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By Thomas R. Smith

This paper covers oil shale resources in those countries that border the Pacific Rim. The major known resources around the Pacific Rim occur in the Western United States, Australia, the People's Republic of China, (PRC) and the Thailand/Burma region. The location of these deposits is shown in Figure 1. In 1965, the U.S. Geological Survey estimated world oil shale deposits of over 4 quadrillion tons having a potential oil yield of over 2 quadrillion barrels. If all this were extracted, it could meet the world's entire energy needs far into the future. However, the Survey also estimated the spent shale waste could cover all of the surface of the world to a depth of about 10 feet. Thus, for this and many other technical and economic reasons, it does not appear to be feasible to develop a large portion of the world's oil shale resources in this century; nor will shale in itself solve our energy problems. Nevertheless, shale oil and other ' synthetic fuels are expected to play an important role in new energy supplies in the longer term. WHAT IS OIL SHALE OR SHALE OIL? The term "oil shale" is sometimes a misnomer, in that the rock is often more of a limestone or siltstone than a shale. The common link between resources termed “oil shale" is that they all contain an insoluble substance cal led kerogen (which is from the Greek words for waxmaking). Kerogen is a form of organic carbon derived from a variety of plants ranging from algae to higher plants. When heated sufficiently, the kerogen generates hydrocarbons called shale oil, a form of synthetic crude oil that in most cases is lower in hydrogen content than conventional crude oil. The amount of oil in oil shale is relatively small --roughly 10 percent (by weight) in the richer shales. To upgrade this synthetic oil to usable products, additional processing is necessary. This brief sketch gives an idea of what this different, but significant, form of hydrocarbon is like. ENVIRONMENTS OF DEPOSITION Most oil shale deposits fall into three environments of sediment deposition: 1ake (called lacustrine), sea (marine) and river (fluvial-deltaic). In each case, the deposition of oil shales took place in quiet water environments where plant life, particularly algal plants, could flourish and, after dying, be deposited in unoxygenated water where the kerogen precursors would be safe from destruction by oxidation. The oil shales that were deposited in large lake basins (lacustrine) have attracted the most attention for development over the years. They often have multiple seams, deposited in a cyclic nature with extensive areal distribution and rapid vertical changes in kerogen content. Grades are moderate to high, ranging from 80 to 200 liters per tonne. Rundle in Australia and the Piceance Creek Basin in Colorado are examples of this type. Both deposits represent large volumes of oil shale in small areas which could provide the large volume of feedstock needed for future commercial operations. The stratigraphic sections of these two deposits feature thick oil shale seams with average grades of 80 - 125 liters/tonne conducive to both open pit, and underground operations. However, the rock strength of the Rundle shale is not sufficient to - support underground mining. On the other hand, the Colorado deposits, being more carbonate in nature, are sufficiently strong to support either type of mining depending on the overburden to ore ratio. These latter types of deposits will likely provide the first target for development of a commercial industry. The marine type is characterized by extensive areal distribution with relatively thin seams. The grades are generally low to moderate, ranging from 50 to 120 liters per tonne. The marine oil shales are common worldwide, and their attractiveness for mining is dependent on the overburden to ore ratio. Because of their widespread areal distribution, their in situ resources can be quite large. The Toolebuc Formation in Central , Queensland, Australia is a good example of this type of deposit being 7-10 meters thick over an extensive area. The Julia Creek deposit with its favorable overburden-to-ore ratio is being studied for possible development. In a fluvial-deltaic environment, there are many small lakes or bogs associated with rivers in which a very pure type of oil shale called torbanite could form. Torbanites are very high grade containing up to 75 percent hydrocarbons. The known occurrences are generally small lenticular deposits associated with coal seams. Even with the high grades, it is not likely that any of the known deposits would warrant commercial development because of their small size. The torbanite deposits in New South Wales, Australia were processed prior to World War I1 near the town of Glen Davis. However, today's known resources of this type are not large enough to warrant a commercial plant.

