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By H. F. Bishop, F. A. Brandt, W. S. Pellini

The solidification mechanism of experimental steel ingots (7x7x20 in.) was studied by thermal analysis. It was determined that solidification proceeds in wave-like fashion at rates which are determined by the carbon level, superheat, and mold thickness. The thermal cycles of the mold walls were related to the course of solidification. ESPITE marked advances in the field of solid state transformation, metallurgical research has contributed comparatively little exact quantitative data on the mechanism of solidification of metals. There is, therefore, a great need for such data in the various metallurgical industries. The mechanics of solidification of ingots have been investigated in the past primarily by studies of the rate of skin formation as indicated by bleeding or "pour out" tests. The "pour out" method, however, is a tool which gives only approximate information. In the case of alloys with wide solidification ranges, such as irons and certain nonferrous alloys, the method will not work at all; in the case of alloys of intermediate solidification ranges, such as commercial steels, the information may be misleading. Thus, the general adoption of this method has resulted in divergent conclusions regarding the solidification process. Chipman and Fondersmith1 by means of bleeding tests have shown that the linear growth of a solidifying ingot wall follows a parabola of the general form, D = K C, with the start of solidification delayed until superheat is exhausted, as indicated by the constant C. These tests were carried only to a wall thickness of about 5 in. using an ingot of approximately 17x39 in. in cross-section; hence the latter stages of solidification were not studied. Matuschka2-3 indicated that linear solidification of ingots is rapid at first, then slow, but toward the end of solidification the rate becomes extremely rapid again. Spretnak's4 bleeding studies indicated that, wall growth is expressed more rigorously by two parabolas, and that their point of intersection corresponds to a change of solidification mode from columnar to equiaxed. Spretnak also showed that the K values of the first parabola are always the same regardless of superheat. Nelson bled ingots of square cross-section and found that linear wall growth is initially rapid but decreases continually until the end of solidification. He also concluded that rate of solidification in ingots of square cross-section increases 2.15 pct for every 10 pct increase in cross-sectional area of the mold. The mold ratios considered (ratio of cross-sectional area of the mold to cross-sectional area of the ingot) were all less than 2 to 1. The subject of solidification has also been treated mathematically in many cases, but because of the lack of accurate thermal constants and the simplifying assumptions required, as their authors generally acknowledge, they represent only approaches to the actual conditions of ingot solidification. A third method of studying solidification is the electrical analogue method promulgated by Pasch-kis6-7 and by Jackson and coworkers.8 This method treats solidification as a heat transfer problem with the solidification cycle synthesized on an electrical circuit. Paschkis in his treatment of solidification considered the fact, which was generally ignored, that solidification of steel is not simply the growth of a plane solid wall but a more complex process occurring over a temperature range as indicated by the constitution diagram. Undoubtedly, the anomalous results obtained by bleeding tests arise from the inability to measure quantitatively this mushy condition. The shape of Paschkis' solidification curves are more nearly in accord with those of Matuschka, in that they indicate rapid linear solidification at the beginning and end of solidification with intermediate solidification occurring at a slower rate. Paschkis indicates a definite lengthening of solidification time with increasing superheat. Thermal analysis is a direct method providing exact information for all types of metals regardless of solidification range and was thus adopted in the present program to follow the entire course of solidification from the surface to the centerline of the ingots. The method has the added advantage of being adaptable to following the thermal cycle of the ingot mold during the course of solidification. Test Methods The ingots studied were of square cross-section, 20 in. long, tapered from 71/4 in. at the top to 63/4 in. at the bottom, and fed with a hot top 7 in. in diam and 12 in. high. The molds were uniform in wall

