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By John Wulff, J. H. Hollomon

The opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was re-deposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May16 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to a1pha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,a in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As2O3),

Jan 1, 1942

By T. Egleston

THE ores of mercury of North California are composed of metallic mercury and cinnabar. They are found in serpentine, and are very often associated with chalcedony, in masses more or less irregular, often concentrated enough, however, to furnish ores yielding from three to ten per cent., and sometimes richer. This deposit makes its appearance in Vallejo where it has been worked. North of here the mines are more developed. Most of the quicksilver mines, how¬ever, are situated in Sonoma and Napa Counties. On its outcrop the serpentine rocks have become decomposed, and have often been washed away to a considerable depth, so that in many cases in their neighborhood, what is apparently nothing but ordinary dirt, will frequently contain from two to three per cent. of metallic mercury, with but a trace of cinnabar, in which case, as at the Sonoma mine, it is made up into adobes and distilled. Such material does not require to be mixed with dirt to be made into adobes. Very often, also, the outcrop of the rock, where it is not decomposed, is filled with metallic mercury, so that by striking a pick into it, as at the Rattle-snake mine, a pound or more of mercury at a time will sometimes spurt out. Such rock as this is found in several localities in every stage of impregnation, and usually makes very rich ore. There is generally, however, very little of it, and it is found only in the first workings ; the ore in depth is always cinnabar. At the Rattlesnake mine near Pine Flat, where large quantities of metallic mercury are found, the rock contains so much petroleum that it has been necessary to make special arrangements to burn the carbides of hydrogen, since the distillation of the petroleum causes an extra quantity of poor soot to be formed in the condensation-chambers. At the Geysers the ore is associated with large quantities of sulphur and gypsum, so that in a hand specimen there is often more sulphur than cinnabar, which is a serious impediment to working, especially for the modern style of furnace with iron condensers, and causes so much soot to be formed that it has been known to penetrate as far as the blower, and to so completely clog it as to prevent its revolution. The ore coming from the mine is more or less hand-picked. In one or two cases attempts have been made to treat the poorest, and especially the very fine ores, mechanically as at the California works.

Jan 1, 1875

By Walter Rosenhain

In selecting solid solutions for the subject of this lecture I have been guided by several considerations. The bodies known under that somewhat paradoxical name play a most important part in all types of alloys; consequently, a deeper knowledge of their constitution must 'be of fundamental importance to both metallurgical science and practice. Further, having been asked to deal with some of the more theoretical aspects of metallurgy, I have been tempted to describe certain considerations, which I believe to be novel, in regard to the nature of solid solutions. These considerations constitute a theory that requires much experimental confirmation, but they have passed the stage of speculations, for experimental evidence has become available and one inference after another, that can be derived from the theory, is found to be in accord with well-known facts. In putting before you these ideas and inferences, it must be understood that detailed quantitative proof of every step cannot be furnished. Our conclusions must therefore be stated with the reservation that their acceptance must depend on the manner in which the discovery of fresh facts may either confirm or confound them. If we wish to understand the structure of solid solutions we nust carefully realize the manner in which these bodies are formed in alloys. The formation of solid solutions is by no means confined to alloys, but it is desirable to confin5 attention, at the outset, to intermetallic solid solutions. It is not easy to formulate a precise definition of the term "solid solution." It may be said that a solid solution is a crystalline body formed from a liquid solution or from an intimate mixture of solids, or of liquid and solid, that retains in the solid state an admixture of the two substances (solvent and solute) as intimate as that which exists in a liquid solution. The term is undoubtedly paradoxical, for one usually associates solution with a liquid, but the difficulty cannot be evaded by using such a term as solidified solution, for this might refer to a solution that has set, or congealed, without undergoing crystallization. The German term mischkry stall avoids the difficulty and appears to

