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By N. J. Grant, D. Carne, J. B. Seabrook

IT is unnecessary to review much of the literature on hydrogen embrittlement of steel since several excellent reviews and bibliographies exist.1-3 Hot acid pickling and cathodic charging have been known to cause hydrogen embrittlement of steel and have been used as laboratory methods to charge steels with hydrogen.4-8 Experimental Procedure The problem of prime concern in all instances, except in the work of Sims and coworkers,10 is that at no time was there a definite known hydrogen value reported which could be related to a particular value of the degree of embrittlement. It was the purpose of this research to determine the relationship between hydrogen content and degree of em-brittlement quantitatively. The 1020 stock used for the specimens was hot-rolled 7/16 in. diam rod of the following analysis: 0.19 pct C, 0.40 pct Mn, 0.012 pct P, 0.036 pct S' Vacuum-fusion analyses for nitrogen and oxygen gave 0.014 pct O2 and 0.0011 pct N2. Cathodic charging was used to cause embrittle-ment. The advantages of this method were that no quenching was necessary, the impregnation was reasonably controllable, and representative samples for analysis could be prepared simultaneously with the charging of the tensile bars. Analyses for hydrogen were made in a vacuum-fusion type of apparatus which extracted gas from the samples by fusion in a molten tin-iron bath' This apparatus, which has recently been described in detail elsewhere, will not be discussed here.". " Consecutive samples can be analyzed every 15 min with an accuracy of 0'03 ppm. A A from an electrolytic or pickling bath can be charged for analysis in about 3 min, and analysis completed in 15 min. Samples of as-received 1020 stock were analyzed and found to contain a negligible amount of hydrogen (0.06 ppm). Preliminary pickling and electrolytic charging gave highly variable results. Cold-worked samples showed higher values but ranged from 0.6 to 6.0 ppm of hydrogen. Charging at 90°C gave higher values of charged hydrogen, but troublesome films on many of the specimens resulted. It was not until a few drops of a catalytic poison, prepared from 2 g of yellow phosphorus dissolved in 40 ml of carbon disulphide,8 was added to the electrolytic cell that fairly consistent high values of hydrogen could be charged into the as-received 1020 steel at room temperature. The cell used is sketched in fig. 1. The anode and fixture for the tensile specimens were fastened to the cell cover as shown, and the specimen was screwed in place, centrally located with respect to the anode. At first, anodes of lead and graphite were tried, but they contaminated the electrolyte and gave a slight deposit on the specimen. Later, a platinum wire was used in the form of a uniform helix. A current of 2 amp, corresponding to about 0.5 amp per sq in. of cathode, was used for most specimens. The electrolyte was 4 pct H2SO4 solution. Fig. 1 shows the form of the special tensile bar, the main portion of which was an ordinary 1/4 in. diam, 1 in. gauge length test bar, except that two to four small cylinders of stock were left attached by small links to the bottom end of the tensile bar for the purpose of providing samples for hydrogen analysis. Thus the bars and samples were charged with hydrogen simultaneously and an analysis could be made while the bar was being tested mechanically. Experiments were performed to determine how representative the test cylinders were of the middle of the test bar proper. While the bar center was being analyzed, the small cylinder was stored in dry ice, since it had been shown that such storage prevents loss of hydrogen for many hours.12 The results of these checks are shown in table 1. The checks are very good (0.3 ppm) and indicate that it is permissible to use the small end cylinders to establish the hydrogen content of the tensile test bar proper-

Jan 1, 1951

A preceding paragraph treats of the irregular manner in which ore deposits occur and the complex factors that control their distribution; the occurrence of metals in oreshoots in individual deposits is equally irregular, and the factors that control such segregation are equally complex. While the dimensions of oreshoots in individual deposits may not be foretold with any degree of accuracy, the occurrence of ore in shoots is not accidental, but is controlled by laws some of which are understood. Any one familiar with permutations and combinations who stops to consider the variety of factors that control ore deposition, and their varying relative importance, will admit that the science of economic geology must advance greatly before the occurrence of oreshoots may be predicted accurately in advance of exploration. The segregation of minerals in any oreshoot must be referred to some condition, or combination of conditions, local to the oreshoot as compared with the remainder of the deposit of low- grade or barren minerals. Among the localizing factors that have been recognized are, in filled fissures, the amount and distribution of open spaces available for ore deposition, and in replacement deposits, the degree of brecciation giving access to the replacing solutions; the intersection of veins with other veins, dikes, sheeted zones, or porous strata; the impounding of solutions by impervious strata; and the differing precipitative influences of enclosing rocks. A large proportion of important and well- defined oreshoots, especially in deposits of deep-seated origin, are not assignable to any of these factors. While a knowledge of the character of oreshoots in general is important, a knowledge of the behavior of the known oreshoots

