Search Documents

By H. Ries

Introduction BODIES of pyritic ore in schistose rocks have long been known in different parts of the world. The several occurrences resemble each other in being usually of more or less lenticular shape, inclosed in walls of schist or gneiss, and carrying pyrite, chalcopyrite, and pyrrhotite in varying proportions, as the chief ore minerals. The deposits differ, however, in that sometimes one, sometimes another, of the three sulphides mentioned may predominate. The orebodies in general are more or less closely conformable with the schistosity of the wall rocks, although in cases this may not hold true. The boundaries may or may not be sharp, but in general are fairly distinct. The lenses vary in size, may occur singly, or in groups; in the latter case they may be in line, overlapping, or occasionally parallel. Pinching and swelling of individual lenses is not uncommon. The genesis of these pyritic bodies has provoked much discussion, and they have been variously classed as sedimentary, igneous intrusions, hydrothermal replacements or impregnations, etc. Indeed, in some cases different geologists have most positively assigned widely diverse origins to the same deposit, as in the case of Rio Tinto 1 and Rammelsberg.2 It is true that in the light of modern criteria, we have been able in a few cases to decipher clearly the process of origin and so there seems no doubt now regarding the genesis of the deposits at Rio Tinto, Spain;3 Rammelsberg, Germany ;4 Ducktown, Tenn.;5 southwestern Virginia;6

Jan 8, 1917

By Walter R. Hibbard

THE increased strength of a polycrystal-line metallic aggregate compared with that of its individual crystals generally has been associated with complex stress distributions at the grain boundaries resulting from atomic irregularity between grains. This disregistry, together with the necessity for adjacent crystals to deform 'compatibly regardless of the single crystal crystallographic strain mechanism, complicates this mechanism so as to increase the metal's resistance to deformation. Although Taylor1 has shown from purely mechanical considerations the requirement for at least five active slip systems to absorb the complexities during the homogeneous deformation of polycrystalline face-centered cubic metals, experimental studies by Barrett and Levenson2 indicate that this is feasible only in a qualitative sense because of deviations from homogeneous deformation. Seitz and Read in their review3 state: "Unfortunately . . . present knowledge of the grain boundary influence is not sufficient to complement the work in single crystals and provide us with a good foundation for treating polycrystals." The purpose of this investigation was to attempt to clarify the gap between single crystals and crystalline aggregates by an analysis of the effects of deformational stresses. Some of the results were described by C. H. Mathewson in his 1943 Campbell Memorial Lecture.21 PREVIOUS INVESTIGATIONS Since the performance of single crystals deformed under pure stresses has been relatively thoroughly investigated, the most significant researches are concerned primarily with deviations from single crystal behavior of large grained specimens. Qualitative grain boundary effects involving the observed amount of slip were reported by Carpenter and Elam5 in 1921. Individual crystals in a two or three grained aluminum specimen deformed by tension acted in the normal manner described by Taylor and Elam4 except for marked modifications at the grain boundaries. There the power to withstand deformation was considerably increased, leaving a ridge on the specimen where decreased slip occurred, often noticeable 34 in: from the boundary. Adcock,6 Yamaguchi,7 Seumel,8 Hirst9 and others have also reported this phenomenon as a qualitative trend. Yet attempts by O'Neill10 and Ljunggren11 to measure a difference in hardness at grain boundaries in undeformed specimens were unsuccessful. Miller12 measured quantitatively the reduction in slip near the boundary between the single crystal and polycrystalline areas of zinc specimens. These effects consisted of two parts: I. Next to the polycrystalline interface the distribution of stresses was so altered