Jan 1, 1982

By C. E. Birchenall, W. Batz, H. W. Mean

AT temperatures between 1095' and 1347ºC, 13 runs have been made on the diffusion of silicon in iron. In two of the runs the couple compositions were entirely within the loop of the Fe-Si system; the base alloys contained 0.0 and 1.0 wt pct Si. The other runs in which the couples consisted of a 2.3 wt pct Si alloy welded to a 3.7 pct Si alloy were a phase throughout. The alloys were made by melting electrolytic iron and commercially pure silicon. Trace impurities were not determined. The butt welded couples were diffused in an inert atmosphere of argon or hydrogen. After cooling, cuts of two mils or greater thickness were machined parallel to the weld interface. The chips were analyzed for silicon. When the concentration and distance data were examined on the conventional probability plot,' no marked variation of the diffusion coefficient with concentration was indicated over the narrow composition ranges employed. Therefore, a single diffusion coefficient is recorded for each run in Table I. The temperatures and atmospheres of the diffusion anneal are listed along with the compositions of the base alloys. For a iron the silicon diffusion coefficient is given by the equation: D = 0.44 e-48,000/RT where R is the gas Constant and T, the absolute temperature. However, since the scatter in the data is fairly large, the activation energy may be in error by as much as 6000 cal per g-atom. The two ? iron points do not permit estimation of the activation energy with any reasonable certainty. They do indicate that the coefficients reported by Smithells2 and Jost,3 based on the work of Fry,4 are much too high. Although very dilute solutions in iron of manganese,5 nickel,8 cobalt,7 and molybdenum8 give dif- fusion coefficients quite close to those obtained for self-diffusion in iron, the silicon values are considerably higher, though of the same order of magnitude. This seems to be consistent with the fact that the silicon atom is the only one of those listed here which is appreciably smaller than iron. The authors are grateful to the Office of Naval Research for their support of this work under Contract N6ori-47, Task order IV, Project NR 031-184, to J. K. Stanley and the Westinghouse Research Laboratories for the silicon alloys used, to several steel companies for the silicon analyses, and to C. Wells, of the Metals Research Laboratory, Carnegie Institute of Technology, for numerous suggestions during the course of the work. References 'C. Wells: Atom Movements (1951) Chapter 2. A.S.M. 2C. J. Smithells: Metals Reference Book (1949) p. 405. Interscience. Pub. Co. 3W. Jost: Diffusion (1952) p. 223. Academic Press. 4 A. Fry: Stahl und Eisen (1923) 43, p. 1039. T. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 315. "C. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 329. 7M. F. Hawkes and R. F. Mehl: Trans. AIME (1947) 172, p. 467; Metals Technology (August 1947). .J. L. Ham: Trans. A.S.M. (1945) 35, p. 331.

Jan 1, 1953

By O. Bergmann, R. E. Lueders, R. R. Ellefson, H. M. Brennecke, D. S. Davies

A new hydrometallurgical process has been developed to recover copper from sulfide ores. Copper is leached in a staged reactor system utilizing nitric and sulfuric acids at 105OC. Iron is removed from the pregnant liquor as a jarosite, and cathode copper is electrowon directly from the purified pregnant liquor. The spent electrolyte is recycled. Nitrogen oxides evolved from the leach are reconverted to nitric acid and are also recycled. Sulfur is rejected as So, jarosite, and gypsum. The process is highly versatile and can recover precious metals, molybdenum, and zinc when these elements are present. Continuous, integrated, semi-pilot plant operations using chalcopyrite ores demonstrated 99% copper leaching and production of cathode grade copper. Economic evaluation shows that the process is competitive with pyrometallurgical and other hydrometallurgical processes.

Jan 1, 1982

By K. C. Ko, M. K. McCarter

Experimentation with seismic velocity measurements at Kennecott Copper Corp.'s Bingham mine disclosed that some recognized slide areas are characterized by low velocity profiles. A new traverse technique employed during the investigation allows rapid and precise measurements of a quantity referred to as "apparent velocity." This value is a weighted average of the actual velocity in the overbreak zone near the surface and in the intact rock at depth. The low points on the velocity profile are apparently the result of lower actual velocities and deeper overbreak in less competent material within the slide zones. Experience verifies the usefulness and practicality of the technique in delineating adverse areas prior to detectable failure. The technique may be employed as a rapid and economic means of slope stability surveillance in large open pit mines.

Jan 1, 1973

By G. D. Oxx, L. F. Coffin

The concept of using a phase that is liquid at service temperatures as a component of coatings for refractory metals has been described. The liquid, an alloy of gold and silicon, is retained on a molybdemum surface by a capillary system made of molybdenum disilicide. The coating has the advantage of good thermal shock and has a self-henling chracteristic. In order for highly stressed structures to exceed a service temperature of 2000°F, it has become apparent that a development that does not depend on the traditional iron, cobalt, or nickel-base alloy is needed. Alloys of the refractory metals, i.e., molybdenum, tungsten, tantalum. niobium (colum-bium), and rhenium are potentially useful at extremely high temperatures that more conventional alloys would never be expected to achieve. A new alloy of molybdenum has become available that has a 100-hr rupture strength of 35,000 psi at 2200°F.1 As a result of this work, it may be assumed that a material with adequate mechanical properties at 2200?F is now available. Unfortunately, this alloy and all other known alloys of the refractory metals suffer from not being; serviceable in an oxidizing atmosphere for a very long time. In order to permit general use of refractory metals at high temperatures, it is necessary to prevent destructive oxidation by appropriate alloying or by protective coatings. The liquid phase coating reported here is representative of a concept for the protection of metals that permits higher service temperatures and introduces a new group of materials for selection as coatings. Coating Requirements—Service conditions that represent potential applications for refractory metals vary considerably: however, it is possible to consider two conditions that are usually present. The refractory metal1 component must be heated to the service temperature at least once and usually frequently. When a solid coating is used, usually the coating and basis metal do not have the same coefficient of expansion. This difference causes thermal stress in the coating that is aggravated by rapid heating and cooling and eventually causes coating failure. The second consideration is the probability that there will be damage to the coating by some environmental condition. In jet engines, for example, it is expected that large particles, stones, metal parts, and so forth, will strike a bucket at high speed and cut a hole in the coating. In addition to the above considerations, the coating must also have other fundamental properties. Obviously, it must be oxidation resistant. In addi- tion, it must prevent permeation of oxygen and subsequent oxidation of the basis metal at the interface. Also, diffusion of the basis metal to the outside surface and subsequent oxidation there must be prevented. Finally, the coating must not react with the basis metal to form a weak bond at the interface. It should be noted that the coating need not support a load: it must only remain intact. Liquid Phase Coating Design Factors—In the use of a liquid as a principal coating constituent, it would be expected that the two service conditions mentioned above would be satisfied. A liquid would flow under the influence of the thermal strain developed by coating-basis metal expansion mismatch such that failure from this source would not be expected to occur. It is also probable that the ability of a liquid to flow would provide a self-healing effect. Thus, damage caused by particles in the atmosphere would be repaired. A third advantage is evident in that vapor pressure rather than melting point limits the service temperature. This latter advantage permits use of low melting but oxidation resistant metals such as gold or copper that would be quite useless if the solid state was required. A low viscosity liquid alone. however, is a totally unsuitable coating because it will simply flow off a component, particularly under the influence of a high acceleration field. A method of preventing liquid loss must be devised. In this case, it is desired that the liquid have a low viscosity so that it may easily flow into flaws; thus, raising the viscosity is not a satisfactory solution. One other inherent difficulty is caused by the high mobility of atoms in the liquid state as compared to the solid state. Because of this mobility, it would be expected that gases would diffuse more rapidly through a liquid. It is also probable that the solubility of oxygen in the liquid would be comparatively high. These factors would tend toward rapid permeation of oxygen and oxidation of the substrate. It is most reasonable that this problem could be solved by incorporating a solid phase, which is impermeable to gases, as a component of the coating. To overcome the tendency of a liquid to flow easily, it is possible to use surface tension to advantage. If the surface were made up of a large number of capillary tubes of sufficiently small diameter, then surface tension would hold the liquid even against the acceleration of a centrifugal field.

