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By S. S. Shen, M. J. Pool, P. J. Spencer

Heats of solution of silver and copper in dilute Ag-Cu-Sn alloys at 720°K have been determined using a liquid metal-solution calorieter. Values of the se2f-interaction coefficient n AgAghave been calculated at constant copper concentrations and n Cu Cuhas been determined at constant silver contents. The reliability of the experimental data is shown by the very good agreement between nCujAg and ij &$; these interaction coefficients have experimental values of -9100 and - 9590 cal per g-atom, respectively. Certain solution models are shown to be inadequate for prediction of solute interaction coefficients in dilute Ag-Cu-Sn alloys. In a previous publication' the results of a thermody-namic study of dilute Ag-Au-Sn alloys were presented. The present work represents the continuation of a program to investigate dilute alloys of the noble metals with tin and in particular is concerned with solute interactions in the Ag-Cu-Sn system. By determination of the magnitude and sign of the various interaction coefficients in dilute alloys it is possible to gain some understanding of the different types of solute-solute and so lute-solvent bonding changes that occur as the solute concentrations are varied. Hence systematic studies of alloys with similar physical characteristics as regards size, structure, electronegativity, and so forth, of their components can contribute a great deal to present theoretical knowledge of solutions. The recent definition of an enthalpy interaction coefficient, 11, by Lupis and Elliott2 is of particular value in calorimetric studies such as the present one: where j and i are solutes and s is the solvent; Si is the relative partial molar enthalpy of component i and x represents the mole fraction of solute or solvent. Values of ?Hi can be obtained directly by solution calorimetry and data for n are thus easily determined, often with a high degree of accuracy. ?Hi is related to the relative partial molar enthalpy at infinite dilution, ?Hi and to the enthalpy interaction coefficients by the expression: ?Hi?Hi + X;nz+ ... [2] The aim of the present work was to determine the self-interaction coefficients n AgAgand 178: in alloys of different compositions and also to establish values for n Agcg| and ncuAg. Since it is a thermodynamic requirement (resulting from the Maxwell-type relationships which can be applied to partial molar properties) that nAgcu and ncuAg should be equal, a further aim of this study was to demonstrate the agreement between experiment and theory. EXPERIMENTAL A description of the liquid metal-solution calorimeter used in this research has already been published,3 and no further details of its construction and operation will therefore be given here. Copper supplied by the American Smelting and Refining Co. was indicated by them as being 99.999 pct pure, and the silver obtained from A. D. Mackay, Inc., was also quoted as being 99.999 pct pure. A solvent bath consisting of between 70 and 80 g of 99.99 pct pure Sn was used for each series of experimental drops. Its weight was accurately determined and the appropriate amounts of copper or silver were added to give alloys of the desired composition. Approximately 0.00125 g-atom additions were used for determinations of the heat of solution of silver in the bath, while, for copper, specimens consisting of approximately 0.0015 g-atom were used. The heat capacity of the bath was determined at regular intervals during a series of drops using tin or tungsten calibration samples. The heats of solution of silver and copper in pure tin were first determined as a function of their concentration in order to establish the self-interaction coefficients 7AgAg and ncucu Alloys containing a constant 0.01, 0.02, 0.03, and 0.04 mole fraction of copper were then used to study 17:: in alloys of different copper content, while alloys of the same mole fractions of silver were used to determine equivalent data for 178: at constant silver concentrations. The composition of the bath was held at the desired copper or silver concentration by making calculated additions of the appropriate solute throughout the experiment. From the limiting values of ?HAg in the constant copper content alloys it was possible to study ?HAg as a function of xCu and hence to determine 42:. A similar analysis of the re, values permitted calculation of nAgcu. Heat content and heat capacity data from Hultgren et al* were used to calculate heat of solution values from the measured heat effects at the experimental temperature of 720°K. RESULTS AND DISCUSSION Determinations of ?HAg. A preliminary investigation of the heat of solution of silver in pure tin at 720°K was first made in order to establish the value of nAgAg before additions of copper were made and also to compare the value of ?HOAg(l) with that obtained in the previous study of Ag-Au-Sn alloys.' Then the heat of solution of silver in Cu-Sn alloys was investigated as a func-

Jan 1, 1970

By M. R. Geer, J. D. Davis, H. F. Yancey

ALTHOUGH the mechanical cleaning of coal is carried out at plants on the surface, preparation is actually begun at the face in the mine. Here the character of the coal and the amount, character, and distribution of the impurities within the bed may be seen. Blasting methods, dust-allaying procedures, location of mining cut with respect to bands of impurity, and the practice of discarding segregated impurities underground, all have an important bearing on the successful operation of surface cleaning units. The most important single characteristic of both coal and its asso¬ciated impurities from the standpoint of cleaning is specific gravity. Other characteristics related in one way or another to the preparation of coal are rank, petrographic composition, structure and hardness, and friability. These and still other coal properties are discussed in the first section of this chapter and impurity characteristics in the second. COAL CHARACTERISTICS RELATED TO PREPARATION Rank As a result of work done over a period of several years by committees of the American Society for Testing Materials and the American Standards Association, standard specifications are now available showing the classification of coals according to rank and quality of grade.' The term "rank" expresses the degree to which the original coal-forming material has been changed by metamorphism through successive stages from peat to anthracite. Table 1 shows the classification of coals according to rank as devised by the committees of the organizations mentioned. The basic scheme of classification for the higher-rank coals is according to

