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By Foster Fraas

That variations in the humidity of the air and in the moisture content of a mixture of broken solids being separated electrostatically cause trouble is not new.' Much of the reputation for unreliability commonly ascribed to the electrostatic separation processes is probably due to this one factor alone. Some operators dry thoroughly before separating; and while this is good in many instances, there are others in which it is not the remedy for trouble. Some mixtures behave best in very dry air and with the mixtures fed to the separator while hot to reduce the adsorbed water content. On the other hand, an overdried mixture on coming to equilibrium with more humid air, has been known to take up moisture selectively on one family of particles, as of coal in the presence of slate and clay, and give sharper electrostatic separation. From these observations it is concluded that there is a permissible moisture content for a particle and also for the atmosphere surrounding it, if in equilibrium, at which the particle will have a conductivity or cntact potential2-4 that is ideal for electrostatic separation. This permissible moisture content varies between a wide range of limits for the different materials that are are and with the kind of electrostatic separating process used. Water can be present as a result of adsorption and condensation from the atmosphere, as an accumulation before or during mining, or as a residue from a previous process step. The water may exist as a liquid film or as an adsorbed layer of vapor. If the water exceeds permissible limits it must be removed. Its state determines the method. Drying by evaporation is necessary for adsorbed water, for part of the liquid-film water (that is, up to several percent of the dry weight), and for free water in the internal structure. Large water contents may be removed by drainage Or filtration. At just what point mechanical removal should cease and drying by evaporation begin depends upon the method of mechanical removal and its cost. Particles can also be separated according to their differences in dielectric constant when suspended in a liquid of intermediate dielectric constant. Recovery of this liquid presents a a problem' Permissible Moisture The adsorbed moisture on the outer surface of minerals can be quickly removed or replaced. Accordingly, in speaking of adsorbed moisture contents, either that of the solid or that of the surrounding air may be considered, the two values being connected by a distribution coefficient which varies with the temperature. However, such a condition does not necessarily exist in processes where an initially dry material is suddenly introduced into an atmosphere having a partial pressure of water vapor or where a moist material is suddenly introduced into a dry atmosphere. Here the resultant differences in the

Jan 1, 1949

By Edward Martinez

The reactions occurring in the copper segregation process were studied by heating mixtures of chryso-colla, salt, and a reducing agent. The techniques used in this investigation were differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). The initial chloridizing of the oxide copper occurs below 500°C and cupric chloride may be the compound formed. Volatilization and reduction of the copper chloride take place above 550°C, although these reactions do occur to some extent below 550°C. A difference in the distribution of the metallic copper in the reducing agent was found when sodium chloride was used compared to magnesium or calcium chloride. Segregation was obtained with mixtures of cupric oxide, salt, and charcoal with no quartz or silicate present. Preliminary tests indicate that segregation may occur even in the absence of water vapor. The DTA and TGA techniques were found to be of great value in studying these reactions. The copper segregation process is a method for treating oxide copper ores. The ore is heated, most commonly in a kiln, with a reducing agent and a halide salt, generally sodium chloride, to approximately 700°-750°C and held for 30 to 60 min. The addition of the salt results in the migration and reduction of the oxide copper to metallic copper on the surface of the reducing agent rather than in the original mineral structure. The metallic copper can then be recovered by a subsequent leaching or flotation step.1-4 Experimental work in 1923 on oxide copper ores from the Sagasca mines in Chile led to the discovery of the reduction process. It was found that during the reduction of the copper mineral with coal, at about 700°C, the copper migrated to the surface of the coal instead of remaining disseminated in the ore. The unusual behavior of the copper, which caused it to migrate from the ore particles to the coal, was traced to the presence of a small quantity of sodium chloride occurring in the ore. Further experiments with oxide copper ores proved that the presence of a halide, either occurring naturally or admixed with the ore, caused the copper to migrate from the ore particles and to segregate in the charge. The ratio of salt to reducing agent may vary somewhat, but in general 0.5% to 1.5% sodium chloride and 0.5% to 1.0% coal or coke have been mixed with the ore. Less than stoichiometric amounts of salt are required to convert all the oxide copper to a chloride, so that a cycle of reactions appears to be occurring. Several investigations reported in the literature have proposed reactions to explain the mechanism of the process.5-10 There appears to be general agreement that water is necessary for the reactions to occur; that once the sodium chloride reacts with silica or silicates in the ore, the hydrochloric acid formed will convert the cupric oxide in the mineral structure to cuprous chloride. However, there appears to be a conflict of opinion on the reactions involved in the reduction of the cuprous chloride to metallic copper on the surface of the carbon. Rey has indicated that salt, water vapor, and

Jan 1, 1968

By W. H. Moore, E. T. Powell

IN the early days of mining in the Anthracite field, only the thicker and better seams of coal were mined, because of the limited mining and coal-cleaning facilities, therefore many of the thinner and less productive seams were permitted to remain unmined. With improvements in mining methods, the introduction of modem preparation plants, and the increased market demand for small-size coal, the thinner and more laminated seams have now become assets. In many instances these seams overlie the mined-out beds of the thicker and better seams, from which all recoverable coal was removed by the conventional breast-and-pillar method of mining. Some collieries in certain sections of the Anthracite field are now relying on these thinner and laminated seams. For the purpose of illustration, a large area in the Hickory Swamp-Ridge Basin of the western middle coal field has been selected, where as early as 1898 the No. 4, or Little Buck Mountain, seam was mined and pillars removed. The No. 5, or Buck Mountain, seam lying on a comparatively light pitch and with intervening strata of but 55 ft. of rock was not mined until 1935. Farther east, in the same basin the Nos. 8 and 9 seams, which are two splits of the Mammoth seam, have been mined and robbed and the workings have been abandoned since 1896. The overlying No. 9½ seam, or the upper split of the Mam- moth, and the No. 9¾ or 4-ft. seam remained virgin, with only an interval of 50 ft. of rock separating them, and with 40 to so ft. of rock strata separating the No. 9½ seam from the completely mined area of the Nos. 8 and 9 seams. These seams lie on a pitch of 45° on the south side of the basin and on 75° on the north side of the basin. Mining has been carried on in the 9½ and 9¾ seams for 3 years on both dips of the basin, for a distance of 3500 ft. In some sections the overlying strata of the thicker seams previously mined have settled without any apparent breaks in the upper strata, as indications have shown in the top split of the Mammoth; while in other areas the roof and bottom of this top split of the Mammoth have settled unevenly, thereby causing the bottom and roof to break into blocks. In attempting to mine over a large area of the No. 5 or Buck Mountain seam, a similar settlement has been encountered; the roof of the seam has been broken and a considerable amount of timbering has been necessary in order to make the mining of the seam possible. The conventional breast-and-pillar method, using shaker conveyors, has been used in the No. 5 seam, and a slant-breast method in the mining of Nos. 9½ and 9¾ seams. Mining OF Light-pitch Seams The No. 4 seam was mined and robbed by the conventional breast-and-pillar system. In this area the seam pitched from 5° to 25° on the north dip, averaged 8 ft. in thickness and had a slate bottom and a

