Search Documents

By F. D. Rosenthal, F. J. Dunkerley, G. J. Mills

Activities, free energies, and heats and entropies of mixing of liquid Pb-Zn alloys have been obtained by the electrode-potential method between 400° and 650°C. The large positive deviations observed from Raoult's law are in agreement with the phase diagram, which indicates a wide immiscibility field. A vapor-pressure method was used to extend the activity measurements to 900°C, allowing the maximum of the immiscibility gap to be estimated by thermodynamic calculation. Data on the mono-tectic and eutectic points compare favorably with previously existing work. SEVERAL long-standing methods have been in use for the study of phase diagrams from measurement of the activities of the component metals.' The use of thermodynamic analysis for interpreting equilibria data is comparatively recent, however. Such analysis is usually undertaken by first evaluating the principal thermodynamic functions as, for example, the enthalpy, entropy, and free energy of the alloy constituents. These, in turn, quite often can be correlated with the interatomic potential energies and atomistics of the system, from which a clearer understanding of the causes leading to deviations from ideal behavior is gained. The present study of liquid Pb-Zn alloys is concerned with a determination of these quantities by electrode-potential and vapor-pressure measurements, using these values in calculations involving phase equilibria and to obtain a theoretical insight into an alloy system exhibiting strong positive deviations from ideal metallic solution. A considerable portion of the previously reported work is based on thermal analysis. Supplemented by optical studies of solid alloys, these techniques have revealed the essential nature of the immiscible mixtures that are formed. It is difficult, however, using the phase-

Jan 1, 1959

By Jack A. Simon, M. E. Hopkins

Coal is defined as a combustible rock that originated in the accumulation and physical and chemical alteration of vegetation. Coal can be ignited and burned like the wood that was man's earliest fuel, but coal gives more heat than the same amount of wood and has many industrial uses. Unlike wood, coal is not generally found on the surface of the ground but is mined from the solid rock of the earth. Before taking up the occurrence, formation, and the unique character of coal in the rock sequence, let us briefly consider the general character of all rocks in the crust of the earth. Relatively little is known about the very earliest history of the earth, although a number of logical theories have been developed. Manned exploration of the moon and the rocks returned to earth continue to provide some answers to questions concerning the earth's origin and history. The period of earth history with which we concern ourselves here begins after great areas of water had evolved on earth and substantial land areas of once molten (igneous) rock existed. Weathering and other processes that attacked the surface of the rocks reduced them to small particles. Water provided by rainfall transported this material, ultimately, to large bodies of water where it was deposited. Thus was initiated the geologic sequence of sedimentary rocks that lie above the once molten igneous rocks. The crust and upper mantle of the earth are made up of several large plates along which differential movement (primarily horizontal) takes place. Such movements, although small, are occurring today. These horizontal movements are accompanied by vertical movements causing important changes in the relative position of the continents and oceans. Low-lying coastal swamps with favorable climates are ideal locations for coal accumulation and burial by river-borne sediments, and large areas

Jan 1, 1981

By H. T. Clark, S. Feigenbaum

THE importance of measuring the temperature of molten steel in the open-hearth furnace has been recognized for many years. Poor temperature control may be costly to steelmaking operations and lead to a lowered quality of the steel. Low or excessive temperatures may shorten the life of the furnace, ladles and molds. Rates of reactions in the furnace and efficiencies of deoxidizers are known to change materially with a change in the temperature of the metal and slag. Ladle skulls and mold and stool stickers cause steel to be scrapped instead of being converted into useful products. Finally, the structure, segregation and surface condition of ingots are affected by the teeming temperature. Mill investigations of the effect of bath temperature upon steelmaking operations have been largely qualitative in character, based upon observations by practical melting men. The physical chemist has used the empirical information available and has reached reasonable and useful conclusions with respect to the various melting processes. The introduction of a reliable direct- reading pyrometer will permit accurate quantitative evaluation of the effects of temperature and should furnish a more rational basis for study of the thermo- chemistry of steelmaking. The problem is not merely one of making a small number of temperature measurements in the open-hearth furnace. This has been done by several methods to a degree of precision that was apparently satisfactory. Considerable effort by a number of investigators has been directed rather to the development of an open- hearth bath pyrometer that would be both accurate and practical for routine measurements. To be practical, the pyrometer should be inexpensive to operate; that is, the installation, operating and maintenance costs should be exceeded by the tangible benefits to the open-hearth operator. Temperatures from 2800° to 3100°F. are encountered in the open-hearth furnace. The surface of the molten metal is covered by several inches of slag, which prevents direct observation of the metal surface for optical or radiation measurements. Both slag and metal are highly reactive at these temperatures and will attack to a greater or lesser extent any material immersed in them. Adequate protection of thermocouples, which of necessity must be brought to the temperature of the bath, has generally resulted in a large, heavy assembly made up of .brittle materials, unsuited for handling on the open-hearth floor. The lie of the equipment was short and maintenance was an important consideration. EARLIER WORK Any one of a number of physical proper- ties of liquid steel could conceivably be used as a basis for temperature measurement. Efforts to the present time, however, have been confined largely to measuring either the thermal electromotive force generated between two dissimilar materials immersed in the steel or the intensity of radiation from the surface of the steel. These