Jan 1, 1943

By Robert J. Hite, Samuel S. Adams

Potash, the generic term for a variety of potassium-bearing minerals, ores, and refined products (Table 1), owes its importance as an industrial mineral to the potassium requirement of growing plants. The term potash originally referred to potassium carbonate produced by the leaching of wood ashes. This process, for which the first US patent was issued in 1790, was the basis for the largest United States chemical industry in the early nineteenth century. The agricultural use of potash soon eclipsed the chemical applications following the German discovery in 1840 that potassium is essential to plant growth. The initial discoveries of large deposits of soluble potassium minerals, essential for agriculture applications, were made in 1857 in Germany and in 1914 in the United States. More than 90% of the 27.5 Mt K20 produced in the world in 1980 (Searls, 1981) was derived from marine evaporite deposits and approximately 90% was used in fertilizers. The potassium content of an ore, mineral, or product is customarily expressed as % K20, a unit of measure which is neither a natural nor synthetic compound of potassium (1.0% K is equivalent to 1.2046% K2O). Geology Potassium, the seventh most abundant element in the earth's crust, is present in silicate minerals in igneous, sedimentary and metamorphic rocks. Potassium is also a major constituent of many surface and subsurface brines (Table 2). Economic potash deposits are essentially restricted, however, to widespread, thick accumulations of marine chloride evaporite deposits. These deposits yield high grade, large tonnage ore bodies, many of which are amenable to low cost mining and beneficiation. The products from these deposits are, moreover, ideal for use in fertilizer because of the high relative solubility of the potassium chloride and sulfate evaporite minerals. World potash production and reserves for such deposits so vastly overshadow other sources of potassium that the following discussion will be limited largely to potash deposits in marine evaporites with brief reference to certain potash-rich brines. Approximately 85% of current domestic production is from bedded salt deposits and much of the balance is from brines. Marine evaporite deposits are accumulations of salt minerals deposited in structural sedimentary basins through the evaporation of seawater or mixtures of seawater and other brines. The salt minerals are precipitated in assemblages and sequences of assemblages as determined by the compositions of the brines and the solubility relations in the salt systems (D'Ans, 1933). The evaporation of seawater normally yields carbonate minerals as the first precipitates (Table 3). Further evaporation and concentration of the brine leads to the precipitation, in succession, of sulfate, chloride, and supersaline mineral assemblages including the salts of potassium and magnesium. The common minerals, ores, and products of potassium deposits are listed in Table 1. Many potash deposits contain accessory evaporite minerals together with a variety of detrital and authigenic silicates (Braitsch, 1971). The structural basins within which marine evaporites occur are of two main types: (a) cratonic basins formed by broad epirogenic movements (for example, the Michigan Basin of the midwestern United States and the Permian Zechstein Basin of eastern Europe), and (b) grabens, commonly related to continental

Jan 1, 1983

By K. G. Wikle, W. W. Beaver

A general survey of the mechanical properties of commercially pure beryllium fabricated from powder by vacuum hot pressing and other consolidation methods is presented. The effect of fabrication method, grain size, strain rate, and directionality upon both room and elevated temperature tensile properties is reported. BERYLLIUM metal, in spite of its rather restricted use, has been the object of attention for many researchers in the past half century. However, such work was performed on special experimental lots of metal made in small quantities by a variety of reduction methods. Not until 1946 was there a substantial production of beryllium metal, and not until 1950 was there a steady production of a commercially standard beryllium in the United States. This output was both the result of a requirement of the Atomic Energy Commission for a high grade beryllium of consistent quality and the development of a powder metallurgy process, by the Brush Beryllium Co., known originally as Process Q, which yielded a fine grained beryllium suitable for fabrication. Because this powder metallurgy product, known as QMV, superceded other types of metal made previously and represents the great majority of beryllium in use today, it seems worthwhile to present the results of studies on the mechanical properties of this metal as currently made. To the design engineer and the metallurgist, beryllium has extremely interesting properties. It is as light as magnesium alloys while having a stiffness modulus 40 pct greater than steel and a strength-weight ratio superior to titanium and aluminum alloys and aircraft steels. The melting point is high, 1287°C (2348°F), and it has good corrosion resistance both in air and water. Also, it is highly transparent to X-rays and has good heat and electrical conductivity (electric conductivity is greater than 40 pct of Cu). To the atomic energy program beryllium is considered a valuable material because of its low neutron-capture cross section and high neutron-scattering cross section which make it a good moderator and reflector for the lower velocity neutrons. A major technical difficulty limiting the use of beryllium, especially in structural applications, has been its notch sensitivity and consequent room temperature brittleness. Kaufmann, Gordon, and Lillie1 have reported their work on the mechanical properties of beryllium performed from 1946 to 1950. They studied the room and elevated temperature properties of cast and extruded beryllium and extruded electrolytic flake, Table I. Cast and extruded alloys of 85 to 99 pct Be were tested also. They found that extruded metal developed good strength and appreciable ductility in the extrusion direction and that thermal treatment and alloying provided little improvement in mechanical properties. They concluded that preferred orientation and fine grain size were the means of obtaining optimum tensile properties in beryllium. Other investigators have measured and commented on one of the most striking mechanical properties of beryllium, namely, its abnormally low Poisson's ratio.2 Udy, Shaw, and Boulger3 presented the latest published survey on properties of beryllium but their information is based only on published data available before April 1949 and cites little information on metal fabricated by powder metallurgy

