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By Cyril Stanley Smith

For many years sulphur and its congeners selenium and tellurium have been regarded as very harmful elements in copper and copper-rich alloys. Like many similar prejudices, this has been found to be partly wrong. All three of these elements actually have no great effect on the working properties of copper and its alloys, and are desirable additions in that they considerably enhance the machinability of alloys in which they are present. Because of their possible commercial importance, a study of the machinability and other properties of the pure binary alloys was made, as described in this paper, and the effect of selenium on a large number of copper alloys was determined. The current opinion regarding the deleterious effects of elements in this group undoubtedly arose because of occasional failures of tough-pitch copper containing unusually high tellurium, and because of the well-known fact that sulphur causes spewing and unsoundness in tough-pitch copper. Siebe,1 also Deretchey and Margolina,2 studied the effect of sulphur on copper and showed that in the absence of oxygen it was present in the form of copper sulphide, which was less harmful to the properties than an equivalent amount of copper oxide. No data have been published on selenium and tellurium, although the statement is often made, following Eggleston,3 that tellurium makes copper hot-short. Copper specifications call for only traces of these elements. Skowronski and Mosher4 give data on the effect of selenium and tellurium on the conductivity of tough-pitch copper. In private communication Mr. Skowronski says that the samples were hot-forged from small castings and drawn to 0.081 in. diameter, but it should not be inferred from this that these elements are harmless to the working properties of wirebars and commercial shapes. Constitution and Microstructure Constitution.—Sulphur, selenium and tellurium exist in their alloys with copper in the form of copper sulphide, selenide or telluride. These compounds are practically insoluble in the solid state and possess limited

Jan 1, 1938

By A. L. Fentress, P. R. Bucky

The purpose of this paper is to present a scientific method for determining the proper span and shape of roof for safe and economical mining; at present, these two vital factors wherever pillars are left to support the roof are determined by local practice or general experience. To develop the method described here, experimental laboratory work was done. The arch adopted was a segment of a circle, a flat roof being considered an arch with an infinite radius. Hitherto, arches have been used underground without the background of stress analysis that generally precedes arch construction on the surface. In many cases results have not been as expected, because of the lack of knowledge of the factors affecting its strength and behavior. A theoretical and experimental study of arches should furnish information that will make it possible to design safe and economical surface structures as well as underground openings. For example, on the subject of mine drifts and tunnels, the present idea is that arching their backs increases their strength; this paper will indicate that this is not always true, and if it can be shown that under certain conditions arching becomes unnecessary an economic saving will result. In room-and-pillar work a question may arise as to whether arching the roof and gobbing the excavated material will result in timber saving, and a decrease in the dangers from falls of roof. It is to be distinctly understood that each mine must be treated as an individual problem, and that answers to these questions and many others can now be found after experimental laboratory data have been obtained. Mine-Arch Structure Fig. 1 shows the elements that affect the strength or behavior of the experimental arch. They are the span, crown thickness, radius of curvature, rise and restraint. The restraint in all cases was made sufficient to cause the arch to fail without displacing the restraining sides. Fig. 2a is a photograph of a model arch prepared for testing in the centri-

Jan 1, 1934

By Cyril Stanley Smith

For many years sulphur and its congeners selenium and tellurium have been regarded as very harmful elements in copper and copper-rich alloys. Like many similar prejudices, this has been found to be partly wrong. All three of these elements actually have no great effect on the working properties of copper and its alloys, and are desirable additions in that they considerably enhance the machinability of alloys in which they are present. Because of their possible commercial importance, a study of the machinability and other properties of the pure binary alloys was made, as described in this paper, and the effect of selenium on a large number of copper alloys was determined. The current opinion regarding the deleterious effects of elements in this group undoubtedly arose because of occasional failures of tough-pitch copper containing unusually high tellurium, and because of the well-known fact that sulphur causes spewing and unsoundness in tough-pitch copper. Siebe,1 also Deretchey and Margolina,2 studied the effect of sulphur on copper and showed that in the absence of oxygen it was present in the form of copper sulphide, which was less harmful to the properties than an equivalent amount of copper oxide. No data have been published on selenium and tellurium, although the statement is often made, following Eggleston,3 that tellurium makes copper hot-short. Copper specifications call for only traces of these elements. Skowronski and Mosher4 give data on the effect of selenium and tellurium on the conductivity of tough-pitch copper. In private communication Mr. Skowronski says that the samples were hot-forged from small castings and drawn to 0.081 in. diameter, but it should not be inferred from this that these elements are harmless to the working properties of wirebars and commercial shapes. Constitution and Microstructure Constitution.—Sulphur, selenium and tellurium exist in their alloys with copper in the form of copper sulphide, selenide or telluride. These compounds are practically insoluble in the solid state and possess limited