Jan 1, 1946

By Robert Keeney

THE electric smelting of manganese ore and the production of ferro- manganese did not exist as an industry, in the United States or elsewhere, previous to the outbreak of war in 1914. Ferromanganese had been produced, electrically, during times of high prices by two companies at Niagara Falls and by several European companies, but the production. was spasmodic, and none was electrically produced when ferromanganese sold at from $35 to $40 per ton. Thus the electric smelting of manganese ore must be considered as a development caused by the high prices prevailing during the years 1916, 1917 and 1918, and the necessity of smelting domestic ore in order to fill the ferromanganese requirements of the steel industry of the United States, which increased from 189,088 tons in 1914 to 356,356 tons in 1918. The electric furnace is well adapted to smelting domestic-ore because it can be located in small units near the source of ore supply. In 1918, the ferromanganese production of the United States was 333,027 tons, of which about 7 per cent., or 23,000 tons, was produced in the electric furnace. The electric furnace not only assisted materially in the development of a domestic-ore supply but made a considerable saving of coke, as it requires about 1,4 tons of bituminous or lignite coal per ton of ferromanganese compared with a blast-furnace consumption of 2.9 tons of coke per ton of ferromanganese. Some of the plants in the United States that smelted manganese ore in the electric furnace during the war and in 1920 are listed in Tabled. From early in 1919 to about February, 1920, little ferromanganese was produced in the electric furnace. During this period the price of ferro-manganese (78 to 82 per cent. manganese) was about $100 per ton. During the first half of 1920, several plants resumed operation when the, price of. ferromanganese (76 to 80 per cent. grade) gradually increased to $200 per ton, delivered.

Jan 2, 1921

By Paul D. Conatore

INTRODUCTION There are important reasons for a discussion of tungsten resources, reserves, and production in the Circum-Pacific area. First, the world's chief tungsten deposits, as well as most of the world's tungsten reserves and production, occur in this region. It is well known that the world's largest tungsten reserves are located in southeastern China and that for many years, the largest individual mine in the world was there. Although China still has the world's greatest tungsten production, the very high-grade scheelite mine of Canada Tungsten Mining Corporation in the Northwest Territories is the largest producer of tungsten today. There is certainly a great quantity of tungsten in Asia, but the strategic importance of this fact is now offset by the wide distribution of mines and production facilities throughout the world, especially in other parts of the Circum-Pacific area such as Australia, Canada, and the United States. In addition, much of the Circum-Pacific area is comprised of Mesozoic-Cenozoic orogenic belts. These global tectonic units are regarded as very favorable for additional tungsten deposits, particularly scheelite-bearing tactites, and consequently, prospecting and exploration will most likely be concentrated in the Circum-Pacific area. Second, tungsten must be regarded as one of the, most important metals of modern industry because of its very special properties. It has the highest melting point, the highest tensile strength at elevated temperatures, and the smallest compressibility of any metal. The metal also possesses a very high density, excellent corrosion resistance, good thermal and electrical conductivity, and a low coefficient of expansion. As a result, tungsten has found increasing importance in a wide range of industries. From the filament in an electric lamp, to cutting tools and drilling bits, to the exotic radiation shields that protect supersonic aircraft and spacecraft, tungsten plays an indispensable role in our daily lives. The primary objective of this paper is to present an overview of important facets of known and suspected tungsten in the Circum-Pacific area. Resources, reserves, current production, planned capacity expansions, and new operations, as well as an assessment of the probability for development of deposits in the Circum-Pacific area, are discussed. RESOURCES The average crustal abundance of tungsten has been estimated at 0.0015 kilograms per tonne. A comparison of the abundance of various metals in crustal rocks to that of tungsten is presented in Table 1, which shows that tungsten abundance is similar to that of its commonly associated metals, tin and molybdenum. Table 1. AVERAGE CRUSTAL ABUNDANCE OF VARIOUS METALS (Grams per Tonne) [ ] With careful thought, it can be realized that tungsten ore deposits result from the concentration of the metal, through normal geologic processes, to levels substantially greater than its average crustal abundance. The minimum technologically and economically workable tungsten concentration, or cutoff grade, is a function of (1) deposit tonnage, (2) mining and milling methods, (3) production tonnage, (4) capital and operating costs, (5) tungsten market conditions, and (6) value of associated recoverable metals. The tungsten cutoff grade that is currently exploitable at a profit varies from 0.09% W03 to 1.55% W03, reflecting concentration factors from 470 to 8200, as shown in Table 2. Table 2. CURRENT TUNGSTEN CUTOFF GRADES [ ]

Jan 1, 1982

By R. J. Stokes

This paper compares the room-temperature mechanical behavior of magnesium oxide crystals containing 'fresh' and 'grown in' sources. 'Fresh' dislocation sources introduced by cleavage or mechanical contact move and multiply to generate slip bands at 3000 psi. Macroscopically the crystals yield smoothly at 6000 psi and can be quite ductile. When 'fresh' sources are eliminated by chemical polishing the crystals have to rely on 'grown in' sources to initiate slip. They then deform elastically up to extremely high stresses (-30 to 50,000 psi) yielding with a sharp stress drop down to the level at which Ifresh' sources operate. Grown in' sources are considered to be associated with impurity wecipitate particles or inclusions. Annealing crystals at 2000°C dissolves these particles thereby eliminating sources for slip. The crystals then become consistently stronger (> 70,000 psi) approaching within 1/10 of the theoretical strength. Dislocations of the grown-in network do not move under stress to nucleate slip. It is proposed that they are locked electrostatically. DISLOCATIONS were originally conceived to resolve the large discrepency between the theoretical and real strength of solids. The idea that slip propagates by the movement of dislocations is now well confirmed both by electron transmission and etch pit studies. But this by itself is not sufficient to explain the low yield strength of crystals for there is still the need to understand where slip dislocations originally come from. Theoretical estimates place the stress to generate dislocations homogeneously in the lattice at approximately 1/30 of the shear modulus,' a value 104 to 105 times greater than the stress at which the very first manifestations of plastic deformation have been observed. Only an special cases can the theoretical strength be approached; in crystals of high perfection such as whiskers2 where dislocation sources do not preexist and in covalent crystals where the dislocations present at room temperature are almost completely immobilized by the bond character of the solid.3,4 For the most part it is necessary to assume that the yield strength of ionic and metallic solids corresponds to the motivation and multiplication of dislocation sources present beforehand. The question as to their origin appeared to be answered by the suggestion of Frank and Read5 that dislocations forming part of the grown-in structure could operate as a mill for the large scale production of dislocations. The Frank-Read mechanism is still widely accepted as the source of dislocations but a number of observations have been reported which are in serious disagreement with it. One of the most intriguing of these is that under normal testing conditions dislocations of the grown-in network appear to play no role in the plastic deformation of rock salt structure ionic solids. This was first reported in the etch pit studies on lithium fluoride by Gilman and Johnston6 and is true also for magnesium oxide. To explain the comparatively low yield stress of lithium fluoride it was proposed by a number of authors7,9 that small unresolved prismatic loops formed by vacancy condensation were acting either directly or indirectly as the dislocation sources. This proposal led Gilman10 to perform a series of detailed and careful experiments on lithium fluoride to try to identify the sources responsible for the initiation of slip. He concluded that prismatic loops played no general role and that other sources were more important. Dislocation sources in ionic crystals can be divided into two general categories. First, there

