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By C. M. Shigley

Tan record of the largest magnesium plant in the country utilizing sea water as a primary raw material stands as another victory in the struggle for large-scale production of pure chemical elements from the oceans. Bromine was the first element to be economically and commercially recovered when, in 1933, a six million pound per year unit was built on the Atlantic Coast near Wilmington, North Carolina, by the Ethyl-Dow Chemical Co.1 The bromine was reacted with ethylene to produce ethylene dibromide, a necessary associate of tetraethyl lead in ethyl antiknock fluid. Within eight years that plant was doubled and redoubled, and another large unit was put into operation at Freeport, Texas, taking bromine from the Gulf of Mexico. In 1940, in fortunate anticipation of the impending demand for magnesium and the limitations of the production from natural brines, the Dow Chemical Co. turned again to the sea, and designed and erected a plant at Freeport to produce 18,000,000 lb. of magnesium per year from sea water.2 In March 1941, two months after the new plant had been put into successful operation, construction of an 18,000,000-lb. Government-financed addition was started. Late in 1941, as a part of the $400,000,000 defense program intended to produce 600,000,000 t0 700,000,000 lb. of magnesium per year, Dow was asked to build and operate for the Government a 72,000000-lb. plant near its original plant at Freeport. Within a few days after the Japanese made their attack at Pearl Harbor, preparation of a site was started at Velasco, Texas, for the construction of the Texas plant of the Dow Magnesium Corporation-the largest known magnesium plant utilizing sea water as its raw material. Less than six months after the first piling was driven, urgently needed magnesium was in steady production. Five months later, the plant had exceeded its rated capacity. It remained above rated production until the general magnesium curtailment was applied to Government-owned plants in September 1944. Credit for the construction and operation record of the Dow magnesium plant must be divided among the efforts of a very determined group of men, an extremely favorable location, and a simple process. It is with the two latter aspects of the plant that this article will deal. The site for the new enterprise was chosen near Velasco, Texas, on property bordering the Brazos River at a point approximately 6 miles inland from the original magnesium plant and y miles inland from the Freeport Harbor on the Gulf of Mexico. This location was far enough away from the operating units to reduce both interference from construction and the vulnerability of closely bunched manufacturing operations to the then feared air attack. Yet the distance inland was not too great for the economical construction of a barge canal from the harbor to serve both the transportation of raw

Jan 1, 1945

By Peter J. Szabo

Introduction This is the Pacific Rim. Nearly three fourths of the world's population live on or near its border. In the recent past, on any given day, one could find traversing its„ borders pirates, smugglers, gunrunners, missionaries, slave traders, tourists, and businessmen. If one were not too observant, he would notice that over the last several years the ocean traffic in the Rim has pretty much stayed the same--Polynesian outriggers, passenger ships, general cargo vessels, ore carriers, and oil tankers. If he were to look a little closer, he would notice some coal colliers. A still closer look would reveal that most of them were hauling metallurgical coal destined for the steel mills of Japan, Taiwan, or Korea. If his senses were keen, he would observe that not only were the number of colliers increasing dramatically, but also that a relatively new cargo was being carried to those countries as well as additional areas in the Pacific Rim., This new cargo thermal coal holds the promise of not only exceeding the metallurgical coal trade, but significantly cutting into and decreasing the already vast oil tanker business throughout the Pacific Rim. The high price of crude oil as a result of the oil embargo in the Middle East in 1973-74 has forced the Pacific Rim countries to convert to coal, and as a result, the coal resources of the Rim are being exploited at an ever-increasing rate. Although coal produced outside the Pacific Rim does enter its borders for ultimate consumption from such places as South Africa and the East Coast of the United States, the vast majority of thermal coal that will enter this booming market place will be sourced from countries within the Pacific Rim. Accordingly, this paper will provide an overview of those sources with particular emphasis on the non-communist block nations. This is not to say that countries such as China and Russia will not be players in the Pacific Rim thermal coal arena, but that -most consuming countries in the Rim are basing the majority of their near-term sourcing requirements from countries that provide a stable source of supply. Pacific Rim Coal Resources Figure 1 is a map of the Pacific Rim countries and identification of major coal resource locations within its border. Going in a clockwise direction, the following countries will be the major suppliers of thermal coal through the year 2000: Australia, Indonesia, China, Russia, Alaska (U.S.), Canada, United States (Utah, Colorado, Wyoming, Montana), and Colombia, South America. Other countries such as New Zealand, Malaysia, Philippines, Korea, etc., will play a role in supply, but compared to the ones previously mentioned, will only have a minor impact. When one looks at the vast stretch of ocean that separates the sourcing countries from the consuming countries (Japan, Korea, Taiwan, Hong Kong, Singapore, etc.), one realizes that costs of transportation will play a significant role in determining which countries and in what quantities coal will be purchased. Figure 2 for comparative purposes, shows