Jan 1, 1932

By D. R. Wieland, H. T. Kennedy

The object of the work reported here was to determine the content of elemental sulfur in gaseous methane, carbon dioxide, hydrogen sulfide, and in mixtures of these gases, at pressures and temperatwes encountered in natural gas reservoirs. Sulfur content at equilibrium is reported for pure methane, carbon dioxide, hydrogen sulfide, and on three binary mixtures of each of the three pairs of gases at pressures of 1,000, 2,000, 3,000, 4,000, 5,000 and 6,000 psia and at temperatures of 150°, 200° and 250°F. In addition, the sulfur content of three ternary mixtures at the same temperatures and pressures are reported. The results indicate that the sulfur content is higher in the gases at higher temperatures and pressures. The content is highest in hydrogen sulfide, intermediate in carbon dioxide and lowest in methane. INTRODUCTION At ordinary pressures and temperatures, the concentration of a nonvolatile material, such as sulfur in a gas at equilibrium, is a function of the vapor pressure of the material and is independent of the nature of the gas. As the pressure and temperature increase, the gas assumes some of the properties of liquids, including the power to dissolve other liquids and solids, to an extent dependent on the nature of both the gas and the material dissolved. At equilibrium, the content of sulfur in the several gases considered here may thus be considered as solubilities which are fixed for a given composition of gas, temperature and pressure. The study of the solubility of elemental sulfur in gases is of interest because sulfur is sometimes present in reservoirs producing natural gas and must be present in the vapor phase. Upon reduction of pressure and temperature, the sulfur precipitates from solution in the reservoir and in the tubing and fittings. Due to the fact that the greatest pressure drop in the reservoir is around the wellbore, the volume of sulfur precipitated will be greatest in this locality and can cause a substantial reduction in the permeability of the formation in this area. As the natural gas flows up the tubing string, the pressure and temperature are further decreased, causing further sulfur precipitation. If the volume of free sulfur is large and remedial measures are not taken, complete plugging of the tubing can occur. Knowledge of the content of sulfur as a function of composition, temperature and pressure will enable the operator to determine what changes in pressure and/or temperature are necessary to keep the sulfur in solution. If the sulfur solubility is large and can be controlled, the operator may desire to produce the well at a high wellhead pressure and temperature and reclaim the sulfur at the surface. The high solubility of sulfur in hydrogen sulfide (5.6 per cent by weight at 5,000 psi and 200°F) suggests the feasibility of recovering sulfur by injecting this gas into sulfur-bearing reservoirs and expanding the produced gas to precipitate out the sulfur. The present project was designed to measure the solubility of sulfur in carbon dioxide, methane, hydrogen sulfide and mixtures of these three gases at various temperatures and pressures. These gases were the major constituents of the gas well where plugging by sulfur was encountered. A study of the published literature shows no data on the solubility of sulfur in any gas, although Hannay and Hogarth,' in 1880 reported that it was soluble in carbon disdlide above the critical temperature of carbon disulfide. EQUIPMENT AND PROCEDURE Fig. 1 shows the layout of equipment employed to bring gases to equilibrium with sulfur and to isolate the quantity of sulfur contained in a known volume of gas. Pure gases were measured in the charging bomb at known temperatures and pressures and displaced into the reservoir bomb to make up the desired mixtures. When equilibrium was achieved

By A. Kaufman

More than 3 trillion gal of water are used annually by the mineral industry. Of this, approximately 21/2 trillion gal are recirculated, the rest constituting intake water. The major users are natural gas processing plants and phosphate rock, sand and gravel, and iron ore producers. Water was used by the mineral industry for mining (6%), processing (64%), cooling and condensing (27%), and miscellaneous uses such as boiler feed and sanitary purposes (3%). Whereas total water use is dependent on the quantity of material processed and on the particular process requirements of an industry, recirculation is dependent on processing, as well as cooling and condensing requirements, quality of new water intake, and the necessity for treating new and discharged water. Consumed water, on the other hand, is dependent on the quantity of water recirculated, and temperature and humidity in the area. Based on this analysis, an increase in water use by the mineral industry of 21/2 times by 1985 is forecast. Wster intake, however, will only rise 62%, because of a substantial increase in recirculation. In one report of a special series concerning the water resources of the United States, the Senate Select Committee on National Water Resources, 87th Congress, estimated that water demand would double by 1980 and triple by 2000.' In view of the possible water deficiencies that might result from such expanded usage and the need for research guidance, the Bureau of Mines organized and carried out a statistical canvass of water use in the mineral industry for calendar year 1962. The data used in this paper, unless otherwise noted, are derived from that canvass.' The efforts in this paper are devoted toward summarization of the canvass and analysis of the data. SOME DEFINITIONS Intake: Water introduced from an external source for the first time into a given mine or plant regardless of quality. Intake water is also called new water, water withdrawn, or makeup water. Fresh Water: Water suitable for cooking and drinking. Saline Water: Water containing more than 1000 parts per million of dissolved solids. Contaminated Water: Water not suitable for domestic use, but excluding saline water. Recirculated Water: Water reused to conserve intake water. Solutions that are recycled primarily because of fixed metallurgical practices, such as copper leaching solutions containing sulfuric acid, are excluded. Gross Water Used: Recirculated water plus intake water. Also called total water used. Consumed Water: Water that is lost by evaporation, as well as water lost in product. Seepage and transferred water are not considered consumed. The use of either intake or recirculated water may result in consumption. However, because of difficulties in measuring consulmption, consumed water is defined as the residual between intake and water discharged from the mine or plant. Mineral Industry: For the purposes of this paper, mineral industry includes all metal and nonmetal surface and underground mines and their associated processing plants, as well as custom mills, coal washing plants and associated mines, petroleum and natural gas well drillers, natural gas processing plants, and secondary recovery operations. WATER USE IN THE MINERAL INDUSTRY Water used by the mineral industry constitutes a relatively minor fraction of the water withdrawn by all users. Data compiled by the U.S. Geological Survey in 1960 indicate that water withdrawals, exclusive of that used to generate hydropower, approximate 99 trillion gal annually.3 Our data indicate that water withdrawals by the mineral industry comprise only 1% of this total, or 2% of the water withdrawn by industrial users. Use by Industry: Water used by various mineral industries is shown in Table I. The table indicates that close to one-half of the gross water used by the mineral industry in 1962 was used by natural gas processing plants, followed by sand and gravel, phosphate rock, and iron ore producers. The largest aggregate users of water are also the largest users per dollar of product. For example, Fig. 1 shows that the natural gas processing and phosphate rock industries are very large users of water per dollar of product. Their recirculation per