Jan 1, 1923

By H. M. Chance

Adequate treatment of the difficulties surrounding the valuation of mineral lands requires that agreement be first reached defining value as understood for the purpose of appraisal. To define value as the price of a product is not sufficient, and does not assist us in using the factors that cause variations in values and in relative values. The real value of any product depends primarily upon its relation to the necessities, comforts and pleasures of mankind. As the necessities, comforts and pleasures of the civilized races differ from those of more primitive man, the value of products varies with the degree of civilization and the environment of the consumer. Coal has no value to the savages of warm climates, and arrow-head flint none to the residents of New York. It has long been recognized that what has been termed " intrinsic value " must be limited to materials that are essential to existence—air, water, food. But " intriusic value" cannot be measured in monetary terms. The intrinsic value of a bushel of wheat is due to the fact that it will support the life of an individual for a certain definite time, but this fact does not enable us to measure or to express that value in monetary terms. It has often been proposed to adopt as a measure of the value of any product the quantity of labor necessary to produce it, but this method is of limited application, and will not apply to what may be termed " intrinsic values." For many reasons it might be well, while assenting to the fact that any material may be intrinsically valuable, to abandon the use of the term " intrinsic value." One of these reasons is the tendency to confuse the idea of intrinsic value with a value that is conferred by economic conditions, that is purely artificial and that may be permanent or evanescent. Intrinsic value must from its nature be permanent and unchangeable. Possibly for present purposes the value of any material may be considered as having a dual origin: First, that due to economic

Jan 1, 1914

By C. D. King

THE advances in basic open-hearth practice which have occurred during the past decade, have been principally in the direction of the physical development of larger units, decreased fuel consumption and increased length of furnace campaigns. However gratifying the economies which have resulted from these improvements are, it must be granted that like advances in chemical, physical-chemical and metallurgical knowledge pertaining to open-hearth practice would have added greatly to these already attained reductions in costs and it is the purpose of this paper to stimulate the discussion and study of these phases of cooperation and their relation to ingot yields. DEFINITION AND CALCULATION OF LOSSES In discussing basic open-hearth yields, the writer refers to the ingot yields obtained in the process of converting pig iron, scrap and ore to steel. In this conversion some scrap is produced. The difference between the total weight of ingots and scrap produced and the original metallic charge, constitutes the loss. Basic open-hearth yields vary considerably, and while some of the divergencies can be explained metal-lurgically because of differences in slag analysis, proportion of pig charges, and character of steel made, there often remain differences that apparently do not readily disclose themselves. In reconciling yields by the usual accepted methods of calculation, one is often forced to evaluate large losses as "unaccounted for." Such a system is prone to accept these large losses as inherent to the operation and not susceptible of appraisement and correction. It is obvious that if the ingot yield, plus the scrap recovered subtracted from 100 per cent. determines the loss, a drop in yield may increase the loss or the scrap, and both contribute to a monetary loss. To be sure, one can subdivide these unaccounted for losses into various components, such as metallics in slag, free Fe in slag, spillage, etc., and thereby reduce the amount of losses considered as "unaccounted for." If empirical methods could indicate with some degree of accuracy all losses, however slight, the undetermined losses become appreciably smaller and resultant calculations will check actual

Jan 1, 1929

By Thomas Egleston

The ores of mercury of North California are composed of metallic mercury and cinnabar. They are found in serpentine, and are very often associated with chalcedony, in masses more or less irregular, often concentrated enough, however, to furnish ores yielding from three to ten per cent., and sometimes richer. This deposit makes its appearance in Vallejo where it has been worked. North of here the mines are more developed. Most of the quicksilver mines, however, are situated in Sonoma and Napa Counties. On its outcrop the serpentine rocks have become decomposed, and have often been washed away to a considerable depth, so that in many cases in their neighborhood, what is apparently nothing but ordinary dirt, will frequently contain from two to three per cent. of metallic mercury, with but a trace of cinnabar, in which case, as at the Sonoma mine, it is made up into adobes and distilled. Such material does not require to be mixed with dirt to be made into adobes. Very often, also, the outcrop of the rock, where it is not decomposed, is filled with metallic mercury, so that by striking a pick into it, as at the Rattlesnake mine, a pound or more of mercury at a time will sometimes spurt out. Such rock as this is found in several localities in every stage of impregnation, and usually makes very rich ore. There is generally, however, very little of it, and it is found only in the first workings; the ore in depth is always cinnabar. At the Rattlesnake mine near Pine Flat, where large quantities of metallic mercury are found, the rock contains so much petroleum that it has been necessary to make special arrangements to burn the carbides of hydrogen, since the distillation of the petroleum causes an extra quantity of poor soot to be formed in the condensation-chambers. At the Geysers the ore is associated with large quantities of sulphur and gypsum, so that in a hand specimen there is often more sulphur than cinnabar, which is a serious impediment to working, especially for the modern style of furnace with iron condensers, and causes so much soot to be formed that it has been known to penetrate as far as the blower, and to so completely clog it as to prevent its revolution. The ore coming from the mine is more or less hand-picked. In one or two cases attempts have been made to treat the poorest, and especially the very fine ores, mechanically as at the California works.