Jan 1, 1982

By H. E. Cline, D. F. Stein

A fine lamellar structure with interlamellar spacings ranging from 0.I to 3.7 was Woduced by high-speed directional solidification and used to study the interaction of dislocations with an array of bimetallic bound-am.es. The tensile flow properties were measured at elevated temperatures and the results interpreted in terms of an image force model. As the width of the plates decreases the strength increases according to a Hall-Petch relation, suggesting pile -ups. Considerable strengthening was also observed at elevated temperatures. In recent years composites containing a strong but brittle phase and a ductile but weak phase have been studied extensively in the search for a high-strength material with adequate ductility.' However, the strength of these composites has been limited to a volumetric average of the strengths of the component phases. In this paper we will show that a composite made by directional solidification of a Cu-Ag eutectic has strength properties that substantially exceed the strength of either of the metals in the composite, and an explanation for this increased strength will be presented. The Cu-Ag eutectic is a near ideal material to study for several reasons. The eutectic structure is made up of alternate plates of silver-rich and copper-rich phases with the same crystal structure.2'3 In addition, the mechanical and elastic properties of silver4 and copper5 are known over a wide range of temperatures and the eutectic microstructure is stable to nearly the melting point.6'7 Therefore, the properties of the eu-tectic are readily comparable to various theories involving the mechanical properties of copper and silver. The experiments consisted of producing directionally solidified Ag-Cu eutectic material, determining the structure and performing tensile tests at different temperatures and strain rates. EXPERIMENTAL A) Solidification and structure. A cylindrical ingot 2.2 cm in diam and 15 cm long was prepared from 99.999 pct pure materials and cast in argon. The ingot was placed in an alumina crucible and was direc-tionally solidified at 7 x 10"4 cm per sec in a Bridg-man apparatus in argon. Metallographic examination at both ends and along the length of the ingot showed a uniform structure that consisted of fine alternate plates of silver- and copper-rich phases. The plates were aligned parallel to the growth direction, as shown in the longitudinal section, Fig. 1, and were in small randomly oriented domains of parallel plates as viewed in a transverse section, Fig. 2. Four smaller ingots 0.175 in. in diam were solidified at speeds of 2Xlo-', 4.4 xlo-', 4.4 x 10-3, and4.4x10-4 cm per sec to produce a range of lamellar spacings. Replica electron micrographs were taken to resolve the individual plates as shown in Fig. 3. The copper-and silver-rich plates in the larger ingot were about

Jan 1, 1970

By A. Dubé, G. Letendre, C. E. Beaulieu

An experimental study has been made of the time dependence of internal .friction and modulus of rigidity in- freshly quenched steels at room temperature. The effects of frequency, composition, and various thermal treatments are given. The kinetic 1aws observed cannot be fully explained by the so-called first stage of tempering and the transformation of retained austenite. It is suggested that the observed phenomena are due to the progressive immobilization of dislocations introduced by the martensitic transformation. It is generally agreed that the conversion of tetraginal martensite into cubic ferrite and ce-mentite occurs in three stages which at moderate rates of heating take place in the following temperature ranges:'-3 a) The first stage involves mainly a partial loss of tetragonality of martensite and the formation of ?-carbide between 95" and 175oC. b) The second stage consists of the decomposition of retained austenite between 230 and 290' C. c) The third stage covers the formation of ce-mentite between 290o and 400' C. The kinetic laws of these heterogeneous reactions have also been the subject of isothermal studies. Thus, Roberts, Averbach. and cohen3 report a very low reaction rate with a eutectoid steel at room temperature. For example, less than 10 pet of the contraction associated with the first stage is observed after 50 hr at room temperature. Hollonlon, Jaffe, and Buffum4 show that under the same conditions less than 10 pet of the tetragonality is lost. These results have led to the belief that martensite is a relatively stable phase at room temperature. On the other hand, it is well known that important structural changes occur in martensitic steels during the first few minutes at room temperature after quenching. This pretempering has at least two important consequences. In the first place, freshly quenched steels have a tendency to crack at room temperature, a fact which leads to the necessity of tempering as soon as possible after the quench. Another important consequence of pretempering a steel for short periods of time at room temperature is the stabilization of the retained austenite. Thus, as shown by Cohen,5 a very pronounced stabilization is effected with holding periods of 30 min at room temperature. Since these two effects are apparently not caused by the heterogeneous reactions mentioned above, they must be related to the rearrangement of structural defects within the martensite and retained austenite. According to the modern theory of dislocations, the shears required to effect the austenite-marten-site transformation may be realized through the motion of dislocations at the austenite-martensite interface and within the martensite plates.6 In this way, a martensitic transformation closely resembles a plastic deformation. In cold-worked solids, high concentrations of dislocations are left immediately after the plastic deformation and it seems reasonable to assume that appreciable densities of dislocations should also appear in the wake of a martensitic transformation. A considerable part of the high hardness of martensite would then originate in the obstruction of dislocations in analogy

Jan 1, 1961

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to 1706°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous days burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the day, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By R. F. Mehl, M. L. Swanson, J. P. Hirth, G. M. Pound

The sorption of zinc in a-brass was investigated. By analyzing the elliPtically polarized light reflected from the surfaces of a-brass solid-vapor couples, their optical constants and surface compositions were determined. It was shown that the surface compositions approached an equilibrium value exponentially with time. The bulk diffusion coefficient, surface diffusion coefficient and condensation coefficient for a-brass solid-vapor couples were calculated near 350°C from the experimental results. It has been assumed during various diffusion experiments with bimetallic solid-vapor couples (Dunn,1 Seith and Kraus,2 Jenkins,3 Balluffi and Seigle,4 and others) that the surface composition of such couples reaches its equilibrium value immediately. Although this assumption is probably valid at elevated temperatures, it is certainly not expected to be confirmed at lower temperatures.* consequently, it was decided that a fundamental experiment, designed to solve this problem as well as to examine all aspects of bimetallic sorption, would be the investigation of the rate of approach to equilibrium of the surface composition of solid-vapor couples. The sorption (i.e., adsorption, absorption, and desorption) of metals is obviously dependent on the state of the metallic surface and substrate. Much recent theoretical8"9 and experimental10-12 work on condensation and evaporation of pure metals has shown that the surface contour in atomic dimensions is a critical factor in sorption, so that any deformation or contamination13,14 of the surface exerts a profound influence. It is also known that absorption or diffusion occurs much more rapidly along grain were and in other deformed regions. Thus an effective sorption experiment must utilize a strain-free and clean surface, or at least a clearly defined and reproducible surface state. A mechanically polished surface is in a highly deformed17-l9 state. Because the degree of this deformation is uncertain, it is clear that for most experimental purposes a strain-free (i.e., etched, chemically polished, or electropolished) surface is desirable. Although adsorbed gas molecules on metallic surfaces are unavoidable even in the highest vacuum,20 oxide films can in some cases be removed by suitable vacuum annealing. Electrolytically polished and annealed surfaces, being relatively without strain, smooth and free of bulk oxides, were considered adequate for the present sorption experiments. Measurement of the surface composition of a solid-vapor couple presents a unique problem. Since experiments to determine the approach to equilibrium of the surface composition must be performed at temperatures where diffusion is very slow, solute penetration is so small that conventional analytical methods are unsuitable. An optical reflectivity method utilizing a polarization spectroscope was employed because of the relatively small penetration (~200A) of visible light in metals. By this method, elliptically polarized light reflected from the metal surface was analyzed and compared with that reflected from samples of known composition. The a phase of the copper-zinc system was