Jan 1, 1961

By L. O. Brockway, W. C. Bigelow, J. A. Amy

Specimens of Inconel-X alloy solution-treated at 2050°F and aged for periods of 1, 10, 100, and 1000 hr at 1200°, 1400°, and 1600°F have been examined by electron microscopy and by electron and X-ray diffraction. Four minor phases were identified: titanium nitride, niobium nitride, an M23C6 complex carbide, and the intermetallic ? phase. The two nitrides were found in all of the aged specimens and in the solution-treated alloy, the y' phase formed at all aging temperatures, while the M23C6 carbide formed only on aging at 1200° and 1400°F. Variations in the hardness, rupture strength, creep strength, and yield strength of the alloy have been shown to be related to variation in the size and distribution of the particles of the y' phase within the matrix grains of the alloy, with maximum values of these properties occurring when there is a maximum amount of the phase present and a fine state of dispersion of the particles prevails. THE nickel-chromium alloys containing titanium and aluminum are widely used in applications requiring high strength at elevated temperatures. Studies on relatively simple ternary and quaternary alloys'-4 have indicated that the favorable high-temperature properties of these alloys are related to the precipitation of an intermetallic ?'-phase having a structure based On that of the Ni3A1 phase of the nickel-aluminum system. The present investigation was undertaken to identify the minor phases and to study the microstructural changes occurring in one of the more complex commercial alloys as a result of aging in the service temperature range, with particular emphasis on investigating the role of the ?' -phase. The microstructural changes were studied by electron microscopy and the minor phases were identified by X-ray and electron diffraction. MATERIALS AND METHODS Inconel-X alloy was selected for this investigation because the previous studies of Frey, Freeman, and white6 provided extensive information on the variations in metallurgical properties of this alloy resulting from high-temperature aging treatments. Specimens aged 1, 10, 100, and 1000 hr at 1200°, 1400°, and 1600°F were made available for the present use. These were taken from 1-in. round-bar stock of a commercial heat having the following weight composition: 0.04 C, 0.56 Mn, 6.59 Fe, 0.007 S, 0.38 Si, 0.03 Cu, 73.22 Ni, 14.97 Cr, 0.78 Al, 2.38 Ti, and 1-02 Nb. They were solutjon-treated at 2050 for 4 hr and then water-quenched prior to aging. Powder X-ray diffraction patterns were obtained from insoluble minor phases which were separated from the alloys by digestion in the reagent of Mahla and Nielsen.6 Back-reflection patterns were obtained from electrolytically polished surfaces of the bulk search to detect the ?'-phase' Cu-K a radiation was used in both cases. In the electron-diffraction studies, the general method developed by Heidenreich, Sturkey, and