Jan 1, 1948

INCREASING realization that pouring and ingot-mold practices involve many factors of fundamental importance to ingot quality and general steel-mill operations has caused these phases of steelmaking to become major concerns of operators and metallurgists engaged in control of quality and costs. Methods of pouring steel from the ladle into the ingot molds have some direct effects on ingot quality. The mold itself governs solidification and dimensions of the ingot and in so doing exerts some very tangible influences not only on ingot quality but also on product yields and general steel-mill processing. In addition, practices are employed in the handling of molds during daily open-hearth operations that are important to quality and production costs. Therefore, pouring and mold practices must be considered highly specialized and important steps in steel-mill operations. MOLD DESIGN Mold design is difficult to discuss in a precise manner because it varies greatly throughout the industry, both in theoretical concepts and practical application, and few well developed data are available. Most ingot molds are designed to meet conditions peculiar to a given plant wherein quality standards are dictated by end-use requirements, which may differ considerably even for the same grade of steel. The mold designer must also consider the equipment available to process ingots and the product obtained from them. Such equipment, used for stripping, heating, blooming and finishing operations, is seldom, if ever, exactly the same in any two steel plants. Thus, pronounced contrasts in mold designs can be expected to continue, even among plants making strictly comparable types of product, particularly because some producers are just beginning to realize the benefits possible from specialized designs. Certain fundamentals are used in mold design but even these

Jan 1, 1964

By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By A. E. Wheeler, H. Y. Eagle

The copper industry in the Province of Katanga, in the Belgian Congo, which is now controlled and operated by the Union Minére du Haut Katanga, had its inception many years ago in the vision of a Scotsman, Robert Williams, now Sir Robert Williams, Baronet. He it was who personally negotiated the mineral concession with King Leopold of Belgium, sent in the prospecting parties who located most of the present mines of the company, later arranged for the Belgian participation from which the present company was formed, and has been its active mentor ever since. The idea back of his efforts was the establishment of an industry on the Congo-Zambezi divide, of sufficient importance to draw up to it the head of the Cape to Cairo Railroad, the dream of Sir Cecil Rhodes, and the consummation of which he had left as a legacy to Mr. Williams, his successor. The reports of the prospecting expeditions showed that copper in profitable quantity was there, but many difficulties lay in the way of the establishment of the infant industry. The isolated location of the mines, various tribal wars, the Boer War, and many other factors contributed to making progress very slow. However, in spite of these difficulties the railroad was finally built and a blast-furnace plant erected at Lubumbashi, near Elisabethville, the capital of the Province. Operations of this plant were started in 1911, treating high-grade oxidized ores and producing pig copper by a reducing smelting. Production has been continuous since that time and the company has grown so that at present it ranks as the largest individual copper producer in the industry. It is a fitting monument to the foresight, optimism and driving force of its founder, and the progressive policies of his Belgian colleagues. In January, 1914, the Union Miniere du Haut Katanga engaged as its consulting engineer, Archer E. Wheeler, metallurgical engineer, at that time general superintendent of the Great Falls plant of the Anaconda Copper Mining Co. Mr. Wheeler was commissioned by the Board of Directors to proceed into Katanga, and make all necessary investigations to enable him to report on a comprehensive development program, and to recommend a scheme of treatment particularly for their low grade

Jan 1, 1934

By H. C. Schultz, F. K. Middleton Hunter

Certain local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to develop usefully its full disruptive effect in hard ground. The individual blasts at Chuquicamata arc large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with 1,. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast. Present Liquid-oxygen Plant An experimental unit with a rated capacity of 75 liters per hour was erected during the latter part of the year 1926 to prove the effectiveness of L. 0. X. at this mine, its cost, and possible efficiency of large-scale storage of the liquid. With this experimental unit 200,000 tons of ore

