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By N. Tiner

THE mechanical properties of magnesium-alloy castings are greatly improved by grain refinement, and at present considerable attention is being paid to methods of obtaining fine-grained castings. One method of achieving this end is the use of proper melting and superheating techniques. These have been employed commercially to a great extent, but no comprehensive study of the subject appears to have been published at present. Numerous investigations found in the literature include some reference to superheating techniques, 1-4 and Achenbach, Nipper and Piwowarsky,5 based principally on thermal analysis, ascribe the grain-refining action of superheating to the influence of solid foreign particles or dissolved gases present in the melt upon the course of crystallization. The primary purpose of this paper is to present the principal facts concerning the effect of superheating on grain size of magnesium alloys. Attempts are also made to explain the experimental results in terms of a general hypothesis. The investigations are limited chiefly to common commercial casting alloys. In order to carry on this work, it was necessary to determine the factors influencing grain size and to develop a proper technique for the preparation of samples. The preliminary tests made by the author indicated that the grain size of magnesium alloys resulting from the solidification of a melt is determined by alloy composition, presence of impurities, rate of cooling during solidification, thermal history of the melt and to some extent the structure of the charge used. The rate of cooling is in turn dependent upon the mass of the melt, pouring temperature, and dimensions, properties and temperature of the mold into which the melt is poured. The final grain size of the alloys is still further modified by heat-treatment subsequent to casting. It is not within the scope of the present paper to discuss all of these factors, and it would suffice to note here that when equal amounts of magnesium alloys are prepared from the same alloying materials, melted in graphite crucibles under the same thermal conditions, then cast into graphite molds at a constant temperature, the .resultant solids have the same grain size. By maintaining all other factors constant, it is thus possible to vary thermal conditions of a melt and to examine the grain size of resultant castings. PREPARATION OF SAMPLES AND GRAIN-SIZE TESTING The alloys investigated in this paper were taken from ingots made by Permanente Metals Corporation or prepared by the author with pure carbothermic magnesium and necessary alloying elements. Melting was carried out under a flux in a graphite crucible heated uniformly by an

Jan 1, 1945

By Paul T. Allsman, E. W. Newman

Trenching, sampling, and core drilling in Stillwater and Sweetgrass Counties, Mont., by the Bureau of Mines have delimited over 5,000,000 tons of chromite ore containing more than 20 per cent chromic oxide. The Benbow and Mouat-Sampson mines have been developed and are fully equipped for mining and milling 500 tons and 2000 tons a day, respectively. Introduction The Montana chromite deposits were the first to be explored under the Strategic Minerals Act of 1939. In June of that year, the Bureau of Mines started exploration by trenching, test pitting, sampling and diamond drilling, and completed the project in March 1943. The U. S. Geological Survey cooperated by mapping the geology and logging the cores. The project was to determine the extent and grade of the chromite ore and to indicate sufficient reserves to justify development and exploitation of the deposits for the national emergency. Exploration has indicated that the district contains the largest and most important reserve of chromite ore in the United States. The Benbow and Mouat-Sampson mines have been developed and a 500-ton concentrating mill has been constructed on the Benhow property and a 2000-ton mill on the Mouat-Sampson property. Concentrates were produced from the Benbow mill three months after the attack on Pearl Harbor, when the nation's major chromite supplies from foreign sources were cut off. History It has been known for 50 to 60 years that some chromite deposits existed in an east-west belt along the north escarpment of the Beartooth Mountains about 25 miles north of Yellowstone Park, but nothing was known of their size and extent until the war demand of 1917 and 1918 stimulated the search. In those years two properties in the Stillwater region were actively developed, but no shipments were made. The Benbow property was located in 1918 by a local group. The property comprised seven claims along the strike at the east end of the belt. An adit was driven several hundred feet on the Eclipse claim. The seven claims were sold to the Chromium Products Corporation of Livingston, Mont., and were subsequently patented. In 1929, an eastern group obtained an option, installed some equipment, and erected several log cabins. The "crash" in the market in 1929 caused the operators to drop their lease, and the property remained inactive until 1939, when the Bureau of Mines began its exploration. Fourteen claims were located on the Boulder River in 1918 and subsequently patented by the U. S. Chrome Corporation.

Jan 1, 1949

By Paul T. Allsman, E. W. Newman

Trenching, sampling, and core drilling in Stillwater and Sweetgrass Counties, Mont., by the Bureau of Mines have delimited over 5,000,000 tons of chromite ore containing more than 20 per cent chromic oxide. The Benbow and Mouat-Sampson mines have been developed and are fully equipped for mining and milling 500 tons and 2000 tons a day, respectively. Introduction The Montana chromite deposits were the first to be explored under the Strategic Minerals Act of 1939. In June of that year, the Bureau of Mines started exploration by trenching, test pitting, sampling and diamond drilling, and completed the project in March 1943. The U. S. Geological Survey cooperated by mapping the geology and logging the cores. The project was to determine the extent and grade of the chromite ore and to indicate sufficient reserves to justify development and exploitation of the deposits for the national emergency. Exploration has indicated that the district contains the largest and most important reserve of chromite ore in the United States. The Benbow and Mouat-Sampson mines have been developed and a 500-ton concentrating mill has been constructed on the Benhow property and a 2000-ton mill on the Mouat-Sampson property. Concentrates were produced from the Benbow mill three months after the attack on Pearl Harbor, when the nation's major chromite supplies from foreign sources were cut off. History It has been known for 50 to 60 years that some chromite deposits existed in an east-west belt along the north escarpment of the Beartooth Mountains about 25 miles north of Yellowstone Park, but nothing was known of their size and extent until the war demand of 1917 and 1918 stimulated the search. In those years two properties in the Stillwater region were actively developed, but no shipments were made. The Benbow property was located in 1918 by a local group. The property comprised seven claims along the strike at the east end of the belt. An adit was driven several hundred feet on the Eclipse claim. The seven claims were sold to the Chromium Products Corporation of Livingston, Mont., and were subsequently patented. In 1929, an eastern group obtained an option, installed some equipment, and erected several log cabins. The "crash" in the market in 1929 caused the operators to drop their lease, and the property remained inactive until 1939, when the Bureau of Mines began its exploration. Fourteen claims were located on the Boulder River in 1918 and subsequently patented by the U. S. Chrome Corporation.