Jan 1, 1962

By J. S. McNeil, J. U. Messenger

In the drilling of oil wells the control and prevention of lost circulation of the drilling- fluid is a oroblem which is frequently encountered; in many cases existing materials and methods for alleviating this condition have not been adequate. For severe cases of lost circulation in which the simpler methods, such as application of various bridging materials to the mud system, have proven unsatisfactory. a new material and method for applying to the loss zones have been developed which appear to he superior to existing techniques in many respects. The material, called a clay cement, is capable of being handled as a drilling fluid after initial mixing of the solitl ingredients with water and may be pumped down the drill pipe and squeezed into loss zones. After a short period, the material develops a very high gel strength which seals off the zone against further losses of the drilling fluid. In field tests, the process has been demonstrated to be a very effective method for combatting lost circulation. INTRODUCTION Methods of treating lost circulation in rotary-drilled wells by the addition of special materials to drilling fluids have long been in the process of development and are continuing to improve.' However, the annual drilling costs which can be traced directly to lost circulation difficulties still run into the millions of dollars. The loss of mud materials into highly permeable zones may range up to $50,000 per well in some areas. In addition to mud costs, excessive requirements of casing, cement; rig time, and the attendant blowout hazards further emphasize the importance of the need for improved methods of combatting lost circulation. The shortcomings of presently-used materials and methods have led to the development of a new lost returns material in the form of a time-setting clay cement. In field tests this material has proven very successful in plugging off loss zones. which other more conventional materials had failed to do. REVIEW OF PRESENT CORRECTIVE MEASURES The proper control of such operating factors as pump pressure, clearance between pipe and hole, and speed of running pipe in a holez is of primary importance in preventing and minimizing lost circulation problems. These factors, however, concern matters of drilling technique and do not directly involve lost circulation materials. Aside from setting casing past loss zones, three principal methods are generally employed for the purpose of avoiding or combatting lost circulation: (1) adjustment in properties (principally density) of the drilling fluid, (2) addition of fibrous, flaky, granular or other types of bridging materials to the mud system, and (3) the application of cements to the loss zones. The latter method is usually employed only after the first two have proven unsuccessful. In Table I are listed some advantages and disadvantages of the common corrective measures. Frequently, a combination of bridging material and cementing material is used." This combination is based on the premise that a bridge will

Jan 1, 1952

By Roshan B. Bhappu, Ronald J. Roman, Dexter H. Reynolds

The reaction between manganese dioxide and molybdenite in a water- sulfuric acid medium was studied at atmospheric pressure and from 25° to 103°C. Both solids are dissolved to give, as final products in solution, Mo(VI), S(VI), and Mn(II). Stoichiornetric relationshifis are most simply represented by the equation MoSz + YMnO2 + 15H+ - HMoO-4 + 2HSO-4 + 9Mn++ + 6H20 The rate of this reaction was found to be dependent on temperature, manganese sulfate concentration, acid concentration, and, in a complex way, the surface areas of both manganese dioxide and molybdenite. Both the total amount of manganese dioxide and tnolybdenite and the ratio of manganese dioxide to molybdenite played a part in determining the over-all rate of the reaction. The effect of acid concentration on the rate was also dependent on the ratio of manganese dioxide to molybdenite. SEVERAL reports in the literature describe reactions using manganese dioxide in water-sulfuric acid media as an oxidizing agent. Nearly all previous work describes interactions between an ion and manganese dioxide, such as the oxidation of ferrous to ferric iron,' or the interaction between a molecule in solution and manganese dioxide, such as the oxidation of toluene to benzaldehyde.2 Only a few references describe the use of solid manganese dioxide to oxidize another solid in sulfuric acid. One report3 states, "Manganese dioxide in dilute sulfuric acid solutions had no beneficial effect (in leaching copper from chalcopyrite), but in more concentrated acid solutions the rate of solution was about the same as that for permanganate." In 1902 a German patent4 described a process which used manganese dioxide in strong (50°Be') sulfuric acid for oxidizing chromite ores to soluble iron and chromium salts. The process consisted of mixing the sulfuric acid with the finely ground ore and manganese dioxide. The pulp was then heated to about 120°C and an electric current passed through it. The manganese dioxide apparently dissolved in the strong, hot acid solution, oxidized the iron and chromium and itself was reduced to manganese 11! then was oxidized at the anode back to manganese dioxide, and the cycle repeated. An extensive study5 of the kinetics of the oxidation of pyrite with manganese dioxide indicated that in dilute sulfuric acid solutions (about 0.1 N) and at elevated pressures the dissolution of the pyrite was brought about by air oxidation of the iron to ferrous sulfate, followed by manganese dioxide oxidation of the ferrous sulfate to ferric sulfate. The mechanism proposed by the authors involved the oxidation of the iron at the surface of the manganese dioxide. Also! the oxidation of sulfide sulfur to sulfate was credited to the oxygen in the air, not to the manganese dioxide. Since the metallurgical literature is lacking in information concerning the use of one solid to oxidize another solid. the current investigation was under-