Jan 1, 1942

By J. E. Hilliard

Isobaric sections of the eutectoid region of the iron-carbon phase diagram have been exgerimentally determined at 35, 50, and 65 kb. The phase boundaries were located by metallographic analysis of specimens quenched after equilibriatwn at known temperatures and pressures. With increasing pres -sure a pronounced decrease in the solubility of FesC in austenite was observed together with a depression of the eutectoid temperature. These two effects resulted in a shift of the eutectoid composition toward a lower carbon content; at 65 kb the eutectoid was at less than 0.2 wt pct C. These results are in qualitative agreement with thermodynamic calculations. It has also been shown by calculations that Fe3C in contact with saturated austenite will be stable with respect to both graphite and diamond formation at all pressures above -3.5 kb. 1 HE investigation described in this article was part of a more general study of the effect of high pressure on transformations in Fe-C alloys. Thermodynamic calculations and exploratory runs made in 1959 at the start of the program indicated an appreciable change with pressure in the phase equilibria of Fe-C alloys. However, the calculations were not considered reliable enought to provide the quantitative information required for the interpretation of the effect of pressure on the kinetics of transformations. An experimental investigation was therefore made to determine a series of isobaric sections of the eutectoid region of the phase diagram at pressures up to 65 kb. EXPERIMENTAL PROCEDURE Materials. Seven alloys with analyzed carbon contents of 0.10, 0.20, 0.38, 0.60, 0.77, 0.93, and 1.20 wt pct C were prepared from Ferrovac" iron and high-purity graphite induction melted in magnesia crucibles under argon. The ingots were hot worked and swaged down to 0.19-in.-diam rod which was then centerless ground to a final diameter of 0.125 in. Samples for chemical and spectrographic analyses were taken from each end of the rods. The prin- cipal impurities were found to be Ni, Al, Co, and Si which were present in amounts up to 0.03, 0.02, 0.01, and 0.01 wt pct, respectively. Specimens were prepared by slicing the ground rods into pills 0.06-in. thick which were silver plated to reduce decarburization during the equilibration. Silver was chosen for this purpose because of its very low solubility for carbon and its mutual immisicibility with iron. High-Pressure Apparatus. The high-pressure runs were carried out in the "Belt" apparatus.' As shown in Fig. 1, this consisted of a cylindrical cell compressed between two Carboloy punches loaded by a uniaxle press. Radial support to the cell was given by the "belt" which was a Carboloy die heavily prestressed by a series of steel binding rings. Laminated gaskets of lava and metal separated the punches from the inner surface of the "belt". A cross-section of the high-pressure cell is shown in Fig. 2. Two specimen pills were located inside a resistance heater of 0.20-in.-diam Nichrome tubing. The ends of the tube were sealed with alumina and lava pills tamped in place after the

Jan 1, 1963

By J. C. McCarthy, J. B. Stone

AT Fresnillo a series of veins that has yielded very large quantities of silver and other metals has been developed over a length of 6500 ft. and to a depth of over 3000 ft. In the course of this work striking changes in the mineralogy and metal content of the principal veins have been disclosed and are well illustrated by assay data and ore reserve calculations. This paper describes those changes and suggests their bearing on theories of ore deposition. LOCATION The Fresnillo mines and the adjacent city of Fresnillo are in the central part of the state of Zacatecas, 35 miles northwest of the capitol city of Zacatecas, once a great silver-mining center whose total production is said to place it fourth in the world. Another famous old silver district, Sombrerete, lies northwest of Fresnillo. Fresnillo is connected by a 5-mile branch with Fresnillo station on the Mexican National Railways line from Juarez to Mexico City. Lying near the southwestern edge of the central plateau of Mexico, Fresnillo is surrounded by a semi-arid rolling plain from which rise widely scattered low hills. One of these is Proano hill, an inconspicuous elevation rising barely 300 ft. above the plain, but in and around Proa[n]o hill are the Fresnillo mines, and it is marked now by a great gash cut by gloryhole mining. HISTORY According to an account written in 1834 by Francisco García, then Governor of the state of Zacatecas, Fresnillo was discovered in 1554, and a presidio was established there in 1568 to protect travelers on the road between Zacatecas and Sombrerete. Little is known of the earliest mining at Fresnillo. which seemingly began soon after its discovery, but by piecing together various accounts, it appears that mines there were working in 1717 and were notable active in 1751 under an administrator named Murguía, who left detailed notes describing them. In 1757, however, the mines became inactive because of difficulties with creditors and no doubt also because of increasing water troubles, and they remained abandoned until 1830. In 1830 the mines at Fresnillo became the property of the State of Zacatecas because the interest of Governor García had been aroused by the long disregarded notes of Murguía. Under Garcia's energetic leadership the mines were reopened, and silver production began in 1832 in spite of serious difficulties, including abnormal rains and an epidemic of cholera. In 1833 English capital was sought to allow installation of steam-driven Cornish pumps at the two principal shafts and to build the great hacienda de benefacio (the present Proano hacienda). The company formed in 1835 (Cia. Zacatecano-Mexicana) operated successfully until 1872, when its career was brought to an end by the political and economic disturbances

Jan 1, 1942

By R. C. Buehl, M. B. Royer

A three ton per day blast furnace using blast temperatures up to 2200°F was operated to recover manganese from open-hearth slag and manganiferous iron ore. The spiegel product containing 12 to 24 pct Mn was blown in a basic converter to high manganese oxide slag as described in the paper which follows this one. HE steel industry, which uses over 900,000 short tons of contained manganese yearly, depends on the maintenance of supplies of manganese from foreign sources such as India, Gold Coast, and Union of South Africa. Domestic ores furnish less than 10 pct of the yearly requirements of metallurgical ores and, unfortunately, the United States has no large, or even moderate, grade deposits that could supply a major portion of the requirements for many years. It may be necessary to obtain manganese from low grade materials, even though the cost is appreciably higher than when imported ores are used. An American Iron and Steel Institute questionnaire prepared in 1949 revealed the startling fact that open-hearth slags contained about as much manganese as is imported annually. The quantity of slag produced each year by integrated steel plants (not including cold-melt shops) and the manganese contained in the slag follows: Flush slag, 4,500,000 net tons a year containing 408,000 net tons Mn; tap slag, 7,230,000 net tons a year containing 364,000 net tons Mn; for a total of 772,000 net tons Mn. Some of this slag is returned to blast furnaces but about 75 pct would be available for the recovery of manganese. In several decades, when many of the present sources of high manganese ores have been depleted, open-hearth slag and manganiferous iron ore may become the major source of the manganese required for steel production. In 1948, manganese-ore imports from the U.S.S.R. were 427,000 net tons or 34 pct of the foreign ore. Imports from this source were only 81,000 tons in 1949. It became evident that adequate stockpiles of manganese could not be accumulated for many years. The Bureau of Mines initiated an extensive research program on methods for increasing domestic production of manganese and entered into a cooperative agreement with the American Iron and Steel Institute for recovering manganese from open-hearth slags whereby the Institute provided additional research funds and trained operating personnel. Description of Process and Equipment Numerous pyrometallurgical and hydrometallur-gical processes and combinations of the two can be applied to the recovery of manganese from open-hearth slag and manganiferous iron ore. The process being developed at the Pittsburgh Station of the Bureau of Mines consists of: 1—Reduction of open-hearth slag in a blast furnace to recover the iron and manganese as spiegel-eisen with 12 to 24 pct Mn. 2—Selective oxidation of the manganese from the blast-furnace metal in a basic-lined converter to produce a high manganese slag with up to 60 pct Mn content, which is a synthetic ore for the production of ferromanganese. This process has the advantage over other processes in that the equipment which would be used, such as blast furnaces and converters, has been highly