Jan 1, 1938

By Charles S. Barrett

There is a road into the microscopic realm that has remained untraveled through all these years of intense activity with high-power optical and electron microscopy. The road is worthy of careful scouting by metallurgists and other investigators, for it leads into relatively new country and it makes some areas accessible that heretofore could be reached only by very indirect paths or by the use of imagination. And when the road passes through familiar territory it frequently permits a new view of commonplace things that should prove of value from time to time. An accepted way to interest people in new sights such as this is to present an illustrated travelogue. This I propose to do, using many pictures taken in my recent exploration of this road. In the manner of travelogues, I shall touch briefly upon a large number of different subjects in physical metallurgy and shall attempt to give an exhaustive treatment of none, for the objective is to provide a means for further research, to interest others in it, and to indicate what appears at the moment to be profitable directions for it to take. The method I shall present involves X-rays, but does not make use of the usual accompaniments of X-ray research such as reciprocal lattices, Fourier series, or the stereographic projection. The method is so simple in its fundamentals that it could have been developed 2o years ago, or perhaps even 30 years ago. It is well to have a destination for our travels, so that when we are through we shall have explored some region of importance, despite our preoccupation with the novel means of transportation and our interest in the sights to be seen along the way. So let us name the Cold-worked State as our destination, and make side trips into the territories known as Recovery, Recrystallization, and Precipitation-hardening. A great many investigations have been made of the nature of cold-worked metal, and a great variety of methods used, many of which are indirect, such as X-ray line intensities, X-ray line widths, calori-metric measurements, and magnetic measurements. Since comprehensive reviews of these investigations have been published in recent years, they need not be discussed here. The investigations that were the direct forerunners of the present work should be first mentioned. In 1931 I became interested in the structure of individual spots in X-ray diffraction patterns.l When a crystal is placed in the narrow pencil of X-rays in a Laue camera, the spots recorded on the film are not always uniformly black, but may have an internal structure. The meaning of this may be understood from Fig. I, which represents a narrow beam containing X-rays of many wave lengths (''general radiation") penetrating a crystal in the direction of the arrow and forming a pattern on the vertical film at the right.

Jan 1, 1945

By Arthur Phillips

THE normal method of preparing metallic alloys for commercial use involves the preparation of a melt containing the given components in the chosen proportions and allowing the homogeneous liquid mass to solidify in a mold of the desired form. The solidification is frequently accompanied by a segregation of the alloying elements in different parts of the casting. When the segregation is occasioned primarily by marked differences in density of the solid and liquid phases, it is termed "gravity" segregation. When the segregation conforms to a. selective freezing in harmony with the teachings of the equilibrium diagram of the alloy system-i.e., the lower melting phases are concentrated in the regions of the casting last to freeze-it is often referred to as " normal" segrega-tion. However, in many cases the lower-melting part of the system is concentrated in the parts of the casting first to freeze and the result in this case is termed "inverse" segregation. To complete the. terminology of the subject, normal segregation in a single phase is usually called "coring" and the word will be used in that sense in this paper. Inverse segregation, particularly when the liquid phase is exuded or sweated out on the surface of the casting, is sometimes called "location." Unfortunately, some ambiguity has arisen from the use of this term and it is perhaps advisable to confine its use to the dictionary definition; namely, "The separation of two phases by heat sufficient to melt one but not the other." The gravity and normal types of segregation are both well understood and to some extent are controllable by taking advantage of the most favorable cooling rate for a given casting condition. Inverse segregation has received considerable attention from several investigators- but none of the theories offered seem to account in a convincing way for the many examples of this type. The observations made in the present work on segregation in single crystals, and in some other castings, tend to support one theory of the mechanism of inverse segregation and definitely to

