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By William M. Baldwin

Jan 1, 1946

By AIME AIME

HOWARD H. PRESTON, professor of economics and business at the University of Washington, presented a paper before the North Pacific Section, A.I.M.E., on Jan. 23, on the "Economic Aspects of Gold and Silver." He carefully reviewed recent governmental actions that have affected those metals and gave an interpretation of their effects. A brief excerpt from his address; follows: Including the proclamation of March 6, 1933, the principal steps of the present Administration which have carried the United States off the gold standard and led up to the present program have been: (1) The Presidential proclamation of March 6 controlling gold. (2) The monetary sections of the Emergency Banking Act of March 9. (3) Mobilization of gold under Executive orders issued March 10 and April 5. (4) The gold embargo by Executive order, April 20. (5) The controlled inflation bill, May 12. (6) The joint resolution abrogating the gold clauses, June 5. (7) The Executive orders on newly mined gold, Aug. 28. (8) The President's radio address of Oct. 22 and the R.F.C. gold-buying program. (9) New anti-hoarding order calling in small holdings of gold, Dec. 28, 1933 and Jan. 15, 1934. (10) Nationalization and revaluation of gold' (Message to Congress, Jan. 15).

Jan 1, 1934

By Harrison Schmitt

The definitions of the terms commonly used in connection with metamorphism at elevated temperature near igneous contacts are re-examined. As the study of tactite zones associated with igneous contacts progresses, more and more emphasis is put on the localization of the ore by structural forms. The generally early age of the silicates and late age of the sulphides is well established. Postsilicate structural deformation is likely to localize ore bodies. The silicates are often replaced by the ore minerals. we may not be far from proving that the elements involved in the formation of silicate aureoles are merely normal "volcanic" emanations, that silica, lime, magnesia, and alumina, and probably soda and potash, are likely to undergo local transfers only. The work of Newhouse suggests the agents of the formation of sulphides in deposits of various classifications are the volcanic emanations. Introduction The purpose of this paper is to define the terms commonly used in connection with the subject, to briefly review and discuss the broad features of the aureoles, to indicate some of the features lately recognized: to discuss the genesis, and to suggest how the associated ore deposits can best be studied and developed. When developing a subject in mining geology one is soon conscious of the vast amount of pertinent literature and that most relevant ideas, no matter how obscure, have been considered. One can only hope to make some small contribution in point of view, a few confirmatory observations, or, perhaps, suggest a small new idea indebted to the most recent data. It is nearly impossible, also, to give specific credit, and adequate credit, to all the contributors to a given subject. This study, furthermore, was not intended to cover the field exhaustively, nor is the bibliography complete. Definition OF Terms There is much confusion in the use of the broad terms concerned. Needless to say, metamorphism means change of form; metasomatism, change of substance. The term contact metamorphism, however, has been widely misused possibly by a majority of economic geologists and engineers. As originally adopted by European investigators it meant changes effected largely by heat (thermal effects) in the rocks invaded by plutonic intrusives, but did not include those local changes usually at the immediate contact brought about by the addition of substance, i.e., by metasomatism. The term has become clouded. In Europe it has

Jan 1, 1949

By Harrison Schmitt

The definitions of the terms commonly used in connection with metamorphism at elevated temperature near igneous contacts are re-examined. As the study of tactite zones associated with igneous contacts progresses, more and more emphasis is put on the localization of the ore by structural forms. The generally early age of the silicates and late age of the sulphides is well established. Postsilicate structural deformation is likely to localize ore bodies. The silicates are often replaced by the ore minerals. we may not be far from proving that the elements involved in the formation of silicate aureoles are merely normal "volcanic" emanations, that silica, lime, magnesia, and alumina, and probably soda and potash, are likely to undergo local transfers only. The work of Newhouse suggests the agents of the formation of sulphides in deposits of various classifications are the volcanic emanations. Introduction The purpose of this paper is to define the terms commonly used in connection with the subject, to briefly review and discuss the broad features of the aureoles, to indicate some of the features lately recognized: to discuss the genesis, and to suggest how the associated ore deposits can best be studied and developed. When developing a subject in mining geology one is soon conscious of the vast amount of pertinent literature and that most relevant ideas, no matter how obscure, have been considered. One can only hope to make some small contribution in point of view, a few confirmatory observations, or, perhaps, suggest a small new idea indebted to the most recent data. It is nearly impossible, also, to give specific credit, and adequate credit, to all the contributors to a given subject. This study, furthermore, was not intended to cover the field exhaustively, nor is the bibliography complete. Definition OF Terms There is much confusion in the use of the broad terms concerned. Needless to say, metamorphism means change of form; metasomatism, change of substance. The term contact metamorphism, however, has been widely misused possibly by a majority of economic geologists and engineers. As originally adopted by European investigators it meant changes effected largely by heat (thermal effects) in the rocks invaded by plutonic intrusives, but did not include those local changes usually at the immediate contact brought about by the addition of substance, i.e., by metasomatism. The term has become clouded. In Europe it has