Jan 1, 1955

By Francis Collins, E. R. Brownscombe

A study has been made of the material balance-fluid flow method of estimating reserves and degree of water drive from pressure and production history data. By considering the effect of random pressure errors it is shown that in a particular example a standard deviation of three and one-half pounds in each of ten pressure survey? permits the determination of the reserves with a standard deviation of 8 per cent and the water drive with a standard deviation of 15 per cent, assuming that certain basic geologic data are correct. It is believed that this method of estimating reserves and water drive is useful and reliable in a number of cases. The method is particularly valuable when reservoir pressure data are accurate within a very few pounds, but may also be applied with less accurate pressure data if a relatively large reservoir pressure decline occurs early in the life of the field, as for example in an under-saturated oil field. INTRODUCTION A knowledge of the magnitude of reserves and degree of water drive present in any newly discovered petroleum reservoir is necessary to early application of proper production practices. A number of investigators have contributed to methods of relating reserves, degree of water drive, and production and pressure history. 1-8 Three types of problems of increasing complexity may be mentioned. If a reservoir is known to have no water drive. and if the ratio of the volume of the reservoir occupied by gas to the volume of the reservoir occupied by oil (which ratio permits fixing the overall compressibility of the reservoir) is known, then only one further extensive reservoir property remains to be determined, namely the magnitude of the reserves. A straightforward application of material balance considerations will permit this determination. The problem becomes very much more difficult if we wish to determine not only the magnitude of the reserves but also the magnitude of water drive, if any, which is present. In principle, a combination of material balance and fluid flow considerations will permit this evaluation. Finally, if neither the magnitude of reserves, the degree of water drive, nor the ratio of oil to gas present in the reservoir is known and it is desired to determine all three of these variables, the problem could in principle be solved by a fluid flow-material balance analysis which determines the overall compressibility of the reservoir at various points in its history. The change in compressibility with pressure would provide a means of determining the ratio of gas to liquid present, since the compressibilities of gas and liquid vary differently with pressure variation. However, in practice this problem is probably so difficult as to defy solution in terms of basic data precision apt to be available.' It is the purpose of this discussion to illustrate the second case, which involves the determination of two unknown variables, single phase reserves and degree of water drive, from pressure and production history and fluid property data, and to study the precision with which these unknowns can be determined in this manner in a particular case. Although an electric analyzer developed by Bruce as used in making the calculations to be described, numerical methods necessary in carrying out the process have been devised and have been applied for this purpose. Schilthuis,' for example, developed a comprehensive equation for the material balance in a reservoir. He combined this with a simplified water drive equation, assuming that the ratio of free gas to oil was fixed by geological data and that a period of constant pressure operation at constant rate of production was available to determine the constant for his water drive equation. On this basis he was able to compute the reserves and predict the future pressure history of the reservoir. Hurst developed a generalized equation permitting the calculation of the water drive by unsteady state expansion from a finite aquifer. He showed in a specific case how the water influx calculated by his equation, using basic geologic and reservoir data to fix the constants, matched the water influx required by material balance considerations. Old3 illustrated the simultaneous use of Schilthuis' material balance equation and Hurst's fluid flow equation for the determination of the magnitude of reserves and a water drive parameter from pressure and production history. He used this method to calculate the future pressure history of the reservoir under assumed operating conditions. As a basis for determining reserves, Old assumed a value for his water drive parameter and calculated a set of values for the reserves, using the initial reservoir pressure and each successive measured pressure. The sum of the absolute values of the deviations of the resulting reserve numbers from their mean value was taken as a criterion of the closeness of fit to the experimental data possible with the water drive parameter assumed. New values of the water drive parameter were then assumed and new sets of the reserves calculated until a set of reserves numbers having a minimum deviation from the average was established. The average value of- the re-

Jan 1, 1949

By E. R. Brownscombe, Francis Collins

A study has been made of the material balance-fluid flow method of estimating reserves and degree of water drive from pressure and production history data. By considering the effect of random pressure errors it is shown that in a particular example a standard deviation of three and one-half pounds in each of ten pressure survey? permits the determination of the reserves with a standard deviation of 8 per cent and the water drive with a standard deviation of 15 per cent, assuming that certain basic geologic data are correct. It is believed that this method of estimating reserves and water drive is useful and reliable in a number of cases. The method is particularly valuable when reservoir pressure data are accurate within a very few pounds, but may also be applied with less accurate pressure data if a relatively large reservoir pressure decline occurs early in the life of the field, as for example in an under-saturated oil field. INTRODUCTION A knowledge of the magnitude of reserves and degree of water drive present in any newly discovered petroleum reservoir is necessary to early application of proper production practices. A number of investigators have contributed to methods of relating reserves, degree of water drive, and production and pressure history. 1-8 Three types of problems of increasing complexity may be mentioned. If a reservoir is known to have no water drive. and if the ratio of the volume of the reservoir occupied by gas to the volume of the reservoir occupied by oil (which ratio permits fixing the overall compressibility of the reservoir) is known, then only one further extensive reservoir property remains to be determined, namely the magnitude of the reserves. A straightforward application of material balance considerations will permit this determination. The problem becomes very much more difficult if we wish to determine not only the magnitude of the reserves but also the magnitude of water drive, if any, which is present. In principle, a combination of material balance and fluid flow considerations will permit this evaluation. Finally, if neither the magnitude of reserves, the degree of water drive, nor the ratio of oil to gas present in the reservoir is known and it is desired to determine all three of these variables, the problem could in principle be solved by a fluid flow-material balance analysis which determines the overall compressibility of the reservoir at various points in its history. The change in compressibility with pressure would provide a means of determining the ratio of gas to liquid present, since the compressibilities of gas and liquid vary differently with pressure variation. However, in practice this problem is probably so difficult as to defy solution in terms of basic data precision apt to be available.' It is the purpose of this discussion to illustrate the second case, which involves the determination of two unknown variables, single phase reserves and degree of water drive, from pressure and production history and fluid property data, and to study the precision with which these unknowns can be determined in this manner in a particular case. Although an electric analyzer developed by Bruce as used in making the calculations to be described, numerical methods necessary in carrying out the process have been devised and have been applied for this purpose. Schilthuis,' for example, developed a comprehensive equation for the material balance in a reservoir. He combined this with a simplified water drive equation, assuming that the ratio of free gas to oil was fixed by geological data and that a period of constant pressure operation at constant rate of production was available to determine the constant for his water drive equation. On this basis he was able to compute the reserves and predict the future pressure history of the reservoir. Hurst developed a generalized equation permitting the calculation of the water drive by unsteady state expansion from a finite aquifer. He showed in a specific case how the water influx calculated by his equation, using basic geologic and reservoir data to fix the constants, matched the water influx required by material balance considerations. Old3 illustrated the simultaneous use of Schilthuis' material balance equation and Hurst's fluid flow equation for the determination of the magnitude of reserves and a water drive parameter from pressure and production history. He used this method to calculate the future pressure history of the reservoir under assumed operating conditions. As a basis for determining reserves, Old assumed a value for his water drive parameter and calculated a set of values for the reserves, using the initial reservoir pressure and each successive measured pressure. The sum of the absolute values of the deviations of the resulting reserve numbers from their mean value was taken as a criterion of the closeness of fit to the experimental data possible with the water drive parameter assumed. New values of the water drive parameter were then assumed and new sets of the reserves calculated until a set of reserves numbers having a minimum deviation from the average was established. The average value of- the re-