Jan 1, 1965

By B. M. Larsen

IN endeavoring to put the art of the steelmaker on a more scientific basis, as a means of securing closer control of the product, we must be severely critical of the basis of any theory we use. In particular, we must be careful to distinguish between factors that are primary and those of only secondary importance. The concentration relations that determine the slag-metal equilibria, which are usually more or less closely attained, are of course of primary significance, but a clear picture of the whole process requires that the actual rates of the several reactions be taken properly into account. At the high temperature of the steelmaking furnace, all reactions might be thought to be very rapid, but some of them in fact are not; the essential causes of this condition are important to a proper understanding of the process. This paper aims to present, and to justify, the viewpoint that the most significant reaction is the oxidation of carbon in the metal, the progress of which determines the oxygen pressure levels in slag and metal and produces stirring effects, all of which influence the course of the process as a whole. REACTION RATES AT STEELMAKING TEMPERATURES General experience in reaction rates makes it almost certain that at steelmaking temperatures equilibrium is attained practically instantaneously when the reactants are well distributed in a single liquid phase -that is, in the so-called homogeneous reactions. The actual slowness of some of the reactions in the open-hearth furnace must therefore be attributed to a relatively slow rate of diffusion within the slag or metal phase, which limits the rate at which the reactants can meet each other in the liquid steel or at its surface. That the reactions can be made to go with great rapidity, by proper mixing and stirring of the reacting phases, is indicated by the following illustrations: I. In the Bessemer process there is intimate contact between air and the whole mass of metal, and the reactions are complete in a few minutes. 2. Perrin1 has demonstrated that by pouring liquid steel into slag contained in a deep ladle, and thereby producing almost a slag-metal emulsion, the phosphorus or oxygen content of the steel is adjusted immediately. 3. Barret, Holbrook and Woods observed a quite rapid rate of desulphurization when powdered calcium carbide was stirred vigorously into liquid iron. 4. When a spoonful of liquid steel is poured into a mold containing aluminum wire, the formation and precipitation of alumina occurs in the fraction of a second required to freeze the surface layer of the tiny ingot. The first three examples all show that any means of increasing the effective surface between slag and metal and promoting intimate mixture of the reacting phases, thereby obviating the limitation imposed by diffusion, will enhance the speed of the steelmaking process.

Jan 1, 1941

By B. M. Larsen

In endeavoring to put the art of the steelmaker on a more scientific basis, as a means of securing closer control of the product, we must be severely critical of the basis of any theory we use. In particular, we must be careful to distinguish between factors that are primary and those of only secondary impartance. The concentration relations that determine the slag-metal equilibria, which are usually more or less closely attained, are of course of primary significance, but a, dear picture of the whole process requires that the actual rates of the several reactions be taken properly into account. At the high temperature of the steelmaking furnace, all reactions might be thought to be very rapid, but some of them in fact are not; the essential causes of this condition are important to a proper understanding of the process. This paper aims to present, and to justify, the viewpoint that the most significant reaction is the oxidation of carhon in the metal, the progress of which determines the oxygen pressure levels in slag and metal and produces stirring effects, all of which influence the course of the process as a whole. Reaction Rates at Steelmaking Temperatures General experience in reaction rates makes it almost certain that at steelmaking temperatures equilibrium is attained practically instantaneously when the reactants are well distributed in a single liquid phase —that is, in the so-called homogeneous reactions. The actual slowness of some of the reactions in the open-hearth furnace must therefore be attributed to a relatively slow rate of diffusion within the slag or metal phase, which limits the rate at which the reactants can meet each other in the liquid steel or at its surface. That the reactions can be made to go with great rapidity, by proper mixing and stirring of the reacting phases, is indicated by the following illustrations: 1. In the Bessemer process there is intimate contact between air and the whole mass of metal, and the reactions are complete in a few minutes. 2. Perrinl has demonstrated that by pouring liquid steel into slag contained in a deep ladle, and thereby producing almost a slag-metal emulsion, the phosphorus or oxygen content of the steel is adjustcd immediately. 3. Barret, Holbrook and Wood2 observed a quite rapid rate of desulphurization when powdered calcium carbide was stirred vigorously into liquid iron. 4. When a spoonful of liquid steel is poured into a. mold containing aluminum wire, the formation and precipitation of alumina occurs in the fraction of a second required to freeze the surface layer of the tiny ingot. The first three examples all show that any means of increasing the effective surface between slag and metal and promoting intimate mixture of the reacting phases, thereby obviating the limitation imposed by diffusion, will enhance the speed of the steelmaking process.