Jan 1, 1968

By John Wulff, David A. Stevenson

The solubility of iron and cobalt in liquid lead, the solubility of chromium in liquid tin, and nickel in liquid silver were determined up to 1300°C in an atmosphere of hydrogen. Liquid samples were taken at different temperatures and analyzed. The data obtained were plotted to show the relationship between log mole fraction of solute and the inverse of the absolute temperature. Resulting values for the differential heat of solution (AH) and the excesspartial molar entropy (S)are: for the iron-lead system = _24,200 cal per mole and AT = 5.0 e.u. for the a phase, and AH = 18,300 and S = -0.1 e.u. for the y phase; for the cobalt-lead system AH = 16,500 cal per mole and AS =0.7 e.u.; for the chromium-tin system AH = 15,600 cal per mole and AS = 8.5 e.u.; for the nickel-silver system AH =18,000 cal per mole and AS = 4.0 e.u. RECENT developments in coating, brazing, and heat transfer have focused attention on specific cases of solid-liquid interaction in metal systems, particularly those involving dilute liquid solutions. One fundamental quantity of interest in such systems is the equilibrium phase distribution between solid and liquid phases. In any effort to fully understand such interactions, one must be able to describe the equilibrium state precisely. Furthermore, in order to develop genera! relations for such systems, one must know the equilibrium state in a number of different cases. This investigation was devoted to a study of the equilibrium phase distribution in four binary systems: solid iron-liquid lead; solid cobalt-liquid lead; solid chromium-liquid tin; solid nickel-liquid silver. The iron-lead system was previously studied by Shepard and parkman' and later by Fleischer and Elliott2 with differing results. Both investigations were carried out by sampling the saturated liquid, and analyzing it chemically. The cobalt-lead system was previously reported by Pelzel,3 who noticed no discontinuity near the transformation. A limited investigation of the chromium-tin system was made by Wlodek and wulff4 using a weight loss method. This work was done in conjunction with the development of a process for coating molybdenum with chromium from tin solutions. To more fully under- stand the kinetics of the process, a more accurate determination of a solubility was desirable. No significant data were found in the literature on the nickel-silver system. Data on the latter system were, however, relevant to the investigation of the corrosion kinetics of copper-nickel alloys in liquid silver as carried out by Harrison and wagner,5 EXPERIMENTAL APPARATUS AND PROCEDURE Of the techniques available for the study of such systems the most effective appears to be that of liquid sampling,2,6,7 which is the method used in the present investigation. A schematic diagram of the sampling furnace is given in Fig. 1. Large pieces of solute metal, in excess of saturation solubility, were added to 200 g of the solvent metal, and the entire charge placed in an alundum crucible. Analytical reagent or materials of chemically pure grade were used in all investigations. The crucible was contained in a zircon muffle tube positioned vertically in the uniform hot zone of a Globar resistance furnace. The tube was provided with a number of ports which permitted sampling at temperature and in controlled atmospheres or vacuum; the ports were also useful for evacuation and introduction of gases as well as for thermocouple measurements. A chromel-alumel thermocouple Sheated in a porcelain tube was used for temperature measurements. A purified hydrogen atmosphere was employed in all experiments reported in this paper. The hydrogen was purified by passing it first over hot copper gauze to remove oxygen and then through a molecular sieve immersed in

Jan 1, 1962

By C. A. Stewart

I. INTRODUCTION AND GENERAL STATEMENT OF RESULTS. The field-work upon which this paper is based was done in the summer of 1910, and was made possible by the courtesy of the Imperial Copper Co., which gave me access to its property. For their kindness in this respect I wish to express my thanks to W. F. Staunton and Meade Goodloe. Moreover,. B. F. Smith and G. B. Gentry, mining engineers in the employ of the company, gave invaluable assistance by placing maps,. etc., at my disposal, and by discussing with me the problems of the district; and it is a great pleasure to acknowledge this indebtedness to them. In order that the significance of some of the details that follow may be better appreciated at first reading, a general outline of the conclusions reached is given here. In the Silverbell mining-district a series of Palaeozoic limestone blocks is completely surrounded by post-Palaeozoic igneous rocks, intruded in the following order: alaskite, alaskite-porphyry, biotite-granite, andesite, and quartz-porphyry. The biotite-granite is believed to represent a differentiation of the. magma from which the alaskite-porphyry came ; and this conclusion-has an important hearing on the origin of the ores. The intrusion of both alaskite-porphyry and biotite-granite was followed by the emission of magmatic waters, which sericitized and silicified the alaskite-porphyry and granite, and produced in the limestone, by the addition to it of silica, iron, and alumina, great masses of garnet, quartz, and wollastonite. Following close upon these solutions came metal-bearing magmatic waters, which impregnated porphyry, granite, and alas kite with cupriferous pyrite, and deposited in the garnet zones chalcopyrite and copper-bearing pyrite that make important bodies of contact-metamorphic ores. Secondary enrichment has taken place in the disseminated ores in the igneous rocks,. raising their copper-content to 2 per cent. in some cases,. and extensive drilling has been undertaken to block out these deposits. East of the contact-metamorphic deposits there is a fissure-vein of lead-silver ore in the quartz-porphyry. This rock is distinctly younger than the alaskite-porphyry and the granite; and the lead-silver ores belong, therefore, to a period of mineralization distinctly later than the copper-deposition.

May 1, 1912

By Alan English

INTRODUCTION During the Bicentennial Year in the United States of America, recognition should be given to the fact that 20 years ago the first large-scale commercial pelletizing plant was started and attained rated capacity. This was the beginning of a new industry. Twenty years ago the total production of pellets was principally from pilot plant facilities and totaled in the thousands of tons per year. At the present time the world production is slightly in excess of 280 million tons per year. This truly is a tremendous growth for any industry. Such a production growth obviously is accompanied by a similar growth pattern in the development of process, equipment, and facilities. During the growth and development period, different materials became more adaptable for processing. For example, initially the pelletizing of iron ores revolved around the magnetite concentrates where the heat of reaction constituted a very important part of the process fuel. During this growth period, specular hematite, earthy hematite, mixtures of hematite and magnetite, and even non-ferrous type materials were pelletized, a function previously thought not practical. The demand for the use of pellets has also broadened their concepts. At first they were made to replace the high-grade iron ores used in blast furnaces. Nowadays, not only have they replaced iron units, but they have had a major influence on the design of larger blast furnaces and have contributed to production rates in excess of 10 000 tons per day from a single furnace. They have also been used in the manufacture of steel, principally for coolants in the BOF practice. More recently, with the improved beneficiation techniques that have been developed over the same period of time, pellets have been used for the direct reduction process and can be used directly