Jan 1, 1949

By Hans Lundberg

Jan 1, 1927

David T. Day, Washington, D. C.: The paper of Mr. Adams is chiefly valuable because it emphasizes the ease with which petroleum can migrate in the earth's crust. Concerning this migration, I have little faith in the rôle of water as a carrier of gaseous or liquid hydrocarbon, suspended or mixed in the water in any way. My lack of faith is due to observation of

Jan 1, 1903

By D. H. Davis

There are two general types of oil flotation processes, froth and bulk-oil. In froth flotation, the coal concentrates are removed in the form of a froth or foam composed of air, liquid, and solids. Mechanical or pneumatic agitation of a coal slurry with suitable frothing agent causes a selective action of the bubbles to the coal particles which are carried to the upper portion of the pulp in the flotation cell; the refuse is wetted by the water and does not rise with the froth, but goes out as tailings. The other type of flotation process, bulk-oil, consists of thoroughly mixing the slurry or pulp with 30 to 50 pct of its weight of oil. The coal agglomerates with the oil and drops to the bottom of the cell while the refuse is wetted by the water and is carried away in suspension. The concentrate granules may be screened and drained to 12 to 15 pct moisture. The minus 200 or 300-mesh is very effectively treated by this process. The Trent process is a bulk-oil type which has been used for coal cleaning on a commercial basis, but its use has been discontinued in this country. Froth flotation of bituminous coal should be subdivided into two distinct fields: (I) separation of a dry coal product such as recovered from an aspiration system; (2) separation of a minus 48-mesh slurry such as produced from a thickener in a wet cleaning plant. The capacities, performance, and general operating characteristics are very different in these two fields. The recirculated slurry in a washery becomes oxidized and is much harder to treat than a dry dust. It is difficult to clean a slurry containing an appreciable percentage of plus 48-mesh without also floating some high-ash clays minus 200-niesh in size. On the other hand, while working with an aspirated dust, good results have been obtained in floating coal as coarse as 3/16-in. Because of the relatively low capacity of flotation machines as compared with conventional fine-coal cleaners .and because of the greater quantity of reagents required to float coarse coal, there is usually no point in considering flotation on bituminous coal for anything coarser than approximately 48-mesh. In some coal-cleaning plants, good separations are being made down to 80 or even 100-mesh by a less expensive system of coal cleaning than flotation. The Pittsburgh Coal Co. carried out extensive tests on laboratory batch machines and on small units of both pneumatic and mechanical agitation types from 1930 to 1935 and have operated six, eight, and then twelve mill-size mechanical subaeration cells from 1932 to 1944 This paper will deal with some of the operating phases and results of coal-flotation practices as derived from this experience, and more specifically with the flotation practice at the Champion No. I preparation plant. The experience gained from the research and initial experimental work contributed greatly to the successful operation of the mill-sized flotation units at Champion.