Jan 1, 1941

By B. M. Larsen

In endeavoring to put the art of the steelmaker on a more scientific basis, as a means of securing closer control of the product, we must be severely critical of the basis of any theory we use. In particular, we must be careful to distinguish between factors that are primary and those of only secondary impartance. The concentration relations that determine the slag-metal equilibria, which are usually more or less closely attained, are of course of primary significance, but a, dear picture of the whole process requires that the actual rates of the several reactions be taken properly into account. At the high temperature of the steelmaking furnace, all reactions might be thought to be very rapid, but some of them in fact are not; the essential causes of this condition are important to a proper understanding of the process. This paper aims to present, and to justify, the viewpoint that the most significant reaction is the oxidation of carhon in the metal, the progress of which determines the oxygen pressure levels in slag and metal and produces stirring effects, all of which influence the course of the process as a whole. Reaction Rates at Steelmaking Temperatures General experience in reaction rates makes it almost certain that at steelmaking temperatures equilibrium is attained practically instantaneously when the reactants are well distributed in a single liquid phase —that is, in the so-called homogeneous reactions. The actual slowness of some of the reactions in the open-hearth furnace must therefore be attributed to a relatively slow rate of diffusion within the slag or metal phase, which limits the rate at which the reactants can meet each other in the liquid steel or at its surface. That the reactions can be made to go with great rapidity, by proper mixing and stirring of the reacting phases, is indicated by the following illustrations: 1. In the Bessemer process there is intimate contact between air and the whole mass of metal, and the reactions are complete in a few minutes. 2. Perrinl has demonstrated that by pouring liquid steel into slag contained in a deep ladle, and thereby producing almost a slag-metal emulsion, the phosphorus or oxygen content of the steel is adjustcd immediately. 3. Barret, Holbrook and Wood2 observed a quite rapid rate of desulphurization when powdered calcium carbide was stirred vigorously into liquid iron. 4. When a spoonful of liquid steel is poured into a. mold containing aluminum wire, the formation and precipitation of alumina occurs in the fraction of a second required to freeze the surface layer of the tiny ingot. The first three examples all show that any means of increasing the effective surface between slag and metal and promoting intimate mixture of the reacting phases, thereby obviating the limitation imposed by diffusion, will enhance the speed of the steelmaking process.

Jan 1, 1941

By C. Dean Starr

The physical basis of the equation correlating electrical conductizlity and temperature coefficient of resistance of solid solution alloys has been inzlestzgated and the nature of the constants evaluated. It is shaun that the same form of correlation is valid irrespective of the magnitude of the temperature coefficient. However, the effect of therma1 expansion and change in resistivity with temberature nust be considered when the magnitude of the temperature coefficient of resistance is near zero. In a comprehensive literature survey conducted at the Armour Research Foundation in 1950, it was found that a linear relationship exists between the electrical conductivity, K, and the temperature coefficient of resistance, a, for solid solution alloys. This was expressed by the equation where B, a constant, depends on the solvent metal but not the solute. A continuing investigation by Hansen, Johnston, and Parks showed this equation was generally appropriate for Cu, Ag, Au, Pd, Pt, and Co base binary solid solution alloys as well as for many ternary alloys of copper over a range of conductivities and temperature coefficient of resistances from 0.02 to 0.60 reciprocal pohm cm and-0.00015to0.004Q per 0 per "C respectively. Eq. [I] was not always valid for alloys that exhibited a change in state (magnetic to nonmagnetic) or for alloys that had a temperature coefficient of resistance near or below zero. For example, in nickel alloys, a simple linear curve as predicted by Eq. [l] was not obtained when the conductivity was plotted against the temperature coefficient of resistance. Hansen suggested that deviations observed were caused by transitions from a ferromagnetic to a nonmagnetic state. Subsequent and more extensive data by ronin on Ni-Mn alloys confirmed Hansen's postulate. While both states independently showed a linear relationship between K and a, the value of B was different for the two states. In some copper and gold base alloys, as well as the platinum and palladium alloys investigated by Hansen, the conductivity did not extrapolate to zero at zero a as demanded by Eq. [I]. This deviation can be readily corrected by simply adding a constant to Eq. [I.] whence Eq. [2] shows the K decreases as a decreases but that K has a positive value when a = 0 which is observed for commercial solid solution alloys as well as the experimental alloys tested by Hansen. While other methods of correlation of electrical properties have been made such as the one by Starr and Wang3 who found a linear relationship between resistivity and temperature coefficient of resistance for Ni-Cr-Al-Cu alloys, the data, in general, can also be correlated by a form of Eq. [2]. Thus, Hansen's empirical equation has considerable merit. The objective of this paper is to determine the physical basis for this equation and to examine the region near zero a in more detail. ELECTRICAL CONDUCTIVITY VS TEMPERATURE COEFFICIENT OF FU3SISTANCE The resistance of a metal or alloy is defined as

Jan 1, 1963

By Donald W. Scott, L. A. Roe, B. J. Sweo

INTRODUCTION THIS paper describes the application of ore-dressing methods to the reclamation of milled frit from over-spray, or waste, porcelain enamel. Frit is the name given by enamelers to a granulated glass produced by the smelting and subsequent water quenching of various ingredients capable of forming a glass, usually including a compound to produce opacity. It is the major component of porcelain enamel, and normally commands a price ranging from 7 to 12 cents a pound. In the preparation of a white enamel slip, usually 6 or 7 parts of clay, 2 parts of opacifier, small amounts of electrolytes, in some cases inorganic color stabilizers and organic dyes, and 35 parts of water are added to loo parts of frit; the mixture then is milled to a fineness of the order of 92 to 95 pct through a 200-mesh sieve. The frit forms the base of the enamel; the opacifier imparts opacity or reflectance; the clay suspends the frit while in slip form and serves as a binder' in bisque form (dry and unfired); and the electrolytes control the workability. Spraying is used commercially, in many cases, to apply the finish coat of enamel to the ware, prior to drying and firing. In the spraying operation, only about 50 pct, by dry weight, of the enamel slip adheres to the surface of the ware, the remainder forms the over-spray. From 1/2 to 2/3 of the overspray goes up the flue where it is lost or recovered, depending on whether the plant is equipped with a dust-collecting installation; the coarser portion of the overspray is collected in the spray booth. The former product is termed flue reclaim enamel, and the latter booth reclaim enamel. Although the spraying operation is done in specially constructed booths, which are partially or completely enclosed, it is extremely difficult to keep out contaminating dirt, which joins the reclaim. Some present-day large enameling plants use 20 tons of frit a day, of which 10 tons go into reclaim with a potential value of $1400 to $2400. When two-coat finish enamels were common, the reclaim was used satisfactorily for the undercoat, but the relatively recent advent of one-coat finish enamels prevented use of the reclaim because, even when blended with first-run enamels, it gave dirty finishes with poor gloss. It was thought that the pitting and specking encountered with reclaimed enamels were caused by the contaminating dirt, and that the poor gloss was caused, primarily, by the high clay content; more clay usually was added to give proper suspension properties to the slip when the reclaim was used. A clay content in excess of about 10 pct usually imparted refractoriness to porcelain enamels. Present-day one-coat porcelain enamels must combine high gloss and opacity with freedom from surface defects. Methods of beneficiating the over-spray,