Jan 1, 1949

By T. E. Leontis

The importance of magnesium alloys in the manufacture of aircraft engines has been realized for many years. A concentrated effort has been exerted in the laboratories of the Dow Chemical Co. to develop magnesium-base alloys with improved properties at elevated temperatures whereby greater advantage can be taken of the inherent lightness of these materials. In an earlier publication, attention was called to the superior tensile properties and resistance to creep of cerium-containing magnesium alloys at temperatures up to 700°F. More recently, additional data on magnesium-cerium alloys have been furnished by Murphy and Payne. The present paper deals with the mechanical properties of sand-cast magnesium alloys containing zinc, at temperatures up to 500°F. The study includes binary Mg-Znt alloys containing up to 10 pct zinc and several ternary and some polynary alloys based on the Mg-~Zn,f Mg-jZn, Mg-4.4211, Mg-6Zn, and Mg-roZn binaries. The compositional variation in the tensile properties, hardness, and creep at room and elevated temperatures, and in the electrical conductivity at room temperature has been determined. The results of these tests show that many zinc-containing magnesium alloys exhibit resistance to creep at elevated temperatures significantly higher than that of present commercial magnesium alloys, but lower than that of alloys of the magnesium-cerium type. In addition, they have high tensile properties at room and elevated temperatures and high conductivity. This combination of mechanical properties and conductivity indicates that these alloys should be given serious consideration for commercial applications involving exposure to temperatures higher than those to which present commercial magnesium alloys can be taken safely. Literature The properties of sand-cast magnesium alloys containing zinc as a principal alloying element have not been investigated very extensively, especially at elevated temperatures. The following remarks, which are confined to sand-cast alloys, will serve as a summary of the most important references on this phase of magnesium metallurgy. The first recorded determination of the tensile strength of binary Mg-Zn alloys as a function of zinc content was reported by Aitchison. Similar studies, including the measurement of elongation and hardness, have been performed by Gann and Winston,' Dumas and Rockaert, Haugh-ton and Prytherch,6 and by Spitaler, the last being reported by Beck.' A slight superiority in the tensile strength of chill-cent Mg + 8 es alloy Over the sand-cast alloy was noted by Maybrey.8 That alloys of magnesium containing 5 to 12 pct zinc

Jan 1, 1949

By Herbert H. Kellogg, Hugo Vasquez- Rosas

Recently the long-chain primary amines have been used extensively for the flotation of silicate minerals. The use of amines to float sulphide minerals has been investigated by several authorsl-5-l8 but most of this work has been done with the short-chain (less than six carbon atoms) primary amine compounds or the more expensive secondary, tertiary and quaternary amines. Perhaps the fact that the long-chain amines are good collectors for the common gangue minerals has led investigators to omit them from consideration as collectors for the selective flotation of metallic sulphides. The work reported in this paper was designed to investigate the use of a typical long-chain amine salt, laurylamine hydro-chloride, as a collector for the flotation of galena-sphalerite ores. The results show that laurylamine hydrochloride (LAmHCl), when used in small amounts, is a good collector for the selective flotation of sphalerite and galena from the common gangue minerals. The differential flotation of sphalerite from galena was not accomplished but the amine flotation of sphalerite after the standard xanthate flotation of galena is possible. The experimental work reported herein is not complete enough to be able to say whether amine flotation of lead-zinc ores would prove superior to xanthate flotation, or whether the method is even applicable to a more complex ore than the one used for this work. However, the apparent reagent costs for the flotation operations described in this paper seem to be less than for xanthate flotation. This fact alone should be sufficient to encourage the millman to investigate the use of these amine reagents, especially as these reagents are available on a commercial scale at a reasonable price. This paper has as its secondary purposes to illustrate how contact-angle measurements have aided in this investigation, and to bring forward some evidence concerning the mechanism of the collecting action of primary amines. Contact-angle Tests The contact-angle measurements were made by the method described by del Giudice6 and used in recent work by Taggart and his collaborators.7-9 The mineral specimens for the contact-angle tests were carefully chosen, to avoid cracks and inclusions of other minerals. All specimens were mounted in "transoptic" plastic mounts and the surfaces were cleaned by polishing with levigated alumina on a cloth-coverkd glass polishing wheel. Distilled water was used on the lap during the polishing and at all subsequent steps in the contact-angle tests. The mounted mineral specimens were handled with glass forceps and special care was exercised to prevent exposure of the clean surface to air or any other source of contamination.