By John Wulff, J. H. Hollomon

The opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was re-deposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May16 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to a1pha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,a in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As2O3),

Jan 1, 1942

By Willis T. Burns

I. Introduction.......................................... 703 II. History................................................ 703 III. General Description of Plant......................... 704 IV. AnoDes................................................. 711 V. Cathodes............................................... 714 VI. Electrolyte............................................ 718 VII. Electrolytic Slime..................................... 727 VIII. Power................................................. 728 IX. Operating Details..................................... 732 X. Furnace Refining...................................... 736 XI. Physical Testing oF Products.......................... 739 I. Introduction. These notes are submitted, not as a discussion of the modern practice of electrolytic-copper refining, but as the record of a refinery that was among the pioneers in the field and that is to-day, and has been for 17 years, operating under conditions not to be found in any similar plant in the country. I refer to the current density, which is at least 60 per cent. higher than that regularly employed elsewhere, and to the fact that the anodes treated are the direct product of the converter rather than of the reverberatory furnace. The writer has no knowledge of any other refinery treating anodes of this character. II. History. This refinery, now one of the oldest plants of its kind operating in this country, was built in 1892 by the Boston & Montana Consolidated Copper & Silver Mining CO. to refine the product of its Great Falls reduction works. The estimated capacity of the plant as designed was 65,000 lb. of cathodes per day at a current density of 16 amperes per square foot.

Jan 1, 1914

By Edward Schuster

As THE time allotted is short, we can present only a general idea of the oil laws in the Latin-American republics, as a supplement to Bulletin 206 of the Department of the Interior compiled under the direction of J. W, Thompson of the Bureau of Mines and entitled "Petroleum Laws of All America." We shall not discuss the European colonies in Latin-America nor the island republics. As to the countries discussed, we shall attempt to give the main features of such special petroleum legislation as has been adopted prior to the early part of this year; where no special petroleum" laws exist, we must look to the mining codes for light on the petroleum policy. As the laws and regulations for the extraction of the metals are often difficult of application to, and are lacking in many essentials for, the petroleum industry, it is best for persons or companies desiring to enter, on . a large scale, into the petroleum exploration and development of countries not having special petroleum legislation, to obtain a concession contract from the executive of the country under consideration, and to have the concession approved by the congress. If this concession, which would then be a special law, contains nothing contrary to the constitution of that country and does not infringe on vested rights of third parties, it should be reasonably safe. If in such country there is some doubt as to whether the petroleum subsoil is owned by the nation or the private surface owner, only public lands should be covered with the concession. Guatemala is the only republic in the group that discriminates directly against foreigners. Bolivia, Ecuador, Mexico and Venezuela require waivers of diplomatic protection.1 Colombia requires foreigners to agree to be bound by its alien law. , In addition,Mexico makes it unlawful for foreigners to acquire direct ownership of real estate, including mines, within a zone of 50 km. along the coasts and one of 100 km. along its land

Jan 7, 1922

By H. O. Hofman

The object of refining copper in the reverberatory furnace is to obtain a metal which will have the highest attainable degree of malleability, ductility and electric conductivity, and present at the same time a level surface when it solidifies in the mold after casting. These desirable physical properties are governed by the character of the impurities and the forms in which they are present, by the amount of cuprous oxide retained by the copper, by the quantity of gas held in solid solution, by the casting-temperature, and by the thickness of the casting. The effects of impurities, of cuprous oxide and of gases upon the mechanical properties of copper have been studied by Hampe1 in his classical paper " Colitributions to the Metallurgy of Copper." The most recent research into the effect of metals upon the electrical conductivity of copper is that of Addicks. 2 The influence of cuprous oxide upon the electrical conductivity has been investigated by Walker3 and Addick. 4 The absorption of gases has received attention by Hampe: Stah16 and Heyn 7 The effects of casting-temperature have been noted by Stahl.8