Jan 1, 1962

By W. L. Fink, L. A. Willey

This paper is the nineteenth of a series from the Aluminum Research Laboratories, presenting the results of the investigations of equilibrium relations in aluminum-base alloys made from electrolytically refined aluminum. In previous papers equilibrium relations have been determined and correlated for 12 binary systems. Equilibrium relations have also been determined for portions of the aluminum corners of three ternary systems (aluminum-iron-silicon, aluminum-magnesium-silicon and aluminum-copper-magnesium). The object of the present paper and those to follow is to increase our knowledge of the aluminum corner of the more important ternary systems. In 1926 Dix and Keith † suggested a new method for designating the phases encountered in alloy systems. The system has been used to a very limited extentl,2,3 The system has since been slightly modified and will be used in this and future papers. In the system as modified, a phase is designated by placing in parentheses the chemical symbols of the elements essential to the formation of that phase. The symbols in the parentheses are separated by dashes in order to clearly distinguish them from a chemical formula. Elements that are not necessary to the formation of the phase in question, but which may be present in solid solution, are not indicated in the designation. If two or more phases would have the same designation according to these rules, they are distinguished by prefixing Greek letters, and are definitely identified by X-ray diffraction patterns. Previous Investigations The solid solubility of magnesium in aluminum has been well established by the work of Dix and Keller4, Schmid and Siebe15, and Saldau and Sergeev6. There is no agreement as to the composition of the magnesium constituents at the aluminum end of the binary aluminum-magnesium system. Hanson and Gayler7 report Mg2Al3; Boyer8 found that the alloy

Jan 1, 1937

By Lawrence B. Wright

The occurrence of gold, gold-silver, silver-lead-zinc ores in the post-Cambrian sediments in the Black Hills of South Dakota, and their genetic relationship to the Tertiary intrusives, is well known and accepted, but the occurrence of gold in the pre-Cambrian rocks at the Homestake mine, which underlie this Tertiary gold mineralization, has given rise to differences of opinion as to the period of major gold introduction into the older rocks. Fig. 1 illustrates the distribution of mineralization along the axis of the Tertiary uplift in both pre-Cambrian and post-Cambrian rocks. The following possibilities have been presented: 1. The Homestake gold deposit was formed in pre-Cambrian time and the deposits in the overlying Cambrian sediments formed during Tertiary time. 2. The Homestake lode existed at the beginning of Cambrian time, but was enriched by the passage of Tertiary auriferous solutions. 3. The Homestake lode was represented by pre-Cambrian quartz-chlorite sulfide mineralization, very low in gold content and the gold superimposed on the older nearly barren mineralization during the Tertiary metallogenic epoch. 4. The sulfides and sulfarsenides as well as gold were deposited in both pre-Cambrian and post-Cambrian rocks during the Tertiary period. Those favoring the first proposition feel that the question is pretty well settled, while the proponents of the second theory are more flexible in their view, feeling that the amount of gold introduced in either period is still an open question. The third and fourth theories, with some modifications, are supported by the proponents of the Tertiary theory, who feel that the evidence strongly favors that period. The following pages are intended to present the evidence and to give the reaction of various observers with my own comments and conclusions; also, the accumulated facts of observation gathered over a period of close association with the area under discussion, beginning in 1919.

Jan 1, 1937

By P. R. Bradley

NO thought had been given to deep level mining at the Alaska Juneau mine prior to 1930, but in that year a prospect winze was started and continued for 1000 ft. vertically below the main haulage or adit level. The point at which this winze was started was selected entirely by the prevailing physical conditions, such as proximity to established workings, convenience, and the presence overhead of a substantial pillar of dimensions sufficient to lo¬cate the sheave wheel and loading pocket. It was, therefore, with some surprise that the unusually high-grade ore found just below the collar of the winze persisted, with certain vari¬ations, to a full depth of 1000 ft. vertically. Likewise this unusually high-grade ore was found to persist on the various crosscuts driven on levels at 200-ft. vertical intervals. To be brief, this deep level work found richer ore than any yet found in the mine over like areas, and inasmuch as the area was sufficient to plan for extensive deep level mining, plans for such work were given extended consideration.