Jan 1, 1953

By George H. Cunningham, Allen C. Jephson

The plant for production of electrolytic zinc recently erected by the American Smelting and Rcfining Co. is situated along Nueces Bay, on the Gulf Coast, some 5 miles west by rail and highway from the city and port of Corpus Christi. A ship channel from the port now approaches to within 2 miles of the site. It is expected that this will be extended at some future date and so provide direct water shipment from the plant. In addition to Gulf shipping, an intercoastal waterway connects Corpus Christi with Houston and New Orleans. Factors leading to the establishment oi this plant in the area were: ample supplies of natural gas for the generation of electric power, advantageous shipping lanes, favorable market for acid, adequate supply of labor, and moderate climate. General Description The plant was erected primarily to assist with the production of high-grade zinc much needed for war purposes. Production started during October 1942. The purity of the slab-zinc output meets the American Society for Testing Materials' special high-grade spccifications. Other products of the plant are electrolytic cadmium and sulphuric acid. Residues containing lead, copper and silvcr are sent for treatment to the Company's smelter at El Paso, Texas. The design of the plant includes the use of Trail suspension roasting equipment, contact acid equipment, also batch leaching in mechanically agitated tanks, pressure filtering and washing of leach pulp, batch purification in mechanically agitated tanks followed by clarification in filter presses and cooling of purified solution by evaporation. Electrolysis is performed in cells using Tainton alloy anodes and aluminum cathodes. Cathode current density is 60 amp. per square foot. Except for the portion returned to the leaching division, the cell solution is continuously flowing in closed circuit through the cells to cooling towers, which hold cell temperatures within desired limits. Direct current for electrolysis, is supplied by generators driven by steam turbines. The cathode zinc is melted in a gas-fired furnace and cast in the usual way into slabs for shipment. The plant divides into five major divisions: Concentrates Storage, Roasting and Acid, Leaching, Electrolysis, Melting and Casting. No attempt is made to give many tabulated data in this paper; it is mainly a general description of the divisions and methods employed for operation. A plan is shown in Fig. I and a general flowsheet in Fig. 3. Concentrates Storage The original plan for inward shipments was to receive zinc concentrates by steamer at the port of Corpus Christi, there to unload into open railroad cars and move into the plant by rail. Up to the present, however, concentrates have been received mainly in box cars from mines in Mexico.

Jan 1, 1944

By R. B. Basham, C. W. Macune

Very small anomalies in oil well temperatures are detected and measured by recording the difference in temperature existing between two thermally sensitive elements which are Spaced several feet apart on a small diameter carrier and lowered into the bore hole. The elements operate in a balanced electrical circuit, sending only a reference signal to the surface as long as normal gradient temperatures are encountered. When either element enters a temperature disturbance, the circuit is unbalanced and produces large recorder deflections for minute anomalies. The system is highly sensitive to small changes in thermal gradients caused by gas or fluid movements and to the boundaries between beds of different thermal conductivities. Typical logs show successful applications of the process to locating gas and water leaks in casing, gas entry. and gas-oil contact. INTRODUCTION Temperature measurements in oil wells have been made for many years in the search for additional sub-surface data. It has been generally agreed that many conditions in the bore hole cause temperature anomalies which, if located and measured, could yield useful information. But it has been recognized also that many of the irregularities, such as those produced by small water and gas leaks in casing, might be very small and therefore difficult to detect with certainty.' Although tem-perature measurements have been made which show anomalies of less than one degree deviation from normal gradient temperatures, the results are usually uncertain and unconvincing. The general practice, therefore. has been to apply temperature surveys only to well conditions known to produce appreciable disturbances, such as large gas movements and cement hydration. The recent demand for additional data has focused attention on the problem of making dependable temperature measurements in the many instances when anomalies are small but none the less significant. It was for the purpose of detecting these minute irregularities in bore hole temperature that the program described in the following text was undertaken. It is emphasized that this presentation is not offered as a complete study, for the process is still partially experimental. But it is believed that the results obtained thus far will be of interest to the industry and will indicate some of the system's potential usefulness. DIFFERENTIAL MEASUREMENT The chief value of differential measurement lies in the fact that a difference between two factors can be measured with a scale of values best suited to that difference, a scale that might be cumbersome or impractical if applied to the factors themselves. When it is known that all factors will be nearly equal in value, and therefore the differences consistently small, it is possible to select a scale which will permit very accurate measurement of the differences. This advantage is in contrast to the difficulty of measuring small increments of a single variable, where the increment must be measured by a large scale which is suitable for measuring the entire factor. Gradient temperatures are usually measured under this latter condition where temperature measuring apparatus must have a scale extending over the range of expected temperatures, say 50' to 25O°F, and it becomes almost impossible to detect small irregularities of less than one degree. The use of large strip chart recorders and divided multiple ranges tend to amplify the small anomaly and make it more pronounced. But the instability of instruments, both

Jan 1, 1952

By H. A. Saller, F. A. Rough

Studies of the V-U system have been made to determine the constitutional diagram. The diagram is fairly simple, since no intermediate phases are formed. Additions of vanadium lower the uranium melting point and allotropic transformation temperatures. The maximum solid solubility of vanadium in uranium is 12 atomic pct and the maximum solid solubility of uranium in vanadium is about 4 atomic pct. WITH the advent of high purity iodide vanadium,' it became of interest to study the alloying characteristics of vanadium and uranium. Alloys were prepared covering the entire system and were studied using a combination of metallographic examination and thermal and X-ray analyses. As a consequence of this work, the V-U constitutional diagram was evolved. In order to prepare suitable alloys for equilibrium-phase studies, it is desirable to have the purest possible starting materials. For this investigation, calcium-reduced vanadium, de Boer process crystal-bar vanadium, and good Mallinkrodt Chemical Co. uranium were used. The first work was done using the best vanadium then available, that being calcium-reduced vanadium produced at Knolls Atomic Power Laboratory. Subsequently, the important features of the diagram were checked using alloys made with crystal-bar vanadium produced at Battelle. These checks are in agreement with the earlier work. Analyses of the starting materials are contained in Table I. Only minor amounts of any impurities were present in either the vanadium crystal bar or uranium. Nevertheless, care was exercised in selecting the uranium for the alloys. The procedure followed was to section the stock into suitable pieces for melting, and macroetch each piece. Only those pieces which appeared to be clean by macroetch examination were used for alloying. Experimental Procedure Melting: Alloys with 0 to 50 atomic pct V were induction melted in beryllia (BeO) crucibles under vacuum of 10 microns pressure or better. A number of remelts was frequently required to insure uniformity of the individual ingots. Although no visible reaction between the alloy and crucible was found in any of these operations, the alloys were checked by spectroscopic analysis. Only trace amounts of beryllium were detected in the alloys. Alloys containing 50 to 100 atomic pct V were arc melted in a water-cooled copper crucible under an atmosphere of helium. A tungsten electrode was used. Ingots of 10 to 15 g were produced readily by turning and remelting a few times. Such small ingots were necessary because high purity vanadium was not available in appreciable quantities at this time. After melting, the ingots were examined metal-lographically for segregation and were consolidated by remelting before fabrication was attempted. Spectroscopic analyses showed that only small amounts of tungsten were picked up during the arc-melting process. Fabrication of Alloys: Alloys containing up to 20 atomic pct V could be fabricated by rolling in air at 600°C with 5 min between passes. After each pass through the rolling mill the alloys were returned to