Jan 1, 1928

By R. T. Walker

GROUND waters-hot or cold-containing small amounts of the more common earth acids, such as carbonic acid, silicic acid, hydrogen sulfide, sulfurous acid and sulfuric acid, have only a very limited "solvent effect on dominantly siliceous rocks, whether of igneous or sedimentary origin, but in limestone they often form extensive cavities; and such "limestone caves" are the only openings of considerable size and continuity in rock formations that do not owe their existence directly and almost wholly to dynamic action. Limestone caves such as are developing at the present time must have been formed in all past geological ages in which limestone beds existed and where suitable conditions for the development of such caves prevailed; hence it would seem a reasonable expectation that, in the course of geological history, a certain number of ancient limestone caves must have been utilized as channels for the passage of mineralizing solutions, during portions of their course, at least, and that, in consequence, orebodies must have been deposited in such caves. Such a conception is not novel; it was proposed many years ago, but its possibilities, as explaining certain types of ore deposits, have been rather lost sight of in the development of the theory of the metasomatic replacement of rocks by minerals. It is the purpose of this article to assemble evidence to show that many of the orebodies found in limestone beds have been deposited in pre-existing caves; to discuss the criteria whereby such orebodies can be distinguished from others which have been formed along fissures and fracture zones traversing limestone, by the more common method of metasomatic replacement, analogous to orebodies in other formations; and to describe certain orebodies-particularly the "ore channels" of the Tintic district, Utah-as illustrative of the principles discussed. Limestone caves may be divided into two classes: those formed by cold, descending surface waters, which emerge again at some lower elevation as cold springs; and those formed by hot, ascending waters of deep origin or circulation, which attain the surface as thermal springs. Although these two classes are similar in many respects, there are certain characteristic and inherent differences whereby they can usually be distinguished.

Jan 1, 1928

By D. L. Harris

Chemical upgrading testwork on Stillwater chomite concentrate shows that reduction roasting and leaching (sulfuric acid and/or ferric sulfate) can provide upgraded feed to ferrochromium furnaces for making upgraded ferrochromium. Two-stage reduction smelting in electric arc furnaces can make upgraded ferrochromium also. Sulfating roasts and leaching (acid and/or water) results using gaseous SO2—SO3 or solid ammonium sulfate were not satisfactory for upgrading chromite. Chemical upgrading of domestic Stillwater (Montana) chromite has been considered at various times1'2' to provide a material with higher chromium to iron ratio, more like foreign high grade ore, for the production of standard grade ferrochromium. Physical bene-ficiation of Stillwater chromite ore can provide a ratio, Cr/Fe, no higher than the ratio in the chromite mineral, which is approximately 1.7. For comparison the analyses of a foreign metallurgical grade chromite ore, a high grade electrostatic process Stillwater concentrate and a stockpile concentrate from the Stillwater ore are noted in Table I. Single stage smelting of the high grade foreign ore with a ratio, Cr/Fe, of 3.37 can provide a ferrochromium of over 65 pct chromium content. Similar smelting of the Stillwater concentrate with a ratio of 1.7 can provide a ferrochromium of 50 to 55 pct chromium content.' It has been demonstrated on a pilot plant scale that chemically upgraded Stillwater chromite having a ratio, Cr/Fe, of 3.0 also can be smelted to provide a ferrochromium containing over 65 pct chromium.5 Two major considerations for an upgrading process are the ratio, Cr/Fe, in the product and the chromium recovery. A minimum ratio, Cr/Fe, of 3.0 is required in the product but for economic reasons a higher ratio is desirable for blending purposes as long as the recovery is satisfactory. Data from different kinds of chemical upgrading testwork are presented in this report. Some of the testwork was conducted to make a product which was not intended to be feed for ferrochrome smelting, but the data are considered pertinent to chemical upgrading. Results reported by others are noted also for comparison. WORK REPORTED BY OTHERS The U. S. Bureau of Mines has contributed much to the literature on chemical upgrading of chromite and a summary is given in Table 11. Reduction roasting and acid leaching were reported by Boericke and Bangert,1 by Lloyd and Gorst, et a1,2 and by Boericke3 to demonstrate very good success on a laboratory scale and only fair success in pilot plant tests for Stillwater (Benbow) concentrates. This work included basic studies on thermodynamic properties to explain the reduction and leaching results. Canadian workers, Downes and Morgan,9 have reported experimental success in upgrading a low grade Bird River chromite, similar to Stillwater material by the same process. Russian workers1' have noted results on reduction tests of high grade chromite which may apply to low grade ores and which help in understanding the reduction process. The use of flux additives in the reduction process was an innovation of their work. The Canadian workers9 also reported other kinds of experiments, including autoclave leaching of the chromite in a limited amount of sulfuric acid. An insoluble basic chromium sulfate was formed and separated from soluble iron, magnesium, and aluminum sulfates to provide an upgraded material. U.S. Bureau of Mines workers, Lloyd, Rosenbzum, Home and Davis,' reported on autoclave leaching of Benbow concentrates as a means of obtaining chromium alum for electrolysis. This last work required selective crystallization of alum to separate iron from chromium. Chloridizing roasting of Benbow and Mouat concentrates has been reported by Hunter and Banning6 and others8 to show that the iron chloride could be volatilized from the chromite to provide upgraded residues.

