations1 at zirconium to hafnium welds showed that secondary elements in zirconium can have an appreciable, and somewhat unexpected, effect on hydrogen absorption. This paper lists the thermochemical data in the range 500" to 900°C for the equilibrium reaction of four high-purity Zr-Hf alloys with hydrogen. Phase boundaries and thermodynamic functions are determined while the structural data will be presented in a future paper. In general, the Zr-Hf-H system approximates the well-known, eutectoidal, Zr-H diagram2,3 with modifications introduced through the behavior of hafnium.4,5 The Hf-H system,' published while this work was in progress, provided a consistent trend with the Zr-Hf-H data. PREPARATION OF Zr-Hf ALLOYS Table I presents a complete flow chart of the preparation procedure. The zirconium and hafnium crystal bars were completely immersed in high-purity kerosene and slowly cut into thin wafers. Wafers were then cold-sheared into approximately 1-g pieces, thoroughly cleaned, weighed, and inserted into the furnace. The alloys, B-2, B-4, B-6, and B-8, were then nonconsumable arc-melted under 500 mm of purified argon. Additional purification of the argon was accomplished by melting a large titanium button each time an alloy was re-melted or a different alloy melted. Each alloy button, which weighed 25 g, was remelted four times in an approach to complete homogeneity. Material losses were less than 0.02 wt pct. Alloy buttons were alternately cold-rolled and vacuum-annealed into 10- and 20-mil sheets. Table I1 gives the composition of the four alloys used. Very little elemental segregation existed be-

Jan 1, 1965

By J. Nutting, D. H. Kirkwood

The oxidation of lead sulfide in air between 200° and 350°C has been investigated by electron diffraction from thick sulfide films and from galena surfnces. It has been demonstrated that sulfate is the stable reaction product up to 570°C. Sulfate is HAGIHARA has investigated' single crystals of galena roasted in air by the reflection electron-diffraction technique, which owing to the very limited penetration of the beam into the crystal gives information of the nature of the surface only. He has shown that up to 280°C the first oxidation product is lead sulfate, followed by lead mono-oxysulfate (PbO . PbS04). At longer times and higher temperatures more complex patterns appeared which could not be analyzed. All of these patterns were of streaks or spots arising from crystals oriented on the galena surface, and it is probable that these crystals are lead compounds whose structures have not been determined, such as the other oxysulfates (2Pb0 • PbS04 and 4Pb0 . PbS04) or a number of oxides. Certain lead sulfide films, formed chemically, give ring patterns in transmission electron diffraction2 because they are polycrystalline, and should also give ring patterns of the products after oxidation. It was thought that a diffraction study would reveal the sequence of phases produced in the reactions at different temperatures, since X-ray powder patterns are available for many lead compounds. PREPARATION OF FILMS The films were prepared by passing H2S over a saturated solution of lead nitrate in water. Once a silvery film had formed on the solution surface, no further thickening was apparent. The films were transferred by a gauze to a bath of distilled water for washing and pieces of film were caught on small discs on which they were dried. The discs were formed initially on galena up to temperatures of 300°C, followed by oxide and oxysulfates in turn at longer times. The appearance of- these phases is believed to result from an inadequate rate of supply of sulfur to the top surface 01. the crystal. standard Siemens mounts, made of platinum alloy, and had seven 20-p apertures drilled through them. The parts of the film which had dried onto the disc surface were light blue in color, which is the interference color of a film about 600A in thickness. A strong pattern of lead sulfide was obtained in transmission electron diffraction through the apertures but slight broadening indicated a crystallite size of around 200A. Tilting a sulfide film in the beam produced arcing of the rings, increasing the intensities of the (Ill), (3111, and (222) rings and reducing (200) and (220). This arises from preferred orientation in the film, a [loo] direction of the crystallites being normal to the plane of the film. These specimens were oxidized in an oven maintained at the required temperature. The reported times include that taken to heat the film to the reaction temperature. STABLE PHASES FORMED IN OXIDATION The conditions in which various oxidation products of lead sulfide are stable have been considered by the authors in a previous paper.3 It was shown that in a normal atmosphere, taken as containing lo-' atm of SOs, lead sulfate would be stable up lo about 570°C. This was confirmed by oxidizing thin films of sulfide for several days, and the analysis of the transmission-diffraction pattern is given in Table 1. The fit with the patt$rn from X-rays is good, except for the missing 3.62A ring. Some disagreement in intensities of reflections given by X-rays and electrons is to be expected. Up to 570°C a spotty pattern of sulfate was still obtained, indicating grain growth, but above this temperature the film disintegrated. Probably this is associated with the decomposition to PbO . PbS04. It needs to be emphasized that the atmosphere