Jan 1, 1947

By Herbert H. Kellogg, Hugo Vasquez- Rosas

Recently the long-chain primary amines have been used extensively for the flotation of silicate minerals. The use of amines to float sulphide minerals has been investigated by several authorsl-5-l8 but most of this work has been done with the short-chain (less than six carbon atoms) primary amine compounds or the more expensive secondary, tertiary and quaternary amines. Perhaps the fact that the long-chain amines are good collectors for the common gangue minerals has led investigators to omit them from consideration as collectors for the selective flotation of metallic sulphides. The work reported in this paper was designed to investigate the use of a typical long-chain amine salt, laurylamine hydro-chloride, as a collector for the flotation of galena-sphalerite ores. The results show that laurylamine hydrochloride (LAmHCl), when used in small amounts, is a good collector for the selective flotation of sphalerite and galena from the common gangue minerals. The differential flotation of sphalerite from galena was not accomplished but the amine flotation of sphalerite after the standard xanthate flotation of galena is possible. The experimental work reported herein is not complete enough to be able to say whether amine flotation of lead-zinc ores would prove superior to xanthate flotation, or whether the method is even applicable to a more complex ore than the one used for this work. However, the apparent reagent costs for the flotation operations described in this paper seem to be less than for xanthate flotation. This fact alone should be sufficient to encourage the millman to investigate the use of these amine reagents, especially as these reagents are available on a commercial scale at a reasonable price. This paper has as its secondary purposes to illustrate how contact-angle measurements have aided in this investigation, and to bring forward some evidence concerning the mechanism of the collecting action of primary amines. Contact-angle Tests The contact-angle measurements were made by the method described by del Giudice6 and used in recent work by Taggart and his collaborators.7-9 The mineral specimens for the contact-angle tests were carefully chosen, to avoid cracks and inclusions of other minerals. All specimens were mounted in "transoptic" plastic mounts and the surfaces were cleaned by polishing with levigated alumina on a cloth-coverkd glass polishing wheel. Distilled water was used on the lap during the polishing and at all subsequent steps in the contact-angle tests. The mounted mineral specimens were handled with glass forceps and special care was exercised to prevent exposure of the clean surface to air or any other source of contamination.

Jan 1, 1947

By C. R. McEwen

The displacement equations of Buckley and Lever-ett' have been successfully applied to the prediction of oil recovery in frontal drives for a number of years. Commonly, the capillary pressure term is omitted from Leverett's fractional flow formula. The resulting satura-tion-vs-distance curves become multi-valued, however. Buckley and Leverett, recognizing that the neglect of capillarity was most likely the cause, proposed that this part of the solution he ignored. An ingenious method of propagating a discontinuity in place of the multi-valued portlon of the curve was devised by Cardwell using "non-capillary displacement theory". However, it would seem that a completc description of the displacement pracess would require the inclusion of capillary forces. Three publications on displacement theory have appeared in which capillary pressure was included. Ter-williger. et al', calculated saturation profiles which matched those which they observed when gas displaced water vertically downward. Based on their study, Jones-Parra and Calhoun5 roposed a method of computing saturation distributions sufficiently removed in time from the initial conditions so that all saturations in the flood front region were assumed to move with the same velocity. This latter assumption corresponds to the tangent construction on the flowing fraction-vs-satura-tion curve proposed by Welge." A numerical solution to the problem of water displacing oil from a water-wet porous medium was recently presented by Blair, ef at'. The initial conditions included a uniform saturation slightly above interstitial water saturation. that is, the permeability to water ahead of the front was not zero. This appeared to result in a region of slowly rising water saturation ahead of the front, at least for the particular set of relative permeability and capillary pressure data used to illustrate the computation. The authors also postulated an "end-effect" at the outflow face of the system, whereby no water could pass out of the system until the water saturation had built up to a high value. The saturation profiles computed under these assumptions show water accumulating at the downstream end of the system while the flood front proper is still traveling toward the outlet. The purpose of this paper is to present the results of a numerical solution to the one-dimensional water-flooding equation in which no outlet end-effect is considered and where there is no flow of water ahead of the flood front. It should be noted that the contemporary paper of Fayers and Sheldon8 deals with the problem under discussion. For a thorough treatment including both capillarity and gravity the reader is referred to their paper.

By Walter Craft, John L. Lamont

Adequate hardenability has long been recognized as one of the first requirements for producing desired mechanical properties in a heat-treated steel. Since the introduction of the Jominy end-quench test' and the development of correlative information to expand its use, industry has had an effective measure of hardenability. Prediction and control of the hardenability have been made possible by Grossmann's principle2 for calculating hardenability from chemical composition; and Field's conversiona from depth of half-martensite hardening to Rockwell C hardness has made the relation more quantitative. These developments have facilitated the design of new steels and the control of standard grades to the extent that it has been possible to establish tentative hardenability bands for some of the more commonly used alloy steels.4 As the depth of hardening of the Jominy test specimen is usually measured by Rockwell C hardness, it was considered that it should be possible to predict the hardness by a more direct calculation. It has been found that this can be accomplished by the addition of Rockwell C units proportional to the carbon and alloy content, grain size, and position in the Jominy test specimen. The calculation has been found to be fairly accurate, and because of its additive character is relatively simple to use. In principle the method of calculation is somewhat similar to the expressions developed by Herty, McBride, and Hollen-back,5 Burns, Moore, and Archer,= and Burns and Riege1.l The calculation is started from a base that includes the effects of carbon content and position in the Jominy test speimen. Rockwell C units are added to the base in proportion to the alloy content and grain size. This sum represents the Rockwell C hardness up to the level at which a disproportionate increase of hardness is caused by the formation of martensite, and above this level an increment for martensite hardening is added. The effects of alloys are directly proportional to the amounts present and are independent of each other, the carbon content, and the position in the specimen. Furthermore, the factors for determining the martensite increment are dependcnt only on carbon content and are independent of cooling rate and alloy content. It is this absence of interrelation between the different factors that makes it possible to calculate the hardness and makes the method of calculation consistent with the principle that the character of the hardening reaction is governed primarily by carbon and that alloys exert their effect chiefly through control of the critical cooling rate. The principle of the calculation, and the effects of alloys on the critical cooling rate,