Jan 1, 1964

By Marcel Daly

THE writer has devoted a number of years to practical operations and to the study of geology in the oil fields. In consequence, he has been brought to investigate the theories advanced to account for the accumulation of oil and gas in commercial deposits. It is the result of these investigations and his personal conclusions that he wishes to sum up in this paper. The writer is an advocate of the organic origin of petroleum found in pools. He has been led to believe that the present theories of oil and gas accumulations are incomplete and, in certain respects, incorrect, although they may embody certain elements of truth; that the forces that are called upon to explain the movement are only secondary forces in the process, and insufficient, by themselves, to cause this movement; and that the phenomenon of accumulation is of much larger order than heretofore admitted and bears an intimate relation with the general as well as with the local deformations of the crust and is a direct consequence and a mechanical effect of these deformations to which the term "diastrophic" has been applied. As a complement to this theory, the writer offers a new interpretation of the "rock pressure" and of the mechanism of the "sealing up" of this pressure in oil and gas pools.

Jan 7, 1916

By Michael S. Roscoe

In order to more accurately predict longwall surface subsidence over the Pittsburgh No. 8 Coal in Eastern Ohio, North American Coal Corporation's Quarto Mining Company undertook or participated in several subsidence studies. Due to the changing roof geology and rapid variations in the amount of cover two separate areas were investigated at two different mines to determine the subsidence response if any to these changes. Data generated from these studies were compared with NCB derived,data for accuracy and then used to predict subsidence under houses, gas lines and other critical man made structures. The following report summarizes the results of these studies as well as the subsidence case histories of gas lines, transmission towers, houses and water wells. Problems that were encountered during both phases of this process (investigation and subsequent application) are also included.

A shrinkage stope is an overhand stope in which the broken ore accumulates until the stope is completed to, or near, the level above. As broken ore generally occupies at least 60 per cent. more space than ore in place, about a third of this must be drawn out as the stope advances to leave a working space under the back. The ore remaining supports the miners and gives temporary support to walls, and is all withdrawn when the stope is finished. The shrinkage-stope method is applicable to steep-dipping deposits of strong ore with strong walls. It may be applied to narrow or wide veins, and is simple and cheap. Five examples, which include important and varied types of deposits, are given: namely, Kennecott, Homestake, Jarbidge district, Mogollon district, and Cripple Creek district.

Jan 1, 1925

By C. W. Mac Gregor

THE observation of the flow layers, or Lüders' lines, produced in mild steel when it is stressed into the plastic range often provides considerable useful information for the study of the fundamental mechanism of the plastic flow of metals. It is a commonly observed fact that as soon as the upper yield point in a mild-steel tensile-test bar is passed, an unstable condition develops in the equilibrium, the load on the testing machine drops and if the surface of the bar contains a thin mill scale, the latter begins to flake off rapidly along certain "lines." These "lines" are in reality traces of wedge-shaped flow layers and are formed by the inter-section of the surface of slip and the surface of the bar. The average plane of the flow layer itself has been found by various experimenters to be inclined at an angle of approximately 45° to the axis of the test bar. In a body of more complicated shape stressed in possibly a different man-ner, the tangent planes to the flow layers at each point seem in many cases to be inclined at an angle of about 45° to the principal stress direc-tions at the point. As examples of the latter may be mentioned the logarithmic spirals obtained when a rivet hole is punched in a thin plate, or when a tube is subjected to internal pressure only, etc. Hence if the flow layers are observed from an experiment, the shear-stress trajectories -the curves indicating the directions of the maximum shearing stresses in the body-may then be approximately determined. Since the latter curves form an orthogonal family inclined at 45° to the principal stress directions, the family of principal stress trajectories, or the curves indicating the directions of the principal stresses, may be thus obtained. Although the discontinuous type of stress-strain curve at the yield point is commonly observed with test bars of mild steel, more recent experiments have shown that this is by no means the only material exhibiting this interesting phenomenon. A similar effect has been observed in zinc and cadmium crystals, by Becker and Orowan;1 in duralumin and other aluminum alloys, by Dawidenkow, 2 Elm,3 Fell, and others; in copper and copper-alloy crystals, by Elam;5 in brass by Elam;5 in brass wires by deForest;6 in higher carbon steels, tungsten steel, and