Jan 1, 1949

By L. A. Rapport, J. R. McCord, W. P. Drews, K. H. Coats

Water movement about an oil or gas reservoir can be predicted provided an aquifer influence function is known. This function is generally determined from an electric analyzer study or by fitting an idealized mathematical model to field data. A prohlem arises in determining that influence function which best reproduces field data and satisfies certain smoothness requirements, without making any idealizations concerning aquifer geometry and heterogeneity. This study shows the problem to be solvable through the linear programming technique and presents applications to one oil reservoir and two gas storage reservoirs. In addition, a theorem is stated and proven which confirms influence junction smoothness requirements heretofore accepted on physical intuition and establishes additiotzal smoothness constraints formerly not recognized. INTRODUCTION The pressure decline accompanying production results in water encroachment into oil and gas reservoirs situated adjacent to aquifers. The importance of this water movement derives from the significant dependence of production rate upon reservoir pressure and of pressure, in turn, upon water encroachment. Pressure and rate of water movement are uniquely related through an "influence" function which may be in the form of reservoir pressure response to a unit water encroachment rate or of water movement caused by a unit reservoir pressure drop. This influence function reflects the heterogeneity and geometry of the aquifer and is therefore particular to each reservoir. If the influence function is known, then reservoir pressure may be predicted from a production rate schedule, or vice-versa, with the aid of the material balance equation which relates water influx to reservoir production and pressure. The problem of determining this influence function for a given reservoir has been approached in three different ways. Van Everdingen and Hurst calculated and tabulated certain influence functions pertinent to idealized mathematical models which satisfy simplifying assumptions such as aquifer homogeneity and elementary reservoir-aquifer geometries.' Other studies developed additional tables for a variety of elementary reservoir-aquifer geometrical con- figurations and demonstrated their validity and utility.:' Hicks, et al. described the use of an electrical network to determine an influence function giving "best" match of field history and allowing prediction of future performance.' Finally, Hutchinson and Sikora5 and Katz, Tek and Jones attempted to develop a calculation method for deriving the influence function directly from field data with no idealizing assumptions concerning aquifer geometry and homogeneity. They encountered difficulties with inaccuracies in field data and with satisfaction of well-known smoothness requirements of the influence function. This study is concerned with the determination of influence functions from field data and, more specifically, treats the following problem: given field pressure-production data of arbitrary accuracy, how does one determine the influence function which, subject to satisfaction of known smoothness requirements, gives best agreement with field history? A rigorous solution to this problem is ohtained through linear programming as described below. Example applications to one oil and two gas storage reservoirs are presented. In addition, a theorem is proved which confirms influence function smoothness requirements heretofore accepted on physical intuition and establishes additional smoothness requirements formerly not recognized.

Jan 1, 1965

By Gordon M. Yocom

A pRopeR consideration of the subject of this paper should include economic aspects as well as the technical phases of the metallurgy, production, and properties of the product. The metallurgical phases of the processing and properties of the product will be considered only from practical aspects and within the scope of the writer's experience with tonnage production. The Bessemer process was invented 85 years ago and became important because it put steel manufacture upon a larger and less costly basis. In America the Bessemer production has declined for many years and has not maintained its proportionate place with the rapid advances of the open hearth. The achievements in the open-hearth field were attained by the greater number of technical people attracted to that branch of the industry. The antipathy of technical students for the older and less popular Bessemer field gradually weakened the forces defending it and retarded the development of new and better methods. In Europe the economic advantage of the basic Bessemer process has not been overlooked and the tonnage usually is greater than that of the open hearth. The acid process has been the subject of renewed attention in America during the past few years and those who are more familiar with it are striving to show that the method is too valuable to abandon. A considerable tonnage of Bessemer-blown metal, in both molten and ingot forms, used in connection with the open-hearth practice makes it an important auxiliary unit to the industry. This practice aids in modifying the price level of heavy remelting scrap in addition to speeding up the open-hearth operation. The use of Bessemer steel has continued not only because of periodic economic advantages but also because of certain inherent qualities of machinability, weldability and stiffness, which are valuable for many applications. The properties of stiffness and rather high reaction to cold-work require some modification in order to meet the demands of modem methods of processing, which involve cold-reduction and cold-forming. At least one factor contributing to the stiffness of this steel is the relatively high phosphorus content of the acid product. The phosphorus content of the Thomas or basic Bessemer steel of Europe is considerably lower than the normal acid product in America. The American industry has continued the use of the acid process chiefly for the reason that the available ores are more easily adapted to this process from both metallurgical and economic standpoints. In European practice the basic process is necessary with the highly phosphoric ores available and it is sustained to some degree by the sale of the rich phosphate slag as a by-product. The basic process was used in this country at several plants many years ago, but was abandoned for economic reasons. A part of the past history of these trials is given here because the author believes it has not been published and it has some bearing on the subject of this paper. The information is authentic to the extent that he possesses chemical laboratory notebooks

Jan 1, 1941

By Gordon M. Yocom

A pRopeR consideration of the subject of this paper should include economic aspects as well as the technical phases of the metallurgy, production, and properties of the product. The metallurgical phases of the processing and properties of the product will be considered only from practical aspects and within the scope of the writer's experience with tonnage production. The Bessemer process was invented 85 years ago and became important because it put steel manufacture upon a larger and less costly basis. In America the Bessemer production has declined for many years and has not maintained its proportionate place with the rapid advances of the open hearth. The achievements in the open-hearth field were attained by the greater number of technical people attracted to that branch of the industry. The antipathy of technical students for the older and less popular Bessemer field gradually weakened the forces defending it and retarded the development of new and better methods. In Europe the economic advantage of the basic Bessemer process has not been overlooked and the tonnage usually is greater than that of the open hearth. The acid process has been the subject of renewed attention in America during the past few years and those who are more familiar with it are striving to show that the method is too valuable to abandon. A considerable tonnage of Bessemer-blown metal, in both molten and ingot forms, used in connection with the open-hearth practice makes it an important auxiliary unit to the industry. This practice aids in modifying the price level of heavy remelting scrap in addition to speeding up the open-hearth operation. The use of Bessemer steel has continued not only because of periodic economic advantages but also because of certain inherent qualities of machinability, weldability and stiffness, which are valuable for many applications. The properties of stiffness and rather high reaction to cold-work require some modification in order to meet the demands of modem methods of processing, which involve cold-reduction and cold-forming. At least one factor contributing to the stiffness of this steel is the relatively high phosphorus content of the acid product. The phosphorus content of the Thomas or basic Bessemer steel of Europe is considerably lower than the normal acid product in America. The American industry has continued the use of the acid process chiefly for the reason that the available ores are more easily adapted to this process from both metallurgical and economic standpoints. In European practice the basic process is necessary with the highly phosphoric ores available and it is sustained to some degree by the sale of the rich phosphate slag as a by-product. The basic process was used in this country at several plants many years ago, but was abandoned for economic reasons. A part of the past history of these trials is given here because the author believes it has not been published and it has some bearing on the subject of this paper. The information is authentic to the extent that he possesses chemical laboratory notebooks