Jan 1, 1949

By John C. Sawyer

The mechanism of catastrophic oxidation of chromium and 446 stainless steel is examined. Data are presented to show that accelerated oxidation of these two materials, as caused by lead oxide, can occur in the absence of a liquid layer contrary to presently accepted theory. An alternate theory is proposed in which the rate of accelerated oxidation is a function of the rate at which lead oxide destroys the protective oxide formed on the base metal. An example of the application of the theory is given for the catastrophic oxidation of chromium in the presence of lead oxide. WHEN stainless iron-, nickel-, or cobalt-base alloys are heated in air to moderate temperatures in the presence of certain metallic oxides, oxidation will proceed at an accelerated rate. This phenomenon, often called "catastrophic oxidation", is most pronounced for the stainless steels. With these alloys the condition is so severe that large masses of oxide will form on the surface of the alloy in 1 hr or less at temperatures of 1200o to 1700oF. While a number of oxides are known to cause this effect, PbO, V2O5, and Moo3 are the most familiar, having been the subject of one or more investigations which have appeared in the literature.1-7 In presenting the results of these investigations, many of the authors have offered possible explanations to account for the more rapid rate of oxidation observed; however, the liquid layer theory as proposed by Rathenau and Meijering 2 has been the most commonly accepted mechanism. The liquid layer theory proposes that a low-melting oxide layer is formed on the surface of the alloy as the result of the interaction of the alloy oxide and the contaminating oxide. When the temperature of oxidation is above the melting point of the oxide on the surface, a liquid layer will form and oxidation will proceed at an accelerated rate. At temperatures below the melting point of the surface oxide, oxidation will proceed more slowly in the normal manner. It is argued that the rates of diffusion of oxygen and metal ions through the liquid layer are extremely rapid thereby accounting for the high rate of oxidation. Various experimental data have been presented to show that the temperature at which accelerated oxidation first becomes apparent coincides with the melting point of the eutectic oxide which would be present on the surface. Some exceptions have been observed, e.g., silver will oxidize in the presence of Moo3 at temperatures below the lowest melting eutectic; on the other hand, stainless steel will not be catastrophically oxidized at 1500oF in a molten bath of PbO and SiO2. In reviewing the various theories which have been used to explain catastrophic oxidation, Kubaschewski and Hopkins 8 favor the liquid layer theory, but note that, ".. .as experimental observations are not altogether in agreement with this theory (liquid layer theory), one should consider it a necessary but not a sufficient condition." In contemplating the liquid layer theory, it appears that sufficient evidence has not been presented to establish the theory beyond question. As a means of further clarification, a program of research was undertaken to determine in greater detail the mechanism of accelerated oxidation as caused by lead oxide. The first part of the program deals with a comparison of the oxidation of both AISI 446 stainless steel and chromium metal in the presence of lead oxide, vs the oxidation of these two materials in air alone. These comparisons are made at a number of different temperatures, most of which are below the melting point of the surface oxides. The second part of the program is concerned with a presentation of an alternate theory of accelerated oxidation exemplified by the system Cr-PbO-Air. PROCEDURE AND RESULTS Several experimental methods are commonly used to follow the progress of oxidation. One of these, the weight-gain method, was chosen for this work. This procedure requires that a specimen of the alloy be weighed, oxidized for a given period of time at an elevated temperature, and reweighed—the difference between the two weights being noted. The weight gain of the specimen represents the amount of oxygen acquired from the atmosphere to transform a portion of the specimen to oxide. In those cases where there is a tendency for the specimen or oxide to volatilize at the testing temperature, additional data must be collected so that a correction factor can be determined. This factor must be applied to the weight change in order to ascertain the actual amount of oxidation which has taken place. The specimens used for this work were 1 1/2 in.