Jan 1, 1965

By Allan T. Gwathmey, J. Bruce Wagner, Kenneth R. Lawless

Between 250°and 550°C in oxygen pressures of 10 to 760 mm Hg, the relative oxide thicknesses formed per unit time on the (100), (111), (110), and (320), decreased in this order. The predominant oxide orientation was (001)Fe3O4 and [110] Fe304 A small amount of a-Fe2O3 which exhibited a fiber pattern was observed in all oxides except those formed at 250°c in low oxygen pressures. IN order to understand the properties and behavior of thin films, particularly their role in oxidation reactions, there is needed more experimental information on their structure, composition, and kinetics of formation on clean surfaces of known geometry. The present study was undertaken to obtain such information for thin oxide films formed on single crystals of a body centered cubic metal, iron. Crystals in the form of spheres were used in order to expose all possible crystal planes to the reactant gases simultaneously. Using this procedure the relative rates of oxidation of all planes could be estimated, and those exhibiting, maximum or minimum oxidation rates could be selected for a more intensive study of composition and expitaxy. Since the three types of information were obtained from the same experiment using a single crystal substrate, any differences between rate, composition, and expitaxy on the several planes may be attributed to the influence of the substrate structure. EXPERIMENTAL The starting material for this study was Armco iron rods, 6 in. long and 3/8 or 1/2 in. in diam. The analysis was reported to be 99.8 pct Fe, with major impurities listed as carbon 0.018 pct, manganese 0.027 pct, phosphorous 0.005 pct, sulfur 0.029 pct, silicon 0.005 pct, and copper 0.11 pct. These rods were cleaned with ether and heated in an atmosphere of moist hydrogen at 950°C for three days. The purpose of this treatment was to decarburize the iron and to provide a consistent, uniform grain size for the growth of single crystals. Crystals in the form of rods, up to 1/2 in. in diam and 2 in. long, were prepared by a method similar to that reported by Leidheiser and Buck.2 Spherical crystals, 3/8 and 1/2 in. in diam and having a handle about 1/4 in. in diam by 112 in. long, were machined from the single-crystal rods. After machining, each crystal was etched in aqueous nitric acid to remove the cold-worked metal at the surface. Before each experiment, the crystal was polished mechanically with metallographic papers through number 4/0, and electropolished in a perchloric acid-acetic anhydride mixture by the method of Jacquet and Rocquet.3 The crystal was washed in running distilled water for at least 5 min. The excess water was blotted with a soft paper tissue, and the crystal was placed in an all-glass reaction vessel (See Fig. 1). The crystal was heated at 550°C in hydrogen for at least 8 hr prior to the oxidation in order to reduce any surface oxides and to help relieve any stresses in the metal. For the structure and composition studies, flat faces were cut parallel to (loo), (111), and (110) planes on the iron crystal spheres. The orientation of these faces was checked by a back-reflection X-ray diffraction technique. The faces were within 2 deg of the desired orientation. The flat faces were treated as described above except that prior to electropolishing they were given an additional polish on metallographic felt saturated with twenty-minute levigated alumina. After the crystal was heated in hydrogen for at least 8 hr, the temperature was adjusted to the desired value, and the hydrogen was evacuated. Commercial oxygen which had been purified by successively passing through tubes containing magnesium perchlorate, Ascarite and magnesium perchlorate was admitted to the desired pressure as measured by a mercury manometer. A resistance-wound furnace surrounded the oxidation chamber, and a temperature controller maintained the temperature within ±3°C. The furnace was provided with a small window for observing the crystal. The changes in thickness of the oxide films were followed by observing the interference colors. The oxidation was allowed to proceed until the desired oxide thickness was attained on a given crystal plane. The experiment was terminated by evacuating the oxidation