Jan 1, 1908

By A. H. Grobe, F. N. Rhines

THE constitution of the indium-zinc alloy series has been investigated by Wilson and Peretti,1 who determined the liquidus and eutectic temperatures by the conventional method of cooling curves and the eutectic composition by analyzing eutectic exudations. Recent developments affecting the availability of indium and consequent increased interest in its applications make a more complete knowledge of the constitution of its alloys desirable. As a part of a program for the reexamination of the constitution of indium alloys by precision methods, the indium-zinc phase diagram [ ] (Figs. I and 2) has been redetermined in its entirety. The eutectic temperature (143.5°C.) reported by Wilson and Peretti has been confirmed exactly, but their value of the zinc concentration at the eutectic, 4 per cent, was found to be high; the new value is 2.8 per cent of zinc. There is also a rather large difference between the forms of the liquidus curves of Wilson and Peretti and those found in the present studies. The solidus curves herein have been located for the first time and the limits of solid solubility have been tenta-

Jan 1, 1944

By G. S. Rice, Clark H. H.

When mines in the interior coal fields of the United States began the practice of blasting the coal without undercutting, or what is known as…

Jan 1, 1915

By P. W. George

This paper presents geological data regarding deposits of over 7,500,000 tons of fine-grained sulphide ore in barite gangue. A series of pyroclastics and arkoses was intruded by sills of quartz porphyry in connection with batholithic intrusions of granite 3 miles from Buchans. Gentle folding, with fracturing and shearing of tuff beds and intruded quartz porphyry, accompanied and followed the intrusion of granite and porphyry. The sulphide-barite mineralization is localized primarily in fractured and sheared tuff beds, but also in the sheared quartz porphyry. Two structures have proved particularly favorable for mineralization-one, the center of an anticline; the other, a series of weak, incompetent tuff beds intruded by thin sills of quartz porphyry and located between strong beds of arkose. During the folding the weak tuff with intruded quartz porphyry was intensely sheared and contorted and subsequently mineralized by sulphides and barite. INTRODUCTION Buchans is 5 miles north of Red Indian Lake, in Central Newfound- land, at an elevation of 900 ft. above sea level and 400 ft. above Red Indian Lake, and is reached by a 37-mile private railway from Miller- town Junction. The first ore body found at Buchans was discovered some 30 years ago in the bed of Buchans River, by Matty Mitchell, an Indian woodsman employed by the Anglo-Newfoundland Development Co. Ltd. In the years following the discovery the ore was developed by shaft-sinking and drifting, with results indicating a lenticular ore body in a shear zone, containing about 100,000 tons of extremely fine-grained sulphide ore in barite gangue averaging about 0.05 oz. Au, 4 oz. Ag, 1.5 per cent Ch, 10 per cent Pb, 18 per cent Zn. Because a profitable metallurgical treatment for the ore was not found, the mine was closed down in 1911. In 1915, Mr. H. A. Guess, Vice President of the American Smelting & Refining Co., learned of the Buchans River ore body, and after metallurgical tests had been carried on from time to time in his company's testing plant a satisfactory separation of the sulphides by selective flotation was finally effected in 1925. Prospecting for additional ore bodies was begun in 1926, utilizing geophysical methods under the direction of Hans Lund-