Jan 1, 1977

By M. E. Lombardi

THE Coalinga oil field is located on the west side of the San Joaquin Valley, California. The structure is in general a monocline, the edges of the oil horizon resting on the foot hills and dipping gently toward the east. One prominent anticline occurs plunging southeast. The earlier drilling was done in the foot hills comparatively near the outcrop and the wells were shallow. The sands were followed eastward and, in the case of the anticline, along the plunge, the wells becoming deeper and deeper until the depth of 4,000 ft. was reached and passed. There is nothing to show that the oil will not be found in quantity at still greater depth. In fact, some of the best producers have tapped the sand at close to 4,000 ft. The recovery of oil still farther to the east, and therefore at greater depth, seems to be mainly a question of drilling. In this territory the formations drilled through are chiefly sands and shales; they will not "stand up" in an open drilling hole; the casing has to be carried close to the bit, and it is always difficult to keep the casing free for any considerable distance. Ability to carry casing of comparatively large diameter without conductor pipes for distances of 2,000 or 3,000 ft. or over is desirable in such territory chiefly for two reasons. It makes it possible to enter the oil sand with a pipe of ample diameter; it eliminates one or more expensive strings of casing which act only as conductors for the water string, and furthermore, in territory where waters are encountered which corrode steel rapidly, it makes possible the construction of a rust- and alkali-resisting water string. It is always desirable to shut off top waters, which may lie within 100 ft. or less of the oil sand, with 10-in. pipe. Where the depth is so great that a practical weight of 10-in. pipe will not withstand the probable collapsing pressures, 8 ¼ in. at least is desirable. About the limit of rotary drilling to date in California seems to be the setting of the 10-in. string at 3,200 ft., although the rapid advance in rotary work during the past year seems to indicate that this depth may soon be increased. It is my purpose now, however, to treat only of cable-tool drilling.

Jan 2, 1915

By H. A. Fisch, A. J. Opinsky, J. L. Bartos

Fort?-six- two-grain bounduries were studied in doped tungsten 1amp wire that had been heated to 3450°K very vapidly. Back-reflection Laue photograms were taken of the grain boundary partners and solved, using a computer. The resulting distribution of large-grain orientations was analyzed. Rotational axes were calculatedfor each grain boundary pair. The axes of least rotation show an anisotropy of rolalional angle. WhILE the orientations of large grains in straight doped tungsten wire have been studied extensively, little has been done to characterize the boundary that separates them. Rosi.1 upon seeing the jagged interlocking boundary in doped tungsten wire. inferred that the grains should have a preferred orientation, and proved it. He interprets his data as indicative of a single ideal orientation—(531)— being parallel to the wire axis. Rieck2, 3 and Mannerkoski' have essentially confirmed this finding. Opinsky, Orehotsky, and Siegle argue that the data suggest that (211)—a plane-is parallel to the wire axis instead. This (211 ) contains the (531). and hence would appear to be a more general case.5 Ahlborn and wasserman6 report that their orientation data stretch from (110) through (531) to (311). This path is the locus of {211 Recently. Opinsky has suggested that the data can be interpreted as a series of ideal orientations that can be related by coincidence relationships to the (110) fiber texture. All these investigators have determined the orientations of the large grains by the back-reflection Laue technique, and they have all obtained similar results. Only Rieck5 as methodically looked at the large grains along a wire. He was apparently not concerned with the relationships of the large grains across their common boundary, but only with their individual orientations. This research was undertaken to fill this gap in the under standing of the mechanical properties of tungsten wire. Only the crystallographic aspects of the problem will be reported here. In addition, the large number of large-grain orientations, which was accumulated in this study. will also be analyzed. EXPERIMENTAL MATERIAL AND TECHNIQUES All of the data were obtained from four pieces of the same 7-mil-diam General Electric tungsten lamp wire. Twelve-inch lengths of the cleaned wire were heated in vacuum by the flick of a switch to 90 pct of the amperes necessary for fusion (a temperature of approximately 3450°K) and held for 1 min. On the basis of other data. it is estimated that the rise time is of the order of 0.5 sec. The four pieces of wire could have come from anywhere within about 18 ft of wire. Consecutive segments of each piece of wire were mounted in bakelite and polished metallographically The polishing procedure followed that described by woods. "nly boundaries between two grains that each occupied the entire cross section of the wire were photographed and X-rayed. The metallographic sample was mounted accurately with respect to the X-ray unit. Steps were taken to read the films as accurately as possible with the conventional Greninger net. The data were then entered into computer programs that solve the Laue film by precisely the same techniques that are used in the solution of the film by means of the stereographic projection. The use of the computer has probably shifted the main source of error from the stereographic plot to the reading of the film. On the basis of several experiments, it is thought that the error associated with the entire process, from mounting the sample through the computer solution, is of the order of about one-half degree. The output of the computer is the direction cosines of the fiducial direction (the wire axis) and the locations of the three cube axes. The former data were used to calculate the differences in orientation between the two grain boundary partners, and the latter were used in the calculation of the rotational axes that could bring the two grains

Jan 1, 1970

By H. Biloni, B. Chalmers

Metallographic studies of the segregation of solute in and near the surfaces of chill-cast alloys have shown that, under sufficiently severe conditions, nucleation on the cold mold surface is followed by the formation of a disc of solid of the same composition as the liquid. This disc is surrounded by two concentric rings in which the concentration first decreases and then increases. The discs and rings are surrounded by a region in which arms of low solute concentration separate regions of high concentration. These arms start at the periphery of the outer ring and are initially radial; they make a gradual curved transition from the radial direction to a crystallographic direction. A normal dendritic substrcture is established beyond the position at which the arms have become crystallographically aligned. When the cooling is less severe, the disc becomes less irregular in shape and has a concentration minimum at the center. The term "Predendritic" is proposed for these transitions. A qualitative explanation is outlined for the phenomena observed at the surface and in the equiaxed region of the ingots. It is well-established1-' that the normal mode of solidification for alloys under most conditions is dendritic. A characteristic of dendritic solidification is the growth of rods or plates in specific crys-tallographic directions. The remaining liquid solidifies later, usually with a higher concentration of solute than the original liquid. Very little is known, however, about the transition from a crystal nucleus until the dendritic pattern is established. It is clear that there must be a transition because the nucleus is much smaller than the characteristic spacings found in the "steady-state" structure. And it also seems clear that the initial conditions must be important since the undercooling existing during the nucleation of the grains has a remarkable influence upon the grain size4 and the segregation pattern. The present paper reports a study of the micro-segregation in regions where crystals have nucleated, and the conclusions that can be drawn regarding the early stages of growth, in connection with the details of the solidification process. Aluminum of 99.993 purity, A1-Cu alloys containing 0.5 to 20 wt pct Cu, and Pb-Sn alloys with 5 wt pct Sn were cast and examined metallographically at the as-cast surface, close to the surface, and in the interior after casting. The alloys were cast from controlled temperatures against surfaces at different temperatures ranging from room temperature to approximately the liquidus temperature of the alloy. The surfaces were, in various experiments, graphite, stainless steel, copper, and aluminum. The methods used for metallographic examination were as follows. 1) The Nomarski phase contrast interferometer6 was used to obtain information on the topography of the as-cast surface. 2) The distribution of any solute present in A1 99.993 pct and copper in the A1-Cu alloys was studied by the anodic film technique originated by Lacombe and Mouflard7 and previously applied in the study of the solidification of aluminum by Biloni.8 The electropolished surface of the specimen is anodized under controlled conditions so that the thickness of the oxide film and therefore the interference colors under white light are sensitive to the local composition. This technique was applied to the as-cast surfaces and to metallographically prepared surfaces from the interior. 3) If in Al-Cu alloys, the surface is anodically oxidized for several minutes, instead of seconds as in the color-film technique, the copper segregation is outlined by a different level with respect to the matrix. This method is less sensitive but complementary to that for the color films. 4) The distribution of copper revealed and mapped by the metallographic techniques was confirmed by electron probe. 5) In samples with high concentration of copper, evidence for the copper distribution could be seen optically after electropolishing.