Jan 1, 1937

By Edwin B. Wilson, Joseph W. Leonard, Richard W. Borio

preparation of specification coals for the utility industry is approached from the standpoint of a cooperative effort with the power company to assure that the shipped product will be a noncorrosive coal. Selective mining, coal preparation, the use of additives, and coal blending are mine-site techniques proposed as means for upgrading corrosion-retarding constituents of utility coals (CaO and MgO) while, at the same time, reducing the concentration of those constituents of coal (Na20 and K,O) which cause corrosion. Data obtained from large-scale boiler testing in combination with bench-scale physical and chemical tests are used as a basis for the formulation of mine-site procedures to improve coal combustion utilization. Electric power generation remains the greatest market for coal in the United States. A major reason for this strong market has been the ability of the coal industry to supply a superior product for combustion while maintaining competitive prices. Now that the coal industry is engaged in intensive competition with nuclear power for future energy demand, it becomes ever more imperative that superior coal products are produced. One important problem when burning some coals is a liquid phase corrosive attack on boiler tube metal in the superheater and reheater areas of the furnace where steam temperatures may exceed 1050°F. In addition to causing power outages and high maintenance costs, corrosion is a continuing barrier to the future development of more efficient steam cycles which permit lower generation costs when using coal. Research methods of the past which have been directed at finding solutions which could be applied at the power plant site have been only partially successful and are generally costly. This paper contains a suggested --method of corrosion control through investigation of the problem at the source of the trouble—the coal supplier facility. It is proposed that mine-site pre-ventative procedures be considered as an effective means of cooperative corrosion control between the power company and the coal supplier. Economic justification must be applied to the individual situation. This paper is based on recent work by Combustion Engineering, Inc. and the Coal Research Bureau of West Virginia University under a contract from the Department of the Interior Office of Coal Research.',' Results which are of importance to this discussion may be summarized as follows: 1) The alkali minerals of coal (Na2O and K2O), as measured by an acid leaching process, can be related to corrosion rate in utility boilers. As these constituents increase in a coal product, its corrosiveness can be expected to worsen. 2) The alkaline-earth minerals contained in coal, reported as total CaO and MgO reduce corrosiveness 2s their concentration increases. 3) Naturally occuring, alkaline-earth-bearing materials, such as limestone and dolomite, may be added to a coal to reduce its corrosiveness. 4) Coals with very low iron contents tend to be less corrosive. These results provide the groundwork for examination of the system of operations which occur at the supplier facility from the seam face where mining is begun to the point of loading for shipment. The Mining System Fig. 1 is a cross section of one of the typical coal seams (designated coal A) that was boiler tested during this research program. This seam is overlain by material which consists primarily of a gray-black shale. In the lower third of this seam, there exists a thin rock parting of less than 4 in. in thickness which is consistent throughout the seam. The floor material is fireclay. In order to examine mineral distribution throughout this particular seam, the Coal Research Bureau collected a

Jan 1, 1971

By Calvin Pierson, R. S. Dean, E. P. Barrett

MANY studies have been made of the properties of steel produced by adding varying amounts of sponge iron to the charges used in steelmaking furnaces.1-3 The results of these previous studies, however, have failed to disclose a reason for the belief of steelmakers that steel made in this way is definitely different from steel made entirely from scrap or iron melting stock. This paper deals chiefly with the structure of the sponge iron, of the wrought iron made by welding the sponge iron into blooms, and of the steel made by melting the forged and rolled blooms. It is believed that the structure of the final steel is inherited from the ore and that this inherited structure produces marked differences in the properties of the steel and explains the feeling of steelmakers which is based on their experience. Three kinds of sponge iron were used in this investigation: One made from a limonite ore reduced with natural gas, one made from a hematite ore reduced with natural gas, and one made from a magnetite ore reduced with charcoal. The sponge iron made by reduction with natural gas

Jan 1, 1935

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10' to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970