Jan 1, 1953

By C. D. Michaelson

Bridging the gap between have and have-not nations is one of the necessities of the present era. The responsibility for accomplishing this must be assumed by the affluent industrial societies of the world, both through their governments and through private enterprise. Despite a discouraging number of instances where companies established in underdeveloped countries have been expropriated, U.S. industry must not abandon such ventures. Instead, it should tailor them to the needs and aspirations of the host nations. One way in which industry can minimize the danger of expropnation is to enter into partnership with the government of the host nation. Kennecott Copper has recently done this in Chile, becoming 49% owner of a company formed to expand and operate the El Teniente mine. So far, the partnership has produced marked benefits not only for Chile, but also for Kennecott. The memory of D.C. Jackling serves chiefly to remind us how much we owe to the pioneers of our industry. Jackling was one of the giants. Orphaned at the age of two, he made his way through sheer persistence and plain hard work. His brilliance gave rise to a vision, and his tenacity made his vision a reality. Foreseeing that economies of scale would make the handling of low-grade ore profitable, he introduced the revolutionary concept of open-pit copper mining. During World War I, the defense effort of the United States was irnrneasurably strengthened by the tremendous supplies of copper from the western mines that Jackling had made possible. Again in World War 11, the demands for copper were supplied, and the nation once more had profound reason to be grateful to this rugged, stubborn man who had long ago ventured into the mountains and unlocked their wealth. We are now embarked upon another great era of change, and we must devise new concepts to meet it. The task is not only to create new techniques of mining, but to forge better ties between men and institutions which will let us work in harmony with the techniques we have. We might recall that while Jackling was a man of towering pride and formidable will, he was also adept at getting others to share his vision and join his purpose. Today our reach for cooperative endeavor must go far beyond our own shores as we seek to develop the buried riches of distant lands. And we would do well to remember that Jackling's remarkable insight would have come to nothing had not British investors been willing to provide much of the initial capital. As was true of so many early enterprises in America, European capital was absolutely essential. CORPORATIONS ABROAD - AN EXPANDING ROLE Today the situation is quite different. The United States is now a capital-surpIus nation and looks abroad for opportunities to employ its capital profitably. On the other hand, we have become dependent on foreign sources for supplies of vital raw materials, while we seek

Jan 1, 1970

By Edward W. Parker

Note.—The material from which this paper has been prepared was collected tor the U. S. Geological Suvey Bulletin, No. 316, Contributions to Economic Geology, 1906, and appears also, though in somewhat more extended form without illustrations, in that publication. Although the briquetting of coals and lignites has been carried on for many years in Europe, and has reached a particularly high state of development in France, Belgium, and Germany, it has made comparatively little progress in the United States. The causes for the backwardness of the United States in this regard are several, and first among them has been the abundant supply of cheap raw fuel with which the manufactured article has to compete. With our millions of acres of coal-productive territory, from which the product can in moat cases be cheaply extracted, it has appeared in many districts more economical to waste the slack or culm, which constitutes a considerable percentage of the product, than to attempt to save it at the additional expense required for briquetting. It is for this reason that the view in all sections -of the anthracite-region of Pennsylvania is marred by the unsightly culm-banks which encumber the ground, and that in some of the bituminous-districts one sees huge piles of unmarketable slack allowed to burn up in order to get rid of them. When the coal is of a coking quality, or when the slack can be used for steaming-purposes, these losses are not sustained, but many thousands of tons of what might be converted into usable fuel have been wasted every year simply because of the increased expense involved in its preparation.

Jan 1, 1908

Trans No. Place Date Vol. 1. Wilkes-Barre, Pa. May, '71 1 2. Bethlehem, Pa. Aug., '71 1 3. Troy, N. Nov., '71 1 4. Philadelphia, Pa. Feb., '72.. 1 5. New York, N. Y. May, '72 1 6. Pittsburgh, Pa. Oct., '72 1 7. Boston, Mass. Feb., '73 1 8. Philadelphia, Pa. May, '73 2 9. Easton, Pa. Oct., '73 2 10. New York N. Y. Feb., '74 2 11. St. Louis, Mo. May, '74 3 12. Hazleton, Pa. Oct., '74.. 3 13. New Haven, Conn. Feb., '75 3 14. Dover, N. J. May, '75 4 15. Cleveland, Ohio Oct., '75 4 16. Washington, D. C. Feb., '76 4 17. Philadelphia, Pa. June, '76 5 18. Philadelphia, Pa. Oct., '76 5