Jan 1, 1963

By R. W. Newcomb

THE constancy of calibration, and to a great extent the life, of a thermoelement is dependent on the suitability of the primary protecting tube in which the wires are mounted, particularly when used at high temperatures. An ideal thermocouple protecting tube would be com-posed of materials that would not contaminate the thermoelement wires contained in it-one that would remain absolutely gas-tight ,it all temperatures of usage, that will not be attacked by gases, or other surrounding agencies, that is not destroyed by heat, that withstands sudden and extreme temperature changes, that affords a high degree of mechanical protection and does not deform at high temperatures, that is a good heat conductor and obtainable in small diameters so as to keep down lag factors. It has not yet been possible to produce tubes of any known mate-rials that will meet all of these conditions. In selecting protecting tubes, therefore, one should be chosen the characteristics of which best fit it to the particular conditions of usage. Frequently conditions are such that two tubes have to be used, a primary gas-tight protecting tube inside of a secondary protecting tube, because certain agencies will attack the primary gas-tight tube unless it is guarded by the outside tube.

Jan 9, 1919

Since I have had the pleasure of watching the development of this process very closely, I feel that I ought to say a few words on the subject, although I cannot add much to what Mr. Roe has already said. I wish, however, to bear witness to the hard work, persistence and skill which have been exercised during the past two years, and which have so well deserved the success attained. Those of us who remember the history of the past efforts in this line, such as the rotary puddlers, in which also some of us had a part, can easily appreciate the problems involved, and may well be skeptical as to the outcome. Such, at least, was my frame of mind when the process first came under my notice. Now, after having seen every heat, but three, of the many made, it really seems to me that a process and plant for the mechanical puddling of iron has at last been developed which is practical, economical and successful. Of course I do not mean by this that either the process or the machines are developed to their highest point, technically or economically, but that, in my opinion, these goals are in plain view, and that the difficulties which remain are such as will be overcome by developing the skill of the operator through practice ;

Jan 1, 1903

By Daniel M. MacNeil, Carle R. Hayward, Raymond L. Presbrey

At the February, 1916, meeting of the Institute, a paper presented by Hayward and Raymond gave the results of a study on the effect of time in tempering medium-carbon steel, when the following conclusions were reached: It is not fair to consider the question settled when only three specimens were used for each treatment, but the results obtained indicate that for reheating quenched medium-carbon steel to temperatures below 500" it is only necessary to heat it through. Longer heating has little or no effect on the tensile strength, ductility, or hardness. At temperatures above 500°, increasing the time of treatment causes a slight falling off in hardness and tensile strength with a corresponding increase in ductility. In the discussion of the paper these conclusions were attacked and evidence was presented that seemed to throw doubt on their accuracy. The authors, however, showed that this evidence was based on high-carbon or alloy steels and no facts regarding medium-carbon steel were presented. During this study the heat treatment was carried out in a small electric resistance furnace. It held nine specimens, but when these were placed in the furnace the temperature was lowered to such an extent that 30 to 40 min. were required to reach the desired heat. The authors pointed to this as a weak point in the investigation and it seemed wise to supplement the research by work on similar steel but using a different method of heating. This has been done and the results are given in the present paper. The Rhode Island Tool Co. coöperated by furnishing the steel and turning the tensile specimens. The steel used in this investigation came in three bars 3/4 in. in diameter; analyses are as follows: Carbon. MaNGanese, Phosphorus, Sulfur Bar NUmber PeR Cent. Per Cent. Per Cent. Per Cent. 1 0.46 0.56 0.010 0.055 2 0.44 0.58 0.007 0.042 3 0.48 0.58 0.007 0.048

Jan 1, 1922

By Daniel M. MacNeil, Raymond L. Presbrey, Carle R. Hayward

At the February, 1916, meeting of the Institute, a paper presented by Hayward and Raymond gave the results of a study on the effect of time in tempering medium-carbon steel, when the following conclusions were reached: It is not fair to consider the question settled when only three specimens were used for each treatment, but the results obtained indicate that for reheating quenched medium-carbon steel to temperatures below 500" it is only necessary to heat it through. Longer heating has little or no effect on the tensile strength, ductility, or hardness. At temperatures above 500°, increasing the time of treatment causes a slight falling off in hardness and tensile strength with a corresponding increase in ductility. In the discussion of the paper these conclusions were attacked and evidence was presented that seemed to throw doubt on their accuracy. The authors, however, showed that this evidence was based on high-carbon or alloy steels and no facts regarding medium-carbon steel were presented. During this study the heat treatment was carried out in a small electric resistance furnace. It held nine specimens, but when these were placed in the furnace the temperature was lowered to such an extent that 30 to 40 min. were required to reach the desired heat. The authors pointed to this as a weak point in the investigation and it seemed wise to supplement the research by work on similar steel but using a different method of heating. This has been done and the results are given in the present paper. The Rhode Island Tool Co. coöperated by furnishing the steel and turning the tensile specimens. The steel used in this investigation came in three bars 3/4 in. in diameter; analyses are as follows: Carbon. MaNGanese, Phosphorus, Sulfur Bar NUmber PeR Cent. Per Cent. Per Cent. Per Cent. 1 0.46 0.56 0.010 0.055 2 0.44 0.58 0.007 0.042 3 0.48 0.58 0.007 0.048