Jan 1, 1954

By B. M. Harra, F. G. McCutcheon, O&apos

Until about 1930, the universal practice of horizontal-retort zinc smelters in the United States, as far as the writers are aware, was to operate the retort furnaces on a 24-hr cycle; that is, the retorts were charged in the early morning of one day, and in the early morning of the following day the residues were cleaned out, the retorts recharged, and a new cycle started. During the business depression of the early thirties, zinc production fell off to the extent that zinc smelters had idle retort capacity. Rather than continue to run some of the retort furnaces on a 24-hr cycle and shut down the remainder, a few companies decided to try out a longer cycle. Although the output of zinc per retort per day is lower, the longer cycle permits a larger charge per retort and improved zinc recovery. Advantages of the longer cycle were soon evident, and the practice spread rapidly. Various lengths of cycle were used, typical examples being 28-hr, 32-hr, 36-hr, and 48-hr. The 48-hr cycle fits in best with the standard routine of smelter practice that was built up on the basis of the 24-hr cycle; that is, the retort furnace "maneuver" always comes at the same time of day, and can be performed in the cool hours of the early morning. Under some conditions, particularly in some of the older plants, where the retorts are smaller than in newer plants, a 48-hr cycle is longer than necessary, and some intermediate length of cycle may theoretically be most economical. Use of an intermediate cycle, however, means that the maneuver comes at different times on consecutive days, and that sometimes it comes during the hottest part of the day. The work on the retort furnaces is extremely hot and arduous at best, and it is much worse, of course, if it is done during the heat of a summer day. When labor was plentiful and tractable, many plants were able to operate on cycles of intermediate length, but the workmen did not like the working hours. Under present labor conditions, it is hardly practicable to operate with a cycle of intermediate length, so the choice has narrowed down to the alternatives of 24-hr or 48-hr cycles. In any discussion of economics, too comprehensive generalization is not warranted, because local conditions affecting economics vary greatly. The best economic practice at one plant at any given time may be uneconomical at another plant, or even at the same plant at another time. To determine the length of cycle that is the better practice at a given plant at a given time requires a weighing of the advantages and disadvantages of each cycle, taking into consideration all the local conditions. some of the factors that must be considered in making the comparison are discussed briefly in the following paragraphs.

Jan 1, 1949

By L. L. Melton, W. T. Malone

Fluid mechanics research conducted with non-Newtonian fluid systems now permits prediction of the behavior of these fluid systems in both laminar and turbulent modes of flow through circular pipes. Present work concerns non-Newtonian fluid systems currently used in the hydraulic fracturing process. During fracturing treatments, an unsteady-state condition may frequently be encountered arising from. the reaction rate of a chemical additive. This condition must be evaluated in order to predict the actual behavior of a particular fluid during field application. Design and operation of the apparatus used to determine fluid-flow behavior permit obtaining data under such non-equilibrium conditions. This paper shows methods used to obtain rheology measurements, develop hydraulic relationships and evaluate chemical reactions producing unsteady-state conditions. Engineering application of this research is illustrated by employing measured rheological values and developed hydraulic retationships to produce frictional pressure loss (psi/100 ft) us flow rate (bbl/min) charts of common tubing and casing sizes for an example fracturing fluid. How these charts and chemical reaction rate information are then combined to predict actual turbulent hydraulic behavior during unsteady-state field conditions is also discussed INTRODUCTION Many fluids used in hydraulic fracturing contain chemical additives which impart non-Newtonian fluid properties that may drastically alter their hydraulic behavior. Equally drastic alteration in wellhead pressure, injection rate and hydraulic horsepower requirement may result from these fluid properties. Prior research conducted to relate non-Newtonian fluid properties with hydraulic behavior has not as yet produced a universal relationship, particularly for the turbulent flow region. which of the many Possible non-Newtonian fluid properties is responsible has not been conclusively established. A systematic description, suggested by Metzner, of the many possible non-Newtonian fluid properties exhibited by real-fluid behavior, and a current discussion of theoretical and applied aspects of non-Newtonian fluid technoloy can be found in Handbook of Fluid Dynamics. f Little or no research has previously been attempted with fluids exhibiting time - dependent properties. Addition of chemicals during a fracturing treatment is often accomplished by continuously mixing and displacing the fluid. This produces a time-dependent effect or unsteady-state condition while the fluid is progressing through surface and wellbore conductors. This condition is due to solution or chemical reaction of the additive. Considerable departure from conventional methods of obtaining and interpreting data was found necessary to consider these conditions. Therefore methods were developed to obtain hydraulic behavior information under these complex, unsteady-state conditions. Relationships presented in this paper to predict hydraulic behavior of non-Newtonian fluids in circular pipes were obtained by constructing and operating a small pipeline apparatus in the manner of a pilot-plant study. These relationships are suggested as scaleup equations and are not proposed as fundamental rheological parameters. While perhaps deficient from a fundamental research viewpoint, a pilot-plant study does permit the determination and convenient evaluation of variables pertinent to a process. A pilot-plant study can result in a valid engineering application procedure even when fundamental relationships are still undefined. An excellent series of articles by Bowen has appeared in the chemical engineering literature.2-8 These give a thorough review of proposed hydraulic relationships and their limitations for non-Newtonian fluid behavior in circular pipes. A graphical method is presented to scale up data for a fluid exhibiting an anomalous hydrau1ic behavior in the turbulent flow region. Considerable assistance has been obtained from these articles to interpret the anomalous behavior noted during this investigation. These articles also provided assurance that a pilot plant is a practical approach to evaluate the hydraulic behavior of non-Newtonian fracturing fluids. _____________