Jan 1, 1937

By C. Wachmann

The theory presented ill this paper makes possible examination of the phenomenological aspect of secondary oil recovery by alcohol flooding. Limitutions of the theory are contingent on three primary assumptions: (1) chemical equilibrium, (2) no fingering, and (5) no dispersion. The second assumption implies one-dimensional flow. In a geometric sense the theory extends the Buckley-Leverett construction to systems of two slightly miscible fluids and to systems of three components. This is made possible by considering single-phase fluids to be made up two phases, namely of an excess of one phase and a negative amount of the other phase. The procedure is discussed in the paper. The theory also permits direct determination of the relationship between the aqueous phase saturation and the concentration of water in the aqueous phase in a zone of variable composition. The velocity of planes of constant water concentration and of constant saturation can be computted likewise and the existence of saturation discontinuities inferred. Consequently the behavior of such a Zone, which may exist at some time between a displaced and a displacing fluid, May be determined. mathematical details are given in Appendices. Problems of experimental verification are pointed out on the basis of a supporting experiment. Implications of the theory and effects of violations of primary assumptions are discussed briefly. The major conclusion is that, if the primary assumptions are met, with pure alcohol and alcohol-rich .slugs piston-like displacement of oil and water is possible. INTRODUCTION The recovery of oil from porous media by alcohol displacement has been studied for several years. Extensive experimental investigations into alcohol flooding have been carried out in the laboratory although little has been done in the field. A large amount of practical information is available, the extent being indicated by the first three papers cited 1-3 and their respecrive bibliographies. This has permitted the Formulation of inferential theories. A more analytical approach in which theories are developed primarily by reasoning from known physical principles and relationships has, however, lagged behind. In fact, an analytically derived theory of alcohol displacement has not been available. The theory presented in this paper on oil and water displacement by alcohol from a porous medium is a result of the analytical approach. The theory is idealized, as certain assumptions had to be made to make the mathematics tractable and reduce complexity of argument. In particular, major assuptions concerning conditions of equilibrium, interfacial stability, longitudinal mixing, etc., led to the exclusion of fingering, for example, from all considerations. In many laboratory experiments reported in the literature fingering could not be avoided. There is, therefore, disagreement between theories based on experimental evidence available and the analytically derived theory presented here. This theory presented is based on known physical data and makes use of the Buckley-Leverett construction and its suggested extension. The mathematical derivation of the theory is given in Appendices. Three examples relevant to alcohol displacement are discussed to explain the use of this theory: (1) system of two immiscible fluids (the Buckley-Leverett case); (2) system of two slightly miscible fluids involving an extension of the Buckley-Leverett construction; and (3) system of three components, including injection of pure alcohol or alcohol-rich fluid as a special case, which involves a more general extension of the Buckley-Leverett construction. In these discussions strict assumptions were made to impose equilibrium conditions and exclude mixing and fingering. Effects of relaxing these assumptions and consequent extensions of the theory are indicated. The complexity of the alcohol displacement process makes experimental verification of the theory essential. Some relevant evidence is offered in this paper.

Jan 1, 1965

By Gerhard Derge

The rapidity of oxygen steelmaking has created renewed interesl in the mechanisms and kinetics of the various processes involved. These studies can now be approached with increased confidence because of the more adequate thermodynamics, physical chernislry, and relevant engineering infornzation available. These combine to offer promise of useful control and automation if the details of each specific problem can be sufficiently well-defined. The hot filament microscope provides new insig-hi into many of these problems by direct observation at temperature, allowing the appraisal of the relative importance of thermal gradients, convection, and intermediate phases. All of these have a direct bearing on the overall rates and control of most pyrometallurgical processes. It is one of the special privileges of the Howe Lecturer to become better acquainted with this distinguished man. All of us interested in the metallurgy of iron and steel have developed some sense of his widespread influence by the annual reference to his work in these Memorial Lectures. Each lecturer since 1923 has been able to identify his personal specialty with the broad interests of Professor Howe. This has become even more rewarding with the background information from Professor Gensamer's monograph, "Henry Marion Howe's Contributions to Metallurgy, which brings out his happy combination of intellectual and professional activities. Beyond this, I found my personal bond with Professor Howe in his book on The Metallurgy of Sleel first published in 1891.' After a detailed discussion of the dephosphorizing action of slags, he relates the mineral species identified in the frozen sample to the chemistry of the fused slag with the question, "Is it not most philosophic to hold that these independent entities were wholly integrated in the initial magma; that their presence in it was wholly

Jan 1, 1968

By Manuel Eissler

INTRODUCTION THE history of copper metallurgy in Japan goes back into remote ages, of this there is abundant proof, and that the working of this metal is closely connected with the artistic development of this nation is evidenced by some of the glorious monuments which have been produced by these ancient metal workers. The traveler sees to-clay in a perfect state of preservation bronze statues 150 ft. high, and over, 300 ft. in width, and 170 ft. in depth, delicately chased and beautifully marked, and when one reflects that some of them date back to the eighth century A. D., the question naturally suggests itself, how did these ancient metallurgists with their crude and primitive appliances accomplish this stupendous task? The bodies of these images are formed of bronze castings 10 to 12 in. thick, which were gradually built up and soldered together, but other pieces of magnitude, like the heads and other portions of the body are single castings. In many cases another method of construction must have been adopted. The walls of the molds were gradually built up and as the lower portion of the castings cooled, the walls were raised higher and higher and fresh metal must have been added, instead of constructing the whole mold first and then making the casting in one piece. There are still traces of substantial gilding visible on these statues, and how the pious Buddhist priests who were the constructors of them got the precious metal, is preserved in legendary tales.