Jan 1, 1965

By John Chipman, Minu N. Dastur

This paper presents equilibrium data on the reaction of water vapor with vanadium dissolved in liquid iron at 1600°C. The thermo-dynamic behavior of vanadium and oxygen when present together in the melt is discussed. A deoxidation diagram is presented which shows the concentrations and activities of vanadium and oxygen in equilibrium with V209 or FeV2O4. STUDIES of the chemical behavior of oxygen dissolved in pure liquid iron1-3 have served to determine with a fair degree of accuracy the thermody-namic properties of this binary solution. The practical problems of steelmaking, however, involve not the simple binary but ternary and more complex solutions. Only a beginning has been made toward understanding the behavior of such systems. The silicon-manganese-oxygen relationship was studied long ago by Korber and Oelsen4 and more recently by Hilty and Crafts." The carbon-oxygen reaction was investigated by Vacher and Hamilton6 and by Marshall and Chipman.7 A number of deoxidizing reactions have been studied empirica1lys'10 with the object of determining the appropriate "deoxidation constants." The work of Chen and Chipman" afforded a clear-cut view of the effect of the alloy element, chromium, on the thermodynamic activity of oxygen in liquid ternary solutions. These investigators determined the oxygen content of experimental melts which had been brought into equilibrium with a controlled atmosphere of hydrogen and water vapor and were able to show that the presence of chromium decreases the activity coefficient of oxygen. They determined also the conditions under which the two deoxidation products, Cr2O3 and FeCr2O4, were formed and showed that the activity of residual oxygen is considerably less than its percentage. It was the object of this investigation to apply a similar method to the study of molten alloys of iron, vanadium, and oxygen. Vanadium was once considered a moderately potent deoxidizer, but this is now known to be erroneous, in the light of its behavior in steelmaking practice. Its reaction with oxygen retains a certain amount of practical interest in that a high percentage of one element places a limit on the amount of the other that can be retained. As a deoxidizer it will be shown that vanadium lies between chromium and silicon. Experimental Method The apparatus was that used by the authors3 in their study of the equilibrium in the reaction: H2(g) +O = H2O(g);K,= [1] PII., ao Crucibles of Norton alundum or of pure alumina were used. The latter were made in this laboratory and were of high strength and low porosity. Under conditions of use they imparted no significant amount of aluminum (less than 0.01 pct) to the bath. Temperature measurements were made with the optical equipment and calibration chart of Dastur and Gokcen.= The charge was made up of calculated amounts of ferrovanadium (20 pct V) and clean electrolytic iron totaling approximately 70 g. The first few heats were made in alumina crucibles with an insufficient amount of vanadium so that no oxide of vanadium would be precipitated under the particular gas composition. All the heats were made at 1600 °C under a high preheat and with four parts of argon to one part of hydrogen in the gas mixture to prevent thermal diffusion. The rate of gas flow was maintained constant at 250 to 300 ml per min of hydrogen. The time for each heat was three quarters of an hour after the melt had melted and attained the required temperature (1600°C). The water-vapor content of the entrant gas mixture was gradually raised in succeeding heats, keeping the vanadium content of the melt constant. This was controlled by manipulation of saturator temperature. A point was reached when for a given H2O:H2 ratio some of the dissolved vanadium was oxidized and appeared as a thin, bright oxide film on top of the melt. By raising the temperature of the melt it was possible to dissolve the oxide film which reappeared as soon as it was cooled down to 1600°C. The temperature readings taken on the oxide film were consistently higher by 80" to 85 °C as observed by the optical pyrometer. The heat was allowed to come to equilibrium under a partial covering of this oxide film. At the end of the run the power and preheater were shut off and the crucible containing the melt was lowered down into the cooler region in the furnace. This method of quenching proved quite