Jan 1, 1947

By John L. Lamont, Walter Craft

Adequate hardenability has long been recognized as one of the first requirements for producing desired mechanical properties in a heat-treated steel. Since the introduction of the Jominy end-quench test' and the development of correlative information to expand its use, industry has had an effective measure of hardenability. Prediction and control of the hardenability have been made possible by Grossmann's principle2 for calculating hardenability from chemical composition; and Field's conversiona from depth of half-martensite hardening to Rockwell C hardness has made the relation more quantitative. These developments have facilitated the design of new steels and the control of standard grades to the extent that it has been possible to establish tentative hardenability bands for some of the more commonly used alloy steels.4 As the depth of hardening of the Jominy test specimen is usually measured by Rockwell C hardness, it was considered that it should be possible to predict the hardness by a more direct calculation. It has been found that this can be accomplished by the addition of Rockwell C units proportional to the carbon and alloy content, grain size, and position in the Jominy test specimen. The calculation has been found to be fairly accurate, and because of its additive character is relatively simple to use. In principle the method of calculation is somewhat similar to the expressions developed by Herty, McBride, and Hollen-back,5 Burns, Moore, and Archer,= and Burns and Riege1.l The calculation is started from a base that includes the effects of carbon content and position in the Jominy test speimen. Rockwell C units are added to the base in proportion to the alloy content and grain size. This sum represents the Rockwell C hardness up to the level at which a disproportionate increase of hardness is caused by the formation of martensite, and above this level an increment for martensite hardening is added. The effects of alloys are directly proportional to the amounts present and are independent of each other, the carbon content, and the position in the specimen. Furthermore, the factors for determining the martensite increment are dependcnt only on carbon content and are independent of cooling rate and alloy content. It is this absence of interrelation between the different factors that makes it possible to calculate the hardness and makes the method of calculation consistent with the principle that the character of the hardening reaction is governed primarily by carbon and that alloys exert their effect chiefly through control of the critical cooling rate. The principle of the calculation, and the effects of alloys on the critical cooling rate,

Jan 1, 1947

By Earl G. Alexander, W. R. Runyan

The nature of silicon growths which form on amorphous silicon dioxide during epitaxial deposition in unmasked areas was investigated. Octahedral silicon crystals nucleate and grow on the oxide at pinholes, adjacent to foreign matter, and probably at oxygen-deficient sites. Generation of these oxygen-deficient sites on the oxide surface is shown to be thermody-namically favorable under usual deposition conditions. The conditions which affect saturation (SiCl4 concentration, flow rate, temperature) determine the number of sites on which silicon will nucleate and grow. Reaction product HCl is likely responsible for suppressing silicon growths on the oxide near exposed areas of silicon. Evidence is given that the oxide-silicon interaction occurs in hydrogen only and involves water as a transport agent. SINCE shortly after the first epitaxial layers of silicon and germanium were grown over large areas, efforts have been underway to grow selectively on specified portions of the surface. Such selective growth should be particularly applicable to monolithic integrated circuits. Usually the approach has been to use a mask to delineate the desired area,'-7 but the VLS methoda can also be used, and direct programmed atomic beam deposition has been suggested.9 The masking techniques may embody two forms: in one the mask is a material which can later be removed along with any growths attached to it; in the other, attempts are made to prevent growth on the mask, so that over a whole slice the only deposition that will occur is in the unmasked regions. The present work is concerned with only the latter case, and specifically with silicon. Joyce and Baldrey1 suggested the use of thermally grown silicon dioxide as a mask material and showed that for the proper choice of operating conditions (total flow, SiCl4 concentration, total deposition time, and temperature) spurious growth could be minimized and that if the deposition times were not too large, and the criteria not too stringent, a usable process occurred. Later Schnable et al 4 observed that after extended deposition times, during which most of the silicon dioxide became covered with growth, there was always a band of oxide around the exposed silicon area that was quite free of spurious silicon crystallites. This latter observation is particularly intriguing since it extends the hope that with proper precautions masking can be much more versatile than it presently is. EXPERIMENTAL PROCEDURE Silicon substrates oriented to within 1.5 deg of a (111) plane were prepared by etch polishing lapped