Jan 1, 1962

William M. Courtis, Detroit, Mich. (communication to the Secretary*):—I have a few items to add to the history of the Lake Valley mines. In December, 1879, I was sent to the Bassic mine of Colorado and then to Lone mountain, near Silver City, N. M., and to various copper-camps in Arizona. I staged from Glorietta, N. M., to Tucson, Ariz., stopping at Silver City to see the Cosette mine. This mine led to the opening of the Lake Valley mines, and is a deposit of similar formation. New Year's day, 1880, found me crossing the Rio Grande above the Jornado del Muerto. At Aleman, Victorio's band crossecl four hours ahead of us. We picked up four wounded soldiers to take to Fort Bayard, for during the day the colored troops under General Hatch had been driving the Indians back through the San Andreas mountains. The traveler of to-day little realizes the dangers of these trips, when over very rough roads we made about 100 miles in a day and a night. I subsequently made this trip six times, up to 1882, and each time I missed an Indian attack by from one to four days. The day I arrived at Silver City news had come of the massacre of 75 women and children at the San Francisco ranch. The fighting-men of' Silver City had gone to rescue others. I was the only passenger from Socorro, N. M., until we picked up the soldiers. The next day we came suddenly on 5 of Victorio's band, but we had picked up several miners, so our stage bristled with guns, and we mere let alone. At or near my stone quarry, 6 miles from Socorro, 9 men, were killed by the band that, a day or two after, killed George. Daly, Lieutenant White, and all their men. During this raid, our miners and women at the mine slept in the tunnel. At the Cosette mine I had 35 men at work. These Indian raids had

Jan 1, 1910

Allan Gibb, Queensland, Australia (communication to the Secretary*):—It is gratifying that Mr. Edward Keller,' who has clone so much work elucidating the principles of copper-metnllurgy, should have subjected only that portion of our investigation relating to magnetic iron oxide to anything like adverse criticism. Situated as we were on a rnining-camp, it was impossible to undertake work that would cover all the intricate possibilities connected with the materials commonly classed as matte. We therefore began the investigation on matte produced from ores that contained no other components than the sulphides of copper and iron that would be likely to enter into the composition of matte. We were, accordingly, free from ally possibility of magnetic iron oxide entering the matte, unless it were formed in the operation itself. The work done on this subject was incomplete, and the results thereof recorded as giving only negative evidence as to the absence of magnetic iron oxide. It would have been better to have left the matter open, as " not proven." The trend of the investigation was to account for the insufficiency of sulphur in matte to satisfy the requirements of ferrous and cuprous sulphides. So far as our deductions are correct, it was unnecessary to consider the (in our samples) somewhat doubtful constituent, magnetic iron oxide. The mattes that mere investigated were among those mentioned by Mr. Keller, " which scarcely show ally magnetic property." The samples showed no such property. There was no unaccountable variation in the specific gravity, which only varied, as would be expected, with the proportion of ferrous sulphide. I have had experience in smelting ores of which the gangue was a siliceous magnetite, both in blast- and rever-beratory furuace. The mattes so produced contained magnetic