Jan 1, 1959

By H. I. Aaronson

Isothermally formed plates of proeutectoid a, lengthen at approximately the rates predicted by the Zener-Hillert equation, indicating that their lengthening kinetics are controlled by the volume diffusion of chromium in the ß matrix. Solution annealing treatments in the vicinity of the transus introduce a second mode of transformation, in which the lengthening rate is at least 1.8 x 104 faster than predicted by this equation. Little or no volume diffusion appears to accompany the latter transformation. The Presence of oxygen is evidently a Prerequisite for the occurrence of this reaction. X HE effects of thermal history prior to the initiation of transformations which proceed by nucleation and diffusional growth are currently evoking considerable interest. The rate of nucleation (but not the rates of growth) of pearlitel and of bainite,2 and the over-all rates of aging reactions in Al-cu3 and Al-si4 alloys have been shown to be appreciably dependent upon thermal history in the solid-solution region"' or in the two-phase region prior to the onset of pre~ipitation.3,4 In none of these reactions, however, was the transformation mechanism changed by variations in the temperature-time path used to reach the reaction temperature. Preliminary experiments reported by M. K. McQuillan5,8 and a systematic investigation by Farrar and Margolin7 have disclosed that the transformation behavior of hypoeutectoid Ti-Cr alloys is considerably more sensitive to thermal history. Qualitative evidence strongly suggests that not only the rate of nucleation but also the rate of growth and even the mechanism of the ß — a reaction can undergo remarkable changes when a solution annealing treatment in the vicinity of the ß/a +ß, or transus temperature, is interposed between a high-temperature solution anneal (conventionallq at 1000°C) and the isothermal reaction treatment. The present investigation was undertaken in an attempt to ascertain the nature and origin of these effects. Study of the changes in the kinetics and morphology of the ß - a, reaction produced by varialtions in thermal history was the primary means employed for this purpose. EXPERIMENTAL PROCEDURE The compositions of the alloys used in this in~esti~ation are given in Table I. These alloys were homogenized for 5 days at 1050° C in evacuated (2 x 10 -5 mm of Hg), zirconium-gettered fused quartz capsules. The capsules themselves were enclosed in a porcelain chamber evacuated with a mechanical pump during the homogenization anneals. Upon completion of homogenization, the alloys were cooled to room temperature and then reheated to 550°C for 3 1/2 days in order to transform the alloys to a finely divided mixture of a and TiCr2, and thus provide an approximately constant initial mi-crostructure. Individual specimens were sealed in evacuated and internally gettered Vycor capsules and heat treated as previously described.8,9 EXPERIMENTAL RESULTS Ti-10.64 Pet Cr. This investigation was largely performed on the 0.64 pet Cr alloy. The "base"

Jan 1, 1962

By H. S. Coe

ENGINEERS have long recognized the desirability of correlating the data obtained from small-scale slime-settling tests with commercial work as carried on in large tanks. This need, though most apparent in designing new installations, frequently arises also in existent plants, since a large range of experimental work can be performed without interfering with regular operation. GENERAL SETTLING PHENOMENA In order to develop rational methods of laboratory testing, it becomes necessary to study the general phenomena of settling. Since it was desired to give the public the benefit of these methods at as early a date as possible, together with the knowledge of the general principles of slime settling necessary for a clear understanding of the laboratory tests, we have ventured to discuss the subject in so far as brought out by the work which we now have under way. We realize that certain of our preliminary conclusions may be subject to modification, but it seems probable that, with but few exceptions, the general laws enunciated will cover the settling behavior of all pulps encountered in metallurgical plants. However, it must be recognized that there is still a vast amount of work to be done upon certain phases of the subject; therefore, at this time we will attempt only a discussion of the behavior of ore pulps during the process of settling or dewatering, under certain given conditions. The laws and principles controlling these conditions are not fully established, so that a complete discussion of them will not be attempted in this paper. In metallurgical practice, slime pulp consists of water, finely divided sand

Jan 3, 1916

By E. A. Nichols

The purpose of this paper is to present a contour map that shows the geographical variation in geothermal gradients in the Mid-Continent and Gulf Coast oil fields. Introduction Frequently there arises the need for an estimation of the temperature to be expected at a predetermined depth in working with a wildcat or in deepening old production into 'Ones that are relatively unknown. The study of geothermal gradients in oil fields has been made previously by many investigators. One of the pioneers in this work was C. E. Van Orstrand,' who, as well as most of the other investigators, was primarily interested in the relation between temperature and depth in a given locality. Between 192r and 1929, American Petroleum Institute Research Project NO. 25 fostered a thorough study of earth temperatures.2 K. IV. French did some work in California, the results of which were published in 1939.3 In most of these studies, an attempt was made to correlate temperatures in a rather localized area. This paper will show the results of an attempt to correlate temperature gradients over rather large Portions of the Mid-Continent and Gulf Coast area. Method of Obtaining Data It has been found that for complete thermal equilibrium to be established in a well, the well must stand undisturbed for a period of several hours to several weeks, depending upon the way the well was produced prior to the shut-in period. The data in this paper were obtained in conjunction with running pressures in wells or in taking samples of reservoir fluid. Glass maximum recording thermometers were used in all but a few instances. The wells had been shut in from one hour up to I. or 12 days. Since the wells were normal producing wells, some of the shut-in times undoubtedly were insufficient for complete thermal equilibrium to have been established and the temperatures measured do not necessarily represent the true earth temperatures. They do represent the temperature conditions that will be encountered in a well that is producing oil. The data, therefore, can be useful in working with or in estimating the temperatures to be expected in producing reservoirs. In obtaining a thermal gradient by dividing the difference in temperature of the formation and the mean annual surface temperature by the depth of the formation, one is assuming the depth-temperature line to be straight. Depth-temperature curves are almost straight lines (Fig. I). However, on close examination of accurate data, a slight curvature usually is observed. Most wells yield curves with slopes increasing with increasing depth. These curves are believed to be from wells that are in and are underlain by sedimentary material. Some few curves have slopes that decrease with increasing depth. These curves are believed to be from wells that are underlain rather closely by granite or some other igneous rock. Most investigators