Jan 1, 1936

By Harry K. Ihrig

The hot-working of iron and steel is an art dating back to antiquity, but until about 25 years ago, relatively few alloying elements were used, and these were present only in small percentages. With the exception of sulphur, the amounts of other elements in steels did not markedly affect their hot-workability. The references in the literature on the effect of other elements on the hot-workability of steel are usually reports of failure of these steels in forging or rolling.1-8 With the increased use of alloying elements, and their use in larger amounts, it was observed that many of the new steels were red short in certain critical ranges or at all hot-working temperatures. The stainless steels are particularly difficult to hot-work. The determining of the correct conditions for piercing, rolling and forging of these alloys by experimentation in the mill often results in large losses of these expensive metals. It also is found that the hot-workability limits of many types vary from heat to heat, and hence poor results are obtained on changing to a new heat after a previous one has rolled satisfactorily. To determine the effect on hot-workability of iron to which various elements have been added, it was necessary to devise a method that could be used on small quantities of metal. In such a method, the minimum number of variables should be present, and the procedure should be simple, quick and correlatable with large-scale hot-working operations. Sauveur,9 in the first Henry Marion Howe lecture in 1924, described the effect of carbon on the ductility of steels in torsion near their critical points. He found that carbon increases the plasticity of gamma iron. In the 1930 Campbell Memorial lecture,10 he gives the effect of carbon, chromium, and chromium and nickel on the ductility of steels under 2000°F. in torsion. Ellis11 has studied the malleability of steels at various elevated temperatures by means of a single-blow drop-hammer test. In this test the percentage decrease in height of standard cylinders is taken as a measure of their malleability. He has shown that in the low-alloy steels studied, carbon has a greater effect than nickel, chromium and vanadium. In 1938 the first tests were run on a new quantitative hot-workability test in the laboratories of the Globe Steel Tubes CO. Thum12 mentioned it in 1940. An illustration of the apparatus was published in January 1942.'' The effect of a few alloying elements on the hot-workability of metals was shown in a description of the test in 1944.14 Description of Test Method The method adopted after a trial of several others is a rapid twisting of bars to failure in a furnace. The standard-size bar was chosen as 9/16 in. It is prepared from larger pieces by forging and cold-

Jan 1, 1947

By Harry K. Ihrig

The hot-working of iron and steel is an art dating back to antiquity, but until about 25 years ago, relatively few alloying elements were used, and these were present only in small percentages. With the exception of sulphur, the amounts of other elements in steels did not markedly affect their hot-workability. The references in the literature on the effect of other elements on the hot-workability of steel are usually reports of failure of these steels in forging or rolling.1-8 With the increased use of alloying elements, and their use in larger amounts, it was observed that many of the new steels were red short in certain critical ranges or at all hot-working temperatures. The stainless steels are particularly difficult to hot-work. The determining of the correct conditions for piercing, rolling and forging of these alloys by experimentation in the mill often results in large losses of these expensive metals. It also is found that the hot-workability limits of many types vary from heat to heat, and hence poor results are obtained on changing to a new heat after a previous one has rolled satisfactorily. To determine the effect on hot-workability of iron to which various elements have been added, it was necessary to devise a method that could be used on small quantities of metal. In such a method, the minimum number of variables should be present, and the procedure should be simple, quick and correlatable with large-scale hot-working operations. Sauveur,9 in the first Henry Marion Howe lecture in 1924, described the effect of carbon on the ductility of steels in torsion near their critical points. He found that carbon increases the plasticity of gamma iron. In the 1930 Campbell Memorial lecture,10 he gives the effect of carbon, chromium, and chromium and nickel on the ductility of steels under 2000°F. in torsion. Ellis11 has studied the malleability of steels at various elevated temperatures by means of a single-blow drop-hammer test. In this test the percentage decrease in height of standard cylinders is taken as a measure of their malleability. He has shown that in the low-alloy steels studied, carbon has a greater effect than nickel, chromium and vanadium. In 1938 the first tests were run on a new quantitative hot-workability test in the laboratories of the Globe Steel Tubes CO. Thum12 mentioned it in 1940. An illustration of the apparatus was published in January 1942.'' The effect of a few alloying elements on the hot-workability of metals was shown in a description of the test in 1944.14 Description of Test Method The method adopted after a trial of several others is a rapid twisting of bars to failure in a furnace. The standard-size bar was chosen as 9/16 in. It is prepared from larger pieces by forging and cold-

Jan 1, 1947

By John Burns

THE object of this chapter is to present data concerning the effect of the introduction of relatively slight amounts of carbon and nitrogen into supersaturated solution in iron. The study is confined to the alpha temperature range of both the Fe-C and Fe-N systems. The age-harden-ing characteristics of these two systems are considered. These data are compared to those of other age-hardening alloy systems and a "classifica-tion" is essayed. A.-RELATION OF LATTICE PARAMETER AND ELECTRICAL CONDUCTIVITY TO CHANGES IN PHYSICAL PROPERTIES DUE TO AGING OF FE-C ALLOYS Since Whiteley1 in 1927 showed that some of the iron carbide that is normally present in slowly cooled low carbon-iron alloys disappears on rapid cooling from just below the A1 point, interest has been manifested in the possibilities of age-hardening in these alloys. Masing and Koch,2 and at the same time and independently, W. Koster,3 proved these alloys to be age-hardenable. A. A. Bates4 a little later also published an interesting paper on changes in physical properties due to the aging of low-carbon steels. Many other papers have appeared showing changes in physical properties in specific instances due to this same phenomenon.