By Arne Bergholm

Australian rutile was chlorinated in the presence of CO or carbon. The chlorination velocity in CO was found to be strongly influenced by temperature and proportional to the CO concentration, but independent of the Cl, concentration. In the presence of carbon, the reaction velocity is much higher. The reactivity of the carbon and the distance between the carbon and the rutile surfaces are important variables. The reaction velocity is approximately proportional to the Cl, concentration and independent of the CO concentration of the surrounding atmosphere. Experiments with fluidized-bed chlorination of carbon-rutile mixtures indicate that the motion of the bed has little influence on the reaction velocity. At low temperatures, the chlorination velocity of dense tablets is much greater than that of TiO, coke mixtures suitable for fluidization. The reaction mechanism is discussed. In the industrial production of TiCl, rutile is chlorinated in the presence of carbon. Disregarding intermediate steps, the reaction may be expressed by the following equations: The ultimate object of this study was to find out whether the reaction velocity was higher in fluidized bed operation compared with chlorination of pelle-tized carbon-rutile mixtures. From a literature survey and preliminary experiments it was learned that some basic knowledge about the reaction mechanism was needed for a good experimental design. Therefore the following sets of experiments were carried out: 1) Studies on the reaction velocity in the chlorination of rutile with CO as the only reducing agent. 2) Chlorination of separate rutile-carbon tablets. 3) Chlorination of rutile-carbon tablets at different temperatures with various kinds of carbon, various grain sizes, and various tablet-making techniques. This series of experiments was carried out not only with pure chlorine but also with mixtures of chlorine with argon, CO and CO,. 4) Chlorination of rutile-carbon tablets made in a strictly standardized manner. 5) Chlorination of static-bed rutile-carbon mixtures. 6) Fluidized-bed chlorination of the same mixture. The experiments 4 to 6 formed the final and direct test of the main question: Static bed vs fluidized bedo. Although there are many patents and papers dealing with the general aspects of chlorination, only few experiments from which detailed information can be obtained have been reported in the literature. Pamfilov and coworkersl3 have studied chlorination of TiO, with CO or carbon as the reducing agent. They found that the weight decrease per hour at 600o to 800°C amounted to 11 to 14 pct with CO and 45 to 51 pct with carbon. They suggest that phosgene might be an intermediate in the chlorination of TiO,. Takimoto and Hattori have chlorinated reduced titanium oxide (TiO) and found a very high rate of TiC1, -production. They proved that the composition of the gas from the chlorination of rutile-carbon mixtures contained mainly CO. They reported for instance 74.7 pct CO, and 5.6 pct CO at 800°C at which temperature the Boudouard equilibrium composition is 12 pct CO and 88 pct CO. Seligman and Segerchano6 have studied the chlorination of TiO. They proved that Ti0 and chlorine react rather rapidly at temperatures as low as 300°C. Above 400°C, the reaction was complete. At 500°C the velocity of this reaction was much higher than was chlorination of TiO, + C. McTaggart,7 Nishimura, et al. and Wilskam have chlorinated mixtures of carbon and various kinds of rutile or beneficated ilmenite. Nishimura, et al. also report the results from reduction of TiO, with H2, CO, or carbon. At 900°C only 1 pct Ti O is formed in 2 hrs. At 1100°C 23.1 pct Ti, 0, was formed if elementary carbon was present. No carbide formation occurred below 1400°C. McIntosh and Cofferll have observed that the CO, content of the exit gases from chlorination of rutile and calcined petroleum coke is appreciably higher than found in the Boudouard equilibrium. At 900°C the ratio (CO, /CO + CO) is about 80 pct, whereas the equilibrium value is about 2 pct. W. E. Dunn12 has studied the chlorination rates of several TiO,-bearing minerals with CO + Cl, or COCl . Chlorinations were carried out either in a fluidized reactor or a fixed-bed reactor, both having a 30-mm diameter. The results obtained in both reactors were comparable. It was proved that benefi-ciated ilmenite (i.e., ilmenite from which the iron oxide had been removed by chlorination) was chlorinated 10 times faster thanrutile. Sore1 slag showed an intermediate rate. When phosgene is used, the

Jan 1, 1962

By H. F. Yancey, O. L. Furse

Although usually coal is screened with punched plate screens having round-hole perforations, there has been an increasing use of wire-cloth screens with square apertures, especially at pneumatic coal-cleaning plants and at other plants that use vibrating screens. It is therefore desirable to establish a relationship between round-hole and square-hole screens for use not only in experimental investigations of coal-preparation problems, but also for use in commercial operations. This need is apparent whenever it is necessary to substitute wire cloth for punched plate and still retain the familiar trade-size product. Although similar work probably has been done by industrial organizations concerned with the screen sizing of coal, the only recorded study of the subject other than the one described herein of which the authors are aware is that of Roesler,1 who screen-sized two samples of limestone and two of zinc concentrates crushed to pass 1/2 in. with a set of square and round-hole screens and found the ratio to be 1:1.23. Procedure In the course of a study of various methods for determining the friability of coal,2 it was necessary to screen-size the products of a series of friability tests of three different coals with both round-hole and square-hole screens. The coals used were from the Roslyn No. 3 and the Bayne mines in Washington and the Rolapp mine in Utah. Twenty 25-lb. samples of each of these three coals at 3 to 2 1/2 in. round-hole size were dropped from a height of 10 ft. to a concrete floor, and then screened with