Jan 1, 1922

By Richard Franchot

IN the inevitable conquest of the blast furnace by metallurgical science in the solution of the problem of how to make more and better iron or to burn less coke, or both, it is highly desirable first to find out why the efficiency of the furnace generally is no better than it is. The immediate need would seem to be a theory to account for the existing facts. Explanation for the quantitative results obtained in current practice has been strangely lacking. One reason for this may be found perhaps in the custom of think-ing of efficiency in terms of coke consumption. Before efficiency can be explained there should be a fairly exact knowledge of what it is. A statement of the pounds of coke used per ton of iron made may have value in indicating comparative results in smelting similar ores with similar cokes, but it tells very little of the efficiency of the operation. When the materials are different, one practice burning 1800 lb. may be less efficient than another using 2000 lb. A better measure is the pig and slag per unit of coke. What is needed is a specific description of efficiency as a' definite quantity having an exact meaning. Such description is afforded by expressing efficiencies in terms of the respective proportions of the fuel energy absorbed in and chargeable to the various actions known to be -taking place in the furnace. Concretely, the energy value of a pound of coke having 85 per cent carbon blown with air heated to 1200° F. is about 7650 lb.-cal. (13,770 B.t.u.). And the work done in smelting a pound of average iron from hematite, comprising reduction and melting with production of a half pound of free running slag from an equal weight of limestone,

Jan 9, 1926

By W. A. Barrows, Carl Zapffe

Jan 1, 1913

By AIME AIME

THAT neither the Reconstruction Finance Corp. nor its subsidiary, the Metals Reserve Corp., are in competition with private enterprise was stressed by Charles B. Henderson in an informal talk before the N. Y. Section, A.I.M.E., on Sept. 23. Among other things, the speaker stated that the R.F.C., since its establishment, had authorized loans of $12,000,000, of which over $8,775,000 has actually been distributed. Of this amount, over $6,600,000 has been repaid. None of this money was appropriated by Congress, the sole assistance from that body being the initial authorization of $500,000,000 capital stock.

Jan 1, 1941

By T. T. Field, M. Gell

MUCH has been learned about plastic deformation behavior in crystals through the use of dislocation and slip band etchants. Slip in nickel and nickel-base alloys has previously been revealed by various etching techniques.l-5 The techniques for nickel-base super-alloys4,5 were successful only in the Udimet 700 composition in specific heat-treated conditions. The objective of this work was to develop a more generally applicable slip-band etching procedure. The nominal compositions of the alloys used in this study are listed in Table I. The low carbon Mar-M2OO alloy referred to in the text is the same as listed in Table I with the exception that the carbon content is less than 100 ppm. Mar-M200 and Udimet 700 were solutionized at 2250" and 2150°F, respectively. The aging treatment for both cast alloys was 32 hr at 1600°F and for wrought Udimet 700 was 4 hr at 1975"F, 24 hr at 1550°F, and 16 hr at 1400°F. The new slip-band etching technique consists of a chemical etch followed by a short electropolish, Table 11. Fig. l(a) shows the best result obtained on an internal section of a plastically deformed single crystal of Mar-M2OO when using a conventional slip-band etching procedure which consists of electropolishing followed by etching. Ghostlike traces corresponding to planar slip bands are observed, but the contrast between the bands and the background is weak. Fig. l(b) shows the same field using the new slip-band etching technique. After the etching step of this technique, the same ghostlike traces of Fig. l(a) are observed, but the subsequent electropolishing accentuates the slip bands and the subgrain boundaries while the rest of the matrix is being polished. Longer electropolishing obliterates the slip bands. The new slip-band etching technique makes use of the etchants and electrolytes that are normally used for a given material. Because of this, it should be possible to slip-band etch other nickel-base superal-loys by using existing etchants and electrolytes for a material and following the procedures outlined in the "Comments" section of Table 11. All the illustrative examples given below show internal plastic deformation in single crystals of regular and low carbon Mar-M200 in the solutionized and