Jan 1, 1967

By Charles T. Baroch, Charles J. Baroch

In 20 years of commercial development, nuclear reactors have demonstrated that they are a safe, dependable, and economical source of power. Operating experience with commercial power reactors has firmly established nuclear power as a practicable source of energy. For both boiling-water (BWR) and pressurized-water (PWR) reactors, performances to date have generally met design predictions. Furthermore, it has become possible to analyze and understand the nuclear, chemical, and physical behavior of this class of reactors. The United Kingdom has had similar success with gas-cooled reactors. The Experimental Boiling Water Reactor (EBWR), the first United States experimental power reactor, began operation in 1956. It proved to be capable of supplying 4500 kw (kilowatts) of power. This reactor was followed in 1957 by the Pressurized Water Reactor at Shippingport, Pa. It was the nation's first full-scale central-station nuclear power plant and the first in the world designed exclusively for the production of civilian electric power. The Shippingport reactor was originally designed to produce 60 megawatts (MW) of electricity, and it was increased to 100 MW in 1964. In 12 years of operation, this reactor generated over 4.5-million MW-hr of electricity in spite of many shutdowns for experimental alterations. By 1969, a total of 15 central-station nuclear power reactors were operable in the United States with an aggregate electrical capacity of over 4200 MW. Early in 1964, Jersey Central Power & Light Co. announced plans for constructing a 515-MW nuclear plant at Oyster Creek, N.J., to be built without government financial assistance. The company stated that a nuclear plant had been selected competitively with fossil fuel. Their economic analysis stated that the plant would generate electricity at less than 4 mills per kw-hr, competitive with coal at 200 per million Btu (British thermal units). Coal cost in 1964 for that region averaged 26.00 per million Btu. The Jersey Central report created wide interest in public-utility circles; nevertheless, no other nuclear plants were announced in 1964. However, in 1965, six nuclear plants were announced by utilities, followed by 26 in 1966, 29 in 1967, and 10 in 1968. By Sept. 30, 1969, 97 reactors were operable, being built, or planned. The cost of these, all committed by electric utilities, was estimated at about $12 billion. When constructed, they will have an electrical capacity of 72,000 MW. The unprecedented surge in power reactors that started in 1965 tapered in 1968, and only seven reactors were announced in

Jan 1, 1976

By W. L. Fink, M. S. Hunter, R. H. Brown

Early workers attempted to study the structure of alloys by measurement of equilibrium electrode potentials in aqueous solutions containing ions of the metals from which the alloy was made.' The method was subject to such limitations (e.g., the difficulty in attaining electrochemical equilibrium at low temperatures) that it has not been widely used by metallurgists. Recently, Seltz and co-workers have introduced a greatly improved method for studying alloys by measurement of equilibrium electrode potentials in molten salts.2"4 The mathematical treatment is the same, of course, as for equilibrium potentials of amalgams in aqueous solutions.5 This method will probably find extensive use, since it makes possible not only the determination of phase fields of equilibrium diagrams but also the determination of certain thermodynamic quantities which can be used advantageously in metallurgical calculations. However, the method presents difficulties. With many metallic and alloy electrodes, reversibility is not readily obtainable. Also, the difficulty of obtaining suitable material from which to make the cells is increased as the temperature is increased. Moreover, the necessity of carrying out measurements in a vacuum requires additional apparatus and introduces considerable difficulty, especially at the higher temperatures. Apparently, no consideration has been given heretofore to the metallurgical use of irreversible electrode potentials that exist when a specimen is immersed in a suitable aqueous solution at room temperature. The apparatus and the method required for such measurements are very simple, and if the results of such measurements could be demonstrated to be reproducible they might be very valuable in studying the structure of alloys. The method would not have the scope of that developed by Seltz and his co-workers because no thermodynamic quantities could be calculated from the data. However, the utility and the simplicity of the method might warrant extensive use for the determination of phase fields and similar applications. Theory of Irreversible Potentials A brief review of the theory of irreversible potentials will be given before showing how to interpret the potential readings in terms of alloy structure. It is known that heterogeneity of a metal surface in an electrolyte will produce points of different potentials, with the result that current flows between these points and electrochemical reactions occur. The points at which oxidation reactions are localized are known as anodes, and those at which reduction reactions are localized are known as cathodes.6, 7, 8 For the benefit of those who are not familiar with the terms anode and cathode as applied to a primary cell, the potential difference between anode and cathode of such a cell can be measured when

Jan 1, 1941

By M. S. Hunter, W. L. Fink, R. H. Brown

Early workers attempted to study the structure of alloys by measurement of equilibrium electrode potentials in aqueous solutions containing ions of the metals from which the alloy was made.' The method was subject to such limitations (e.g., the difficulty in attaining electrochemical equilibrium at low temperatures) that it has not been widely used by metallurgists. Recently, Seltz and co-workers have introduced a greatly improved method for studying alloys by measurement of equilibrium electrode potentials in molten salts.2"4 The mathematical treatment is the same, of course, as for equilibrium potentials of amalgams in aqueous solutions.5 This method will probably find extensive use, since it makes possible not only the determination of phase fields of equilibrium diagrams but also the determination of certain thermodynamic quantities which can be used advantageously in metallurgical calculations. However, the method presents difficulties. With many metallic and alloy electrodes, reversibility is not readily obtainable. Also, the difficulty of obtaining suitable material from which to make the cells is increased as the temperature is increased. Moreover, the necessity of carrying out measurements in a vacuum requires additional apparatus and introduces considerable difficulty, especially at the higher temperatures. Apparently, no consideration has been given heretofore to the metallurgical use of irreversible electrode potentials that exist when a specimen is immersed in a suitable aqueous solution at room temperature. The apparatus and the method required for such measurements are very simple, and if the results of such measurements could be demonstrated to be reproducible they might be very valuable in studying the structure of alloys. The method would not have the scope of that developed by Seltz and his co-workers because no thermodynamic quantities could be calculated from the data. However, the utility and the simplicity of the method might warrant extensive use for the determination of phase fields and similar applications. Theory of Irreversible Potentials A brief review of the theory of irreversible potentials will be given before showing how to interpret the potential readings in terms of alloy structure. It is known that heterogeneity of a metal surface in an electrolyte will produce points of different potentials, with the result that current flows between these points and electrochemical reactions occur. The points at which oxidation reactions are localized are known as anodes, and those at which reduction reactions are localized are known as cathodes.6, 7, 8 For the benefit of those who are not familiar with the terms anode and cathode as applied to a primary cell, the potential difference between anode and cathode of such a cell can be measured when