Jan 1, 1934

By P. S. Miller, S. H. Ash

EXTENSIVE and diversified resources justify large populations and great industries. To carry on the business of commerce and meet the demands of large populations, the utilization of tunnels in some form for transportation purposes constitutes an important link in modern civilization. The driving of tunnels has been appropriated by the tunneling branch of the heavy-construction industry, and the progressive steps taken by modern tunnel builders were not even dreamed of 50 years ago. Great strides have been made toward more rapid progress in tunneling in the United States during the past 10 years. Tunneling consists of a definite cycle of operations developed from ideas that are crystallized and translated into action programs through various engineering phases that begin with the first preliminary survey and do not end until the job is completed. Once the line of the bore is established and a time set for the completion of the work, the face must advance according to estimates prepared before the work commences. This schedule must be followed in regular sequence from the moment the drills start against a new face of rock until they are ready again to drill the succeeding face, constituting a round.1 Mining is largely tunneling carried on under conditions often more inherently hazardous than actual tunnel construction, but for various reasons1 tunneling is more hazardous than mining in any branch of the mineral industry, On the other hand, obstacles are sometimes encountered in heavy-construction tunneling projects that when met in mining enterprises do not offer comparable tasks to avoid or overcome them. One of these is the existence of water under high pressures. In mining enterprises, various alternatives offer a solution in driving a tunnel, even to the extent of its discontinuance or the abandonment of the mine, but a "construction" tunnel usually must go forward because some important project depends largely if not entirely upon it. This paper describes an unusual method of driving a water-supply tunnel through rock carrying water under pressures and conditions that did not permit the use of ordinary tunneling methods. THE DELAWARE AQUEDUCT The new Delaware aqueduct is a Manhattan project of some magnitude; when completed, it will contain what probably will be, for some time to come, the longest tunnel in the world. Various features in its construction are currently described in the trade journals of the construction industry, and informative engineering details are given in the Delaware Water Supply News, published twice a month by the Board of Water Supply of the City of New York. Work was begun on this project on March 24, 1937. The tunnel will convey water from reservoirs at the headwaters of the Delaware River to the City of New York.

Jan 1, 1942

By Thomas T., Read

ALTHOUGH the first colonists in the area that is now the A United States, whether Spanish, French or English in nationality, were usually keenly interested in the possibilities of mineral wealth, it is a curious and interesting fact that none of them happened upon the mineral deposits that eventually were to make this the greatest mineral-producing country; up to 1800 it would probably have been rated as rather poor in minerals. Spanish explorers traversed the southeastern United States with- , out finding the Appalachian gold deposits that aroused so much interest in the early nineteenth century; Coronado sought in vain for the seven golden cities of Cibola; and the important gold \ deposits of California were not discovered until the political sovereignty of the region had passed from Mexico, which had held it for three centuries. The French also held Canada for nearly two centuries (and the British for another century) without finding the mineral deposits in Ontario and Quebec that now are so important. Though they knew of the copper of the Keweenaw peninsula, the lead ores. of Wisconsin and Missouri, and the coal of Illinois in the seventeenth century, these deposits were all too remote for exploitation. In the area held by Great Britain, iron smelting was planned at Jamestown as early as 1619 and was actually begun at Lynn, Mass., in 1643. The industry grew slowly, at first, but had reached considerable importance before the Revolution. Commercial bituminous coal mining began about 1750 in Virginia but anthracite mining in Pennsylvania was not started until 1800. As a result there was naturally little interest in the technical aspects of mineral prodnction here before 1800 by any except the few people who were actually engaged in it. Students of natural science were much interested in minerals, however. The activities of those who rank as geologists are so thoroughly covered in