Jan 1, 1947

By E. A. Nichols

The purpose of this paper is to present a contour map that shows the geographical variation in geothermal gradients in the Mid-Continent and Gulf Coast oil fields. Introduction Frequently there arises the need for an estimation of the temperature to be expected at a predetermined depth in working with a wildcat or in deepening old production into 'Ones that are relatively unknown. The study of geothermal gradients in oil fields has been made previously by many investigators. One of the pioneers in this work was C. E. Van Orstrand,' who, as well as most of the other investigators, was primarily interested in the relation between temperature and depth in a given locality. Between 192r and 1929, American Petroleum Institute Research Project NO. 25 fostered a thorough study of earth temperatures.2 K. IV. French did some work in California, the results of which were published in 1939.3 In most of these studies, an attempt was made to correlate temperatures in a rather localized area. This paper will show the results of an attempt to correlate temperature gradients over rather large Portions of the Mid-Continent and Gulf Coast area. Method of Obtaining Data It has been found that for complete thermal equilibrium to be established in a well, the well must stand undisturbed for a period of several hours to several weeks, depending upon the way the well was produced prior to the shut-in period. The data in this paper were obtained in conjunction with running pressures in wells or in taking samples of reservoir fluid. Glass maximum recording thermometers were used in all but a few instances. The wells had been shut in from one hour up to I. or 12 days. Since the wells were normal producing wells, some of the shut-in times undoubtedly were insufficient for complete thermal equilibrium to have been established and the temperatures measured do not necessarily represent the true earth temperatures. They do represent the temperature conditions that will be encountered in a well that is producing oil. The data, therefore, can be useful in working with or in estimating the temperatures to be expected in producing reservoirs. In obtaining a thermal gradient by dividing the difference in temperature of the formation and the mean annual surface temperature by the depth of the formation, one is assuming the depth-temperature line to be straight. Depth-temperature curves are almost straight lines (Fig. I). However, on close examination of accurate data, a slight curvature usually is observed. Most wells yield curves with slopes increasing with increasing depth. These curves are believed to be from wells that are in and are underlain by sedimentary material. Some few curves have slopes that decrease with increasing depth. These curves are believed to be from wells that are underlain rather closely by granite or some other igneous rock. Most investigators

Jan 1, 1947

By R. W. Raymond

This paper is simply a summary, prepared at the request of the Council of the Institute, of the report of Mr. Albert Ladd Colby, of South Bethlehem, Pa., presented at the New York meeting (October, 1896) of the Association of American SteelManufacturers, on " The Advisability of the Endorsement by the Association of the United States Standard Gauge, approved by Act of Congress, March 3, 1893, to the Exclusion of the Birmingham Gauge, the .Brown and Sharpe, and all Others:" a subject on which, at the Pittsburgh meeting (April, 1896) of the said Association, Mr. Colby had been appointed as a committee. The report favors the adoption, not of the United States standard gauge to the exclusion of others, but of a decimal system of gauging all materials in thousandths of an inch, thus doing away entirely with arbitrary gauge-numbers running in inverse order to the actual thickness. The American Institute of Mining Engineers originated this movement. The report of its committee on a standard wiregauge, presented in October, 1877,* recommended the abandonment of the system of fixed gauges for commercial use, and of the system of representing the diameters and sizes by numbers, and the adoption, in lieu thereof, of the system of expressing sizes in thousandths of an inch or fractions of a millimeter, and the use of the micrometer-gauge as a means of measuring sizes. In 1892 the American Society of Mechanical Engineers appointed a similar committee, and corresponding action was

Jan 1, 1898

By H. B. Bell, P. C. Lidster

A study has been made of the use of ThO2-Y2O3 solid electrolytes to determine activity of chromium in Fe-Cr and Ni-Cr alloys in the temperature range 1300° to 1700°K. This method has been shown to give results which agree with the best vapor pressure measurements. SEVERAL investigations1"5 have been made of chromium activities in Fe-Cr alloys. Most of these have been made by vapor pressure measurements using knudsen cell techniques while one has been made using gas equilibration with H2/H2O gas mixtures. In the present investigation electromotive force measurements have been made on this system using a thoria yttria solid electrolyte. This system was -chosen to establish the technique of measurement at low oxygen potentials, before extending it to Fe-Ni-Cr alloys. The cell used was Pt Cr • Cr2O3 ilThO2 • Y2O3 llalloy • Cr2O3 IPt Since the oxygen pressure of the chromium-chromic oxide mixture lay in the range 10"19 to 1027 atm in the temperature range investigated, thoria yttria electrolytes were used. It was soon found during the investigation that considerable care was required to prepare satisfactory electrolytes and a study was made to find the best method of preparing pellets of TI1O2-Y2O3 solid solution of as near theoretical density as possible. Various compositions in the range 2 to 15 mole pct Y2O3 were studied but the experimental measurements were made with electrolytes containing 4 to 5 pct Y2O3. The method of preparation finally adopted was to use thorium oxalate and yttria as raw materials. The thorium oxalate was decomposed at 900°C for 6 hr to give a reactive powder. This powder was then mixed with the appropriate amount of yttria and ground in an agate mortar for about 4 hr. The powder was moistened with absolute alcohol as a lubricant and pressed in a metal die at a pressure of 7 tons per sq in. The pellets were then heated at 1100°C for 24 hr followed by 24 hr at 1250°C. After this firing cycle the material was reground and repelleted and again fired at 1100° and 1250°C followed by heating for 7 days at 1600°C. It was found in later experiments that a further firing of 4 hr at 2000°C improved the density further and gave pellets of only 2 pct porosity. After firing, the pellets were polished on emery paper and finally with the 2 µ diamond paste. The polishing was followed by a final firing of 24 hr at 1500°C. Investigation showed that this final treatment minimized reaction between the electrolytes and chromium oxide. It was believed that this was because of a lowering of the surface energy of the electrolyte surface. Two types of investigation were carried out to check that the pellets were satisfactory oxygen ion elec-