Jan 1, 1932

By Henry M. Otte, Ralph P. I. Adler

The changes of line position and integral line breadth in the X-ray diffraction pattern of a polycvys-talline Cu-30Zn tensile test piece, incrementally loaded (and unloaded) up to fracture, have been an-alyzed in detail. The stacking-fault probahility, cv, increased linearly with increasing strain, E, wheveas the effective domain size, De(hkl), decreased with decreasing E-1 Over the greater part of the stress-strain curve the rate of work hardening was essentially constant (about 86 kg per sq mwz), and could be correlated with the slope of stage II of the single-crystal stress-strain curve. Consequently the theories of work hal-dening (particularly those parts relating to stage 11) as developed by Mott and Hivsch and others could be applied to the observations made on the polycrystalline brass. A relationship of the form Aa = Aao - MhklEhkl between the change, Aa, in the extrapolated lattice pararneter and the rvns strain, Ehkl, was derived and found to fit the results acceptably well. From this and other relationships developed in the papev it was estimated that the equilibrium stacking-fault energy of Cu-30Zn was between 8.4 and 12.5 ergs per sq cm, in fuirly close agreement with the (corvected) value obtained by Howie and Swann (1961)43 using transmission electron microscopy. The theory of work hardening in the jorm developed and recently presented by Hirsch (1964)3 successfully described all the pvesent observations. In order to test certain aspects of the theories of work hardening, as developed by Mott,1 Hirsch,2,3 Seeger et el,4-7 and others (for review see Nabarro, Basinski, and Holt8), several recent investigations have been concerned with relating the dislocation density, p, with the shear stress, 7 (and strain, y), applied to the specimen. The results of these investigations have shown that the square root of the dislocation density appears to be linearly related to the applied shear (or flow) stress for fcc as well as bcc metals and alloys. Furthermore, the relationship appeared to apply not only to the deformation of poly-crystalline specimens, but also to stages I and I1 of the deformation of single crystals. An expression of the form has thus come into wide use. Here b is the Burgers vector for a total dislocation, G is the shear modulus, and 70 and q are constants. A review9 of available values of q shows it to have values (at room temperature) in general between 0.3 and 0.6. Forms of Eq. [1] can be deduced from, or predicted by, the current theories, and the various constants adjusted so that they are compatible with the experimentally found value of q . No unique relationship has yet been found between the dislocation density and the applied shear strain. There are several serious objections to the use of Eq. 11]. In the first place, it relates the shear stress to the density of the dislocations without regard to their arrangement, type, or distribution; the significance of the relation may therefore be justly questioned.5 In the second place, the values of the experimental quantities usually substituted into Eq. [11 are those of the applied shear stress and the total dislocation density measured after unloaditzg. The dislocation density value that should in fact be used is that for the mobile dislocations present in the specimen when under the applied load.* Finally, in cases where the values used for p, the dislocation density, are those obtained by electron microscopy, p is subject to considerable error,' both systematic and random. The corrections to be applied are still controversial. Dislocation densities can also be measured by etch-pit and other techniques,'' each having their specific limitations. An objective of the present investigation has been to obtain information about the dislocation configyration and distribution by analyzing the changes in the position and shape of X-ray diffraction profiles as a function of deformation. The X-ray techniques employed, also open to criticism, have certain advantages, however. Thus, although the X-rays diffract only from the surface layers to an effective depth of about 20 p, the measurements can be made while the specimen is under load. The value of the dislocation density obtained by the X-ray method is also subject to errors, which are different from those of the electron microscope. Though a considerably larger volume of material is sampled by the X-rays, thereby reducing some of the statistical errors inherent in the electron microscope data, the information obtained is less detailed and is dependent on the method of analysis used to obtain a value for the dislocation density. Nevertheless, important observations can be made because the aforementioned advantages outweigh some of the limitations. In the present paper the X-ray method is briefly described and applied to a brass specimens deformed in tension. The results are then discussed in terms of some of the current concepts of work hardening. 1) EXPERIMENTAL PROCEDURE Details have already been extensively published elsewhere11-14 and therefore will only be dealt with briefly here. 1.1) Materials and Specimen Preparation. Commer-