Jan 1, 1965

By E. C. W. Perryman

The wide grooves formed at the grain boundaries when high purity aluminum is attacked by hydrochloric acid or sodium hydroxide have been attributed by earlier workers to the high energy of the grain boundary material. The effect has been investigated for high-purity AI-Fe alloys with up to 0.055 pct Fe as a function of iron content and heat treatment. It is shown that the explanation given above is untenable, but that the results can be explained on the assumption that iron segregates to the grain boundary in solid solution. IN 1934, Rohrmann¹ showed that aluminum of 99.95 pct purity suffered intercrystalline corrosion when immersed in 10 to 20 pct hydrochloric acid, and that the susceptibility to intercrystalline corrosion depended upon the heat treatment given. The greatest susceptibility was found for specimens quenched from a high temperature (600°C) and the lowest susceptibility for specimens cooled slowly from that temperature. Lacombe and Yannaquis2 have shown that super-pure aluminum (99.9986 pct) annealed at 600°C suffers intercrystalline attack in 10 pct hydrochloric acid and that this attack is intensified by anodic dissolution in the same solution at a current density of 10 milliamperes per sq dm. No difference in extent of intercrystalline attack was found between the 99.993 and 99.986 pct Al, which led the authors to suggest that impurities played only a secondary role in the mechanism of intercrystalline corrosion. It was found, however, that the attack at the grain boundaries depended upon the relative orientation of the grains, large differences in orientation favoring rapid attack. Boundaries where the two neighboring grains were similarly orientated showed high resistance to attack as did boundaries between grains which were in twin relationship. These observations led Lacombe and Yannaquis to suggest that the intercrystalline attack was due to lattice discontinuities present at grain boundaries. Assuming that the grain boundary is a layer three to five atoms thick and has a crystal structure which is a compromise between the two neighboring grains it is clear that the discontinuities will increase with increasing difference in orientation between the neighboring grains and hence the increasing tendency to intercrystalline attack. Roald and Streicher³ investigated the effect of heat treatment of aluminum alloys ranging in purity from 99.2 to 99.998 pct on the corrosion resistance in 20 pct hydrochloric acid and 0.30N sodium hydroxide. They found that in hydrochloric acid the intercrystalline attack appeared to be determined by the type and quantity of impurities present and by the relative orientation of the grains. No difference in the susceptibility to intercrystalline attack was observed between specimens quenched and those furnace cooled, from 575°C. In 0.30N sodium hydroxide some materials exhibited intercrystalline attack, this taking the form of V-notches. Rohrmann¹ offered no explanation for the greater susceptibility to corrosion of material quenched from 600°C. It seems possible that this difference is connected in some way with a different distribution of impurity elements in the quenched and slowly cooled specimens. The fact that Roald and Streicher8 observed no difference between quenched and slowly cooled specimens may possibly be due to differences in either rate of cooling or silicon content or possibly both. Both these would be expected to have an effect on the distribution of impurity elements. Although the rate of cooling used by Rohrmann was slightly more rapid than that used by Roald and Streicher the position cannot be clarified because Rohrmann does not give the silicon content and Roald and Streicher give the silicon contents of only a few of their alloys. That Lacombe and Yannaquis2 found no difference in corrosion behavior attributable to impurities between the two materials they used may be because both were of high purity compared with the aluminum used by Rohrmann.¹ Although they found no difference in the corrosion behavior of their two materials it is possible that the results obtained by Lacombe and Yannaquis may, nevertheless, have been influenced by impurity distribution, since, on the transition lattice theory of grain boundary structure, it would be expected that sparingly soluble impurities would tend to segregate to boundaries where the orientation difference is such that there is a greater density of atomic sites of suitable size to contain them. It was considered worth while, therefore, to examine the corrosion properties of a series of materials of differing impurity content with the objects of confirming the experimental observations made

Jan 1, 1954

By R. D. Saltsman

This paper deals with the evolution of a test procedure devised to totalize a coal's ignitibility, its degree of caking, and its coke reactivity and the development of a method for assigning proper combustion indices to stoker coals. The application of this type of work to stoker design is also discussed. It is believed that this work may be the prelude to understanding the effect of various petrographic constituents on the combustion characteristics of a coal or a blend of coals. The inadequacy of our knowledge of the coal combustion process has long been recognized. This was expressed very well by Spicer and Finney.1 "The control of combustion processes in industry and the design of the equipment necessary for efficient burning to take place have always been very much branches of an industrial art rather than of an exact science. This has been especially true of the utilization of coal, a substance so heterogeneous and complex in character that all too little is known about its chemical and physical composition." During the past several years one branch of coal utilization, that of high temperature carbonization, has made significant advances from being an art into being an exact science. This has been accomplished by the development of petrographic techniques for identifying, measuring, and determining the thermal properties of the organic materials which affect the carbonization of coal and the correlation of this information with a pre-existing standard of coke quality, the stability index. The success in using petrographic analysis for predicting the coking properties of coals and their blends suggested that petrographic techniques might be applied to the combustion process for predicting the combustion characteristics of coals. Certainly the different organic entities2 influence the combustion characteristics of a coal as they influence its coking properties. If it were possible to predict combustion characteristics from an analysis of a coal's petrographic composition, it would seem logical that an intelligent investigation could then be made into methods of altering stoker coals to improve their combustion characteristics. The successful application of petrographic analysis in the field of high temperature carbonization was made possible by the pre-existence of the stability index, which is a numerical value of coke quality. The quality of combustion is determined by the sum of the effects of the ignitibility, the caking, and the coke reactivity characteristics of a coal. While the literature is filled with papers reporting the correlation of various analyses to the ignitibility, or to the caking, or to the coke reactivity characteristics of coals, none of these earlier studies could be related to one index. The lack of a single index for combustion quality precluded the application of petrographic techniques for predicting combustion characteristics. SELECTION OF THE COMBUSTION TEST EQUIPMENT The primary prerequisite of any test developed to evaluate the relative performance of stoker coals must reflect the three characteristics of the coal burning process: 1) ignitibility, 2) degree of caking, and 3) coke reactivity. The widespread variations in these combustion characteristics of the available stoker coals are well known. The ignitibility, which has been defined as that characteristic which determines the ease with which the fuel may be brought to a condition of self-supporting active oxidation, varies from where a coal is deemed to be flashy to the opposite extreme of being fireproof. The ignitibility of a coal influences its ability to pick-up from hold fire, greatly affects the degree of bed stability during swing loads, and is a factor in determining the average burning rate obtainable on a given grate. The caking characteristic affects the degree of bed porosity during the devolatilization period, and coals are classified on a scale varying from free burning to highly caking. Caking is not synonymous with bed swelling since a bed may swell two to three times its normal depth during the period of devolatilization yet remain very porous, allowing an efficient and high rate of combustion to take place. Caking is melting