Jan 1, 1970

By F. W. Bloecher

DETERMINATION of the surface area of finely divided minerals is of interest to mineral engineers engaged in flotation, comminution, and de-watering studies. In the industrial minerals field, many materials are classified as to fineness according to their specific surface (surface area per unit weight). A method of surface area determination has been tested and used in the Richards Mineral Engineering Laboratories at M.I.T. It involves low temperature krypton adsorption measurements using the technique described by Beebe.' During the past fifteen years a number of new surface measurement techniques have been developed. Those that are broadly applicable to materials dealt with by mineral engineers include the permeability method in which a gas or liquid is passed through the sample, and the low temperature gas adsorption methods first described by Brunauer, Emmett, and Teller."" Efforts to make surface determinations from size distribution curves have long been attempted"."." but because of the uncertainty of sub-sieve size distribution and inaccuracies in screen analyses, the method is at best only a rough approximation. The most widely used gas adsorption method utilizes nitrogen gas." Nitrogen adsorption, however, is not particularly suited as a tool for most mineral engineers because the method is not applicable for surface determinations on coarse materials, that is, materials coarser than approximately 150 to 200-mesh. Other gases have been used in mineral engineering studies, particularly ethane."' lo The use of ethane gas, however, involves .a technique that is too sensitive for most mineral engineering work. The permeability method of surface area determination has the disadvantage of not being sensitive enough to detect the surface represented by minute cracks, the so-called internal surface of a particle. The low temperature krypton adsorption method described by Beebe1 utilizes apparatus and techniques that are essentially the same as those used in the ethane adsorption method."1° The surface area is calculated by the B.E.T. method."-' The krypton adsorption technique is particularly suited to the needs of the mineral engineer because: (1) The method can be used for making surface area measurements of rather coarse materials (35 to 48-mesh), as well as extremely fine materials, such as clays or colloidal slimes with specific surface that might be as high as 20 to 30 mb er g. (2) The use of krypton gas offers the advantage of low saturation pressures (2-3 mm) at the conveniently obtained liquid nitrogen temperature. Therefore the krypton vacuum system need not be designed to measure or withstand internal gas, pressures above one atmosphere as is the case with the nitrogen gas method. (3) The krypton technique offers the safety feature of employing liquid nitrogen, as contrasted to the ethane technique in which liquid oxygen is required. Furthermore, ethane vapor pressure at liquid oxygen temperatures is low (about 10 microns), and a high sensitivity McLeod gage is required for pressure readings. (4) The measurement technique with krypton gas is much simpler and faster, and the apparatus is less elaborate than that required with either nitrogen or ethane gases. Apparatus A krypton surface measurement apparatus like that used at M.I.T. is shown in Fig. 1. It is constructed of pyrex glass. A vacuum is maintained by two mercury diffusion pumps in series backed by a mechanical vacuum pump."' The vacuum thermocouple gage is used for checking the vacuum within the system. This type of gage is quite sensitive down to a pressure of 1 micron of mercury," but may be used to indicate pressures much lower than that

Jan 1, 1952

By Blair R. Benner

This paper describes the installation and operation of a Texas Nuclear on-line silica analyzer (NOLA) coupled with a Leeds and Northrup Microtrac particle-size monitor (Microtrac) at U.S. Steel's Minntac taconite concentrator. An automatic sampling system provides the NOLA with samples of final concentrate. After the sample is analyzed for silica by the NOLA, it is pumped to the Microtrac for size and surface area measurement. A sample is analyzed every six minutes, providing the control room with the silica concentration, the percent passing 270, 400, and 500 mesh, and an equivalent Blaine surface area number. When fed a slurry of final concentrate containing between 20 and 70% solids and 5 to 6% silica, the NOLA analysis is within ±0.2% of the wet chemistry silica. The agreement between the Microtrac output and standard screen analyses is ±1.2% at 270 mesh; ±1.5% at 400 mesh, and ±2% at 500 mesh. The poorer disagreement at the finer sizes is mainly due to inaccuracies in screening at 400 and 500 mesh. The agreement between Microtrac surface area a d laboratory Blaine surface area is about 9 ±80 cm 2/g. These instruments provide rapid and reliable feedback information to the concentrator and feed forward information to the agglomerator.

Jan 1, 1984

By A. Azis

The problem of expressing a nation's mineral resources in terms that convey a sense of economic reality poses a great challenge to those charged with keeping government policymakers informed. A model is presented that can be used to simulate and examine the effects of, for instance, differences in levels of output, transportation costs, mining costs or selling prices on the exploitability and expected order of development of new mineral deposits. The model in its present form can be used to screen, as a first cut, the economic from uneconomic deposits in cases where little or nothing is known about them in detail. To date, this has generally been done - reluctantly - by subjective judgments. This model provides an improvement on the "informed opinion" approach, as it forces those who use the model to be both systematic and explicit in their assumptions. Moreover, the procedure is repeat- able and each step can be defended and justified. Implications can be examined of the uncertainty associated with many of the variables. The model is entirely too general to be of use for actual feasibility studies. It is not useful, in the case of speculative or little-known deposits, to provide a model that has an input format more detailed than the information that is likely to be available. Should the user see a need for it, the model can easily be expanded to allow for the input of more detail or more variables.