Jan 1, 1970

By Fredrick C. Kruger

Anthropological diggings have revealed that the American Indians carried on intertribal trade in flint, obsidian, ochre, and other mineral commodities, indicating that mining was practiced before the arrival of the white man from Europe Carbon datings from the native copper pits on Isle Royal and Keweenaw Peninsula, Michigan, have yielded dates as early as 5555 BC for this mining. As early as Pliocene time, Eolithic-man fashioned artifacts of stones probably found on the surface, but by late Quaternary, Neolithic man was sinking shafts and mining underground for flint. Because placer gold was easily recognized and easily worked, it was used for ornamental purposes by nearly all cultures before other metals were discovered The Chaldeans hammered copper objects approximately 4500 BC and copper was used in India and China about 3000 BC. An ancient trail from the Nile to the Sinai led to the mines of copper and turquoise Paintings and bas-reliefs of Egyptian tombs dating around 3000 BC depict maps, mining, and smelting in this area. It is interesting that despite this widespread and long history of mining, Agricola records that the first mining laws were developed by the Greeks at Laurium about 700 BC. All of the base metals are known to have been produced in small quantities during the Colonial period in America, but perhaps the first commercial production was the iron ore shipped from Virginia to England in 1608, followed by lead in 1621. Among the earliest companies formed in America that still survive (according to the standard reference yearbooks), were: the Jackson Mining Co., predecessor of Cleveland-Cliffs Iron Co. on the Marquette Range, Michigan, in 1844; the Sussex Zinc and Copper Mining & Manufacturing Co., fore-runner of New Jersey Zinc Co. in 1848 (although the Franklin-Sterling body was discovered in 1640); the five companies, Pittsburg and Boston, Quincy Mining, Pewabic, Huron Mining, and Minesota all formed in the decade (1844-1855) that followed the rediscovery of Keweenaw copper, were combined into Calumet and Hecla; and Vermont Copper Mining Co. in 1853 Although southeast Wisconsin lead-zinc was discovered in 1690, Mine La Motte in southeast Missouri in 1720, placer gold in California in 1848, Comstock Lode in 1859, Leadville in 1860, Cripple Creek in 1891, no surviving companies of those early mining periods exist. The first strong producer in the Mississippi Valley was St. Joseph Lead in 1864; Homestake and Pickands-Mather, were formed in 1877, Phelps-Dodge in 1881; Pittsburgh Reduction, the predecessor of Al-

Jan 1, 1976

By D. Walton, B. Chalmers

A preferred orientation is known to occur frequently in the columnar zone of castings. This has been attributed to a preferred direction of growth. However, no satisfactory mechanism was proposed by which the preferred direction of growth led to the preferred orientation. The purpose of this work has been to establish this mechanism. It has been found that in general the observed preferred orientations only develop when the preferred directions of growth reveal themselves by dendritic growth. A mechanism based on this premise is found to be in agreement with the experimental data obtained in the course of this work. WHEN a liquid metal is allowed to solidify in a mold, it usually freezes in three stages, distinguished from each other by the size and shape of the grains. The first zone to freeze (the chill zone near the mold wall) consists of relatively fine grains that are equiaxed in shape and random in orientation. The next zone consists of crystals that are elongated in the direction of heat flow, i.e., normal to mold wall. These crystals are much larger in cross section than the crystals of the chill zone and have a very strongly preferred orientation. This is the columnar zone. The final zone, which is absent in very pure metals, is again equiaxed and randomly oriented, but usually has a much coarser grain size than the chill zone. The purpose of this study is to describe and account for the crystal size and orientation in the columnar zone. The occurrence of a preferred orientation in the columnar zone is well known, and in 1940, Greninger' suggested that it is apparently related to dendritic growth although at that time the only data were for metals with the face-centered-cubic structure. Table I shows that the direction of dendritic growth and the crystal axis that follows the heat flow direction coincide in all cases so far studied. The term "dendritic growth" is used here to represent the branched type of morphology that is characteristic of growth into supercooled melts.' In addition to the supercooling which is necessary before nucleation will occur at the mold wall, the necessary supercooling for continued dendritic growth can be provided in a mold by heat flow into the already formed solid at an interface whose Liquidus temperature is depressed by an accumula-