Jan 1, 1941

By J. D. Rice, P. L. Wearden, W. L. Hensou

Solutions to the unsteady-state partial water-drive reservoir performance problem can be obtained through the use of analogue computers or high-speed electronic digital computers. The solutions that have previously been resolved for use on digital computers, however, demand a knowledge of the aquifer parameters. Generally, the analogue computers now in use do not require this knowledge. A solution is presented herein where the aquifer performance, expressed in terms of difference equations, is related to the reservoir performance as expressed by the modified Scbiltbuis material-balance equation. A numerical procedure for a medium-sized digital computer also is presented in which a solution to the set of equations defining the aquifer and reservoir performance is obtained and the aquifer parameters (permeability and sand thickness) are automatically optimized while simultaneously matching the known pressure behavior. Predicted pressure behavior can be calculated using rates from any assumed future production practice. The procedure provides an output format which presents the cumulative, incremental and average rate of natural water influx, the per cent gas-cap expansion, the calculated reservoir pressure, the measured reservoir pressure, and the difference between the measured and calculated pressures. Results of a test problem are presented in comparison with results obtained by the Bruce Analyzer, Ohio Oil Co. 's Pace General Purpose Analogue Computer, and Sun Oil Co.'s Single-Pool Electronic Reservoir Analyzer. These results indicate that unsteady-state reservoir perlormance for a single-pool system can be adequately simulated by a numerical method employing a digital computer and that the special-purpose analogue computer can be supplanted by this method. INTRODUCTION The numerical approach to the unsteady-state partial water-drive reservoir performance problem heretofore has been limited in that solutions have been resolved only for certain fixed parameters. Also, prior to the advent of high-speed electronic digital computers in the last few years, calculations were so tedious and time-consuming that they ordinarily were neglected, or some other means of obtaining the solutions were used. The analogue approach had been used for obtaining solutions to the transmission-of-heat problem and, consequently, means were developed for applying the electrical analogue to the unsteady-state reservoir performance problem. Bruce submitted a paper for AIME publication in Sept. 1942, in which he described an electronic device (now called the Bruce Analyzer) for analyzing the water-drive performance of any reservoir, based on either steady or unsteady-state flow characteristics. 1 Sun Oil Co. adopted the analogue approach in 1949 and now has two special-purpose high-speed electronic reservoir analyzers in use.2,3 Two main features of Sun's analyzers are (1) the high repetitive rate of reproducing the entire history of reservoir performance cyclically a number of times per second, and (2) the elimination of the necessity of knowing the properties of the associated aquifer. Since the advent of larger and faster digital computers, the possibility of incorporating this second feature into a numerical approach appeared feasible. Previous work has been done and material published covering the application of numerical methods to the behavior of the pressure with respect to time at any point in an associated aquifer? However, the aquifer parameters must be known from some source. The material presented in Ref. 4 has been used to a great degree in developing the numerical method described herein. DIFFERENTIAL EQUATION AND BOUNDARY CONDITIONS The problem of simulating the performance of a reservoir and the associated aquifer is to determine the characteristics of the aquifer such that the

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By F. S. Young, K. E. Gray

Drilling tests with a 11/4-in. diameter roller bit were performed on Berea and Bandera sandstones and Leuders limestone using water and two conventional drilling muds as circulating fluids to evaluate the influence of dynamic filtration on penetration rate. The muds possessed widely differing API fluid-loss properties. Mud filtrate was constrained to flow beneath the bit; no filtrate flowed radially through the borehole wall. Rock pore pressure at three different locations ahead of the bit, cumulative filtrate volume, borehole pressure and bit location were monitored during drilling. The rock samples, cored in three orientations with respect to bedding planes, possessed a wide range of liquid permeabilities. and were drilled at borehole-to-formation pressure differentials of 0, 250, 500 and 1,000 psig. The effect on penetration rate of API fluid loss, borehole pressure and rock permeability was studied. Rock permeability damage and pore pressure gradients beneath the bit were evaluated. The importance of borehole-to-formation pressure differential was illustrated for each drilling fluid and rock permeability combination. Penetration rates decreased with increased borehole pressure and reduced fluid loss. The observed penetration rate reduction due to changing fluid Ioss was attributed to decreased filtrate flow and improved mud cake plastering hy the low fluid-loss mud. The reduction in filtrate flow could not be related to spurt-loss phenomena. Rock permeability influences penetration rate through particle invasion ahead of the hit, which damage leads to high pressure gradients. Penetration rate variance with sample orientation was evident for water-drZled samples but less obvious for mud-drilled rocks. Permeability damage beneath the bit ranged from 1 to 3 cm. Maximum damage occurred in the first 0.1 cm. Pressure gradients varied with API fluid 10.s.s and could be correlated with penetration rate. The pressure gradient was found to influence penetration rare in rocks of all permeabilities tested. INTRODUCTION Early microbit and small-scale drilling experiments proved to be invaluable contributions to understanding the mechanics of drilling at depth. For example, the effect of borehole-to-pore pressure differential on drilling rate was demonstrated conclusively by Murray and Cunningham', Eckel' and others .' However, the effects of various drilling fluid properties on drilling rate, particularly filtration, have not been studied extensively on a laboratory basis. Microbit correlations of penetration rate with different viscosity and API fluid-loss muds led EckelV o conclude that viscosity and density. more than API fluid loss, were the most important fluid properties in controlling drill bit penetration rates. Ferguson and Klotz6 studied filtration beneath the bit and stated that the maximum amount of filtrate which could conceivably flow beneath a drilling bit could be described by a potential function associated with flow from a moving disc source. and be characterized by a depth-of-filtrate invasion. Invasion depth is a function of penetration rate, formation porosity and permeability, flooding efficiency, pressure difference between borehole and formation and borehole radius, assuming that no filtrate flows through the borehole walls. Electric analog and experimental measurements were obtained, assuming no plugging of the formation pores. Theoretically, filtrate invasion was predicted to extend from 1- to 15-hole radii beneath the cutting surface; experimental results indicated that the extent of invasion was only Y2 in. Comparing these data with results of core-plugging experiments by Norwak and Krueger' led Ferguson and Klotz to state that the drilling operation apparently contributes to higher filtration rates than are observed in nondrilling core filtration tests in which the core face is jetted and scraped. Glenn and Slusser: in describing a linear filtering system in which a rotating bit continuously scraped mud cake from the surface but did not penetrate Alundum cores, stated that mud-solids invasion and permeability damage of the cores were most severe in the first 2 to 3 cm. The filtrate flow rate through the core was found to stabilize after sufficient time had elapsed for the formation of an internal mud cake whose effective permeability was estimated to be 50 to 300 times as high as that of bulk filter cake. Krueger and Vogel reported core permeability damage depths up to 12 in. during a 5-day exposure period in which filter cake buildup was prevented. Havenaar pointed out that the discrepancy between reported and calculated values of filtrate volume obtained in the experiments of Ferguson and Klotz was due, among other things, to failure of the reported API fluid loss to truly represent filtration beneath the bit. Williams," Pro-koplz and others"" have shown that dynamic filtration tests (where a flow of fluid parallel to the filter surface continually erodes the deposited filter cake until a dynamic equilibrium between wall-shearing forces and normally directed compaction forces is attained) yield higher filtration rates than do static tests. Cunningham and Goinss reported results of drilling tests in impermeable shales. They found that by reducing