Jan 1, 1977

By Clarence P. Linville

(Pittsburg Meeting, March, 1910.) IT is recognized that, in all metallurgical operations, the greatest possible uniformity in all conditions is essential to the best results. It is the constant aim of metallurgists to secure this uniformity, and their success in this respect has been in many cases the cause of great advances in the metallurgical processes themselves. Of all such processes, the production of pig-iron in the modern blast-furnace is perhaps the most complex and the most difficult of control. Notwithstanding the great progress of recent years, there is still great difficulty in obtaining anything like uniform conditions and results in the manufacture of pig-iron. The reason is not far to seek. The ores vary in composition and physical properties, often carrying a varying amount of gangue material, unevenly distributed The coke may vary in composition, cell-structure, moisture, hardness, and other properties. The blast, the weight of which far exceeds that of any other constituent, varies in its moisture-content and consequently in its chemical composition ; and its temperature, by reason of the method of heating, is not uniform, but, besides varying from time to time with atmospheric and other outside conditions, has a maximum and minimum for every changing of stoves. Now, with regard to these variations, the modern demand for uniformity has been greatly aided. Chemical analysis has made it possible to select ores so that the composition of the charge can be kept fairly constant; coal may be obtained from a given field, and coked in the same kind of ovens under conditions which . make the fuel practically uniform ; the Gayley

Mar 1, 1910

ROBERT E. TALLY,* Jerome, Ariz. (written discussion ?).-Mr. Sherman's paper, entitled "Measures for Controlling Fires at the Copper Queen Mine," embodies two new and very important features: First, automatic closing of doors communicating with the dangerous area; second, the use of a portable storage-battery fan. His other procedures, such as giving a general fire alarm, getting workmen to the surface, etc., are equally important, but have long been in use in other places. Fire and ventilating doors in connections leading to shafts, air raises, and other large timbered areas, have been in use at other mines; but the method described by Mr. Sherman for operating these doors by compressed air, through a valve on the surface, is, so far as I know, original, and should be installed in every mine where there is danger of fire. Nearly all large mines are now using artificial ventilation, with the result that there are strong air currents in the shafts and other important workings. The most important feature in mine fires is a quick and positive control of the ventilation, for it takes but a few moments for smoke to travel over a large area, with the usual results of suffocation, and destruction of property. A strong air current in an upcast shaft acts as a draft in case of fire, and unless quickly cut off the fire would soon get beyond control. An upcast shaft usually changes to a downcast when large amounts of water are used. Human lives are in more danger from downcast currents, as the smoke travels into the workings.

Jan 4, 1918

By W. C. Ellis, M. E. Fine

WHEN certain binary Fe-Ni alloys are worked cold and then stabilized by a stress-relief anneal, their Young's moduli are nearly invariant over a substantial temperature range determined by composition and work-anneal history.' In the present investigation addition of molybdenum to such alloys (besides increasing the yield strength) was found to diminish the sensitivity of the thermal coefficient of Young's modulus to composition changes. Such alloys are of interest for applications requiring 1 a metal with controlled, low temperature coefficient of Young's modulus and substantial magnetic permeability.' Young's modulus ordinarily decreases with rising temperature. In ferromagnetic alloys a change in modulus on heating due to loss of ferromagnetism modifies the .temperature dependence. Far below the Curie temperature ferromagnetism alters the modulus in two ways: a—Addition of the energy of magnetization, a function of interatomic distance, changes the relation between interatomic energy and distance.' This lowers the modulus in the Fe-Ni and Fe-Ni-Mo alloys of this investigation. b—An applied stress changes the ferromagnetic domain arrangement so that linear magnetostriction contributes to the strain and further lowers the modulUs.~ Since in the alloys of this investigation both effects lower the modulus, loss of ferromagnetism on heating changes the slope of the modulus-temperature curve in a positive direction. With increasing temperature the slope of the modulus-temperature curve, due to progressive loss of ferromagnetism, becomes less negative, goes through zero (the modulus is minimum), becomes positive, and resumes its normal negative value above the Curie temperature.' The increase in modulus and decrease in curvature in the modulus-temperature curve occurring on work hardening have been attributed to a reduction in effect (b).'. Vn the absence of ferromagnetism work hardening through introduction of residual strains would be expected to decrease the modulus.' Alloy Preparation—Test Methods Four series of alloys having nominal molybdenum contents of 5, 7, 9, and 10 pct and containing 47 to 58 pct Fe (the analyzed compositions are given in Table I) were melted in air and cast as bars weighing from 2 to 6 lb. The charge consisted of electrolytic nickel, Armco iron, molybdenum (99+ pct) or ferromolybdenum (62 pct Mo), manganese, and aluminum as a deoxidizer. The bars were swaged cold to the desired diameters with intermediate anneals. Alloys in this composition range are reported" to be face-centered cubic and ferromagnetic at room temperature. The Curie temperatures" decrease with molybdenum. For example, keeping the Ni/Fe ratio at unity and increasing the molybdenum from 0 to 17 pct decreases the Curie tempera- ture from approximately 500°C to room temperature. (The 17 pct Mo alloy requires quenching to retain a single phase.~) Young's modulus at a series of temperatures from —50" to 100°C was determined by a dynamic method previously described.', " In this method Young's modulus is calculated from the resonant frequency (in this case approximately 50,000 cycles per second) of a rod sample (approximately 2 in. long) vibrating longitudinally in the first mode. The densities of the samples at room temperature, Table I, were determined by the standard method of weighing in air and reweighing in redistilled bromobenzene. The linear coefficients of expansion, Table I, needed to calculate the sample length and density at the temperature of measurement, were obtained by observing the change in length (22" to 100°C) of an 8 in. gage distance with a two microscope cathetometer. The values of density and coefficient of expansion in the few samples checked are independent of treatment to the accuracy reported. This was assumed to be general for all the samples. The modulus values are accurate to &0.05x101' dynes per sq cm. However, values of thermal change in modulus are accurate to 20.005~ 10" dynes per sq cm. Young's Modulus Values at 25°C: The modulus values of O', 5, and 10 pct Mo alloys at 25 °C are plotted in Fig. 1 as functions of nickel. After working cold, the samples were either recrystallized at 950" to 1000°C or given a low temperature stabilizing anneal at 400° C. The 400°C anneal does not reduce the hardness nor cause recrystallization. Annealing at 400 °C does