Jan 1, 1934

By W. L. Falke, A. A. Cochran

A basic problem in connection with manganese is to find economical ways to utilize domestic resources. As a part of its program to conserve domestic mineral resources and to reduce dependence of foreign sources, the Bureau of Mines had conducted extensive research to broaden manganese technology and to find economical, technically-feasible processes for recovering manganese from these low-grade resources. This paper analyzes some of the major difficulties which have been encountered in previously proposed processes for treating low-grade manganese ores and discusses a process which may circumvent many of these difficulties. Vast deposits of low-grade manganese ore exist in the U.S., yet domestic production is insignificant compared to the more than 2 million tons of ore imported yearly into this country.' A basic problem in connection with manganese is to find economical ways to utilize domestic resources.2 As a part of its program to conserve domestic mineral resources and to reduce dependence on foreign sources, the Bureau of Mines has conducted extensive research to broaden manganese technology and to find economical, technically feasible processes for recovering manganese from these low-grade resources. Although a great many processes have been proposed for treating domestic manganese resources, a failing of many of them is that too many steps are involved for economical operation.' Some of the major processes that have been proposed were reviewed by Norman and Kirby.3,4 Chlorination processes have become increasingly useful as a means of recovering valuable metals from raw materials, because the relative cost of chlorine (Cl2) and hydrogen chloride (HC1) has decreased through the years, and because the corrosion resistance of materials of construction has been improved. The objective of these processes is to form metal chlorides that are more volatile or water-soluble than are the corresponding oxides or sulfides; these compounds then can be separated from the gangue or other minerals by volatilization or leaching. Several chlorination processes for the recovery of manganese have been investigated by the Bureau of Mines5-8 and others; the major chlorination processes were reviewed in 1963, and their main features were compared.4 In all these processes, the simultaneous leaching or volatilization of iron chlorides with manganese chloride (MnCl2) is a problem, and the more iron that is present, generally the greater the problem. The leaching step is not highly selective, and the product of this step is, at best, suitable only for the production of ferromanganese or for further processing to remove iron. The product of the volatilization step is, in all cases, a mixture of iron and manganese chlorides that contains too much iron even for ferromanganese production, and must undergo additional processing steps for iron removal. THERMODYNAMIC CONSIDERATIONS The literature indicates that the desired chlorination reactions will proceed at practical rates at temperatures near 1200°K (927°C). Free energy changes at 1200°K for the critical steps of the reduction and chlorination reactions9-11 follow: Most of the research on chlorination processes for manganese recovery has been done with HC1 rather than with C12, for the following three main reasons: 1) Recycling of the chlorinating agent, which is economically vital, appeared to be easier for HC1

Jan 1, 1968

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

Consolidation of hydride process, electrolytic, calcium reduced, and comminuted thorium powder, as well as saw chips and lathe turnings, by vacuum hot pressing and by cold pressing-vacuum sintering was studied. The mechanical properties of the consolidated material in the extruded form are compared with those of wrought castings. AT present there little little industrial use for thorium metal, although it has some important though small scale applications in electronic equipment. Despite its high inelting point—about 1750°C —a low modulus of elasticity, 11.4xl0 si at 20°C;' relatively low mechanical properties coupled with a high density, 11.7 g per cu cm; and an unusually high chemical activity with normal atmospheres limit any structural applications. The metal is utilized as an alloying element principally in magnesium. Pure thorium finds utility as electrodes in gaseous discharge lamps such as the high intensity mercury lamp' because its low work function and high electron emissivity provide lower starting potentials and more uniform operating characteristics than other available materials. The metal is also found in photoelectric tubes used for the measurement of the ultraviolet spectrum." Thorium metal has been used in germicidal lamps of the cold cathode type as sputtered coatings on nickel in order to provide a low work function surface and a low starting voltage. Other applications have involved the radioactive properties of thorium for the production of ionized particles." The potential value of thorium is much greater than its present use pattern because of possible utility in the field of nuclear power. Th may be converted through nuclear reaction to a fissionable element U which should be capable of acting similarly to U in the g'eneration of atomic power. Thorium has been reported to be about three times as plentiful as uranium in the earth's crust, placing it in the order of abundance of lead and molybdenum." Thus, it is of interest in augmenting the potential supply of fissionable material for nuclear power. Because of its high melting point, thorium is usually produced as a powder through the calcium reduction of its oxide or thermal reduction of halides by sodium, magnesium, and calcium. It may also be produced in flake form by electrolysis of fused alkali or alkaline earth chloricles and fluorides. Therefore, powder metallurgy assumes importance in the fab- rication of thorium metal shapes. Furthermore, it is rather difficult to obtain pure thorium by melting, as the molten metal reacts readily with graphite as well as oxide, carbide, and nitride refractories. These contaminate the melt with oxides, carbides, and metallic impurities." The current investigation was undertaken to examine the fabrication of thorium by powder metallurgy methods which have been used for the commercial production of beryllium and other metals.' A sparcity of data concerning the comparative cold and hot compaction of thorium powders of different derivation existed. Therefore, all commercially available types were examined along with other experimentally produced thorium powders in order to round out the comparison of consolidated thorium powders with melted reguline metal. Review of the Literature By heating a mixture of ThC1, with potassium, Berzelius made the first thorium metal as an impure powder in 1828. Improvements in the basic process, increasing thorium assay to 99 pct, were made by several investigators including Arsem," Lely and Hamberger10 and Von Bolton." Calcium reduction of Tho, to make powders was investigated by Berger," Huppertz,'" Kroll," and Kuzel and Wedekind.'" A thorium powder produced by this method using a CaC1, fluxing agent assayed 99.7 pct, as reported by Marden and Rentschler.'" Compacted and sintered, this product was found to be ductile, and could be fabricated into wire and sheet. Improvements of the calcium reduction process were made later" wherein CaCl, was eliminated from the reaction, producing metal assaying 99.8 pct Th. Further work by Lilliendah118 howed that a coarser metal could be obtained by the substitution of ThC1, or ThOC1, for oxide with consequent advantage of stability to atmospheric reaction. Reports on the technology of thorium developed in Germany during World War II have been made by Espe."' Thorium powder of 99.5 pct Th was obtained by reduction of the oxide by calcium. Screening to —200 mesh, compacting with about 20 tsi, and sintering in vacuo at 1320" to 1360°C for 3 hr resulted in a porous sinter cake. The sinter cake was sufficiently ductile to be worked into bar, wire, and sheet which could be employed as electrode materials.