Jan 1, 1960

By W. E. Showalter

This paper discusses some of the results of combstion-drive tests which were made in a test cell using a sand bed 10 in. in diameter x 10-ft long. The test method is illustrated and described. The relationship between the API gravity of the in situ oil and the amount of air required for combustion drive is discussed in detail. Other things constant, the air requirement for combustion drive increases as the APl gravity of the in situ oil decreases. If the test results apply to actual reservoirs, the lowest-priced oils may cost the most to recover by this method. Information is shown which indicates that the effect of pressure on the amount of hydrocarbon burned is not large. A method of predicting air requirements from the API gravity of the in situ oil is presented. INTRODUCTION Combustion drive is the term used to identify the process of interstitial or in situ burning as an oil recovery method. Part of the in situ oil is burned to generate the energy needed to produce the remainder of the oil. Combustion drive as an oil recovery mechanism remains an economic uncertainty in spite of all the work that has been done by the industry in both laboratory and field?-6 This paper will show some of the results of tests which were made in a test cell for the purpose of studying the nature of the combustion-drive process. It will present data which indicate that the API gravity of the in situ oil is a significant indicator of the amount of air required to drive a burning front through oil sand. Air requirement varies inversely as the API gravity of the in situ oil. EXPERIMENTAL The tests were performed in a cell which utilized a cylindrical sand section 10 in. in diameter x 10-ft long. The thin-walled metal pipe which held the sand was wound with twenty external electrical resistance heaters which, by means of an automatic controller, maintained adjacent sections of the wall of the pipe at temperatures equal to the temperatures of the contained sand. Each heater covered 6 linear in. of the pipe. By this means lateral heat loss from the sand section was minimized, thereby causing the sand section to simulate more closely a horizontal increment of a combustion-drive reservoir. Fig. 1 shows a schematic diagram of the test assembly. Thermocouples to measure the temperature in the sand were located every 6 in. along the length of the sand section. The pipe containing the sand was enclosed in a cell designed for an operating pressure of 500 psig. The inlet air pressure was controlled at the inlet, and the gas flow rate was controlled and measured at the outlet of the cell. The oil sand used for the tests was prepared by mixing first water and then oil with the noncon-solidated sand using a closed mixer similar to a cement mixer. Table 1 shows a screen analysis of the sand. Ninety percent of the sand was 100 mesh or finer. This sand was a mixture of 80 per cent No. 120 Nevada White Sand and 20 per cent Tennessee Hi-Fusion Moulding Sand No. 3. The Nevada sand was a clean silica sand. The Tennessee sand con-

By K. M. Myles

The vapor pressure of palladium over a series of Rlz-Pd alloys has been measured by the torsion-effusion method. The thermodynamic properties of the alloy system at 1575=K have been calculated from the vapor pressure data. The activities and the free energies of formation exhibit large positive deviations from ideal behavior. The enthalpies of formation are endother-mic. The entropies of formation are positive and larger than the ideal entropy of mixing. All of the thermodynamic properties suggest that a strong tendency toward phase separation exists in the solid solutions. The possible origin of the phase instability and the various factors that influence the thermodynamic properties are discussed. RECENT studies of the thermodynamic properties of alloys of palladium with nontransition elements have indicated that a significant contribution to the enthalpy of formation is related to the redistribution of the conduction electrons upon alloy formation.'-' The present work was undertaken to ascertain the importance of this contribution in Pd/transition-metal alloys. The Rh-Pd system was chosen for this investigation for several reasons: 1) The thermodynamics of the system were unknown. 