Jan 1, 1952

By J. S. Crump, C. R. Hocott, A. E. Hoffman

Planning of the efficient operation of a gas-condensate reservoir requires a knowledge not only of the gross phase behavior of the system but also of the equilibrium distribution of the various components between the gas and condensate phases. This equilibrium distribution can be calculated with appropriate equilibrium constants. In this paper are presented equilibrium constants determined experimentally for the oil and gas phases initially present in the same reservoir and for the gas and condensate phases of the gas cap material at a series of pressures below the original reservoir pressure. Also presented is a method for the correlation of the experimentally determined equilibrium constants. The utility of the correlation is demonstrated further by an example of its use in adjusting the equilibrium data to permit their application to another gas-condensate system of similar composition. INTRODUCTION Planning of the efficient operation of a gas-condensate reservoir requires a thorouugh knowledge not only of the gross phase behavior of the particular hydrocarbon system but also of the equilibrium distribution of the various components between the gas and condensate phases. At the initial conditions of reservoir temperature and pressure, the original hydrocarbon materials in a gas-condensate reservoir or in the gas-cap of an associated reservoir exist in a single, homogeneous vapor phase. However, some condensation of hydrocarbons to a liquid phase usually occurs in the reservoir as pressure declines incident to production. Because of this condensation. the produced gas changes composition continuously. The composition of the produced gas, as well as that of the condensed liquid, can be calculated from the composition of the original reservoir material through the application of appropriate equilibrium constants or "K"-values provided these values are known. Equilibrium constants have been used for many years in problems of surface separation of gas and oil and natural gasoline recovery. However, no satisfactory equilibrium data at reservoir conditions have been available for the higher boiling hydrocarbons which acquire abnormal volatility at high pressure and are therefore present in the gas phase in condensate reservoirs. Early work in this field indicated that the behavior of the higher boiling hydrocarbons largely determines the behavior of gas-condensate systems at high pressure.' Consequently, a portable test unit was designed to permit determination of the distribution of the heavier hydrocarbons between the gas and liquid phases of a gas-condensate system. This paper describes the test equipment and presents the results of an investigation of the reservoir fluids from an associated oil and gas reservoir in the Frio formation in Southwest Texas. Also presented is a method for correlation of the experimentally determined equilibrium constants, together with an example of the use of the method in adjusting these data for application to another gas-condensate system of similar composition. FIELD TESTING AND SAMPLING In order to determine the compositions of the reservoir fluids, field samples were secured from two different wells, one completed in the oil zone, and one completed in the gas cap. The oil well was completed through perforations in 51/2-in. casing at a depth of 6,822-6,828 ft subsea. Pressure and temperature traverses made in the well indicated the pressure and temperature to be 3,831 psig and 201 °F, respectively, at a depth of 6.828 ft subsea. Subsurface samples were taken from this well after a four-hour shut-in period.

Jan 1, 1953

By N. S. Keith

No one of the live subjects of the day, to which the attention of the mining engineer and metallurgist should be turned, is of greater practical interest to him than electricity in its applications to various mechanical, chemical, and metallurgical operations. The object of this paper is to call the attention of my fellow-members and associates of the Institute to various new, as well as comparatively old, developments in the science and art of electricity which seem to promise results of advantage. Too many of the comparatively old applications have been neglected by the mining engineer, which; if he had given them a place among his appliances, would have assisted him greatly. The telegraph may be noticed as one. Its. use is, however, confined to a person having skill in the. manipulations of the key, the reading of the alphabet, and familiarity with the sounder. One of the simpler forms-the call-bell-has a range of application far greater as to distance and convenience than the old wire-pull, or the hoarse voice of the windlass-man or the bucket-dumper. A few Leclanehé cells, two or more electric bells, and a mile or more of wire judiciously placed will put the superintendent, at his office, in communication with the foremen of his mills and mines, so that by the aid of a code of signals, great advantages may be gained without necessitating a knowledge of the Morse alphabet, or of the mechanical voice of the sounder. The telephone furnishes a means of communication be-

Jan 1, 1882