Jan 1, 1957

By O. D. Gonzalez, R. A. Oriani

A thermo-osmosis technique has been used to measure the heat of transport, Q* , of hydrogen and of deuterium dissolved in a iron and in nickel, and of hydrogen in Feo.6Nio.4 in the tempevature range 400° to 600°C. For all these systems, Q* is negative and has a large temperature coefficient; an isotope effect can be established for the solutes only in nickel. The magnitude of Q* is considerably larger than the activation energy, E , for migration in the case of these isotopes in a iron, so that all variants of the Wirtz model must be rejected. The phenomenological definition of Q* is developed to show that Q* is related to the mechanisms by which the activation energy is dissipated back into the lattice, and that Q*/E is a function of the ratios of the mean free paths of electrons and of phonons to the distance of jump of the diffusing atom. A correlation is shown to exist between the sign of Q* in thermal diffusion and that of the effective charge in electro migration, and may be understood as due to the large ratio of the mean free path of electrons to that of phonons. THE study of nonisothermal diffusion in the solid state is of interest because certain aspects of the mechanism of diffusion are made manifest which remain concealed though still present in the isothermal case. The thermodynamics of irreversible processes characterizes nonisothermal diffusion, known as thermal diffusion or as the Ludwig-Soret effect, by a quantity, Q*, called the heat of transport, which essentially measures the sign and the magnitude of the steady-state concentration gradient produced by the imposed temperature gradient. The problem then is to understand the quantity Q* at the atomistic level. There does not exist a theory for the atomistic interpretation of the heat of transport. There are, however, two classes of simple models which seem to afford some physical insight into Q*. Wirtz's model1, z and its subsequent generalizations partition the activation energy, E, for the migration of the atom spatially about the region of the migrating atom, so that Q* is the difference between the portion of the activation energy centered about the original site of the jumping atom and that portion about the arrival site. Clearly, the magnitude of Q* cannot on this model be larger than the activation energy for migration. The model of Oriani3 also considers the spatial distribution of E not only before but also after the atomic jump, and Q* is related to the variation of the spatial distribution of E that is produced by the jump. The simplest kind of system with which to compare the consequences of these ideas is the interstitial solid solution, since one may easily choose a temperature at which only the interstitial component moves, the solvent lattice serving as a completely satisfactory frame of reference. Thus, one avoids complications arising when both species in a binary system move. In addition, one avoids the necessity of knowing the energy for the formation of a vacancy, something which is needed for the analysis of thermal-diffusion data on metals which diffuse by the vacancy-exchange mechanism. However, the number of well-measured interstitial systems is extremely small, and, in particular, there are almost no data in the published literature for the temperature dependence of the heat of transport. If one works with solutes which are gases in the pure state at ordinary temperatures, one may use the technique of thermo-osmosis4 which permits thermal diffusion to be measured over a small temperature difference so that the temperature dependence of Q* can be more easily determined. The choice of dissolved hydrogen in iron and nickel was based on these considerations as well as on the desire to look for an isotope effect associated with localized

Jan 1, 1965

By R. J. Burgess, A. R. Ramey, A. R. Adams

During interpretation of pressure buildup tests on gas wells in a tight dolomite gas reservoir, peculiar behavior was noticed. Two straight lines were apparent. Effective permeability to gas taken from either straight line was about the same, and the Miller-Dyes-Hutchinson dimensionless time check for the straight line was proper for both straight lines. Geological data indicated the likelihood of scattered trending fractures in the reservoirs. Since the first straight Iine yielded permeability values close to the geometric mean permeability from core analyses, it was postulated that the reservoir model was that of an acidized well completed in the tight dolomite, but that widely scattered hairline fractures caused the mean permeability of the reservoir distant from the well to be higher than the matrix permeability. Because all other studies of fractured reservoirs to the authors' knowledge assumed that the fracture matrix was dense enough to communicate directly with the well, no interpretative methods were available. The Hurst line-source solution for a radial change in permeability for interference between oil reservoirs was adapted to pressure buildup testing. The result indicated that the first straight line should yield the proper matrix permeability and wellbore skin effect. The second straight line may be extrapolated to obtain static pressure. The time of bend between the straight lines was used to estimate distance to a fracture. Application to field test data is shown. It is believed that the methods developed and the case history presented will add to present tools available for pressure buildup interpretation. Introduction Since the pioneer studies by Miller, Dyes, and Hutchin-son1 and Horner' in 1950 and 1951, well test analysis has become recognized as one of the most powerful tools available to both production and reservoir engineers. Well test analysis serves as a logical basis for well stimulation and completion analysis, and for long-term reservoir engineering. Since the early 19501s, much effort has been placed on the development of well-test analytical methods. Reservoir and well conditions of increasing complexity have been considered systematically to provide the analyst with a catalog of causes and effects. Matthews and Russella state that some 200 papers dealing with this subject have been published in the last 35 years. Developments in well test analysis appear to have originated in one of two ways. Either a physically realistic field condition was anticipated and analytical solutions for the condition achieved, or anomalous field test behavior was recognized and interpretative methods sought for the anomaly. In recent years, it has appeared that the latter has inspired an increasing number of studies. The analyst today finds an increasing number of known cause and effect studies available for well test analysis, the classic of which is that of finding the specific flow problem that generated the answer — the well behavior. Although it may be impossible to achieve this goal uniquely, the analyst often is able to select a useful interpretation that combines all known performance and geologic data — or to show that various logical alternatives would not significantly affect the interpretation. During a recent reservoir study, we observed gas well test behavior that did not appear to fit behavior described previously. Although it cannot be said that we have found a unique interpretation, we shall present in this paper the peculiar behavior observed, and describe the reservoir and interpretative methods developed. Reservoir Description The subject gas reservoir is a 9-mile-long, narrow dolomite reservoir lying within a limestone of Ordovician age. (See Fig. 1.) The dolomitized rock in the field consists of dark brown to buff, dense to coarsely crystalline, vugular dolomite containing numerous hairline fractures, many of which may have been closed in the reservoir and parted when cores were brought to the surface. Larger fractures are also apparent in core, but usually are filled and sealed with euhedral dolomite crystals. Portions of the north flank of the reservoir are known to be cut by a sealing fault downthrown to the north. Gas wells located near the fault have higher open flow potentials than those more distant from the fault. This is believed to be a result of higher permeability near the fault due to more extensive and open fractures. Detailed coring and core analysis have been performed on several of the wells in this reservoir. Fig. 2 presents permeability variation' plots for both horizontal and vertical