Jan 1, 1908

By J. Alfred Berger, O. M. Katz

Selected samples of hydrided Zr-Hf alloys were rapidly quenched to voom temperature and exrtrnined metallographically, by X-ray diffraction, and through micro hardness studies to confirm high-temperutuve data Confirming experiments sllowed that there were five phases in this Lernary system: 1) hextrgonal with lattice parameters similar to that of the initia1 Zr-Hf alloy but slightly enlarged due to dissolved hydrogen; 2) fee with properties of a brittle, intermediate, hydride compound; 3) fct with c/a crvoltnd 1.07 and which appeared as a neetilelike precipitale; 4) hexagonal, designated ?, with c/a ratio of 2.37; and 5) orthorhombic, designated X, with a = 4.67, b = 4.49, and c = 5.093 and whose tnicro-st?ruct~ival nppetrl-nnce depcncled o/i, heat lvecrt~r~ent. The tetragonrrl phase never crppeal-erl witkorct the cubic hydricle. Abpecrrtrnce of 0 and A also tlependet on the hafnium content of the zirconium. A previous paper' on the Zr-Hf-H system described the thermochemical data obtained with a high-vacuum, high-sensitivity mirrogravimetric apparatus. This data presented a fairly complete picture of the phase relationships at elevated temperatures. However, it could not establish the actual crystal structures, lattice parameters, or metallographic disposition of the hydride phases. The present complementary study utilizes X-ray powder patterns along with light and electron microscopy to characterize completely the five hydrided phases found in Zr-Hf-H alloys quenched to room temperature. Crystallographic features of the zr-Hf,2,4 zr-H,5-7 and Hf-H8 systems have been summarized in Table I. Designations of a, ß, and ? were retained in the Zr-Hf-H system for the phase regions through which the pressure-composition isotherms always sloped. However, it was not firmly agreed that these were single-phase regions.' In fact, the region designated y always contained a cubic as well as a tetragonal phase after quenching to -196°C. MATERIALS Preparation of the high-purity Zr-Hf alloys has been described.' The four zirconium alloys which were hydrided contained 37 wt pct Hf (23 at. pct), 51 wt pct Hf (37 at. pct), 73 wt pct Hf (58 at. pct), and 91 wt pct Hf (82 at. pct), respectively. These were designated B-2, B-4, B-6, and B-8. Photomicrographs of the initial alloys showed the material to be quite clean as would be expected from the precautions exercised in producing them. However, there were a number of annealing twins but no other subgrain structure. In addition to the four original alloys, fifteen hydrided samples were observed at room temperature. Hydrogen compositions are given at the top of Tables I1 to V. APPARATUS The phases present at elevated temperatures were studied by quenching hydrided samples to room temperature by two different methods, both under vacuum: 1) fast cooling of the sample tubes of the microgravimetric apparatus1'9 with flowing air and 2) rapid quenching into liquid nitrogen. The cooling rate for 1) was 750° to 250°C in 30 sec. Since the microbalance chamber was not designed to permit very rapid cooling of a hydride sample, all liquid-nitrogen quenching was done in an auxiliary experiment. The auxiliary quenching apparatus consisted of a small-bore, high-temperature furnace, a sealed SiO2 tube containing the sample, and a dewar quenching flask filled with liquid nitrogen. The hydrided sample, previously quenched in the microgravimetric reaction chamber, was placed in a platinum boat in a vacuum-degassed SiO2 tube. A zirconium wire getter and degassed SiO2 rod, to reduce the internal volume, were also in the tube. After sealing the tube under vacuum the zirconium getter was heated to absorb the last traces of gas. Only the sample was heated at the reaction temperature for the desired length of time, and then the tube dropped through the opposite end of the furnace into the dewar. A quenching rate of 200" to 400° C per sec was estimated. Analyses of samples after the auxiliary experiment also showed practically no increase in oxygen or nitrogen content from heating in the SiO2 tube. All of the samples were examined at room temperature by the X-ray powder method. The majority of the powder patterns were obtained with double nickel-filtered CuKa radiation after 8- and 16-hr exposures in an 11.48-cm-diam camera. Cobalt and chromium radiation were also used to spread out the high d value end of the Pattern. Such patterns readily identified the minor phases. NO oxide or nitride lines were found. Where sharp back-reflection lines existed it was possible to reduce the

Jan 1, 1965

By G. A. Koenig, Moritz Stockder

Locality and Geological Occurrence.—The Atpine region of Southwest. Colorado. cort~prieiog the San Juan and Uncon~paghre Mountains, is con~posed of a deeply eroded sheet of acid eruptive rocks, overlying in part gneissic schiets, and in part limestones and sandstones, including portions of the Silurian, Devonian, arid Carboniferous systems. The section is clearly and beautifully exposed along the Uncompghre River from its headwaters to its exit from the mountains. The river's course from the town of Ouray towards the Los Pinos agency is due north, and four miles from Ouray, in this directiou, the Uocampaglire receives from the east the Red Casm Creek. Following up the narrow canon we find the section through white. sandotone in strata dipping to the north and west, and belonging either to the lower or middle Devonian system. Presently the steep cafion-like character of the ravine gives place to more gentle slopes, ad we have entered crysralline rock—porphyry. The contact is well marked, for the sandsbne, to a depth of from six to ten feet, resembles quartzite, i. e., is serui'fusd. Ascending still higher, a small