Jan 1, 1964

By Jun Hino, P. G. Shewmon, P. A. Beck

THE investigations of Crussard,' of Guinier and Tennevin,' and of Dunn and Daniels," indicate that the subgrains formed in a cold worked and annealed metal are capable of growing at each other's expense during annealing, if the temperature of annealing is sufficiently high and the time is long enough. The results of Dunn and Daniels are particularly convincing in showing that subgrain growth is essentially the result of the free surface energy associated with the subboundaries. In subgrain growth, as in ordinary grain growth, energy is gained as a result of the decrease in total subboundary surface area per unit volume. Recently, Wood and Scrutton4 found that the rate of subgrain growth upon annealing increased very considerably, if simultaneously a creep strain was applied to the specimen at a low strain rate. Working with 99.98 pct pure fine-grained aluminum, these investigators found that the continuous X-ray diffraction back-reflection rings of material strained at room temperature remained continuous after heating for ten days at 250 °C. However, when heated at the same temperature under a stress of 1000 psi even for only three days, the formerly continuous X-ray diffraction rings broke up into numerous dots, which were fairly clearly separated from each other. The continuous X-ray diffraction rings were interpreted as indications of a very small subgrain size, not resolved by the X-ray diffraction method used. The breaking up of the continuous X-ray diffraction ring during annealing under stress was taken as an indication of a great increase in subgrain size, so that the individual subgrains could then be resolved. The effect of simultaneous strain at a low strain rate in accelerating subgrain growth, discovered by Wood and Scrutton and designated by them as "cell growth," is of fundamental importance. The experiments described in this note were carried out in order to confirm Wood and Scrutton's results by direct metallographic observation. Also, information was sought as to the minimum creep strain necessary to produce this effect. A fine grained high purity aluminum strip was prepared by alternate 33 pct rolling and annealing treatments for 1 hr at 350°C. Specimens cut from this strip were subjected to a relatively fast creep strain of 7.2 pct in 3.5 min at 300°C under a constant load initially corresponding to 1185 psi. The subgrains set up were large enough (about 0.015 to 0.03 mm) to be clearly observed (Fig. 1) at X200 magnification with polarized light, after electrolytic polishing and anodic etching, producing a fine oxide film." The corresponding X-ray diffraction pattern is shown in Fig. la. After the fast creep strain treatment a portion of the specimen was subjected to a creep strain of 8.3 pct in 44 hr at 350°C under a constant load initially corresponding to 320 psi. Another portion, annealed under the same conditions, but not strained, served as control specimen. The subgrain size of a typical area of the specimen annealed under strain and of the one annealed without strain is shown in Figs. 2 and 3 (X-ray diffraction patterns, Figs. 2a and 3a). Annealing without strain produced clearly observable subgrain growth (subgrain size: about 0.03 to 0.05 mm). The effect of simultaneous strain was to increase greatly the rate of subgrain growth (resulting in a subgrain size of approximately 0.05 to 0.13 mm), in accordance with Wood and Scrutton. In another experiment, the effect of the amount of simultaneous strain was studied. The initial subgrain structure was set up by fast creep, as described previously. The specimen was then heated at 350 °C under a constant load initially corresponding to 320 psi, as above, for 2.2 hr (0.24 pct strain), and 8.8 hr (0.58 pct strain). Comparison with the corresponding unstrained control specimens by means of X-ray diffraction showed that 0.58 pct strain definitely had an effect, but the effect of 0.24 pct strain was doubtful.

Jan 1, 1953

By Lawrence H. Van Vlack, Otto K. Riegger, Gerald I. Madden

The microstructural variations of periclase (MgO) in the presence of oxide liquids are examined under the steelmaking variables of: 1) temperature, 2) liquid composition, and 3) FeO additions under different oxidation levels. Attention is given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. Silicate liquids penetrate more extensively between individual periclase grains than do liquids containing high percentages of Fe2O3 Higher MgO solubilities in the liquid and lower MgO contents of the solid favor more rapid grain growth. The presence of a second solid phase reduces the periclase grain growth rate and increases the amount of the solid-to-solid contact within the oxide microstructures at high temperatures. The service suitability of a refractory depends on many factors. Two are of major importance and include 1) the thermal resistance to melting, and 2) the mechanical resistance to loads at service temperatures. Neither is a simple consequence of the service temperatures because service conditions will alter compositions, produce partial melting, and induee phase changes. Consequently, the equilibrium phase relationships have been rather thoroughly studied and give a knowledge of the thermal resistance to melting, but do not give full information about the mechanical properties because two refractories with the same types and quantities of phase may have different microstructures. Although variations of microstructures with time, temperature, and composition have been subjects for extensive investigation in metals, only a limited amount of comparable microstructural work has been performed for refractory materials.' This study was an attempt to evaluate some of the consequences of service parameters upon the microstructures of refractories so that bases may be established for the analyzing of high temperature mechanical properties. Periclase (MgO) was chosen as the refractory oxide; variables included those which are encountered under steelmaking conditions such as 1) temperature, 2) liquid composition, and 3) FeO additions under various oxidation levels. Specific attention was given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. The most closely related work on microstructures of polyphase materials is that of Van Vlack and Rieg-ger2 on the microstructure of magnesiowüstite [(Mg,Fe)O] in the presence of silica. In that work which pertained to solid solutions with less than 40 pct MgO, most of the quantitative work was performed on FeO microstructures. The chief conclusions concerning these relatively low-melting oxide solids were as follows: 1) the rate of crystalline grain growth is inversely proportional to the grain diameter, 2) grain growth proceeds more rapidly at higher temperatures but is slightly retarded by additional liquid content, and 3) a Silicate-containing liquid penetrates as a film between the individual magnesiowüstite grains independent of time, temperature, amount of liquid, or the MgO/ FeO ratio. The above observations are in contrast to prior work3 on the microstructure of silica in the presence of iron oxide-containing liquids where the liquid does not penetrate as a complete film between solid grains. The phase relationships for the compositions of the present work are shown in Fig. 1 which is a summary of the work of several investigators.4 Of importance is the fact that CaO forms a more stable structure with SiO2 and Al2O3 than do either MgO or FeO. The oxygen potential has little effect on periclase unless iron oxide is also present. The iron oxide is ferrous at moderately low oxygen levels, changing to ferric as the Oxygen potential is increased so the spinels, magnetite, and magesioferrite are formed.5 These two phases are relatively stable in air at steelmaking temperatures. I) EXPERIMENTAL PROCEDURE ractory were made with reagent grade Oxides. The magnesium oxide used was 99 pct MgO after ignition, and the iron oxide raw material had a minimum content of 99 pet Fe2O3. The CaO, SiO2, and A12O3 were also reagent grade raw materials. After mixing, the required compositions were pressed into pellets at a minimum pressure of 5000 psi to insure compaction of the raw materials and prevent excess void content. A silicon carbide element tube furnace was used with thermocouple control for sin-

Jan 1, 1963

By G. F. Leaming

The paper by R.V. Ramani and R.J. Sweigard is a wonderful description of the labyrinthine web that has been spun about the mining industry by energetic bureaucrats and politicians over the past 50 years. The remedy for the problem, however, is not more of the same, but less. That may be difficult for the industry to achieve, for it is not a technical solution but a political one. And the current fervor for more detailed planning at all levels of government and private enterprise has become deeply ingrained. The authors recommend the provision of more information about mining and mineral resources to "macro" (i.e., government) land use planners. They apparently overlook, however, the already strong tendency on the part of most government land use planners to consider themselves omniscient. Thus, giving them more information about the technical problems of mining will only make them want to get more and more involved in the "micro" (private, site specific) mine development and production plans of the individual mining firm. In fact, this has already happened at all levels of jurisdiction from municipal to federal government. Examples are legion. The most effective way to ameliorate the adverse impacts of government land use planning on existing and potential mining operations is to: (1) introduce greater flexibility in the definition of land use zones by local and state governments; (2) adopt realistic and relevant ambient environmental performance standards in governing relationships between mineral land uses and concurrent or subsequent nonmining land uses; (3) allow greater leeway for economic considerations in land use decisions in contrast to the explicit legalistic approach now in vogue; (4) recognize that all minerals are not the same and that sand and gravel mining should not be treated the same as underground metal mining, coal stripping, oil field production, or in situ leaching; and (5) eliminate the notion that mining operators should be responsible for determining in detail the use of land by subsequent owners of mined land. This last bit of conventional ethic really makes no more sense than requiring the builders of every shopping center or government office complex to provide detailed plans for the use of that land when its use for shopping or government is ended. Did the builder of Ebbetts Field plan for Brooklyn after the Dodgers went to Los Angeles? Should the developer of the Bingham Pit plan for suburban Salt Lake City after the copper mining goes to Chile? The nation's mining industry must address these questions before further bankrupting itself to provide more data to planners and spending thousands of dollars per acre to create land that when reclaimed is worth only a few hundred dollars per acre. ? Reply by R.V. Ramani and R.J. Sweigard We thank Mr. Learning for his valuable contribution. His views on the problems of land use planning and mineral resources are most welcome additions to our paper. As the title indicates, our paper was more concerned with the impacts of land use planning on mineral resource conservation than with the details of the planning process. On the whole, his five recommendations would be helpful for mineral resource conservation. However, we would suggest that the argument he presents for his final recommendation does not address the differences between mining as a land use and commercial or institutional uses. We believe that this difference is the crux of the issue. We share Mr. Learning's desire to ameliorate the adverse impacts of land use planning. Possibly the most detrimental impact is the loss of mineral resources. Any development, whether mineral or community, that does not give proper consideration to other resources can result in permanent loss or sterilization of resources. With proper planning, some of these losses can be avoided. As our paper indicated, one factor that limits the consideration of mineral resources, and ultimately leads to their sterilization, is the generally inadequate levels of resource characterization and understanding of the unique nature of mineral resources and mining operations. The last point raised by Mr. Learning is also important. In terms of reclamation and land use planning in mining districts, we certainly do not advocate spending more than what the results are worth. The main thrust of the paper was to explore the avenues for conserving the mineral resources so that, at some appropriate time, the issue of mining and reclamation can still be addressed. ?