By Richard L. Ash

7.3-1. Introduction. All phases of mining competent materials are affected directly by the results achieved from primary blasts. It is imperative that their design suit each particular set of mining conditions. In general, the round design must provide an adequate tonnage of material, properly placed with suitable fragmentation, to ensure that loading, haulage, and subsequent disposal or processing are accomplished at the lowest possible cost. Blasting rounds are designed by the proper application of cratering relationships developed for the single, concentric, confined explosive charge. Blasting for surface mining and most open-cut heavy construction, however, is characterized by the use of rounds, composed of a number of explosive charges with relatively long lengths, which are placed in benches with specific finite dimensions. Therefore, modifications must be made to the classical, single point-charge cratering concepts. It is the purpose of this discussion to outline the basic principles, significant variables, and procedures for their integration in the design of rounds that are applicable to conditions characteristic of surface mining. Because relatively insensitive blasting agents will be used in most instances, particular attention must be given to priming, control of confinement, and selection of charge diameters that ensure complete explosive-reaction execution. 7.3-2. General Considerations. The primary requisites for any blasting round are that it ensure optimum results for existing operating conditions, possess adequate flexibility, and be relatively simple to employ. It is important that the relative arrangement of blastholes within a round be properly balanced to take advantage of the energy released by the explosives and the specific properties of the materials being blasted. There are also environ- mental and operational factors peculiar to each mine that will limit the choice of blasting patterns.