Jan 1, 1939

By Charles Barrett

THE orientation of metal crystals and grains, both large and small,. can be determined conveniently and accurately without the use of X-ray apparatus. This seems to be appreciated by so few metallurgists that it may be useful to explain in detail the method we have found most satis-factory in the laboratory the reflection of light from crystallographic etch pits. This note includes a description of a suitable inexpensive instrument and instructions for etching various metals and for plotting the data. As the stereographic projection is used to facilitate handling the data, this note may be considered as an appendix to an earlier review of the metallurgical uses of the stereographic projection.1 Various methods involving etch pits have been used by other investi-gators, Bridgman's method2 consists of attaching the specimen to a sphere (a transparent sphere is convenient4), holding it at arm's length, and marking a spot on it when it has been turned so that the etch pits reflect light into the eye of the observer from a lamp standing behind him. It has an accuracy of about 2° and is extremely rapid. A greater accuracy can be obtained by having the reflected light fall on a screen, as has been done by Czoehralski, 5 Chalmers,6 and Schubnikov.7 All of these methods have been intended for undeformed single crystals. Tammann and his coworkers"' developed a method for estimating the number of grains in a polycrystalline aggregate having orientations in a given region of the stereographic triangle and thus obtained statistical information about deformation and recrystallization textures. While the method has had some use in recent years,9 it is not applicable to the majority of problems in physical metallurgy. Smith and Mehl10 determined orientations by plotting the directions of the sides of individual etch pits on a stereo-

Jan 1, 1940

By S. M. Wu, R. L. Stone, T. D. Tiemann

The dissolution of silica from quartz in sodium hydroxide solutions was investigated by statistical methods. A second-order predicting equation was developed with 28 experiments expressing the dissolution of silica as a function of the variables quartz size, time, temperature and sodium hydroxide concentration. With this equation a comprehensive picture of the dissolution reaction was gained which included the effect on extraction of each variable and their interactions, fractional extractions, reaction rates and activation energies. A previous investigation of the extraction of silica from low grade siliceous iron ore by digestion in sodium hydroxide solutions presented the extraction as a function of time, temperature and sodium hydroxide concentration.' The present paper is an outgrowth of the previous work and develops by a mathematical analysis the functional relationship between the extraction of silica and time, temperature, sodium hydroxide concentration and particle size. Relatively pure quartz was used in this study in order that the basic quartz-sodium hydroxide reaction could be studied without the influence of other constituents that are commonly found in iron ores. The functional relationship between the dissolution