Jan 1, 1941

By H. J. O’Donnell, B. C. Parks

IN 1930 the late Dr. Reinhardt Thiessen set up a method of microscopic analysis and type classification of coal that has since been followed as standard practice in the coal-petrography laboratory of the Bureau of Mines. Thiessen's terminology which designated the constituent parts of coal in terms of botanical origin was introduced in 1920.l The technique, however, of preparing a completely representative series of thin sections from a column sample of coal for use in making quantitative determinations of coal components with a microscope was developed about 10 years later by Thiessen and coworkers G. C. Sprunk and H. J. O'Donnell.2 Complete thin-section analyses subsequently have been made of 126 column samples of various ranks and types of American coals. The data and information were assembled from these thin-section studies and published in a large number of reports dealing chiefly with investigations of the coking and hydrogenation properties of certain American coals. In the years following adoption of Thiessen's method, a considerable amount of work was done in collecting column samples of many coals, making routine thin-section analyses of these, interpreting the results, and finding practical application for the information in other fields of coal research. The many reports and papers covering the work in coal petrography, however, offer very little discussion that can be considered as critical appraisal of the technique. Criticism outside the Bureau most often has voiced questioning opinions concerning the accuracy of the method used of measuring coal components microscopically and classifying the coal into arbitrary types on the basis of the quantitative determinations. The principal purpose of this paper is to discuss in some detail and present data showing the results of certain investigative work done in the petrography laboratory on the accuracy of the Bureau's method of microscopic measurement of components in coal thin sections. Data from microscopic analyses on file made by G. C. Sprunk and H. J. O'Donnell were freely used in the investigation, and a table of columnar analyses from an unpublished manuscript by Sprunk is included in this paper for reference. In the course of the experimental work a method was developed for measuring instrumentally with a planimeter the components shown in micrographs of selected thin sections. Measuring coal components with a planimeter furnished useful information for studying the accuracy of microscopically measuring the same components in thin sections. PETROGRAPHIC COMPONENTS AND TYPE CLASSIFICATION OF COAL Thiessen considered coal to be composed of two visibly different major components present in various types of coal in greatly varying proportions. He named

Jan 1, 1948

By L. D. Jaffe, J. H. Hollomon

THE effect of tempering temperature and time upon the properties of quenched steel is clearly a subject of great practical importance, as well as of considerable theoretical interest. It would be very desirable to be able to predict the properties of a quenched steel when given any selected tempering cycle, with a minimum of experimental work upon that heat or even type of steel. Two problems are involved: one consists of relating the structure obtained to the physical properties, and will not be discussed here; the other, with which this paper deals, involves the relations of time, temperature and composition with the structure obtained on tempering. Indentation hardness is perhaps the most convenient quantitative measure of the tempered structure, or of what might be called the "degree of tempering." Undoubtedly, it is not an exact measure, and in some cases (as when temper-brittleness occurs) pieces of the same quenched and tempered steel may have widely differing properties at the same hardness. However, hardness has the advantage of being simple to determine and is certainly the most widely used indication of the degree of tempering. Moreover, for fully quenched steels that are not temper-brittle and do not contain retained austenite when quenched, it appears that, in general, if the hardness of the steel is the same, the tensile and impact properties will also be identical, whether a high or a low tempering temperature is used. The tempering charts available in the metallurgical literature usually give the hardness as a function of tempering temperature for only one tempering time. However, in practice, tempering times frequently vary, and a method of converting tempering curves for one time to tempering curves for some other time would be very valuable. It is also advantageous, in determining the tempering treatment necessary for a given part, not to have to temper samples at several temperatures for the time used for the commercial tempering operation. A more satisfactory procedure would be to employ times of the order of 10 to 30 min., rather than 5 or 10 hr., and if possible to use only one temperature. Furthermore, it is frequently desirable, for reasons such as temper-brittleness,* to obtain a given hardness with short times at relatively high temperatures, and it would be convenient to be able to compute without tests the time required to produce this hardness. Remarkably few quantitative studies of the hardness of quenched steel tempered over wide ranges of temperature and time