Jan 1, 1947

By Margaret G. Scroger, Luke L. Y. Chang, Bert Phillips

Using the sealed-system technique, isothermal sections at 1000°, 1400°, and 1700°C for the system Co-W-O hare been determined. The equilibrium data were obtained by microscopic and X-ray diffraction examination of samples winch had been equilibrated in pellet form fit sealed capsules and subsequcelly quenched. The only ternary phase in the system is CoWO, which mells congruentlly at approximately 1280°C. At 1000°C, this ternary phase exists in equilihrinm with all the allows and oxide compounds in the hounding binary systems. At 1400°C, liquid forms in thin oxygen-rick region near the CoWO4 composition and only one phase assemblage in the system (W + WO2 + H'5CV7) contains no In order for tungsten to be used to its full potential as a refractory metal. it is necessary that coatings be developed which will preclude oxidation of the metal. It is true that coatings now in use do protect tungsten for short periods at temperatures near 1700 °C. but no coating has been developed which protects adequately at or above this temperature where the use of tungsten is most required. This situation exists despite the great effort in recent years to develop such coatings. and it has become evident that success in this area can be achieved only after a more fundamental knowledge of the thermochemical and therrnophysical propertics of tungsten oxidation and tungsten -metal oxidation is obtained. In our 1aboratories. a project liclrriel. At 1700°C, tungsten is the ouly solid phase which is stctble, and a large range of compositions melt to two liquids, one metallic and one oxidie. The sealed-system method of etjuilibra lion prevents the determination of the partial pressure of oxygen and the total gas pressure orer the condensed phases at equilibrium. This data is not available and can be obtained only by some other method. We can generalize on these unknowns and indicate that both partial pressure of oxygen and total pressure of the gas phase must increase as compositions change from the W-Co binary toward the oxygen apex and as temperatures increase. has been initiated which is directed at providing some of this fundamental information through a study of metal-tungsten-oxygen reactions and equilibria and the properties of any intermediate phases which result. This paper is based on a part of this program in which the system Co-W-O was studied between 1000° and 1700°C. I) RELEVANT INFORMATION FROM THE LITERATURE A) The Notable Lack of High-Temperature Work on Metal-Tungsten-Oxygen Systems. It should be pointed out that there has been no published report (of which we are aware) which deals with the study of a metal-metal-oxygen system at 1700°C. Also, there has been no report on a complete metal-luugsten-oxgen system at any temperature. As a matter of fact. before this program started. The

Jan 1, 1965

By W. D. Steele, S. D. Brady

THE Pittsburgh coal seam in West Virginia contains the largest coal reserves of any coal seam in that State and is, therefore, one of the most important seams, and attains mineable thickness and purity throughout that part of the seam extending from the Northern Panhandle to Monon¬galia Co. thence south and southwest across the state to Wayne Co. near Huntington. The Pittsburgh coal is also mineable in the Upper Potomac region but is now practically exhausted there. The total mineable areas of this coal amount to 2,165 sq miles and are estimated, by the West Virginia Geological Survey, to contain 13% billion net tons. The largest body of Pittsburgh coal outcrops on the western edge of West Virginia, along the Ohio river as far south as Moundsville, West Va., going under the river at that point and extending at various depths down the river as far as Wetzel Co. line where it thins out to such an extent that it has little practical value, and on the eastern edge this large body outcrops along the Monongahela River. The territory to be covered by this paper is the area known as the Northern. West Virginia District comprising Wetzel, Monongalia, Marion, Preston, Harrison, Doddridge, Taylor, Barbour, Upshur, Lewis, Gilmer, Braxton and Calhoun Counties, and is also known as Dist. 3 under the Bituminous Coal Act. This region was originally opened for commercial mining along and adjacent to the Monongahela River around 1852 when the Baltimore and Ohio Railroad was constructed to Fairmont. It has been extensively developed, first, in 188o (when the Monongahela River Railroad, now B. & O. R. R., was constructed) between Fairmont and Clarksburg, and later, in 1916, between Morgantown and Fairmont when the Monongahela Railway was constructed and placed in operation, this area furnishing the major portion of the production over the past years. With the mining out of a great deal of this territory adjacent to the Monongahela River considerable interest has been developed in the back acreage; and within the past few years a number of diamond core drill holes have been made in the back areas of Monongalia and Marion Counties. In this back area the oil and gas well drilling showed that the Pittsburgh coal seam was of mineable thickness and ranged in depth from 350 to 1,000 ft below the surface of the stream valleys but this drilling did not furnish any definite data as to its thickness and quality. ECONOMIC IMPORTANCE The Pittsburgh seam in Northern West Virginia is of primary importance as a coal resource not only because of its large reserves but because of its contributing a very large part of the coal used in this country for general steam uses. The Pittsburgh seam is a consistently thick seam, averaging 8 ft in thickness, with very easy grades underground, so it has always been