Jan 1, 1965

By Gilbert Santoro

In this study tantalum carbide filaments of various compositions in the fcc region were prepared by heating a tantalum wire in a measured amount of hydrocarbon vapor. Such properties as tensile strength, transverse-rupture strength, microhard-ness, lattice parameter, electrical resistivity, and magnetic susceptibility were measured as a function of carbon content. Some of these properties showed a maximum or a minimum between a carbon-to-tantalum molar ratio of 0.80 and 0.85, the composition range at which the color changes from metallic gray to gold. The recent literature has shown that in the large homogeneity range for the fcc phase of the Ta-C system there is a marked variation for such properties as microhardness,' electrical resistivity, ' thermodynamic properties,z'3 lattice parameter and superconductivity. In addition to the technological interest of these variations within a single phase, important theoretical benefits may ensue from a continuous investigation of properties vs stoichiometry in tantalum carbide and other refractory defect compounds, for example the effect of the metal-metal distance and crystal structure upon bond formation and electronic structure. Whether there is a similar variation of the tensile strength is of practical importance. Of theoretical interest would be the knowledge of how the magnetic susceptibility varies with carbon composition. Both of these properties, as well as the transverse-rupture strength, were determined for tantalum carbide filaments in the fcc phase region. The lattice parameter, the electrical resistivity, and the microhardness were also investigated and compared with values appearing in the literature. EXPERIMENTAL PROCEDURE Material Preparation. Tantalum carbide specimens of various carbon content were prepared by statically carburizing high-purity tantalum filaments in measured quantities of pure hydrocarbon gas. The filaments, which were 10 mil in diameter and 20 or 40 cm long, were heated by their own resistance at temperatures from 1800" to 2200°C using alternating current in some cases and direct current in others. Tantalum wire from two sources was used. One had a reported purity of 99.96 wt pct Ta. The ingot from which this wire was drawn had been electron beam-melted as the final step in its purification. The reported purity of the other wire, which was prepared by a powder metallurgical process, was 99.88 wt pct Ta. The impurities of both tantalum sources are listed in Table I. Spec-trographic-grade toluene or research-grade propane was used as the source of carbon. The apparatus for the carburization of the filaments is shown schematically in Fig. 1. The system was evacuated to 1 x l0-' mm of Hg when using the electron beam-melted tantalum and to less than 1 p when using the less-pure tantalum. Neither the difference in the base vacuum, nor in the hydrocarbon gas, nor in the tantalum filaments resulted in any detectable difference in the properties studied in this work. However, only the carbides prepared from the higher-purity tantalum were used in the magnetic-susceptibility determinations. Once the base vacuum had been reached, the system was flushed with the hydrocarbon and re-evacuated. For any desired composition of the carbide, hydrocarbon gas was allowed to leak into a constant-volume flask to a predetermined pressure. These pressures were measured by a Cartesian diver-type mercury gage with a range from 0 to 20 mm and with a scale expanded to nine times. The hydrocarbon gas was allowed into the reaction tube and the filament was quickly raised to the reaction temperature. The slack in the filament due to thermal expansion was taken up by drawing out the movable electrode with a screw mechanism. The filaments were kept at temperature from a few minutes to 200 hr. In the majority of cases the heating time was 6 hr. The reaction tube was cooled by cascading water on its outer surface. By means of an ammeter and a voltmeter the electrical resistance at the reaction

Jan 1, 1963

By F. J. Escandon V.

The Plomosas stratiform lead and zinc deposits are located in northeastern Chihuahua in a sequence of folded Paleozoic and Jurassic rocks. They consist mainly of channel or blanket-like bodies of ellipsoidal cross section restricted to a 60-in-thick shaly limestone and a 30-m-thick marble horizon of La Casita formation, with some reemplacement veins and shoots within the Plomosas formation. The mineralogy consists of iron-poor sphalerite, galena with a small silver content, and pyrite, in a gangue of calcite, barite, and minor quartz. The ore bodies present a lateral zoning with zinc-lead ratios increasing to the northwest. Vertical zoning shows marked changes in zinc-lead ratios and in the width and tenor of the ore which cannot be related to sedimentary or diagenetic features. Transgressive mineralization and some small fissure veins and breccia pipes also point to an epigenetic origin. Sulfur isotope analysis and geochemical data indicate hydrothermal solutions. Texture of the ores in the Mina Vieja marble is coarse, but in the Cuesta shale it is banded along bedding. The low iron and silver content of the sphalerite and galena and the weak hydrothermal alteration (only marbleization) of the wall rock suggest a telethermal stage of the solutions. There is no evidence of a possible intrusive rock mineralization.

Jan 1, 1976

By Reinhardt Thiessen

UNDER sulfur in coal, is usually understood that form of sulfur which is combined with iron and known as pyrite. It occurs in the form of halls, lenses, nodules, continuous layers, thin sheets, or flakes, both in horizontal planes and vertical cleavage fissures. But pyrites also occur as very fine microscopic particles, or nodules, disseminated through the compact coal. This form has had but very little consideration. Finally, there is sulfur in coal in an amicroscopic form (not visible with an ordinary microscope), probably combined with the organic matter that exists -in tile coal. This form has had considerable attention from a scientific standpoint, but has probably not been recognized enough on the economic side. One or the other, or both, of these two latter forms may comprise the larger part of the sulfur content of coal, especially after it has been washed or otherwise prepared for use.