2) Rhodium and palladium are completely soluble at high temperatures; below 1118OK the solid solution becomes immiscible.', 3) The difference in magnitude between the vapor pressures of rhodium and palladium permitted the use of an existing effusion apparatus. 4) Additional information was known about the alloy system that would facilitate the interpretation of the thermodynamic results. EXPERIMENTAL PROCEDURE The thermodynamic properties of the Rh-Pd alloy system were calculated from the vapor pressure of palladium over solid palladium and over several solid Rh-Pd alloys. The vapor pressure was measured by means of the torsion-effusion apparatus that has been described previously. In this method, an effusion cell is suspended from a tungsten filament inside a high-temperature furnace. Two orifices are located eccentrically such that the effusion of the vapor creates a rotational torque in the filament. The angle of rotation is directly related to the total vapor pressure within the cell. As the vapor pressures of rhodium and palladium are approximately five orders of magnitude apart," the total vapor pressure was considered to be effectively equal to the equilibrium vapor pressure of palladium. The effusion cells were made from high-purity alumina since auxiliary experiments indicated that essentially no reaction occurs between alumina and solid Rh-Pd alloys. Unfortunately, because the orifices were irregular, an accurate calculation of the Free- man-Searcy correction factors" could not be made. The constants were determined in an independent experiment where the vapor pressure of copper, as measured in the alumina cell, was compared with an accurate value of the vapor pressure, which had been determined previously.4 Depletion of palladium from the surfaces of the specimens was minimal as the deflection of the cell remained constant, for at least 15 minutes, at each of the experimental temperatures. Lattice parameter measurements of the postrun alloys also indicated that no changes in the composition of the surfaces had occurred. The alloys were prepared by arc melting the requisite amounts of the 99.99 pct pure elements. The four most palladium-rich alloys were remelted in a levita-tion furnace since complete melting of the components had not occurred in the arc furnace. All of the alloys were subsequently homogenized at elevated temperatures in sealed alumina thimbles. After heat treatment, the alloys were analyzed chemically and were in essential agreement with the nominal compositions. The thermal histories and nominal compositions of the alloys are given in Table I. Lattice parameters of the heat-treated alloys were computed, by means of the method described by Mueller et a1. ,I2 from X-ray diffraction powder patterns obtained with filtered copper radiation in a 114.6-mm-diam Straumanis-type Debye-Scherrer camera. The results, which are tabulated in Table I, exhibit a slightly greater negative deviation from Vegards' law than the values reported by Raub et al.13 The diffraction lines were sharp and well-resolved and thus indicated that the alloys were homogenous. RESULTS The logarithms of the individual values of the vapor pressure of palladium were fit, by the least-squares method, as a linear function of the reciprocal of the absolute temperatures. The constants of the equations are given in Table I along with the temperature range over which the data was accumulated. The latent heat of vaporization at 298.15"K for pure palladium, calculated by the third-law method,14 showed no systematic temperature dependence. The average value of 88,920 * 20 cal per g-atom agrees favorably with the average of the results obtained in the most reliable previous investigations.15"19 The activities of palladium were computed from the vapor pressure data at 1525', 1575", and 1625OK. Consistent with the mass spectrometric study of the atomicity of palladium vapor,lg the vapor was assumed to be monoatomic. The activities of rhodium were determined by integrating the Gibbs-Duhem equation with the aid of the a function.20 In the calculations, the activities of the pure solid metals were assigned the value of unity. From the activities, the partial and integral free energies, entropies, and enthalpies of formation at 1575° K were computed; they are assembled in Table 11.