Jan 1, 1948

By R. V. Smith, M. H. Cullender

Rigorous equations for calculating subsurface pres.tures in flowing and static gas wells, and pressures along horizontal pipelines are presented in this paper. These general equations, based on the mechanical encrgy balance, contain no assumptions regarding temperature and can be used with either straight-line or curved temperature gradients. The friction factors recommended in this report are based on an absolute roughness of 0.0006 in. Flow is always considered to he turbulent. Although these general flow equations are solved by numerical means, the methods are as convenient as many of those used today to calculate pressures in gas wells and pipelines. These numerical methods are illustrated for flowing and static columns of gas in wells and for flow in pipelines. The authors believe that the use of these methods will result in more accurately calculated pressures in gas wells and pipelines and that [he methods are more flexible than any in use at the present time. Also, the methods are easily adaptable to automatic computers. INTRODUCTION The problem of calculating subsurface pressures in gas wells and along flowing pipelines has been studied by many investigators with the results that two widely-used methods have been presented in technical literature. One approximates conditions in a gas well or pipeline by assuming that temperature and compressi- bility are constants tor the entire gas column. The other method assumes that temperature is constant at some average value but permits compressibility to vary with pressure at the constant temperature. While these approximations may be justified for relatively shallow and low-pressure wells, they become more and more unrealistic as the calculations are applied to the deeper high-pressure wells. In wells or pipelines where there is an appreciable change in temperature between the inlet and outlet ends of the flow string, it is equally as important to consider the change in compressibility with temperature as it is to consider the change with pressure. Consequently, the methods presented in this paper were developed to provide a workable procedure for calculating pressures in gas wells and pipelines which makes no assumptions regarding either temperature or compressibility. The friction factors recommended for use with the equations were the result of study of published literature and extensive experimental work with gas wells. The F,. values in Appendix IV which contain the friction factor are equivalent to an absolute roughness of 0.0006 in. as calculated by the Nikuradse equation. The absolute roughness of 0.0006 in. was previously published by Cullender and Binckley2 for gas wells; it is in agreement with 0.00065 in. of Smith, Dewees, and Williams1 for gas wells and 0.00065 in. of Baker and Swerdloff4 for pipelines; it is in reasonable agreement with 0.0007 in. reported by the Bureau of Mines and the American Gas Assn.5 for large transmission lines. However, any type of friction factors may be used in the equations by a change in the F, values in Appendix [V].

Jan 1, 1957

By A. W. Gauger

IT is with some trepidation that I approach my subject, for I know that I shall at once incur the suspicion of the mechanical engineer, with his concern for boiler tests and efficiencies; of the mining engineer, with his mechanization problems; and of the chemical engineer with his unit processes. Nevertheless, it must be recognized that the technology of fuels, the systematic body of knowledge relating to the production, processing and utilization of mineral fuels, has grown to such proportions and involves so many widely diverse applications of fundamental science and engineering that it behooves us to stop and consider just what its status is in relation to other technologies, as well as in relation to the present and future needs of the social order. The time has come when technologists, applied scientists and engineers must consider the possible effects that their achievements may have 0n Society. The development of a machine to replace several hundred men is a fine achievement when considered solely from the point of view of creative endeavor. But what of the men who are displaced by the machine! Does not the responsibility for the development of this machine embrace as well the consequences of obsolescence and technological unemployment resulting from such development? I believe that it does and that we must recognize this fact in our practice of engineering and technology as well as in the training of future engineers and technologists. MAGNITUDE OF THE FUELS INDUSTRY Fuel technology is the body of knowledge that relates to the mineral fuels. The fuels industry is by far the most important of all our mineral industries. The chart in Fig. I, reprinted from U. S. Bureau of Mines Information Circular No. 6643, indicates the comparative values of metals, fuels and other nonmetallic minerals for the year 1929. Of the grand total of 13 1/4 billions of dollars in value of minerals at the mines, the mineral fuels contributed 48 per cent. Coal, with 34.4 per cent, exceeded the value of any other single mineral. In fact, the value of the production of the Pennsylvania anthracite mines alone annually exceeds the value of the gold production of the entire world. Petroleum and natural gas in 1020 contributed 14.3 per cent and 3.3 per cent, respectively, of the total value of world mineral production. So much for the world picture; let us now look at the situation in the United States. Over the 60-year period 1880 to 1939, $46,409,727,000 of metallic products, S80,788,852,000 of fuels (coal, petroleum, natural gas, natural gasoline) and $27,871,000,000 of nonmetallic minerals other than fuels were produced. The mineral fuels have contributed 52.7 per cent of the entire mineral wealth produced over this period that has seen such tremendous industrial development in our country. As a matter of fact, our present industrial civilization has been made possible through the use of the

Jan 1, 1942

By Charles Hart

The art of electric smelting came with the turn of the present century and owes its existence to the introduction of alternating current, which found its first wide use in the establishment of the great power plants at Niagara Falls, N. Y. Prior to that time current was largely direct. The furnaces were electrolytic in nature and found their first metallurgical use in the production of aluminum, and this process still prevails. The normal production of pig iron up to that time was carried on in blast furnaces in which charcoal, coke and anthracite were used as the fuel. This new electric process called for sufficient carbonaceous material to reduce the oxides and impregnate the pig iron with sufficient carbon, but the remainder of the energy was to be supplied by electric power. The chemical reactions are essentially the same in electric smelting as obtains in the older blast furnace. All of these data are so well known in both methods as to need no discussion at this time, for they can be found in scientific : publications and books written during the first two decades of this century. Types of Furnaces The 40 years devoted to the practice of electric smelting may be divided into two . periods of 20 years each. The first was devoted to experimentation with furnace types and with many publications on theories and processes. The second half of this term was devoted to perfecting the types of furnaces and their active commercial operation. The arc furnace may be found in three types: (1) the direct-heating arc furnace with the positive electrode included in the bottom and the other electrode suspended above; (2) the independent arc furnace with its electrodes entirely above the charge, which of necessity depends upon heat reflected from the roof; (3) the direct-heating series arc furnace equipped with two or more electrodes suspended from the roof. Of these three types, only the last is used in electric smelting of iron ore at the present time. The elimination of the other types automatically removed many of the early designs, to the end that there are now only two general types in operation: (I) the " Electrometalls" or high-shaft furnace of Sweden, and (2) the low-shaft or pit-type furnace as offered by Tysland-Hole and Siemens-Halske. The "Electrometalls" furnace takes its name from the corporation formed by the engineers that had undertaken its perfection. After trying several designs they brought forward the furnace shown in Fig. I, which by the way is the highest development of this type of furnace as of today.l Note the trend in the lines, which have kept pace with modern blast-furnace design. The high-shaft furnace lends itself to skip filling and is fitted with tuyeres immediately under the crucible roof, whereby the gases are recycled and the roof preserved. The failure of the Electrometalls furnace in Norway, because of its inability to meet