Jan 9, 1919

By Henry Rawdon

THE structure of wrought iron as usually described by metallographists and workers in metal in general is that of a fairly pure iron. Impurities, if present, are usually considered as being in solid solution in the crystals of the ferrite matrix or as forming part of the ever present "slag streaks." Attention is herein directed to one type of these dissolved impurities; to the detection of such impurities, particularly in low-grade irons, and to their possible influence on the physical properties of the metal. The attention of the Bureau of Standards was first directed to wrought iron of the peculiar and unusual characteristics to be described later, in material which had failed in service and was submitted for test. The examination was extended to other grades of wrought iron, to see whether such features are of common occurrence in this class of material. MICROSTRUCTURE OF WROUGHT IRON Usual Structure The general microstructure of wrought iron is so well known that a detailed description of it here is needless. There is shown in Fig. 2 the structure of a sample of Swedish iron which illustrates well the matrix of ferrite crystals in which are embedded the slag threads so characteristic of the puddling process and the subsequent working of the material. The usual commercial product contains varying amounts of the impurities commonly associated with iron and steel, i.e., manganese, phosphorus, silicon, and sulphur together with small amounts of carbon. Of these, the larger part of the phosphorus and some of the silicon present are held in solid solution in the ferrite while most of the remaining impurities, other than carbon, exist in the inclosures of slag. Aside from the discontinuities introduced by the slag streaks the ferrite matrix has the microstructure and appearance of a pure metal. No definite orientation of the various crystals or grains is apparent; deep etching of the specimens reveals no intracrystalline features (i.e., within the grains) other than those noted in "pure" metals in general (etching pits).

Jan 9, 1917

By F. Forward, H. Veltman, A. Vizsolyi

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By L. J. Howell, R. C. Sommer, H. H. Kellogg

WORK described herein was undertaken with the aim of determining some of the physical-chemical properties of electrolytes suitable for the electrodeposition of pure zirconium metal. In this paper the phase diagram, vapor pressure, and activities in the melt are considered. In a companion paper,' the electrolytic conductivity of some of these melts is reported. The melts studied were mixtures of NaCl and/or KC1 with ZrC1,. Chloride melts were chosen for study because 1) if the electrolyte is to be useful for industrial electrodeposition of zirconium, the chlorides will be preferred to the relatively costly bromides and iodides; 2) fluoride melts were being studied in another laboratory (Horizons Inc., Cleveland); and 3) melts containing oxygen, in any form, are unsuitable for preparation of pure zirconium, because of the great affinity of this metal for oxygen. Unlike electrodeposition from aqueous solution, the fundamental behavior of fused-salt electrolysis is poorly understood. In most cases, such basic electrochemical information as the phase diagram of the melt system, activities in the melt, conductivity, the nature of the current-carrying ions, the equilibrium electrode potentials, and the overvoltage behavior of the electrodes is unknown to the researcher who would develop a new electrodeposition process employing a fused salt. This research project was designed to supply information about some of these basic physical-chemical properties so that an intelligent choice of electrolyte for electrodeposition studies could be made. Experimental The experimental difficulties-encountered in this work result from the properties of zirconium metal and ZrC1,. ZrC1, is a solid which sublimes at 334°C. It is rapidly hydrolyzed by moist air to HC1, ZrOCl,, and ZrO,. Unusual precautions were exercised in this work to prevent hydrolysis of ZrC1, and rigidly to exclude oxygen, nitrogen, hydrogen, and carbon from the melts under study. These elements are known to react with and contaminate zirconium metal. All melts were studied in vacuum systems, i.e., in the presence of ZrC1, vapor only. Transfer of ZrC1, to or from the melts was accomplished entirely by vacuum sublimation. In this way, neither the melts nor the ingredients thereof were permitted to

Jan 1, 1958