Jan 1, 1941

By M. C. Flemings, P. J. Ahearn

Dendvite morphology of unidirectionally solidified Sn-12 pct Bi alloy was determined with the aid of X-ray and macroetch techniques. Columnar growth direction (growth direction of primary arms) in this alloy is [110]; secondary arms grow in the [lii], [111), and [112] directions. Interstices between [112] dendrite arms fill in during early stages of solidification so that well-defined (110) planes are seen in the final structure (parallel to the heat-flozo direction). Similarly, interslices betweex the [111] secondary arrlls fill in to form (112) planes, and interstices between [1111 ] arms fill in to form (112) planes. DENDRITE morphology in alloys is conveniently studied in unidirectionally solidified castings. In this type of solidification, heat is extracted from a single chill surface of the casting while other surfaces are insulated. Solidification progresses from the chill and results in cast grains that are columnar with the long axis of the grain perpendicular to the chill. Dendrite morphology is conveniently studied by examination of etched surfaces parallel and perpendicular to the chill, as previously described.'" Experimental studies on the growth direction for tin are in general agreement. The major growth direction is [110]:-' although this is altered somewhat by supercooling. In one study, tin dendrites pulled from a supercooled melt had a growth orientation 12 deg away from the [110] direction toward the [002] direction.' This orientation could be changed back to the [110] or close to the [110] direction by changing the tempera- ture gradient in the melt. In a study using autoradio-graphic techniques, (111) directions were shown to be directions of preferred growth in addition to the [110) direction.7 PROCEDURE The samples employed in this study were cut from 12 pct Bi-88 pct Sn castings, 1.5 in. in diam and 3.5 in. tall. The casting procedure consisted of heating the charge to 390°C and then pouring the molten alloy directly into a gypsum sleeve mounted on a massive copper chill. Specimens were cut from the ingot, mounted, polished, and etched with Taffs reagent [FeC13 .6H2O, 2 g; HC1, 5 cu cm;H20, 30 cu cm; CzHaOH (95 pct), 60 cu cm].' The dendritic pattern was clearly visible after etching. Photomicrographs at about 8 and 35 times were taken on surfaces parallel and perpendicular to the chill. Laue back-reflection patterns were obtained from three different columnar grains in a singIe polished face 2 in. from the chill. The cut face was polished and positioned in the beam of a Laue camera, so that diffraction occurred from a single dendritic grain. The resulting diffraction pattern was interpreted to determine crystal log raphic orientation in relation to the heat-flow direction and in relation to microstruc-ture of the given grain. RESULTS Fig. 1 shows a horizontal and vertical section of the columnar structure, at low magnification. Light regions are rich in tin, and darker regions tin-poor; the primary phase is tin-rich a phase. The two sections shown were taken orthogonally from the same metallographic specimen. It is readily seen from Fig. 1 that the dendrites have

Jan 1, 1968

By C. M. Weld

(Cleveland Meeting, October, 1912.) IN the course of my professional work in China during the fall of 1907, I had an opportunity to visit the iron-ore mines at Ta-yeh in Hu-pei province (long. 114° 50' E., lat. 30° 20' N.). It occurs to me that a rescript and discussion of my notes taken at that time should be of interest, particularly as supplementing the exceedingly interesting recent paper-of Thomas T: Read on The Mineral Production and Resources of China.1 Ta-yeh is situated near the right bank of the Yangtze river. The mines are at an average distance of about 16 miles from the river-port Shi-hui-yao, which in turn is some 70 miles S-E. of Hankow. The ores are shipped to the works of the Han-Yeh-P'ing Iron & Coal Co. at Hanyang, as also very largely to the Japanese government iron- and steel-works at Wakamatsu, Japan. Smaller quantities have been exported to the Pacific coast of the United States. These ore-deposits have been briefly noticed in a number of publications, but, so far as I know, Mr. Read's description, in his chapter on the iron-ores of the Chinese Empire,2 contains the first attempt to define their geological character. In his more recent paper Mr. Read follows very closely the text of his earlier description. To quote briefly from the recent paper, he says : " The iron-ores at Ta-yeh . . . . lie along the contact between a marble and an intrusive body of a dark-gray syenitic rock." He refers to a figure which exhibits in plan, but not in section, the relative positions of the syenite, ore-bodies, and limestone. The contact is seen to trend approximately E-W., with the syenite on the north and the limestone on the south. " The syenite lies to the north of the marble, and a few miles farther north the marble again' appears, iron-ore again being present along the contact." No litho- 1 Bulletin Bulletin No. 63, March, 1912, pp. 293 to 343. 2 The Iron Ore Resources of the World', vol. ii., p. 913 (Stockholm 1910).