Jan 1, 1945

By Akio Suzuki, P. G. Wahlbeck

AS a part of a study of the vaporization of transition metal-chalcogen systems, the vaporization reactions for the Ti-Se system have been studied. In order to establish vaporization reactions it is important to determine the identity of vapor species in equilibrium with the condensed phases. In some cases, it is possible to deduce the identity of vapor species through observations of composition change of the condensed phase with which the vapor is in equilibrium. Determination of vapor species in equilibrium with condensed phases should precede vapor-pressure measurements and is necessary for proper thermodynamic analysis of vapor-pressure data. Bear and McTag-gart' reported that vacuum heating ot TiSea at 950°C produced a residue with a composition of 1.7 Se/Ti atomic ratio units. Analyses of condensed phases existing for the Ti-Se system have been performed by Bernusset,2"4 Gron-vold and Langmyhr,5 Hahn and Ness,' and Ehrlich.~ Results and conclusions of two types of experiments are described herein: 1) experiments where samples of known composition were vaporized followed by chemical analysis of residues and 2) experiments where the vapor species were identified by means of a mass spectrometer. Experimental Section. Sarnple Preparation. Samples of TiSe2 were prepared in a sealed, evacuated quartz ampule by heating to 1000°C stoichiometric amounts of selenium of 99.999+ pct purity obtained from the American Smelting and Refining Co. and titanium of 99.2 pct purity obtained from A. D. Mackay, Inc. After heating, the sample was ground and reheated to insure homogeneity. Samples containing less selenium than TiSez were prepared by mixing amounts of titanium powder and TiSez appropriate for the desired composition; the titanium and TiSez mixture was heated in the same manner as described for TiSe2. Analyses of titanium selenide samples contained in quartz crucibles were performed by gravimetric oxidation in oxygen at 800°C; the products of the oxidation were solid TiOz and gaseous Se02. The mass of the original sample and the mass of TiOn determined the Se/Ti atomic ratio. The sample of TiSen used in these experiments had a composition of 2.04 Se/Ti atomic ratio units. The compositions for all samples reported were analyzed by this method. Va/!orization Experiments. Samples of titanium selenides were vaporized in tungsten Knudsen crucibles. Some vaporization experiments were carried out in glass vacuum lines followed by chemical analyses of residues, and some vaporization experiments were performed with a Bendjx mass spectrometer as described previously.8

Jan 1, 1967

By E. P. Sadowski, R. J. Raudebaugh

A study of micro structural characteristics of a 30 pct Cr, 42 pct Ni, 26 pct Fe alloy has been correlated with its behavior in creep and rupture tests at 1400°, 1600°, and 1800°F. Nitrogen pickup observed at 1600" and 1800°F was associated withfissur-ing of specimens prior to fracture. IN studying the high-temperature characteristics of a nominally 30 pct Cr, 42 pct Ni, 26 pct Fe alloy certain anomalies were observed, namely: The alloy had greater stress rupture and creep strength at 1800" than at 1600° F for time periods beyond 550 hr. As placed in test, this alloy was nonmagnetic. After test, some specimens were found to be fairly magnetic. The gain observed in magnetic response was not solely a function of time and temperature of testing. This is a report of the observations and a recounting of the results of studies made in an attempt to explain the behavior of the material under investigation. MATERIAL AND PROCEDURE All test material was taken from a production size heat of an experimental alloy melted and processed using commercial practice and having the following percentage composition: C Fe Cr Ni Ti 0.05 25.83 30.13 41.59 0.41 Al Mn Si S Cu 0.42 0.75 0.45 0.011 0.34 The material was tested in two conditions, namely mill-annealed and grain-coarsened. Mill annealing, which consisted of heating to about 1900° F in a continuous furnace for about 30 min and air cooling, gave a grain size of ASTM 8 and finer. To produce the grain-coarsened condition, mill-annealed material was soaked for 2 hr at 2050°F in a laboratory furnace and air cooled. This resulted in an ASTM grain size of 4 to 5. Rupture tests were carried out at 1400, 1600, and 1800° F in accordance with ASTM procedures. In tests where only rupture life and elongation at fracture were determined, specimens of 0.252 in. diam and 1 in. gage length were used. In tests where creep curves were obtained, specimens were of 0.375 in. diam and 4 in. gage length. Several of the tests under relatively low stress were discontinued short of rupture. Three low-stress tests are still in progress at this writing. Structural changes which occurred during testing were determined from examination of the tested specimens by light microscopy and X-ray diffraction. Diffraction pattern recordings were made with a diffractometer using copper radiation on samples heavily etched in a picric-hydrochloric

Jan 1, 1960

By H. J. Donnell, B. C. Parks, O&apos

In 1930 the late Dr. Reinhardt Thiessen set up a method of microscopic analysis and type classification of coal that has since been followed as standard practice in the coal-petrography laboratory of the Bureau of Mines. Thiessen's terminology which designated the constituent parts of coal in terms of botanical origin was introduced in 1920.1 The technique, however, of preparing a completely representative series of thin sections from a column sample of coal for use in making quantitative determinations of coal components with a microscope was developed about 10 years later by Thiessen and coworkers G. C. Sprunk and H. J. O'Donnell.2 Complete thin-section analyses subsequently have been made of 126 column samples of various ranks and types of American coals. The data and information were assembled from these thin-section studies and published in a large number of reports dealing chiefly with investigations of the coking and hydrogena-tion properties of certain American coals. In the years following adoption of Thies-sen's method, a considerable amount of work was done in collecting column samples of many coals, making routine thin-section analyses of these, interpreting the results, and finding practical application for the information in other fields of coal research. The many reports and papers covering the work in coal petrography, however, offer very little discussion that can be considered as critical appraisal of the technique. Criticism outside the Bureau most often has voiced questioning opinions concerning the accuracy of the method used of measuring coal components microscopically and classifying the coal into arbitrary types on the basis of the quantitative determinations. The principal purpose of this paper is to discuss in some detail and present data showing the results of certain investigative work done in the petrography laboratory on the accuracy of the Bureau's method of microscopic measurement of components in coal thin sections. Data from microscopic analyses on file made by G. C. Sprunk and H. J. O'Donnell were freely used in the investigation, and a table of columnar analyses from an unpublished manuscript by Sprunk is included in this paper for reference. In the course of the experimental work a method was developed for measuring in-strumentally with a planimeter the components shown in micrographs of selected thin sections. Measuring coal components with a planimeter furnished useful information for studying the accuracy of microscopically measuring the same components in thin sections. Petrographic Components and Type Classification of Coal Thiessen considered coal to be composed of two visibly different major components present in various types of coal in greatly varying proportions. He named