Jan 1, 1952

By R. D. Begley, A. W. Khair

Introduction The technique being investigated here uses a physical mine model which consists of a plexiglass room-and-pillar model 11.4 x 11.4 cm (4.5 x 4.5 in.). It is placed at the bottom of a larger plexiglass box 25.4 x 30.5cm (10 x 12 in.). The box is then filled with a model material representing geologic overburden. Sand has been selected because of its deformability under gravitational forces. The mine model is capable of creating a cavity and induces movement on the surface of the model material. This surface disturbance can be measured using a photographic technique called holographic interferometry. This paper discusses results of an investigation of the possibility of generating subsidence criteria using physical mine models and laser holographic interferometry. Problem Statement Subsidence appears to be widespread in two states - Pennsylvania and Illinois - although serious subsidence is found in localized areas of numerous other states (HRB Singer Inc., 1977). The US Bureau of Mines estimates that more than 1618 km2 (400,000 acres) of urban areas are threatened by subsidence. Pennsylvania and West Virginia contain 57% of these threatened areas, with the remainder being spread out over 16 states (Johnson and Miller, 1979). Events of subsidence have been reported in urban areas, including Pennsylvania (Gray et al., 1977) and Illinois (Mahar and Marino, 1981). One location has observed three episodes of subsidence beginning in 1950 (Bruhn et al., 1981). These subsidence events all occurred over abandoned room-and-pillar mines. Some mines have been abandoned more than 50 years (Bauer and Hunt,1981) . Available research does not offer much on the problem related to time dependent subsidence, especially those associated with the failure of remnant coal pillars. The physical modeling technique developed at West Virginia University is capable of measuring both instantaneous and time delayed subsidence. Laser Holographic Interferometry Laser holographic interferometry, or holometry, uses the interference properties of laser light to measure small movements of objects. The object requires only optical access and no surface instrumentation. This technique is closely related to photoelasticity. Both techniques rely on the uniqueness of the light reflected off or through an object in any given state of stress. The entire measurement process is done remotely without any surface instrumentation and without using a camera. The interferogram is constructed and visual observation will yield fringes on all areas that yielded or moved. The displacement represented by one fringe was determined by Wilson et al. (1977) and is given by the relationship: [d ='1(1) 2 cos 8 where d = displacement of one fringe 6 = incident angle of laser light A = wavelength of light (632.8 x 10-9 meters for Helium-Neon lasers)] In summary, holometry is capable of detecting very small movements of objects under study. It is a very sensitive process that requires laser light and vibration free experiments. Experimental Program Lab Facilities The primary components of the facilities were the laser and the optical table. The light source was 50 milli-watt, Helium-Neon laser. The optical table was a granite slab weighing nearly one ton. All experiments were performed on the optical table. It consists of a large table sitting on air cells similar to car innertubes. Six air cells were placed on top of two layers of wood and Styrofoam. Figure 1 is a schematic diagram of the vibration free table. Even with these precautions, the experiments still had to be performed at night to reduce potential traffic related vibrations. Room-and-pillar mine models consisting of three different pillar sizes were constructed out of plexiglass. The models were designed to represent three different extraction ratios. Figure 2 shows the models. The extraction ratios were determined by the tributary loading concept (Peng, 1978). These models were the primary component of a seam extraction simulator. A schematic of this simulation device is shown in Fig. 3.

Jan 1, 1986

By J. W. Whalen

The design, operation and evaluation of an instrumental method for the determination of fluid saturation in porous materials during multiphase flow studies is described. The presence of a magnetic tracer comprising approximately 20 per cent by weight of the aqueous phase is necessary in the utilization of this method. The results of two-phase relative permeability studies on two samples of porous media are presented. The realizable accuracy of the magnetic susceptibility apparatus in fluid saturation determination is estimated to be 2 saturation per cent. The response characteristics of the instrument, together with its simplicity of operation and maintenance are sufficient to recommend its use in routine laboratory studies. INTRODUCTION The problem of fluid saturation determination in laboratory multiphase flow studies characterizing oil recovery processes is one which has been given exhaustive study. Briefly the requirements which are considered essential for a method sewing this purpose are: (1) that the measurement be made external to the porous rock sample under study with no interruption of the fluid flow pattern, (2) the saturation indication must be independent of fluid distribution in the volume scanned by the measuring device, (3) the sensing element should have a small field of definition enabling several independent measurements to be made along the length of a core sample, and (4) the properties of the fluid phases should not be too greatly influenced by required tracer substances. Several methods of saturation determination have found acceptance as meeting most of the above requirements. These include resistivity,1 X-Ray absorption,2,3,4 radiotracers,5,6,7 and neutron8 diffraction The merits of these techniques have been discussed elsewhere in detail and will not be considered here. It may, however. be pointed out that the elaborate instrumentation required by the methods mentioned above, with the exception of the resistivity method (which is undesirable from other standpoints) encourages the development of methods of saturation determination which, while meeting the requirements listed, are simple to operate and maintain. It is the purpose of this paper to describe the instrumentation and evaluation of a technique for the determination of fluid saturation which combines relative simplicity with an accuracy and applicability comparable with methods now in practice. DESCRIPTION OF THE METHOD If the magnetic susceptibility of one of the fluid phases contained within a porous material is sufficiently greater than that of the remaining phases, the fluid content of the material with respect to that phase may be determined by an induction measurement. This may be accomplished by measuring the induced voltage in the secondary of a transformer which contains the porous sample and its interstitial fluids as a portion of the magnetic flux path. Since the fluids used in multiphase flow studies involving petroleum reservoir samples possess uniformly low magnetic susceptibilities, the use of a magnetic tracer in one of the fluid phases is required. In view of the relatively high paramagnetic susceptibility of salts of the transition elements, together with their high water solubility. these compounds become logical choices as tracer materials. Cobaltous chloride, having a specific magnetic susceptibility of 17.5 x 106 cgs electromagnetic units, was used as the tracer material throughout this work, in a concentration of approximately 20 per cent by weight in the aqueous phase. MAGNETIC SUSCEPTIBILITY APPARATUS Basically, the magnetic susceptibility apparatus consists of a transformer serving as the detecting head, a

Jan 1, 1955

After months of negotiations, the U. S. has agreed to buy between 6000 and 7000 long tons of Bolivian tin now stockpiled at Peruvian and Chilean ports, at $1.175 per lb, f.o.b. South American Ports. Harry A. McDonald of the Reconstruction Finance Corp. signed the contract with Victor Andrade, Bolivian ambassador. The Mercantile Metals and Ore Corp., of New York City, acted as the agent of Bolivia's Banco Minero in negotiating the deal. The contract is a short term one. Throughout the talks, the U. S. refused to make a long term agreement because of the possibility that Bolivia will soon nationalize its mines. The Bolivians desired to sell the U. S. 18,000 tons during a one-year pact. The price agreed upon is roughly the same as with Malayan producers. In the meantime, American Smelting & Refining Co., signed over control of its operations to the Bolivian Government. The formal act of leasing the mines to the Bolivian Government follows the announcement last July by the company that it was closing operations because of high costs. Contract terms were not disclosed.