Jan 1, 1969

By John A. Fagnant

At Elkol, Wyo., about 80 miles northeast of Ogden, Utah, the Kemmerer Coal Co. and the Utah Power and Light Co. are involved in a joint venture that will soon see 1 million tons of coal going "out by wire" to Ogden. Kemmerer, owner of a multi-seam strip mine, and the utility, now building a steam power plant adjacent to the mine site, expect to begin initial power generation by February 1963. Although capable of producing only 150,000 kw at that time, this plant is expected to be ultimately enlarged to 500,000-kw capacity which will require about 2 million tons of coal annually. The deposit consists of more than 30 seams of coal, usually varying in thickness from 2 to 40 ft, and separated by beds of sandstones and shales. In certain areas the aggregate thickness of all the coal seams measures 300 ft. The thickest and most spectacular of these seams is the lowest one, referred to as the No. 1 seam, which is 118 ft thick in some places.

Jan 8, 1962

By Richard R. Zupp, David A. Stevenson

An experimental method to determine the carbon activity in various solid solutions was developed. Samples of the solid solutions and an Fe-C reference sample were equilibrated with respect to carbon content by annealing them in a Hz-CHI gas mixture in a closed cell. The carbon content of each sample was determined, and the carbon activity was obtained from the carbon content of' the reference sample and well-established data for the dependence of the carbon activity on the carbon content in Fe-C alloys. The influence of vanadium on the activity of carbon in austenitic Fe-C-V alloys at 1000°C was determined by this technique. A general semiempirical correlation was developed to describe the dependence of the activity coefficient of- carbon on the composition of ternary austenitic iron-base alloys containing interstitial carbon and a substitutional solute. The correlation is particularly useful in predicting the partitioning of- carbon between various alloys. THE influence of substitutional solutes on the activity of interstitial solutes in metallic solid solutions is important in the theory of alloy phases. Solid solutions of particular interest are the fcc austenite phases of ternary Fe-C-Z systems, in which carbon is the interstitial solute and Z represents any substitutional solute. Carbon-activity data are also needed in these solid solutions to solve practical problems; the quantitative treatment of diffusion-controlled transformations' is an examvle. Experimental information is available for ternary austenitic solid solutions containing Mn,2 Si,2 and A16 as the substitutional solute. Because qualitative preliminary studies indicated that vanadium appreciably decreases the carbon activity,14 the present investigation was undertaken to determine the influence of vanadium on the activity of carbon in austenite. Although Flender and ever" measured carbon activity over a range of compositions in the Fe-C-V system, they were primarily interested in determining phase boundaries in the ternary system, so most of their measurements were outside the composition range for stability of single-phase austenite. Petrova and Shvartsman' also made limited measurements of the carbon activity in Fe-C-V alloys. The dependence of the carbon activity on the carbon content of an alloy may be determined by passing COCOz or H2-CH4 gas mixtures of carefully measured composition over the alloys, determining their equilibrium carbon content, and utilizing the relevant equilibrium relationships. smith16 used this technique with both CO-COZ and HZ-CH4 gas mixtures to determine the dependence of carbon activity on carbon content in pure Fe-C alloys. His data, which are in good agreement with those of some previous and subsequent investigators,6'17 but not with those of others,lfl'ao are usually considered to be the most reliable. Although the same method can be applied to Fe-C-Z alloys, it is difficult experimentally, because the appropriate gas mixtures are almost pure CO or Hz. A simpler technique is to simultaneously equilibrate the Fe-C-Z alloys and pure Fe-C alloys with the gas mixtures, and then use Smith's data to determine the carbon activity in the pure Fe-C alloy. A number of investigators have employed this technique. others Have used the partitioning of carbon at the interface of a diffusion couple prepared from an Fe-C alloy and a Fe-C-Z alloy. In the present study, a closed-cell method was developed by which carbon was selectively transferred via a gas medium between pure Fe-C alloys and Fe-C-V alloys which were not in physical contact. A similar method was developed independently by Heckler and winchel14 and used to study the Fe-C-Ni system. EXPERIMENTAL METHOD A schematic diagram of the experimental arrangement is shown in Fig. 1. In a typical experiment, a 5-g Fe-C sample was placed in one compartment of a quartz cell, and a 5-g Fe-V sample was placed in each of the other compartments. The cell was evacuated, outgassed, backfilled with approximately 125 Torr of hydrogen, and sealed. After being placed in a fur-

Jan 1, 1967

By Robert B. Sosman

THE relative temperature distribution within a coke oven and among the ovens in a battery can be obtained automatically for the operator's guidance by sighting a total-radiation pyrometer on the face of the coke as it is pushed out, and recording the surface temperature. Keeping the instrument clean and keeping its view of the coke unobstructed by smoke and dust are the principal problems. Typical records from three plants are presented in this paper, showing that the temperature patterns are reproducible. DEVELOPMENT OF METHOD The method of coke pyrometry described in this paper was introduced in 1936 by E. A. Lee, then Assistant Superintendent, now Superintendent, of the Coke Plant at Lorain Works, National Tube Co., Lorain, Ohio. At the request of the Coke Committee of the United States Steel Corporation, the Research Laboratory of the Corporation undertook to adapt the method to the somewhat different conditions met with at the Gary Works of the Carnegie-Illinois Steel Corporation, Gary, Ind., and at the Clairton Works of the same Corporation at Clairton, Pa. This work was done in cooperation with the Leeds and Northrup Co. of Philadelphia and later with the Brown Instrument Co. Division of Minneapolis-Honeywell Regulator Co., Philadelphia. We of the Research Laboratory wish to express our appreciation of the courtesies extended by Mr. Lee, by A. N. Cole, Superintendent of the Gary coke plant, and by D. P. Finney, Assistant General Superintendent in charge of coke-plant operations at Clairton. We are also indebted to the instrument companies for the loan of a part of the equipment. At Gary and Clairton the instruments were installed and various experiments were made by J. W. Bain, of the Research Laboratory of the United States Steel Corporation. PYROMETRY OF COKE The coke inside a by-product oven is almost completely inaccessible to pyrometric instruments. The temperature in the walls can conceivably be measured with thermocouples, but the atmosphere is usually strongly reducing, a condition well known to be destructive to the accuracy of the customary high-temperature couples. In some plants, periodic readings are taken with an optical pyrometer sighted into the top of the combustion flues. This is a useful measure for safety and general control, as it tends to prevent the damage that would result from overheating of the ovens. It does not, however, tell much about the temperature of the coke itself, because of the continually changing gradient in the wall between the coke and the combustion chamber. The best indication of the temperature of the coke itself must therefore be obtained by observation of the product as it is pushed out of the oven. The human eye is very sensitive to variations in brightness of a surface, and particularly to differences in brightness over a continuous hot surface.

Jan 1, 1942