Jan 1, 1941

By Charles Hart

The art of electric smelting came with the turn of the present century and owes its existence to the introduction of alternating current, which found its first wide use in the establishment of the great power plants at Niagara Falls, N. Y. Prior to that time current was largely direct. The furnaces were electrolytic in nature and found their first metallurgical use in the production of aluminum, and this process still prevails. The normal production of pig iron up to that time was carried on in blast furnaces in which charcoal, coke and anthracite were used as the fuel. This new electric process called for sufficient carbonaceous material to reduce the oxides and impregnate the pig iron with sufficient carbon, but the remainder of the energy was to be supplied by electric power. The chemical reactions are essentially the same in electric smelting as obtains in the older blast furnace. All of these data are so well known in both methods as to need no discussion at this time, for they can be found in scientific : publications and books written during the first two decades of this century. Types of Furnaces The 40 years devoted to the practice of electric smelting may be divided into two . periods of 20 years each. The first was devoted to experimentation with furnace types and with many publications on theories and processes. The second half of this term was devoted to perfecting the types of furnaces and their active commercial operation. The arc furnace may be found in three types: (1) the direct-heating arc furnace with the positive electrode included in the bottom and the other electrode suspended above; (2) the independent arc furnace with its electrodes entirely above the charge, which of necessity depends upon heat reflected from the roof; (3) the direct-heating series arc furnace equipped with two or more electrodes suspended from the roof. Of these three types, only the last is used in electric smelting of iron ore at the present time. The elimination of the other types automatically removed many of the early designs, to the end that there are now only two general types in operation: (I) the " Electrometalls" or high-shaft furnace of Sweden, and (2) the low-shaft or pit-type furnace as offered by Tysland-Hole and Siemens-Halske. The "Electrometalls" furnace takes its name from the corporation formed by the engineers that had undertaken its perfection. After trying several designs they brought forward the furnace shown in Fig. I, which by the way is the highest development of this type of furnace as of today.l Note the trend in the lines, which have kept pace with modern blast-furnace design. The high-shaft furnace lends itself to skip filling and is fitted with tuyeres immediately under the crucible roof, whereby the gases are recycled and the roof preserved. The failure of the Electrometalls furnace in Norway, because of its inability to meet

Jan 1, 1941

By Henry J. Welge

The approximate methods which are now in use for calculating oil displacement from reservoirs by gas-cycling or gravity-drainage at constant gas pressure, or by water flooding, make use of fundamental relationships derived by Leverett' and Buckley and Leverett.2 The mathematical equations needed are derived by applying Darcy's law to the flowing phases, and by material balance considerations. ln general, any treatment of this type gives. for any particular exploitation time considered, a plot of oil saturation against distance in the reser-voir. The oil recovery must then be obtained by integrating in some manner the area under the plot. A useful analytical method has been derived for computing the average saturation, and hence the oil recovery. Use of this method simplifies the calculations because it makes unnecessary any numerical integrations. and even the saturation distribution plots are not needed. A further advantage of the method is that knowledge of the relative permeabilities is required only for a limited and intermediate saturation range. In both the Buckley and Leverett method and the method discussed here, a linear sand section is assumed, and in the case of gas drive the gas pressure is assumed sufficiently constant both with respect to reservoir position and time so that changes in gas density. solubility, or reservoir volume factor are negligiklle. Thus, the exploitation contemplates oil displacement as by an immiscible phase. Examples are given to illustrate how the new method can be used. INTRODUCTION AND THEORETICAL BACKGROUND This paper treats a simplified method for computing oil recovery when the oil is displaced, from the reservoir sand by a fluid which, within the limits of accuracy desired, can be assumed to be incompressible and immiscible with the oil. The method makes use of two basic relations originally developed for the case of water displacing oil. However, the case of gas displacing oil saturated with gas at a constant (or nearly constant) pressure may also be considered a displacement by an immiscible fluid. This is possible for the reason that the concentration of the gas in the oil never changes if tile pressure is fixed. consequently, any additional free gas must remain undissolved in the oil, and so must act essentially as an immiscible phase. For convenience, the cape of gas drive will be considered first. Both of the two basic relations needed refer to a linear reservoir, or one which may be somewhat idealized so that a constant cross-section is exposed to fluid flow. Further, the displacing phase is injected at one end, or face; of the reservoir, while the produced fluids are understood to emerge at one point only. which is the opposite face of the reservoir. As indicated in Fig. 1, the reservoir may he inclined by some angle 8. The first of the required equations may be derived by applying Darcy's law to both displacing and displaced phases, and subtracting the two equations. The result for water drive has been given previously, as Equation (13) of the reference by

Jan 1, 1952