Jan 1, 1969

By H. S. George

A method of illumination that enhances the value of microscopic study of opaque materials, as in metallography. By simulating natural lighting, structures. That possess relief are given a natural appearance. An example is included of the revelation of a hitherto invisible microconstituent. Erroneous interpretation is avoided. For example, etching figures in ferrite, heretofore considered to be pits, are revealed as pyramids, standing in bas-relief. Suggestions on technique are given, for, while the method is obvious, practice and attention to detail are requisite. ON one occasion when it seemed desirable to reveal under the microscope not only the metallic structure of an alloy, but certain small non-metallic inclusions, that are ordinarily obliterated by etching, it was discovered that, by partly eclipsing the illuminating pencil of light rays, the residual light was thrown on the object from one side and the structure was brought out in relief. At the same time, the non-metallic inclusions were retained in clear view. In this first demonstration of lighting obliquely through the objective a card was thrust part way into the light beam between the arc iris, and the light filter; the shadow of the card on the filter served to locate its position. Next several stiff-paper disks of various diameters were mounted on flexible wires some plasticine on the other end of the wires made it easy to adjust and maintain a disk at any desired position in the light beam. To facilitate manipulation, an assortment of disks, was mounted on a wheel, as shown in Fig. 1. The purpose of partly eclipsing the light beam was discussed in an earlier paper.1 There it was pointed out that the usual methods of illuminating opaque objects for microscopic examination lend an, un-natural appearance to, the view, while the new method, which has been termed conical illumination, revels the true relationship of constituents by simulating natural lighting.

Jan 3, 1924

By C. R. Knopp

Gas-oil relative permeability ratio is an important relationship in oil reservoir predictive calculations. A correlation has been developed from 107 gas-flood k/k tests on Venezuelan core samples. The correlating parameter is based on restored-state water saturation tests and' is applicable to both consolidated and poorly consolidated sandstone reservoirs. Data of the correlation show that there are no distinguishah1e differences between the mass-data groupings for the two c1assifications A procedure is recommended for running .sufficient relative. permeability analyses to compute a geometric mean of the sample group. The geometric mean is more representative of the total core, and probably the entire reservoir. For example, while only one in four of the k,,/k,., test curves agreed closely with the resultant correlation of this report, the geometric mean curves of the 16 suites (three samples or more). showed good agreetment ill three cases out of four. INTRODUCTION The gas-oil relative permeability ratio is an important, fundamental relationship in most oil reservoir predictive calculations. Predictive calculations are made to estimate future reservoir production characteristics and ultimate oil recovery. The k1,/k2, relationship is specifically needed to relate the surface gas-oil ratio to the reservoir oil and gas saturation, and to calculate the relative movement of these phases within the reservoir whenever some of the more complex driving mechanisms are present. Laboratory k1/k2, tests are not generally run as a routine analysis. Consequently, k1/k2 data often are not available when needed because the cost of laboratory work could not be justified or the need for such data had not been properly anticipated. When laboratory k1/k2, data are available, they are often very difficult to interpret. For example, wide divergence is sometimes shown in a family of k1,/k1, tests representative of the producing horizon in a single well. With these considerations in mind, a study was made to determine if a relationship might exist between the k1,/k2, curve and some other simple laboratory test criteria. The most probable k1/k2, curve correlation for Venezuela described in this paper is the result of the investigation. The presented correlation defines the most probable gas-flood k,,/k,, curve through the medium of air-water capillary displacement and centrifuge water saturation tests. The laboratory procedures of these tests are. relatively simple, and inexpensive; test data should be. widely available- from routine analysis. DATA AVAILABLE, LABORATORY METHODS The report correlation utilized 107 gas-Hood k1/k2, tests run on sandstone cores of Venezuelan reservoirs. Table 1 is a general tabulation of data pertinent to the tests, while Table 2 summarizes the data. Thetests include 96 from Western Venezuela and 11 from Eastern Venezuela. Eighty-two- of the 107 test samples were sandstones that varied from poorly consolidated to-unconsolidated; 25 were consolidated. The average sample porosity was 26.7 per cent and the average permeability was 1,121 md; these values typify the better sandstone reservoirs of' Venezuela. The Welge gas-flood technique,' based on fundamental Buckley-Leverett frontal displacement theory, was introduced in about 1952 and is widely accepted in the industry. The laboratory procedure is relatively simple, rapid, and can be performed on small core samples. While there have been some minor variations in sample preparation and laboratory procedure in the tests used for the correlation, these tests can be generally summarized as follows. The core sample was first sol vent-extracted and dried. Connate-water saturation was restored by the oil-flushing or evaporation-blow down methods. At the beginning of gas flood the hydrocarbon pore volume was completeiy saturated with the test oil phase. Unsteady-state gas-oil displacement then began with the injection of nitrogen or helium. while the displaced oil and gas phases were incrementally metered at the out-flow face. From the test data, the k,,/k,, curve was calculated by the Welge method.' The individual oil and gas relative permeabilities were also calculated." CORRELATING PROCEDURES In attempting to establish a basis of correlation, we found that broad mid-range sections of 105 of the 107 k,,/k,, test curves could be closely duplicated by a straight line. Only two curves did not show a degree of linearity in this region. Correlation-curve definition parameters were subsequently developed from this observation of consistent mid-range linearity. Possible correlating variables were limited to the physical properties measured on core samples that (1) were widely available as common test data and (2) could be easily and cheaply obtained through future laboratory work. The more obvious possibilities were porosity, permeability and