Jan 1, 1986

By R. V. Higgins, A. J. Leighton

Interest by petroleum engineers in the flow of three phases—oil, gas and water—in irregularly bounded porous media lies mostly in the performance calculation of water floods of reservoirs that have been partially depleted as the result of expansion of much of the originally dissolved gas. The authors present a method to forecast three-phase flow in complex geometry and explain the details by the use of a specific example of a five-spot water flood of a partially depleted stratified reservoir. In this example, the fluid and rock properties of a field given by Prats, et al,' were used. The computed results fit the field performance more accurately than Prats, et al, and Slider.' The time required for the high-speed digital computer to make the calculations, including the contributions from the different layered zones, is about one minute. INTRODUCTION The declining rate of discoveries of new oil fields in the United States makes the recovery of more oil from known reservoirs more attractive than previously. Water flooding has an excellent proved background for recovering additional oil economically. Accordingly, the main interest of this paper is in this type of recovery. In petroleum engineering studies, commercial interest in three-phase flow is mostly in the water flooding of reservoirs in which the oil has been partially produced by the expansion of dissolved gas. When water is pumped into these reservoirs, three-phase flow takes place. Although this paper is concerned with these conditions, the principles involved could be used for other conditions when and where they come to the fore. Many investigators have made contributions to non-empirical forecast methods using basic scientific engineering principles. Several of these used the oil in place at the start of the water flood and the oil remaining after a large quantity of water has passed through a core for key values in their calculations. Recently, Prats, et al,' and Slider have reduced assumptions by adding the third phase—gas—in their forecasting methods. Slider uses the mobilities in the immediate vicinity of inlet and outlet wells as an aid to simulate the resistance effect in the five-spat pattern of the flow of oil, gas and water. Prats, et al. minimize assumptions by using previously determined laboratory data for determining sweep efficiency in the five-spot pattern. In neither of these papers is the saturation profile continuously affected by permeability-saturation curves. Sheldon and Dougherty- recently described a method that employs continuously changing saturation profiles using permeability curves, has a minimum of assumptions and needs no prior sweep efficiency. The Higgins-Leighton method, described in this paper, has all of these features; however, many of the techniques are different from those of Sheldon and Dougherty. The Higgins-Leighton method, tested in May, 1961, is direct and easy to apply and requires very little computer time to calculate a forecast. The short computer time is especially helpful in the study of a reservoir containing many layers of different relative permeabilities. In the Higgins-Leighton method, the individual pressures do not have to be calculated, as the resistance to flow in each cell in the flow pattern is readily determined without the use of any iterative techniques. The saturation and permeability distributions are readily determined. These data and the shape factor, which is measured only once from the potentiometric model when mobility ratio is one, determine the resistance to flow in each cell. THEORY The authors showed in a previous paper4 that, as an aid to calculating performance, the reservoir can be divided into channels using the streamlines of a potentiometric model as a guide. See Fig. 1. This procedure also was used in this paper. The authors also showed that, by treating conduits as approximately one-dimensional and neglecting pressure gradients transverse to the main flow, the Buckley-Leverett equation may be expressed as The principles expressed by this equation are employed extensively in the three-phase flow, as they were in two-phase flow. In the three-phase flow, the channels (the size and shape of which are taken from a potentiometric model)

By R. Q. Shotts

This paper is a review of recoverable reserves of bituminous coal in the Southern Appalachian area, according to the latest published estimates. A few comparisons are made, some apparent trends are discussed, and some comments are made regarding the limitations of present estimates. The definition of Southern Appalachian area used in this report is somewhat arbitrary. It includes all the bituminous coal deposits of Alabama, Georgia, and Tennessee. All of West Virginia has been excluded. The East Kentucky and Virginia counties included were selected in connection with a literature study the writer made in 1959 of possible coal supply areas for the Tennessee Valley Authority. The selected counties were considered to be the only ones from which TVA might expect to obtain coal. The availability of coal from some of these counties is doubtful, but no other East Kentucky counties were considered more than remote possibilities. With these limitations, the Appalachian area covered is that from which producers of electric power and steel and commercial coal users, located in the Southeastern U. S., may expect to obtain their supplies of coal. Of course, it is recognized that coal from the eastern interior fields is also available to many of these same organizations. RANK AND QUALITY OF THE COALS Practically all the coals in the Southern Appalachian region are of high volatile A bituminous rank. An occasional sample indicates a slightly lower rank, but such samples may be oxidized or otherwise not representative. Some thin beds in Lookout Mountain and Sand Mountain in Alabama and Georgia, are low volatile bituminous coals, but they have not been mined extensively in modern times. There is a possibility that some of the deeper beds along the southeastern edge of the Warrior field of Alabama are near the Low-medium volatile bituminous dividing line. The Sewanee bed and some other minor ones of the Southern Tennessee field, some of the lower beds in Virginia, many beds in Sand and Lookout Mountains in Georgia and Alabama, one or more beds in the Coosa field, possibly some lower beds in the Cahaba field, and most of the beds along the southeastern edge of the Warrior field and the southern end of the Sequatchie anticline of Alabama, are of medium volatile bituminous rank. The quality of the Southern Appalachian coals is highly variable. Some of them, particularly such prevailingly thin ones as the Black Creek bed of Alabama and the Straight Creek bed of Kentucky, are unusually low in mineral matter— probably the lowest in the U. S. With the exception of certain beds and local areas, Alabama and East Kentucky coals probably have as low average ash and sulfur content as can be found in any sizeable coal area in the country. The sulfur content of Southern Appalachian coals is also variable, but few beds are consistently high in sulfur. In Alabama, sulfur generally increases from southeast to northwest across the Warrior field, but this trend is not quite as clear in the other states. A few beds in Northern Tennessee are prevailingly high in sulfur. All Southern Appalachian coals are potential coking coals if they can be prepared to meet chemical requirements. Only a comparatively small part of the medium volatile A bituminous coal, but most of the medium volatile bituminous coal mined is actually used for coking purposes. An estimate of reserves of coking coal under the requirements of present practice, could be compiled comparatively easily, but this probably has never been done. The reserve of coal that can be coked as an ingredient of a suitable blend is probably many times the size of the reserves of coal that will yield suitable blast furnace and foundary coke without blending. WHAT CONSTITUTES ECONOMICALLY RECOVERABLE COAL RESERVES? When one first realizes the vast extent of the coal-bearing rocks in the Southern Appalachian area, (see Fig. 1) the thought is likely to occur that the supply of coal is inexhaustible. This is particularly true on realizing that in some of the basins of thicker coal-