Jan 11, 1914

By Robert D. Pike

IN November 1939, on behalf of the Harbison-Walker Refractories Co., the author undertook the study of the problem of utilizing the dolomite of northwestern Ohio for the manufacture of calcined magnesia suitable for use in refractories. Grateful acknowledgment is made of the unfailing assistance and encouragement throughout this work from the executive and technical staff of Harbison-Walker Refractories Company. The dolomite of the Niagara formation that is exposed or near the surface of a wide area in northwestern Ohio1 constitutes a vast supply of almost pure dolomite. It offers a virtually unlimited supply of cheap raw material of uniform dependable analysis for the manufacture of magnesia. A typical analysis of dolomite from the vicinity of Luckey, Ohio, follows: [ ] Brines containing magnesium chloride or sea water can be reacted with calcined dolomite to produce magnesia.2,3 In such reactions the MgCl2 of the brine supplies some of the magnesia and the amount of dolomite required is thereby reduced by an equivalent amount, but brines of commercial importance containing magnesium chloride are some distance away from the purest grades of the dolomite of northwestern Ohio. It was decided therefore to concentrate upon the development of a suitable process for separating the lime and magnesia of dolomite, depend¬ing upon the dolomite itself as the sole source of magnesia. This would make it possible to place a plant at the dolomite quarry, thus eliminating the cost of transporting the stone and also rendering the calcined magnesia available at a most convenient production point, considering the cost of delivery throughout the steel industry. The selection of a process depending solely upon the dolomite as a source of magnesia also necessarily entails production of the lime content of the dolomite as a by-product. It was recognized that if such a lime by-product could be produced in a suitable form, a plant location in northwestern Ohio would also be advantageous for marketing the lime. The problem, therefore, was the discovery and development of a low-cost process for separating the magnesia and lime of the dolomite of northwestern Ohio and producing each in a form relatively free from the other, and meeting the respective requirements of established markets. A satisfactory solution of this problem has been found, and it is the

Jan 1, 1947

By A. L. Benham, W. E. Dowden, W. J. Kunzman

The mechanism involved in creating a miscible fluid displacement of typical reservoir fluids through porous media by light hydrocarbon mixtures usually involves a number of mixing and separation stages in the contact area. This mechanism has been illustrated on ternary diagrams for miscible displacement of reservoir fluid by rich hydrocarbon gases. A relatively simple method has been devised for calculating the approximate conditions for a miscible displacement of reservoir fluid by rich, light hydrocarbon gases or by LPG mixtures. Miscibility is favored by increased pressures, decreased temperatures, light reservoir fluids and light hydrocarbon-displacing fluids rich in the heavier components. The conditions for miscible displacements of five typical reservoir fluids by various light hydrocarbon mixtures were determined for a range of temperatures from 70" to 260°F and pressures from 1,000 to 3,000 psia. A correlation of these conditions was obtained using the variables of temperature, pressure, C,+ molecular weight of the reservoir fluid, C,+ molecular weight of the displacing fluid, and mol per cent methane in the displacing fluid. This correlation has been applied to data appearing in the literature with very good success. A partial check of the correlation has been made using a step-wise procedure with a windowed PVT cell. INTRODUCTION The term, "miscible fluid displacement", may be defined as any oil-recovery displacement process where there is an absence of a phase boundary or interface between the displaced and displacing fluids. A water flood would not be a miscible fluid displacement, although cycling in a condensate reservoir would be. Another example is displacement of oil by gasoline. Not so obvious, however, are the conditions under which fluids (such as propane, mixtures of propane and methane, or other similar systems) will give a miscible fluid displacement of oil. There are four standard miscible-fluid-displacement processes being used for the recovery of oil from an "nderground reservoir—(1) high-pressure dry-gas miscible displacement, (2) rich-gas miscible displacement, (3) miscible slug using a slug of LPG followed by a lean dry gas under miscible conditions, and (4) gas driven-slug process using a slug of LPG followed by a lean dry gas under immiscible conditions. The first problem faced by the engineer designing a miscible displacement process is to determine the conditions for miscibility. A number of papers have included discussions of the process of obtaining miscibility in these processes.1-8 However, methods for calculating the conditions for miscibility have not been published. This paper includes a method for calculating the conditions for a miscible displacement of reservoir fluid by a rich gas (LPG diluted with methane or natural gas). In this paper, a rich-gas miscible displacement process is defined as an oil-recovery process in the reservoir. The cost of a rich-gas miscible displacement will be decreased by diluting the LPG with methane or natural gas as much as possible. Therefore, it is important to be able to predict the maximum dilution for miscibility. MECHANISMS The mechanisms for obtaining miscibility between a displacing mixture of light hydrocarbons and displaced reservoir fluid often involve a number of displacing and mixing stages. As stated previously, the cost of a rich-gas miscible displacement is decreased by diluting available LPG with natural gas. The problem is to predict the maximum dilution allowed while maintaining miscibility. To get a picture of the displacing and mixing stages, it is helpful to consider these complex hydrocarbon mixtures as pseu do-ternary systems. Graphical representation of a complex system as a pseu do-ternary system can be thermodynamically rigorous if enough variables are used to describe the character of each pseudo-component in one of the phases. However, even if the characterization of each pseudo-component is not complete, pseudo-ternary representation does serve to illustrate the mechanism for obtaining miscibility and can be used to make some general conclusions concerning the conditions for obtaining miscibility. A phase diagram for the ternary system, methane-