Oct 1, 1912

By H. E. Elliott, R. S. Busk, A. T. Peters

ONE of the problems of the fabricator of metals and alloys is the propensity of some composition ranges toward abnormal grain growth during certain stages of fabrication. In this respect magnesium alloys are no exception among alloys. Fortunately, convenient foundry control methods have been developed by which the abnormal grain growth possible in certain magnesium-alloy castings can be suppressed. An unusual characteristic of magnesium alloys, however, is that castings of some composition ranges are subject to local grain growth during heat-treatment without the necessity of intentional mechanical stressing of the part prior to heat-treatment. This effect occurs only under certain critical casting conditions, and only in certain alloys of greater than about 8.5 per cent aluminum content, such as C alloy (Mg, o per cent Al, 2 per cent Zn, 0.2 per cent Mn) and G alloy (Mg, i0 per cent Al, 0.2 per cent Mn). The first observation of this phenomenon in cast magnesium alloys occasioned much surprise, since it is not observed in other metals. Jeffries and Archer' have stated that "the grain size of cast metals, provided they have not been plastically deformed, cannot be changed by heating below the melting point." The study of the conditions leading to abnormal grain growth in cast magnesium alloys, and of the mechanism of this phenomenon, has led to some very interesting observations. Perhaps the most significant of these was the observation that stresses originating from cooling contraction in magnesium-alloy castings are the only stresses necessary, under certain conditions, to cause local recrystallization and subsequent grain growth in the casting during heat-treatment. of abnormal local grain growth was a definite problem in the production foundry on C alloy sand castings. Illustrated (Fig. r) is a picture of a casting scrapped because of this defect. A mottled effect is produced in coarse-grained areas by suitable etching solutions. The properties of metal in the affected area are much impaired by such grain coarsening. Ultimate tensile strengths of half the normal value have been measured in metal of this nature. In this paper are described the techniques that have been developed by The Dow Chemical Co. for studying, and in large measure solving, this production problem. Also discussed are studies of the mechanism by which excessive grain coarsening occurs, and the fundamental conditions that produce this effect. The abnormal grain growth discussed in this paper will be referred to as "germination," since this term has been defined' as any process leading to an abnormally coarse grain size. This paper deals only with abnormal local grain growth that may occur during the solution heat-treatment of certain magnesium-alloy castings, as dis-

Jan 1, 1945

By Carl Wagner

This paper contains solutions of the differential equation of diffusion in binary alloys if the diffusion coefficient is an exponential function of the concentration of one of the components. THE general differential equation for one-dimensional diffusion in a binary system can be written as: where c is the concentration of one of the two components in any suitable units; x, the distance from a reference plane; t, time; and D, the diffusion coefficient. Hartley and Crank&apos; have pointed out that eq 1 with conventional length units for measuring the distance x holds only if the alloy can be regarded as a rigid framework. In general, this is not the case, especially if the lattice parameter varies appreciably with composition. If a modified coordinate system is used instead of an orthodox system based on the centimeter a:: length unit, eq 52 is obtained, which has the same general form as eq 1 and is generally valid. The necessary transformations are presented in the appendix. If&apos; D is independent of concentration, analytical solutions of eq 1 are known for numerous boundary conditions. If D depends on concentration, solutions based on known analytical functions are not available. Among others, Boltzmann2 and Matano3 have shown that the concentration c depends only on (x/t1/2) in the case of diffusion between two semi- infinite spaces with uniform initial concentrations: c = c, for x < 0, t = 0, i.e., x/tl/2 = — x [21] c = c2 for x > 0, t = 0, i.e., x/tl/2 = + a Moreover, Boltzmann and Matano have shown how D may be calculated as a function of concentration over the whole range of composition from c -c, to c = c2 if c as a function of (x/t1/2) for the initial conditions stated in eq 2 has been determined experimentally. Thus, for instance, in principle, the diffusion coefficient in silver-gold alloys may be calculated as a function of concentration for the whole range of composition from only one diffusion experiment with a couple of pure silver and pure gold welded together. If the diffusion coefficient D as a function of concentration c is known, a solution of eq 1 for boundary conditions as stated in eq 2 with arbitrarily chosen values of c, and C2 may be wanted. For instance, if the diffusion coefficient in an alloy A-B as a function of concentration has been derived from an experiment with a diffusion couple involving 0 and 30 pct B as initial. concentrations, the calculation of the concentration distribution in a diffusion couple involving other initial concentrations, e.g., 5 and 20 pct B, may be desired. This problem may be solved by numerical or graphical integration of eq l. The solution of an ordinary differential equation of second order, which results from using (x/t1/2) as an independent variable, can be computed quite rapidly if two conditions for the same value of the independent variable are given. In eq 2, however, two conditions are given for two

Jan 1, 1953

By George Harrington

THIS paper is a brief description of the design and equipment of a new coal mine in southern Illinois, which has many features not common practice in shaft coal mining and which is laid out and equipped for such unusually large capacity that it promises soon to become one of the largest mining operations of its kind. Shaft sinking for the mine, New Orient, was commenced in May, 1921, by the Chicago, Wilmington & Franklin Coal Co. In October, 1924, the plant was practically completed and was producing over 6000 tons of coal per day. There is good prospect that within a few years, when the mine is fully developed and manned, the output will attain a daily rate of 12,000 tons. The coal seam at New Orient lies approximately horizontal, about 500 ft. below the surface, and may be said to run from 9 to 12 ft. in thickness. The tendency in Franklin County has been toward large mining units (5000 to 6000 tons per day) with great care being given to protection against fire and explosion hazards, and usually with quite elaborate surface plants permitting careful preparation of the coal into graded sizes comparable with those made in the anthracite region. The field is unionized, with uniform conditions of wages for various classes of work, hours, etc., and the Illinois mining laws are quite specific with regard to fireproofing and safety measures. These conditions make it difficult for any but well-equipped and well-operated mines to meet the competition of the numerous fine properties of which this county can justly be proud. The coal company&apos;s property was already developed on the western side by the Orient. mine-a much visited and written about operation (with which many of you are possibly familiar through the Department of Mines&apos; film "The Story of Coal ") which until recently held the 8-hr. production record with 8218 tons and usually ran quite consistently with production of slightly over 6000 tons per day. Experience at Orient was naturally one of the greatest influences in determining the location and character of the New Orient.