Jan 1, 1952

By J. A. Berger, R. J. Towner

A method for determining the disorientation between sub-grains that .share a common tilt or twist boundary from measurements on X-ray micrographs is described. The method may be applied to subgrains of almost any orientation having boundary angles in the range from about 1 min to 1 deg of arc. An adaption of the Berg-Barretl method has been made to allow calculation of small angles of about 1 min to 1 deg of arc: between adjacent subgrains from the relative displacement of their images on X-ray micrographs. schulz4 gave equations for determining subgrain disorientation where the axis of subgrain rotation and the reflecting crystal planes were parallel to the specimen surface. In our method, however, they need not be parallel and, indeed, may have va:rious orientations. His camera setup, involving a fine-focus X-ray tube for obtaining high resolution with continuous radiation, was different from the one used in the present investigation (a 1.2 x 1.2 mm effective source and characteristic radiation). The X-rays produced a slight magnification in the subgrain images in the Schulz method, but not in the present method. The commonly available type of X-ray tube used permitted relatively short exposure times with a fine-grained photographic plate, which could be magnified optically many times for the examination of small subgrains. The method is illustrated by results obtained on {110} tilt boundaries in a polygonized aluminum single crystal of 99.994 pct purity. The flat crystal was stretched 6 pct in tension and then heated at 500°C for a cumulative time of 5 hr. Earlier, cahn5 studied subgrains formed by polygonization in stretched and heated aluminum crystals. He observed kink bands to have well defined boundaries lying in (110) planes, at least in the early stages of deformation. Cahn found that the (110) tilt boundaries formed by polygonization were directly related to the lattice bending about the <211> axis which lay in the (111) slip plane perpendicular to the <110> slip direction. DESCRIPTION OF THE CAMERA Our camera was similar in detail to Honey-combe&apos;s.6 Unfiltered copper radiation was used at 35 kv, and 20 ma. With the particular specimen used here to illustrate the method, a 1.2 by 1.2 mm effective source and a distance of 780 mm from target to specimen were employed, giving a convergence of 5 min of arc in the primary beam. The distance was 9.5 mm from the specimen to film. The upper 1/2- by 1-in. portion of the front surface of the specimen was irradiated with the film in parallel position. Since the specimen had been inhomogeneously deformed, many regions were in a position to reflect characteristic radiation at the Bragg Angle. Five minute exposures were satisfactory with Kodak Single Coated X-ray Film, 1 1/2 hr

Jan 1, 1961

Jan 1, 1952

By C. H. Benedict, H. C. Kenny

A 2000-ton ammonia leaching plant has been operated by the Calumet & Hecla Mining Co., at Lake Linden, Mich., continuousl~ since February, 1917, except from April, 1921, to April, 1922, during the period of depression following the European war. A description of this plant has been published elsewhere.1 The present article describes the operation of the plant since 1917, together with the changes in the process that have been found to be advisable. In spite of the fact that this plant and that of the Kennecott Copper Co. are the only ones operating on a large scale, much experimental work is being done on ammonia leaching, as applied to oxidized ores, and it is to aid these and other investigators that this detailed account is given. For the benefit of those unfamiliar with the original article, the following short abstract is given, as an introduction to a more detailed account of the process and the reasons for present practice. Rêsumê of Previous Article Leaching on a commercial scale began in July, 1916, and by Februsry, 1917, the plant of 2000 tons capacity was in commission. The ore treated is a conglomerate containing native copper and no sulfides or oxidized copper minerals. Before leaching, the ore is crushed by steam stamps and Hardinge pebble mills to pass a 28-mesh screen. Free copper is removed, by gravity concentration, on Woodbury jigs and Wilfley tables, and colloidal slime for oil flotation is removed by quadruplex Dorr classifiers. The leaching sand remaining contains about 2 per cent. + 28-mesh material and 15 per cent. — 200-mesh and carries from 8 to 14 lb. of copper per ton, depending on the grade of ore worked. The solvent employed in leaching is a water solution of ammonium carbonate,

Jan 1, 1924

CONTENTS PAGE ANDERSON, ROBERT J., and ENOS, GEORGE M.-Corrosion of Brass as Affected by Grain Size. Discussed by Henry S. Rawdon, Robert J. Anderson, Francis B. Coyle, William B. Price, and W. R. Webster 1 RAWDON, HENRYS., and MUTCHLER, WILLARD H.-Effect of Severe Cold Working on Scratch and Brinell Hardness. Discussed by W. H. Bassett, John Livermore Christie, John R. Freeman, Jr., W. R. Webster, William B. Price, Norman B. Pilling, D. J. McAdam, Jr., F. G. Smith, Zay Jeffries, F. E. Carter 3 WILLIAMS, ROBERT S., and HOMERBERG, VICTOR 0.-Relation of Heat Treatment to the Microstructure of 60-40 Brass. Discussed by 0. W. Ellis 14 Corrosion of Brass as Affected by Grain Size Discussion of the paper of ROBERT J. ANDERSON and GEORGE M. ENOS, presented at the New York Meeting, February, 1924, and issued as Paper No. 1282, with MINING AND METALLURGY, December, 1923. HENRY S. RAWDON,* Washington, D. C. (written discussion).-So numerous and so varied are the factors that affect the corrosion of metals that particular care is necessary in corrosion tests to eliminate so far as possible all extraneous factors. It appears to the writer that the question may well be asked as to whether all the necessary precautions have been observed in this investigation. It may be that the points to be mentioned were considered by the authors and found to be insignificant; however, there is nothing in the report to show this.