By G. L. Tufford, R. L. Bleifuss

Low-grade manganiferous iron ores of Minnesota's Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite with subsequent magnetic separation and flotation have not given satisfactory results because, in many instances, concentrate grade and manganese recovery are low. Metallization of iron and concurrent reduction of higher manganese oxides to MnO, as in the R-N process, followed by recovery of iron by magnetic separation and manganese by leaching, seems to be a technically feasible process. High-temperature x-ray diffraction studies show that solid-state reactions between iron and manganese, with the formation of intermediate iron-manganese oxides, occur during reduction and affect recovery of both iron and manganese from the final product. Solid state reactions also occur between FeO, MnO, and SiO, at temperatures as low as 900°C. The kinetics of these reactions are such that they become an important factor in the treatment of ores by the R-N process. These investigations suggest a temperature and gas composition cycle that would maximize both iron and manganese recovery. During the past ten years, iron ore shipments from the Cuyuna Range of Minnesota have decreased sharp1y. Because of adverse grade, structure, and cost, many Cuyuna ores are no longer competitive with high-grade foreign ores and domestic pellets. The low-grade manganiferous iron ores from the Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite for subsequent magnetic separation and flotation has not given satisfactory results because concentrate grade and manganese recovery are often low. However, a technically feasible process appears to be metallization of the iron and concurrent reduction of manganese oxides to MnO with recovery of metallic iron by magnetic separation and extraction of manganese from the tailings by leaching. In 1962 the R-N Corp., with a grant from the Area Redevelopment Administration, conducted an amenability study of the metallization of manganiferous iron ore from the Cuyuna Range. The results of this preliminary investigation were sufficient to interest the Economic Development Administration in sponsoring further studies of the process with emphasis on secondary recovery of manganese from the nonmagnetic tailings. Inasmuch as the metallization process has considerable influence on the final form of the manganese - its texture and distribution between the magnetic concentrate and nonmagnetic tailings-the investigation included a study of metallization of the ore as well. Therefore, the investigation conducted at the Mines Experiment Station covered three interrelated phases: (1) laboratory R-N roasting studies and magnetic separation tests, (2) laboratory chemical extraction experiments of the nonmagnetic tailings, and (3) a mineralogical study of the crude ores and their various roast products. High-temperature x-ray diffraction investigation of the Fe-Mn-Si0,-0, system is the main topic of this paper and an extension of the mineralogical work. GENERAL GEOLOGY The Cuyuna Range is known for its complicated geologic structure, complex orebodies, and generally indifferent response to attempts at conventional beneficiation. Several geologists have made intensive studies of the Cuyuna Range, including Leithl (1907), ~darns' (1910), Zapffe3 (1925), Grout and Wolff4 (1955), and schmidt5 (1963), whose study was the most comprehensive of all. The Range is covered with glacial deposits - till, out-wash, and lake sediments -up to 250 ft thick. Bedrock stratigraphic units of the Cuyuna Range consist of three tightly folded Precambrian sedimentary formations. The lower unit is the Mahnomen formation, composed of 2000 or more feet of argillite, slate, siltstone, and quartzite. The middle unit is the Trommald formation, which varies from 45 to 500 ft in thickness and comprises the major iron-bearing formation. The upper unit is the Rabbit Lake formation, consisting of over 2000 it of argillite, slate, and interbedded lenses of lean iron formation. In the central part of the Cuyuna Range, the units have been folded into a series of