Jan 1, 1881

By M. T. Abasov

Among a host of challenges dictated by the explosively developing scientific and technical revolution, the improvement of control and management is one of the most essential problems. This problem is also of far-reaching importance for the oil and gas industries. An oil and gas extracting complex is an involved multilink system characterized by a great number of elements and by intricate interconnections between these elements. Of paramount importance for these systems is the quality of control. Any deviation of the control from the optimum reduces the effectiveness of the system and deteriorates its basic technical and economic factors. In case of large systems, even a relatively small deviation from the optimum may result in considerable material and power losses. Optimization of control of large production systems is therefore one of the basic means to enhance their effectiveness. The present paper discusses a development control problem for a multilayer gas deposit using the method of simultaneous exploitation of several strata by means of a single well. The optimum control is achieved by determining the dynamics of changes in the number of producing wells in a reservoir with regard to the depth of occurrence of these reservoirs as well as the difference in the time of introduction of the wells from drilling and their transfer to another reservoir. A mathematical model was constructed for the problem under consideration and a method was given to solve this problem. The problem was dealt with under the assumption that either each of the reservoirs or a part of them have vertically overlying areas and that there is no hydrodynamic interference between the horizons. It was

Jan 1, 1977

By C. H. Herty

During the past few years frequent reference has been made to a certain type of iron known generally as "bad iron," "dirty iron," etc., both by steelmakers and producers of iron castings.' Open-hearth operators have claimed that such iron was entirely within the specified limits as to ordinary analysis but it was difficult to make good steel from it. It has been suggested that unreduced material in the iron is responsible, also that most trouble is experienced with the iron when the blast furnace is delivering a product whose analysis is more or less variable. Other reasons suggested are the use of scrap or borings, unsintered flue dust in the burden, a cold hearth, too high a proportion of unsuitable grade of ore, or the form of the carbon in the iron. Accordingly, a subcommittee was appoint at the fall meeting of the Open-hearth Committee of the Americ m Institute of Mining and Metallurgical Engineers held in Pittsburgh in October, 1926, to investigate the reasons for the occurrence of this bad iron and suggest methods for preventing its appearance. This committee enlisted the cooperation of the U. S. Bureau of Mines Experiment Station at Pittsburgh in undertaking a study of pig-iron quality as affecting the open hearth. The following is a report of the findings to date: Method of Testing Inasmuch as a "spell" of dirty iron occurs without warning and may be of short duration, it was deemed advisable to attempt to simulate the conditions existing before and during such a period and compare the quality of the steel made with the normal and with the dirty iron. The Bourne-Fuller Co., of Cleveland, which has a single furnace that supplies

Jan 1, 1929

By Eugene Coste

Although some of the observers who first paid especial attention to the occurrences of oil and gas in the strata (such as Hunt in 1859, Andrews in 1861; Winchell in 1865, Mendelejeff in 1876, Höfer in 1876, Minshall in 1881, and I. C. White in 1883) seem to have been impressed with the fact that oil and gas deposits were connected with the disturbances in the rocks caused by their upheavalll yet, with the exception of Mendelejeff, and possibly Andrews, these observers do not appear to have understood what is really the one essential factor in the occurrence of oil and gas in the strata: viz., the faulting, uplifting, fracturing, fis-suring, and jointing always accompanying even slight rock disturbances, and in certain districts (petroliferous provinces)2 allowing solfataric hydrocarbon emanations to force their way up from the interior and to reach and impregnate the porous portions of sediments subjected to the disturbances. Instead of this simple explanation to account -for the observed connection between petroleum deposits and rock disturbances, most of the observers mentioned above, and many others who have foliowed them on the same lines since, have entirely reversed the problem. To them, instead of the dissemination of gases from fissures into the sediments, it presented the accumulation and concentration, according to anticlinal or other geologic structures, of oil and gas originally present throughout the whole mass of the strata where they were produced by the decomposition or distillation of organic remains. Whether this important problem involves accumulation from sources within the strata themselves, or infiltration and dissemination from outside sources, may be easily determined if all preconceived ideas are put aside and the established facts only are considered. Physical Facts Sedimentary strata are composed of alternate beds of shales, sandstones, and limestones, most of which are sufficiently close-grained to