Jan 1, 1949

By Henry P. Ehrlinger, James C. Bradbury

Tripoli is a naturally occurring, very finely divided form of silica found chiefly in some midwestern and southeastern states and used commercially as fillers and abrasives. Definitions Tripoli is a microcrystalline, finely particulate, more or less friable form of silica that appears to be the product of leaching of siliceous limestone or calcareous chert. The term was originally applied to a deposit near Seneca, Mo., that resembled material of that name found near Tripoli in North Africa (Hovey, 1894). The two deposits were subsequently found to have different physical characteristics -the North African tripoli, now called tripolite, is a diatomite, composed of the siliceous skeletons of microscopic marine plants called diatoms, and the Missouri tripoli contains no diatom remains; the term tripoli, however, continued to be used for the Missouri material and is now applied in a general way to most silica deposits similar to it in characteristics and geologic origin. In commercial trade tripoli is commonly understood to designate material from the Missouri-Oklahoma field; silica from southern Illinois, the other major producing area, is referred to commercially as amorphous silica. Each term, however, may be used commercially for material, regardless of place of origin, that has the characteristics or uses commonly ascribed to the material from one or the other major producing area. For example, in the commodity price listings, Engineering and Mining Journal routinely lists under Tripoli, prices "f.0.b. Elco, III." and "f.0.b. Seneca, Mo., and Rogers, Ark.," and under Silica, amorphous, prices "f .o.b. Ill.," and "f .o.b. Dierks, Ark." Amorphous silica, the commercial designation given to southern Illinois tripoli, is, like the term tripoli, a misnomer. Mineralogically, the southern Illinois deposits are composed of microcrystalline quartz, and no amorphous material has been detected during X-ray and scanning electron microscope investigations (Leamnson, Thomas, and Ehrlinger, 1969; Thomas et al., 1970). Soft silica is another term that has been applied to Illinois and Tennessee tripoli, presumably to distinguish it from the more compact Missouri material. It has also been used in the ceramic trade to distinguish tripoli from "hard" silica, or silica flour, produced by pulverizing silica sand (Heinz, 1937). Rottenstone, produced commercially in Pennsylvania, is similar to tripoli in that a major constituent is finely particulate silica, and its uses are much the same as those of tripoli- as abrasives and fillers. The origin of rottenstone also is similar to that of tripoli-decomposition of a siliceous sedimentary rock. The parent rock is defined as a siliceous limestone (Gary, McAfee, and Wolf, 1972; Thrush, 1968) or as shale (personal communication). Heinz (1937) quotes a brief statement describ-

Jan 1, 1975

By Phillip B. Bucky, Fred D. Wright

The present known petroleum reserves are limited, and unless important new fields are discovered the Nation will be dependent, in the not too distant future, upon imports or upon synthetic liquid fuels to supplement domestic petroleum supplies. As a national defense measure, it would appear desirable to develop a substitute source of liquid fuels within the borders of the country if new discoveries of petroleum should Prove disappointing. Congress undoubtedly had this in mind when it passed the Synthetic Liquid Fuels Act (78th Congress, approved April 5, 1944). The act directed the Bureau of Mines to construct and operate demonstration plants for producing synthetic liquid fuels from coal and oil shale, and from forestry and agricultural products. As a part of this program, the Bureau of Mines has built a demonstration plant at Anvil Points, near Rifle, Colo., for retorting the oil shale, and has developed a mine to supply the plant with oil shale. At the beginning of mining operations, the physical qualities of the oil shale, which would have a bearing upon the selection of mining methods and practices for exploiting the deposits, were largely unknown. A comprehensive mining-research program has been set up to determine the best methods and practices to follow to obtain the lowest overall practicable mining cost for producing the oil shale on a large scale. Unusually low mining costs will be necessary for shale oil to be produced commercially. Consideration now is being given to exploiting a series of flat-lying beds 70 ft thick by a room-and-pillar method of three benches with the advance heading at the top. This report is one of a series giving the results obtained in research on mining problems, The structure and physical qualities of the oil shale indicate that the 70-ft interval of the oil-shale measure can be safely mined in open stopes; studies indicate that this method would be the most economical one to use.' As labor will be a major item of expense, the largest equipment that could be operated efficiently in the workings would be required to obtain the lowest practicable mining Cost. It Was therefore desirable to know the maximum safe span of unsupported rooms and the size of pillars necessary to support the overburden. This paper describes the work done at the Columbia School of Mines Barodynamic Laboratory in determining the maximum safe unsupported roof spans and the minimum safe pillar dimensions for the oil-shale mine at Rifle, Colo.

Jan 1, 1949