Jan 1, 1969

By Henry R. Linden

The demand for natural gas continues to increase at higher than anticipated rates, partly because of its widening price advantage over most other fossil fuels when the cost of air-pollution control is included. However, there are clear indications that the natural gas supply from the conliguous 48 states and continental shelves will not keep up with this rapid growth in demand indefinitely. Projections are presented which define the extent of potential deficiencies from the 1970's to the year 2000. Among the sources of supplemental gas - imported pipeline natural gas from Canada and Mexico, tanker import of liquefied natural gas, and synthetic pipeline gas from coal and oil shale -by far the most abundant at potentially competitive costs is pipeline gas from coal. The state of development and relative economics of the various coal gasification processes are reviewed. It is shown that synthetic pipeline gas could become a very substantial market for bituminous coal and lignite at current mine-mouth prices - 60-70 million tons of coal for each trillion cubic feet of synthetic pipeline gas produced. This corresponds to only slightly more than the current annual increase in gas demand. Although annual discoveries (gross additions to proved reserves) of natural gas in the United States are still on a general upward trend from the current level of 22 trillion cu ft annually, most forecasters do not expect this to increase substantially in the foreseeable future. For example, the updated (to include 1966 and 1967 data) mathematical model of natural gas discovery and production in the U.S. developed by the Institute of Gas Technology (IGT)' projects that discoveries will level out at about 25 trillion cu ft annually in the late 1970's and during the 1980's and then decline to about 21 trillion cu ft by the year 2000 (Fig. 1). This adds up to a new supply for the period 1968-2000 of about 790 trillion cu ft. Experts who usually reflect the producers' viewpoint, such as Radford L. Schantz of Foster Associates,* are relatively more pessimistic. In contrast, a forecast just made by the U.S. Dept. of the Interior is much more optimistic.3 It assumes an increase in gas discoveries of 2.2% per year over the period 1965-80, reaching about 30 trillion cu ft in 1980. If this rate of increase were extended to the year 2000, annual discoveries would reach 46 trillion cu ft at that time, for a total over the period 1968-2000 of about 1100 trillion cu ft. To these forecasts of new gas discoveries must be added proved reserves of roughly 290 trillion cu ft,4 bringing total U.S. supplies for the rest of the century to nearly 1100 trillion cu ft (IGT) and possibly as high as 1400 trillion cu ft (U.S. Dept. of the Interior). This is approximately the same range as that of two estimates of total remaining recoverable natural gas supply: Potential Gas Committee, 980 trillion cu ft5 and IGT, 1450 trillion cu ft.6 Only the 1965 estimate by the U.S. Geological Survey7 suggests that economically recoverable natural gas supplies will not be exhausted around the end of the century. These forecasts are, naturally, based on the assumption that changes in technological, economic, and regulatory environment as they affect the gas industry will be of an evolutionary, not revolutionary, nature. The various forecasts of potential natural gas supply must now be compared to forecasts of natural gas demand (Table I). The general consensus is that the recent Future Requirements Committee projection to 1990' (extended to the year 2000 by the most recent U.S. Bureau of Mines (USBM) projection9) represents the minimum gas requirements (Table 11). They add up to a total of 1030 trillion cu ft for the period 1968-2000. Even this minimum anticipated gas demand exceeds the total remaining supply estimate by the Potential Gas Committee and would nearly exhaust the proved reserves plus new discoveries projected by IGT. The supply situation would appear much tighter if the demand projections of the Texas Eastern Transmission Gorp.10 and the American Gas Assn.(A.GA.)'' were used (Table I). Yet, these higher forecasts probably do not include the effects of such new markets as gas fuel cells, use of liquefied natural gas as a transport fuel, etc. They also may not fully reflect the impact of air quality control on the fuel market. Obviously, the probable discrepancy between projected supply and demand can only be accommodated in four ways. 1) Rapid increase in exploration and drilling activity to provide new supplies in the amount projected by the optimistic U.S. Dept. of the Interior forecast, coupled with an increase in net pipeline imports from Canada and Mexico from the present 0.5 trillion cu ft per year

Jan 1, 1970