Jan 1, 1915

By W. K. Hartley

INTRODUCTION AND HISTORY The Kimberley Division of De Beers Consolidated Mines Limited includes four underground mines in Kimberley viz. Dutoitspan, Bultfontein, De Beers and Wesselton Mine and two outside mines, viz. Finsch, an opencast operation and Koffie- fontein, an underground operation. Figure 1 is a map of the Kimberley district showing the location of these mines. Finsch is 150km west of Kimberley and Koffiefontein is 80km south of Kimberley. The head office of the De Beers Company is in Kimberley. The diamond sorting and trading companies for diamonds produced in South Africa are also in Kimberley. Diamonds were first discovered in the Kimberley area at Hopetown in 1866 on the banks of the Orange River. This, and later finds, triggered the start of the great "Diamond Rush". In 1870 the Jagersfontein (now closed) and Dutoitspan pipes were discovered, followed by those at Bultfontein, De Beers and Kimberley Mine (now closed) in 1871, Koffiefontein in 1880 and Wesselton in 1891. Finsch Mine was a more recent discovery in 1961. Finsch, due to go underground in 1986, and Koffiefontein, are fully self-contained with their own treatment plants, housing, services etc. The four Kimberley mines deliver ore by conveyor to a central treatment plant and use joint ser- vices. ,+lining is presently carried out mainly by Block Caving which has replaced the earlier Chambering method. De Beers Mine, on a limited scale, and Wesselton Mine have recently started to use Sub-Level Caving, and both Bultfontein and Du- toitspan are scheduled to use the same method at a later date. The combined ore tonnage produced by the Kimberley Mines is 17 400 tons per day, Koffiefontein 12 000 tons per day and Finsch Mine 17 000 tons per day. THE EVOLUTION OF MINING METHODS Initially, the open-cast mining was carried out to as great a depth as safety would permit. In the early stages of open-cast mining, the Kimberlite was removed in horizontal slices from levels 13m to 20m apart. The rock broken in the workings was raised to the surface by means of endless rope haulage inclines. As lower levels were attained these rope haulages were replaced by aerial hoists, inclined shaft haulages or inclined skip-ways. These methods were dependent upon the strength of the unsupported pipe walls, which became increasingly unstable with depth and a system was adopted whereby the ground mined in open excavations was tipped down passes to tunnels connecting with vertical hoisting shafts sunk in the country rock. As work in the open pit became more and more impracticable due to extensive falls of ground, this system was replaced by a combination of open-cast and underground mining, and eventually by wholly underground methods. Chambering With the advent of underground mining, a system known as "Chambering" (or "Inclined Chambering") was evolved. It was essentially a combination of shrinkage stoping and caving, whereby advantage was taken of the high pressure exerted by the loose rock that had accumulated in the open excavations due to the collapse of the pipe walls. This mining method was introduced around 1890 and was successfully employed, with little change, up to the early nineteen seventies. In this system each mine was served by a main hoisting shaft situated about 300m in the country rock. Main haulage cross cuts were driven from the shaft to the pipe at 200m (600ft) vertical intervals. A sub-vertical shaft, situated close to the pipe provided access to the working levels. Chamber levels were established from the sub-vertical shaft at 13m (40ft) intervals. See figure 2. On each of these levels successive 6,8m wide “cuts" were mined out across the pipe, from one rock contact to the other, and extended vertically to the footwall of the level above. Every 6,8m cut was made up of a chamber and a "back-pillart1, each approximately 3,401 wide. The chamber was mined by overhand shrinkage stoping. The levels were carried "en echelon", with each chamber on a level approximately three cuts ahead of the chamber on the level