Jan 1, 1968

By Walter J. Johnson

The coals in northern Wyoming and Montana are free-burning and non-caking and range from lignite to bituminous C in rank. Strip and underground mining are employed to supply railroad, utility, industrial, and domestic fuel. The market area includes Iowa, Nebraska, Minnesota, North and South Dakotas, Wyoming, Montana, the Pacific Northwest, and western Canada. THE larger producing coal mines in northern Wyoming are located in the Powder River Basin lying between the Black Hills region of South Dakota, eastern Wyoming, and the Big Horn Mountains in north central Wyoming, see Fig. 1. The mines are located particularly in the area along the route of the Chicago, Burlington & Quincy Railroad from Gillette, Wyo., to a point approximately 15 miles northeast of Sheridan, Wyo. Fig. 2 is a graph of coal production in the state of Wyoming from 1918 to 1951. Across the Big Horn Mountains lies the Big Horn Basin, situated between the Big Horn Mountains and the Rocky Mountains proper. Mining in the Big Horn Basin is almost entirely confined to a small area known as the Gebo Field, near the town of Kirby, which is located on the Chicago, Burlington & Quincy Railroad. This paper will describe present operating areas, making only brief reference to the history of mining and marketing primarily because of the large area to be discussed. The coal beds presently mined in the Powder River Basin are all of Tertiary age and are of Fort Union and Wasatch formations of Paleocene and Eocene ages, see Fig. 3. The Fort Union formation, consisting of 2000 to 3200 ft of alternate sandstone, shale, and coal, is divided from oldest to youngest into the Tullock, Lebo Shale, and Tongue River members. Most of the mineable coal is in the Tongue River member, which is 500 to 800 ft thick. The Carney coal bed, varying from 7 to 20 ft in thickness, is considered the base of the Tongue River member. About 85 ft above the Carney is the Monarch bed, ranging from 18 to 42 ft in thickness. At approximately 210 ft above the Monarch is what is locally known in the Sheridan district as Dietz No. 3 bed, which varies from 12 to 30 ft in thickness. One hundred feet above the Dietz No. 3 is Dietz No. 2 bed, which is 7 to 12 ft thick. At about 100 ft above the Dietz No. 2 is Dietz No. 1 bed, 7 to 15 feet in thickness. Two hundred and fifteen feet above Dietz No. 1 is the Smith bed, approximately 5 ft thick. One hundred twenty-five feet above the Smith is the Roland bed, which is estimated to be approximately 13 ft thick. The Roland bed is considered the base of the Wasatch formation, which in the Powder River Basin is 1000 to 3500 ft thick and is composed largely of shale, sandstone, and coal. The foregoing measures are the only ones above the Tongue River member that have been mined in the Sheridan field. To the east of the Sheridan field, particularly in the area of Gillette, the Roland bed is considerably thicker and is considered the thickest and most extensive coal bed in Wyoming, reaching a maximum thickness of 106 ft. From 125 to 225 ft above the Roland lies the Arvada bed, average thickness 9 ft. Three hundred seventy-five to four hundred feet above the Arvada is the Felix bed, which reaches its maximum thickness of 30 ft near Echeta on the Chicago, Burlington & Quincy Railroad. East of the Powder River the bed averages more than 10 ft in thickness, but it thins in a northwesterly direction. The highest mineable coal in the Powder River field is the Healy bed, about 400 ft above the Felix bed and exposed only in the highest parts of the area where much of it has been burned along the outcrop. Where it has not been burned, the thickness at most of the outcrops is 10 to 15 ft.

Jan 1, 1954

FRIENDS of the late Charles F. Rand presented in 1930 a sum of money from which the income is available to support various phases of the work of the Institute in which Mr. Rand was so deeply interested. At present the fund amounts to $10,400. The specific terms of the deed of gift are as follows: "The fund collected to establish a memorial to the late Charles F. Rand shall be placed in the custody of the Board of Directors of the American Institute of Mining and Metallurgical Engineers, to be set up as a trust to be known as the `Charles F. Rand Foundation,' the income of which shall each year be applied to a distinct purpose to be decided upon in that year by vote of the Board of Directors. This purpose shall be such as to promote the general welfare of the Institute and to constitute a permanent memorial of the usefulness of Mr. Rand, who for many years gave unstintingly of his time and talents in its service. "It shall be within the discretion of the Board of Directors to establish a medal to be known as the Charles F. Rand Memorial Medal to be awarded at such a time and under such rules as may be determined by the Board of Directors, for Distinguished Achievement in Mining Administration." The establishment of this medal was announced at the annual meeting in February, 1932, the term "mining" being defined in its broad sense to include metallurgy and petroleum. Robert Linton is chairman of the Charles F. Rand Foundation Award Committee.

Jan 1, 1943

By Robert H. Richards

Jan 1, 1897

By Patrick H. O’Neill

The Choco placers, mined continuously since the earliest expeditions of the Spanish conquistadors, were exploited by the Indians prior to the conquest. Platinum is found in varying percentages with gold throughout the Choco placers and is found in minor percentages in some placers in other parts of Colombia. The Choco Department is on the west coast of Colombia between the western range of the Andes and the Pacific Ocean and extends from the San Juan River north beyond Panama to the Caribbean. The first reference in European literature to platinum was by Julius Caesar Scaliger in 1557. He did not assign any name to it but referred to it as an infusible metal found in the mines in the New World. The Spaniards had given it the name platina, which is the diminutive for plata, the Spanish word for silver. Don Antonio de Ulloa first recorded the name while on an official visit to the Choco from Spain in 1735.

May 1, 1956