Jan 1, 1962

By T. W. Watson, D. R. Flynn

Measurements have been made of the thermal conductivity and electrical resistivity of two specimens of 0.005-cm (2-mil) Be-Cufoil over the temperature range -140° to +200°C. The thermal cmductivity of Be-Cu Alloy 125 was found to be significantly higher than that of Alloy 25, which had a higher impurity content. The thermal conductivity and electrical resistivity values obtained were in concordance with the Smith and Palmer relation for copper alloys which states that ? = 0.0239 (T/p) + 0.075 where A is thermal conductivity (W cm-' deg-'), p is electrical resistivity (microhm-cm), and T is absolute temperature (OK) , indicating that the Smith and Palmer relation can be used to predict the thermal conductivity of this type of Be-Cu alloy over the temperature range -140" to + 200°C to within an accuracy suitable for most engineering applications. THE National Aeronautics and Space Administration, Goddard Space Flight Center, Greenbelt, Md., requested the National Bureau of Standards to measure the thermal conductivity of 0.005-cm Be-Cu foil which was to be used to fabricate antennae for use in Radio Astronomy Explorer space craft. It was felt that measurements had to be made on the actual antenna material, rather than on a thick bar of similar material, since the cold-working and age-hardening properties of the alloy would make it very difficult, if not impossible, to place a thick bar in the same metallurgical state as the 0.005-cm material. As discussed in Section 111 of this paper, the thermal conductivity of many copper alloys can be computed rather accurately from electrical resistivity data using an empirical relation developed by Smith and palmer' and further confirmed by owell.' However, there has been very little work done on correlating thermal and electrical conductivities on Be-Cu alloys. We were reluctant to assume the validity of the Smith-Palmer relation on Be-Cu alloys because of the very large mass difference between beryllium and copper. As will be seen, however, our experimental results indicate that the Smith-Palmer relation is valid for the two alloys on which we made measurements. I) DESCRIPTION OF SAMPLES Samples of Be-Cu Alloy 25 and Be-Cu Alloy 125 were furnished to NBS in the form of rolled strip material, 0.005 cm thick by 5.08 cm wide. The Be-Cu Alloy 25 was purchased by NBS in the form of a continuous length of flat strip. The Be-Cu Alloy 125 was furnished to NBS by Goddard Space Flight Center in the form of two lengths of strip that had been formed into "tubing" of about 1.2 cm diam, with one side of the strip overlapping (but not connected to) the other side by about 90 deg. This "tubing" had been opened up to be flat and then rolled onto spools of about 3 cm diam. When unrolled, the strip would spring back into tubular form. Samples of both of the Be-Cu alloys were chemically analyzed by the NBS Analytical Chemistry Division. The beryllium content was determined quantitatively by the phosphate-gravimetric method to be 1.83 wt pct for Alloy 25 and 1.80 wt pct for Alloy 125. The two alloys were also examined by a general qualitative spectrochemical method for metallic elements. The Alloy 25 specimen contained between 0.1 and 1.0 wt pct Al, Co, Fe, and Si and between 0.01 and 0.1 pct Ni. The Alloy 125 specimen contained between 0.1 and 1.0 pct Co and between 0.01 and 0.1 pct Al, Fe, and Si. Other metallic elements present were in amounts less than 0.01 pct. The NBS Engineering Metallurgy Section measured the tensile strength, elongation, and Knoop hardness of both the Be-Cu Alloy 25 and the Be-Cu Alloy 125. These are given in Table I. The NBS Engineering Metallurgy Section also prepared photomicrographs of the two alloys; these are shown in Figs. 1 and 2.

Jan 1, 1969

By A. D. Mutch

IT has long been known that there are wide variations in the thermo-electric potential of pyrite. In the last few years a study of this variation and other properties of pyrite was carried out at the University of Toronto by F. G. Smith on specimens of pyrite from many localities.1-3 As a result of these studies the pyrite geothermometer was developed by Professor Smith. The calibration of the pyrite geothermometer is based on the assumption that "crystals of any one electronically conducting mineral species deposited at a high temperature have a more positive thermo-electric potential than crystals deposited at a low temperature, and the thermo-electric potential varies continuously between any given limits of the temperature of deposition." The cause of the variation was postulated to be crystal discontinuities, such as lineage boundaries. As yet this postulated relationship has not been established as fact. On theoretical grounds it is indicated that the thermo-electric potential of pyrite or any other partial conductor is dependent upon a number of factors as well as the temperature of formation. For this and other reasons there is ground for doubt as to the validity of the relationship postulated above. To date a large number of readings have been made with the pyrite geothermometer which have been recorded in terms of the calibration of the instrument in degrees centigrade. So far most of the pyrite tested by this technique has been in association with gold ore. The values for the temperature of formation obtained in these tests appear to be reasonable and, in relation to geological problems, to vary in the right sense. Determinations on some specimens not in association with gold ore have given readings that appear to be much too high, taking into account the probable maximum temperature of the host rock. To sum up, although many determinations made with the. pyrite geothermometer appear to give reasonable values for the temperature of formation of the pyrite, there are at the same time other readings which seem anomalous. On the basis of an examination of available results of work with the pyrite geothermometer, two problems must be considered: 1-the validity of the calibration of the pyrite geothermometer; and 2-the nature of the distribution of the thermo-electric potentials of pyrite in relation to the specific problems that have been examined. In this paper the academic problem relating to the validity of the calibration of the pyrite geothermometer will not be discussed. Instead, the variations of thermo-electric potential of pyrite in association with gold veins will be discussed with regard to specific examinations. The first of these two examinations deals with the distribution of thermo-electric potentials of pyrite in association with a gold vein and was carried out in the McIntyre Porcupine Mine, Schumacher, Ont., in the summer of 1949 as part of a study with this technique. The second problem deals with variations of thermo-electric potential of pyrite in gold ore specimens from all over the world. The specimens used in this study were part of the private collection of Frank Ebbutt, geologist for Howe Sound Exploration Co. Results of Detailed and Reconnaissance Studies In discussion of the results of determinations made in these two studies the values of thermo-electric potential in millivolts will be used. It will be noted that in some of the diagrams the determinations are recorded in terms of pyrite geothermometer temperatures. Fig. 1 is a calibration chart relating, pyrite geothermometer temperatures and thermo-electric potentials. A full discussion of the technique is given in the original paper by F. G. Smith.' Briefly, the determinations are made by placing two stainless steel probes, one hot and the other cold, against the surface of the pyrite crystal being tested. The thermo-electric potential that is developed is read with a null-point potentiometer that is calibrated in what

Jan 1, 1952