Jan 1, 1981

By David J. Mack, Dennis R. O’Boyle

The mechanical properties of three polycrystalline intermediale Phases that have the y bvass structure were measured in compression between 400° and 900°K. At the lower testing temperatures— termed Region I— no plaslic deformalion occurred prior to brittle fracture. A1 higher temperatuves— lermed Region III—the three phases deformted plaslically for all strain rules from 1.5 to 36.0 x 10-4 sec-1. The homologous temperature for the inilialion of plaslic flow increased in the same order as tile atomic size difference between atoms in each plmse (0.50Tmp for y AgZn, 0.62Tmp for y CuZn, and 0.76 Tmp for y CuCd). The increased flow resistance oj. y CuCd above 0.50Tmp is explaitzed in terms of the more random arrangement of copper and cadmiwn atoms on the laltice sites of&apos; the y bvass slrilctlire. Plaslic deformation of the three intevmiediate phases in the smooth plaslic flow region appears to be controlled by oacancy-induced dislocation climb. RESULTS are reported in this paper on the mechanical properties of three binary intermediate phases having the complex cubic y brass structure (D82, 143m) containing fifty-two atoms in the unit cell. The structure of the prototype y brass phase, y CuZn, was first analyzed by Bradley and Thewlis&apos; based on the X-ray work of Westgren and Phragmen.2 The y brass structure can be visualized as an arrangement of twenty-seven body centered cubes (3 by 3 by 3) into a unit cell containing fifty-four atoms. From this cell the center atom and the four corner atoms are removed and the remaining fifty-two atoms are slightly displaced, resulting in the y brass structure. Approximately thirty-five binary intermediate phases that have an electron to atom ratio of 21:13 have been reported to form the y brass structure. The three y brass intermediate phases selected for this study are formed from elements in groups IB and IIB of the first and second long period. Each compound exists over a composition range that includes the stoi-chiometric composition A5BB (Cu5Zn8, Ag5Zn8, Cu5Cd8). y CuZn (a0 = 9.944A) has solubility limits extending from 57 to 67 at. pct Zn at 500°C apd melts peritecti-cally at 834°C; y AgZn (a0 = 9.326A) has a solubility range from 58 to 63 at. pct Za and melts peritectically at 661°C. y CuCd (a, = 9.596A) melts congruently at 563°C and has a maximum range of solubility extending from 58 to 64 at. pct Cd. In order to minimize coring and microporosity during solidification, the composi- tion of the compounds that form peritectically (y CuZn and y AgZn) was chosen so that the temperature difference between the liquidus and the solidus is only a few degrees centigrade. In selecting y brass compounds for this study, phases were avoided that contained a transition element or that had an electron to atom ratio greater than 1.70. Hume-Rothery et a1.3 has observed that, when the electron to atom ratio of y brass intermediate phases exceeds 1.70, atoms begin to drop out of the unit cell to maintain a constant electron to unit cell ratio. EXPERIMENTAL PROCEDURE Each of the three intermediate phases was prepared from elements having a purity >99.999 pct. Only trace quantities of impurities (<0.0001 pct) were detected by spectrographic analysis of the four elements. A master alloy of each compound weighing approximately 130 g was prepared by melting the elements in evacuated sealed quartz tubes heated in an electric furnace. Specimens having the desired diameter for the mechanical property measurements were obtained by remelting the master alloy in a Vycor tube under argon and drawing specimens from the melt into 4-mm-diam quartz tubes. To obtain a smooth surface on specimens drawn from the melt, the inside of the quartz tube was coated with a thin layer of graphite formed by thermally decompositing acetone. All specimens were imbedded in sealing wax and cut to the proper length with a diamond-impregnated cut-off wheel. The individual specimens (4 mm diam by 8 mm long) were then sealed in evacuated Pyrex tubes and homogenized at 500°C for 72 hr. Chemical composition, variations over the length of the rod (10 cm long) were generally less than 0.2 pct and the analyzed composition differed from the desired composition by less than 0.5 pct.4 Metallographic evaluation of the specimens after homogenization showed no evidence of a second phase in any of the compounds. The average grain size of the specimens after homogenization was 1 to 2 mm. All mechanical property measurements were carried out in an argon atmosphere using a compression apparatus described previously.5 Prior to applying the load to the specimen, the test apparatus was evacuated, back-filled with argon, and heated to the test temperature for 20 min to establish thermal equilibrium. EXPERIMENTAL RESULTS Mechanical properties measured as a function of temperature and strain rate for each of the three y brass phases were similar. From room temperature to the ductile-to-brittle transition temperature, only elastic deformation was observed prior to fracture.