Jan 1, 1966

By Lawrence A. Shepard, Richard H. Krock

A series of ductile, two phase W-Ni-Fe composites, sintered in the presence of a liquid phase, were tested in tension. Identical room temperature stress-strain curves were obtained for specimens containing from 80 to 92 wt pct W (58 to 75 vol pct W particles). The composites exhibited a maximum elongation of 29pct at room temperature, and 10.7 pct at 77 °K. The tungsten particles in the composite elongated by the same amount at these temperatures. Single-phase alloy specimens matching the composition of the composite matrix showed about one half the flow stress of the composites. The test results demonstrated that the mechanical properties of W-Ni-Fe composites are determined by the tungsten particles alone and are independent of matrix volume fraction or mean free path over the composition range studied. A general prediction of the plastic behavior of two-phase alloys or composites from a knowledge of the properties, size, shape, and dispersion of the individual components is not, at present, possible. The excellent theoretical and experimental exposition of the dispersion-strengthening problem applies only to cases where the stronger phase is present as fine particles and in volume fractions of a few percent. Materials in which the stronger phase constitutes a significant fraction of the volume, although of broad engineering interest, have received comparatively little analytical attention. This important group of materials is the concern of the present study. The degree of deformation of each phase during the plastic working of a ductile two-phase alloy has been established by Boas and Honeycombe,1 Clare-brough,2 and Clarebrough and berger.3 These workers empirically correlated the recrystallization temperature of the individual phases with the degree of cold work sustained by each. It was shown that the deformations of both phases are equal and therefore the same as that sustained by the composite whole when the volume fraction of the stronger phase exceeds 35 pct. At yielding, however, deformation begins in the weaker phase. A direct correlation of composite strength, as a function of deformation, with the strength of the individual components cannot be made. In the presence of stronger phase particles, the flow stress of the weaker matrix phase is enhanced by an additional hydrostatic component. The development and potential magnitude of matrix strength promotion upon straining has not even been experimentally established. Quantitative work in this field has been confined to ceramic-metal composites. These materials fracture at strains considerably below 1 pct by cracking of the ceramic particles.4-6 An indication of the potential constrained matrix strength capacity is given by the observation by Nishimatsu and Gur-land4 that the maximum tensile strength of a WC-Co composite is almost double the bulk strength of the cobalt matrix. The relationship between composite strength and geometry is ordinarily expressed in terms of the mean-free matrix path (referred to subsequently as MFP) between the stronger particles.* This factor takes into account both the volume fraction of matrix phase and the average size of the particles. unke17 concluded that composite strength varied directly with the decreasing log MFP, following the Gen-samer8 relationship. However, Gurland and ~radzil~ reported a strength maximum at an MFP of the order of 1 p in WC-Co composites. A ductile two phase metallic composite was chosen for the present investigation of composite mechanical properties with the view of avoiding the difficulties and ambiguities noted above. The W-Ni-Fe heavy alloy of Green, Jones, and pitkin9 contains 80 to 94 wt pct W, and nickel and iron in a weight ratio

Jan 1, 1963

By Orville R. Lyons

THE Russellton preparation plant of Republic Steel Corp., located north of Pittsburgh, Pa., prepares 3 1/2x0-in. Thick-Freeport coal by means of a 13-ft 6-in. diam Chance cone and 16 No. 7 Deister tables. The plant feed ranges between 370 and 410 tons per hr, of which approximately 31 pct is ¼x0-in. size, and the plant reject ranges between 14 and 16 pct of the feed. The 3½xY4-in. washed coal, the cone product, is dewatered and desanded by a double-deck Parrish-type shaking screen 46 ft long and 7 ft wide. The 1¼x¼-in. portion is further dewatered by two 4x12-ft single-deck vibrating screens. The ¼x0-in. washed coal from the tables is distributed to three 54x70 in. Bird centrifuges. The dewatered centrifuge product is combined with the product of the de-watering screens prior to loading into railroad cars. During the early part of 1951 complaints were received from officials at Republic's coke ovens concerning the moisture content of Russellton washed coal. The records revealed that during the first half of 1951 the shipped washed coal moisture averaged

Jan 1, 1954