Jan 2, 1925

By Karl D. Libsch, Modesto E. Erneta

Both battery design and environmental pressures are forcing the secondary lead industry to consider new and different processes. Trends in battery design are making normal decasing increasingly difficult. Lead in air, sulfur dioxides, and solid/liquid waste heavy metal restrictions are tightening. There is no clearly defined industry trend toward a given process, but it is clear that plants will be larger, less labor-intensive, and automated.

Jan 1, 1977

By Edward H. Robie

HOW have recent events affected the general trend in world mineral production? What effect has the World War, with its resultant boom and depression, had on the long-term trend of output? Have all of the principal metals and fuels been similarly affected, or have some boomed or slumped much more than others? The trend of world production of coal, iron, the principal nonferrous metals, and petroleum is shown in the accompanying chart, covering the period from 1882 to 1931 inclusive-the last fifty years. The curves are plotted logarithmically to show the comparative trends. In the lower left-hand corner of the chart is a slope diagram to aid in visually evaluating. the average yearly rate of increase in production; from this one can easily see, for example, that the petroleum production curve indicates an average annual increase of around 8 per cent, and that up to the period of the World War the average annual increase in copper production was about 6 per cent.

Jan 1, 1932

By V. A. Phillips

Transmission-electron micrographs of electro-thinned samples of bulk-aged Cu-3.1 pet Co alloy show an aging sequence, supersaturated solid solution — coherent particles — quasi -coherent particles — noncoherent particles. Hardening is due to precipitation of coherent spherical fee coball-rich particles showing coherency strain fields, which are resolved at between 15 and 30A diameter. Loss of- full coherency did not occur until well into the overaged region, even with the assistance of deformation after aging. Different average particle diameters of 123, 92, and 149 ± 10Å were observed in samples aged to peak yield strength at 600°, 650°, and 700°C, respectively, indicating that there is no critical size for peak hardening. Noncoherent particles tended to develop (111) faces and became octahedral in shape. Dislocations tended to nucleate spherical coherent particles which eventually grew together forming large elongated particles. The surface energy of a noncoherent (low-angle) inter-phase boundary is estimated to he about 50 ergs per sq cm. A number of particle lining-up phenomena were observed. Overaging is principally attributed to increase in particle spacing, progressive loss of coherency, and increase in amount of discontinzdous precipitation. COPPER dissolves about 5.6 at. pet (5.2 wt pet) of cobalt at 1110oC1 and the solubility decreases to 0.75 at. petl (0.54 at. pet)2 at 650°C and to 0.1 at. pet or less at lower temperature.&apos; It has been known for many years3-5 that Cu-Co alloys are capable of age hardening. Since cobalt is fee above 417°C and its atom size is only about 2 pet smaller than that of copper, precipitation of coherent particles would be expected. The equilibrium phase precipitated at 700°C and below contains about 10 pet Cu in solution which tends to stabilize the fee structure, lowering the transformation temperature to 340oc.l The alloy is known to undergo discontinuous precipitation in addition to general precipitation; while the former can be seen with an optical microscope, the latter precipitates are not visible except in the grosly overaged condition.5, 6 Extensive use has therefore been made of the ferromagnetic properties of the precipitate in order to follow the course of aging, and it has proved possible to measure the average particle size, spacing, approximate shape, and volume fraction and to determine that the particles are coherent without ever seeing a particle (see for example Refs. 2, 7, and 8). The magnetic measurements of particle size are limited to diameters below about 120Å.7 The present study was undertaken using the techniques of transmission-electron microscopy in order to check the above conclusions, to extend the previous magnetic work to larger particle sizes, and to attempt a more detailed correlation of properties and structure. A portion of this work has already been published.9-11 The present paper is concerned with the metallographic features of precipitation in relation to aging curves. Bonar and Kelly12&apos;13 have published preliminary results of a similar study on single crystals of Cu-2 at. pet Co. EXPERIMENTAL Preparation of Alloy. A Cu-Co alloy, containing 3.12 wt pet (3.36 at. pet) Co by analysis, was prepared from 99.999 pet purity oxygen-free copper and electrolytic-grade cobalt. The alloy was melted and cast in vacuo in a high-frequency furnace using a graphite crucible and mold: Analysis showed chat 0.004 pet C was picked up during melting. The 1-1/2-lb ingot was homogenized in hydrogen for 24 hr at 1000°C. Slices were cold-rolled to 0.005 or 0.003 in. thickness, with an intermediate 650°C anneal in hydrogen at 0.080 in. thickness. Batches of six to ten strips were solution-treated in sealed-off quartz tubes in high vacuum in a vertical furnace and quenched by dropping into iced brine containing a device which snapped off the nose of the tube. Solution treatment consisted of 1 hr at 990°C or 2 hr at 965°C. The latter was employed for all mechanical-property studies, since a tendency was noted for the higher temperature to give porous material. Strips were usually aged individually in a horizontal vacuum furnace, inserting into the hot zone and withdrawing into a cold zone without breaking the vacuum. This method gave a rapid heating rate, permitting the use of short aging times. In some cases, particularly for the longer aging times at the higher temperatures, samples were sealed individually in quartz tubes in high

Jan 1, 1964