Jan 1, 1968

By Donald B. Evans, Robert D. Pehlke

The solubility of nilrogen in liquid binary alloys of iron with Litanium. zivconium, columbium, vanndiurn, and tantalum was measured for alloy composiLions up to the solalbility limils of lhe alloy nitrides. All five alloying agents were found to decrease markedly the activity coefficient of nitrogen in liquid ivon. The metal/nitvogen mole ralios in the alloy nitrides formed were generally .found to be slighlly greater than 1.0, but in no case greater than 1.5. From the experimental data, the standard free energies of fortmation of titanium and zir-conium nitrides have been calculated for the Lemperaluve range 1550° to 1750 C. The solublily Products for columbium, tantalum, and vanadium nitrides are also reported. A number of research investigations have examined the effect of refractory metals on the solubility of nitrogen in liquid iron. Although data on zirconium are not available, investigators are in agreement that titanium, vanadium, columbium, and tantalum markedly increase the solubility of nitrogen in liquid iron. This fact alone makes desirable the acquisition of thermodynamic data for these elements in liquid iron. Since refractory metals are known to be stable nitride formers, they have been suggested as steel denitrifying agents, and some of their nitrides have recently been considered as containment materials for liquid iron and iron alloys. Most available thermodynamic data for these metals relate to their dilute concentrations, but effective thermodynamic treatment of these applications requires data at concentrations near the solubility limit of the alloy nitride. Although some work has been done at relatively high alloy concentrations in liquid iron (particularly for vanadium 2,3 and titanium 2,4), the results have been somewhat contradictory. Disagreement may be partly attributed to the fact that the compositions of most refractory metal nitrides have been shown to be nonstoichiometric, and to vary 2,5-8 depending on the temperature and nitrogen gas pressure with which the solid nitride phase is in equilibrium. One purpose of this study consequently has been to determine the compositions of the refractory metal nitrides precipitated from a liquid iron solution. EXPERIMENTAL PROCEDURE Rao and Parlee2 and Evans and Pehlke 9 have discussed the technique for measuring the solubility product of an alloy nitride phase in liquid iron by finding the point of departure of the nitrogen solubility from Sieverts&apos; law. The method consists of measuring the solubility of nitrogen in a melt of iron containing a known concentration of a second metal as a function of the nitrogen gas pressure over the melt. In this study the second metal was one of the refractory metals titanium, zirconium, columbium, vanadium, or tantalum. When the nitrogen pressure at which the refractory nitride forms is reached, a deviation of the measured solubility of nitrogen in the melt from Sieverts&apos; law is observed in the form of a "pressure halt." The concentration of nitrogen in the melt associated with this breakpoint in the nitrogen-absorption curve is then used to calculate the nitride solubility. The Sieverts method was used to measure nitrogen solubility as a function of nitrogen pressure and temperature. The experimental equipment for this technique has been previously described in detail. 1,9 Charge materials used were vacuum-melted high-purity iron (Ferrovac-E) and the best commercial grades of the refractory metals obtainable (in all cases at least 99.8+ pct pure). Recrystallized alumina crucibles were used to hold all melts except those containing zirconium, for which zirconia crucibles were necessary. Temperatures were measured by a disappearing-filament type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diameter sight hole in the crucible lid. By means of a technique previously described, 9 in which the refractory-metal nitride was precipitated at one temperature then redis-solved by raising the temperature 50°C and precipitated again at a higher temperature, it was possible to obtain data over a temperature range of up to 200°C on a single melt. It was found that this technique could not be used with melts containing zir-

Jan 1, 1965