Jan 5, 1924

By G. R. St. Pierre, S. W. Gilby

The equilibrium vapors established over Fe-Cr-Ni alloys containing up to 50 pct Cr at 1600°C were determined by collecting the effusate from thoria Knud-sen cells. From these data, the activities of iron and nickel in the ternary alloys have been calculated. In a separate set of measurements, a mass spectrometer was used to determine the activities of the three components in a series of Fe-Cr-Ni alloys. In binary Ni-Cr melts, the activity coefficient of chromium referred to pure solid chromium as standard state is less than one at low chromium contents but is greater than one for melts containing more than 30 at. pct Cr. For Ni-Cr melts containing less than 10 at. pct Cr, In ?Cr = 0.15-0.92 N2. Ternary activity diagrams for Fe-Cr-Ni alloys are presented. In iron-rich alloys, the interactions between the three components are negligible; however, in nickel-rich alloys, the three principal interactions have significant positive values. THE activities of components in binary Fe-Ni alloys have been measured both in the solid solution1-3 and liquid solution4-6 temperature ranges. The determination for Fe-Ni melts have been made by three different methods: transpiration,4 Knudsen-cell effusion with analysis of an accumulated condensate,&apos; and Knudsen-cell effusion with direct measurements of relative component intensities by mass spectrometric methods.6 The results obtained by the three different methods in three different laboratories are in excellent agreement and considerable confidence is placed in the activity coefficients for Fe-Ni melts. At 1600°C, the activity coefficients in dilute solution are ?°Ni = 0.66 and ?oFe = 0.40 for the pure liquid components as standard states. Measurements made on solid solution Fe-Cr alloys7-10 indicate that the component activities are slightly greater than ideal. The measured activities in iron-rich Fe-Cr liquid alloy11-16 indicate almost ideal behavior for this system. The recommended activity coefficient of chromium in dilute solution in liquid iron at 1600o C, ?oCr, is 1.18 when referred to pure solid chromium as standard state and 1.04 when referred to pure undercooled liquid chromium as standard state." The conversion factor of 1.14 is based on a melting point of 1857°C and an enthalpy of melting of 4047 cal per g at. for chromium.21,37 The activity coefficient of iron in dilute solution in liquid chromium has not been measured. Activity measurements on solid Ni-Cr alloys have been made by several investigators.17-20 During the review of this manuscript, Fruehan12 published the results of a study on liquid Ni-Cr alloys at 1600°C. He used galvanic cells22 with ZrO2(CaO) as the electrolyte and Cr/Cr2O3 for the reference electrode. His results indicate that ?oCr in nickel at 1600°C is about 1.01 when referred to pure solid chromium and about 0.89 when referred to pure undercooled liquid chromium as standard state. The activity coefficient of nickel in liquid chromium is unknown. The compositions of vapors freely evaporating from some molten Fe-Cr-Ni alloys have been measured by Lyubimov, Granovskaya, and Berenstein.23 Their results, combined with known vapor pressures, indicate strong positive deviation for chromium in iron-rich alloys and strong negative deviation for chromium in nickel-rich alloys. EXPERIMENTAL PROCEDURES This research was undertaken to determine the activities of components in ternary Fe-Cr-Ni melts containing up to 50 at. pct Cr. At the initiation of the research, we decided to use a Knudsen-cell method wherein a portion of the effusing vapor is condensed on a cold plate.&apos; The composition of the equilibrium vapor for each alloy composition is determined in this method by holding the system under constant conditions for a period of time sufficient to collect enough condensate on the cold plate for chemical analysis. The activities of components in ternary alloys can be calculated from such vapor composition determinations by Eq. [1].24

Jan 1, 1970

By D. Muraoka

Introduction Soda ash, anhydrous sodium carbonate, is produced from underground trona deposits occurring in the Green River Basin of southwestern Wyoming. Stauffer Chemical Co. of Wyoming, a jointly owned subsidiary of Stauffer Chemical Co. and Rocky Mountain Energy Co., mines the trona and processes it into high-purity soda ash. Stauffer Wyoming has been in operation since 1962 with a current production capacity of about 1.8 Mt (2 million st) per year of soda ash. The refinery has five parallel operating trains using the monohydrate process which is a series of chemical processing unit operations described below. Screening and Crushing The mined trona is brought to the surface in two counterbalancing ore skips. The ore is initially screened with refinery feed (less than peagravel size material) entering the process. Oversize is conveyed to an outdoor stockpile. Ore is recycled from under the stockpile via cone feeders as the refinery needs require. The ore is conveyed to hammer type crushers and screened. The refinery feed enters the process and the oversize is recycled to the crushers. Calcining The first step in refining trona to soda ash is calcining the trona ore. This is accomplished in concurrent flow, rotary kilns that are direct fired with natural gas. [2 (Na CO NaHCO 2H O) Heat 3Na CO + 5H20 + CO 2 3~3~ 2 ~~2 32] The trona ore is fed to the kiln at the burner end and is intimately mixed with the hot exhaust gases from the burner. Direct contact with the flame is avoided. The ore moves down the kiln by gravity and rotation aided by the kiln&apos;s internal lifters. The exhaust gases are cleaned to 99 + % particulate removal and discharged to the atmosphere. Dissolving the Calcined Trona The calcined trona is conveyed from the kiln discharge to a rotary drum dissolver where it is mixed with water and weak solution (unsaturated solution of calcined trona in water). The calcined trona is soluble whereas the impurities, primarily shale, are insoluble. The discharge from the dissolver is a slurry containing saturated solution (about 30% dissolved calcined trona in water), some undissolved calcined trona, insoluble impurities, and organic impurities. The dissolver discharge enters a rake classifier that makes the first solid/liquid separation in the process by removing the heavy undissolved material from the saturated solution. This undissolved material is conveyed to a second rotary drum dissolver and mixed with water to dissolve any remaining calcined trona. The secondary dissolver discharges to a second rake classifier that separates the solids from the liquid. The solids are now primarily insoluble impurities with very little unrecovered calcined trona. These wastes are conveyed to evaporation ponds for disposal. The liquid from the secondary rake is recycled to the primary dissolvers&apos; weak solution system. Returning to the primary rake classifier, the saturated solution which contains suspended insoluble muds is pumped to a thickener. Flocculant is added to aid settling of the suspended muds. The flocculated muds are collected at the bottom of the thickener and pumped to vacuum cloth filters. The adhering saturated solution is separated from the muds that remain on the filter cloth. The recovered solution is returned to the dissolvers&apos; weak solution system. The muds are reslurried and pumped to the evaporation ponds for disposal. Saturated solution, containing some suspended insoluble muds along with the organic impurities, overflows the thickener. Filtering the Saturated Solution The saturated solution overflowing the thickener enters a holding tank where it is pumped to a bank of pressure leaf filters. The suspended muds are captured on the filter leaves while the cleaned saturated solution is pumped to polishing filters. The polishing filters are also leaf pressure type, intended to remove any suspended solids that may pass the primary filters. Organic impurities are removed with activated carbon. The purified solution is now free of insoluble muds and has most of the organic impurities removed. Crystallizing and Drying the Monohydrate The purified saturated solution is pumped to evaporative crystallizers. The solution is circulated from the crystallizer vessel through a heat exchanger. Indirect contact with steam in the heat exchanger causes the saturated solution to boil, thus crystallizing the soda ash in its monohydrate form. Slurry crystal density is maintained in the crystallizer by simulta¬neous feed of fresh saturated solution and drawoff of the slurry.

Jan 1, 1986