Jan 1, 1968

By Yap Chu-Phay

IN the previous paper, the writer showed how, on the basis of thermodynamic reasoning, it seems probable that when true equilibrium conditions obtain, carbon exists as Fe3C in the liquid state and as elementary carbon in the solid state (7 Fe), in which case the solidus would be a straight line from 0.18 to 1.70 per cent. carbon (Fig. 1). In the same paper he concluded that the solidus obtained by Honda 'and his co-workers1 probably does not represent the same conditions, insuring a complete equilibrium. Except for a downward temperature displacement, the solidus obtained by Gutowsky,2 using the Heycock and Neville method, practically coincides with Honda's solidus as shown in Fig. 1. The writer at first thought that perhaps in some way Gutowsky's thermocouple was improperly calibrated for high-temperature measurements, as his liquidus was also much lower than those obtained by Carpenter and Keeling3 and by Ruer and Goerens.4 However, the eutectic temperature obtained by Gutowsky agrees with the generally accepted value of 1130° C., so that the validity of the inference regarding improper temperature calibrations is to be strongly doubted. In Fig. 1, Gutowsky's solidus is shown both in the original and in the corrected form. In the latter, a correction of 29.2° C. is made for all temperatures above 1416° C. in accordance with-

Jan 1, 1931

Jan 1, 1970

By R. G. Gifkins

Mean boundary migration depended linearly upon creep extension under various conditions. Prolonged annealing or air-casting increased the proportion of immobile boundaries at a given stage of tests. Grain growth during annealing followed a power law. The linking of migration and sliding in creep and models for migration are examined; activation energies are calculated from these models. Segregation of oxygen to boundaries appears to be a controlling factor. THE idea that boundary migration and boundary sliding during creep are linked has often been suggested,'-5 especially when evidence has been obtained for an alternation between the two processes. In simple bicrystals sliding can occur without any migration6 but in more complex bicrystals7 it is observed. McLean' and Couling and Roberts 5 made measurements of both sliding and migration; McLean concluded that there was no linking of the two processes whereas Couling and Roberts supported the idea. McLean' also developed a model for migration during creep and annealing. The present work was initiated as part of a study of the recrystallization of lead during creep9 but has been extended to examine some aspects of the mechanism of migration. MATERIALS AND METHODS Specially refined high-purity lead* was used; the total of impurities, excluding oxygen, was 0.0008 wt pct. Oxygen was removed as far as possible by melting in vacuo, treating at 550" to 600°C with hydrogen and then casting at 450°C under a vacuum of 10-2 mm Hg; the oxygen was then believed to be 0.00005 wt pct. Specimens were made from extruded strip and then annealed at the required temperature in an air oven, controlled to 5 lac. They were then polished in a mixture of acetic acid and hydrogen peroxide. At this stage some specimens were etched to give grain contrast and their grain sizes determined by the intercept method. Migration of boundaries during creep was measured on the surface of polished (not etched) specimens, directly loaded at room temperature (22°C) or 50°C (52"C) to initial stresses of 300 to 700 1b per sq in. Twenty six vacuum-cast hydrogen-reduced specimens were used and, in addition, two specimens were from material air cast after hydrogen reduction ("partial" air cast) and two from air-cast material not treated with hydrogen ("full" air cast). Duplicates were made in the majority of tests. At intervals through the creep tests, specimens were unloaded and the migration measured, normal to the direction of migration at the point of measurement, for each boundary along standard traverses. Usually between 110 to 180 boundaries were measured at each of some twelve stages of the tests. Migration was measured on the projected image (X100) using prism illumination. Fig. 1 illustrates the method of measurement and shows the kind of variation of migration found from boundary to boundary and along particular boundaries. Fig. 2 gives an example of more extensive migration. The mean value of distance migrated was generally reproducible to *10 pct but occasional points gave a scatter of *20 pct. The correctibn applied by McLean8 to allow for the contribution sliding makes to the apparent distance of migration could not be used, for the sliding at most boundaries was too small to measure with the equipment available. There were two reasons for supposing the correction unnecessary in the present work;

Jan 1, 1960

By James E. Little

(Wilkes-Barre Meeting, June, 1911.) OF the several extensive deposits of brown iron-ore in Cuba, including those of Mayari and Moa, that of Mayari was the first to be systematically explored, and was selected as the scene of the first operations in the development of this class of ore. Construction-work, begun in the spring of 1907, involved the building of 16 miles of standard-gauge railroad and two large double-track inclines, the installation of mining-machinery, a nodulizing-plant, power-plant, shops and shipping-facilities, and the dredging of an extensive basin for deep-draught vessels. Unusual weather-conditions delayed the completion of portions of this work so that the entire plant was not in operation until December, 1909. The ore in its natural state contains a very large percentage of water, which increases to some extent with the depth below the surface. Near the surface it is red in color, with somewhat granular structure. The color gradually changes with depth, finally reaching a bright yellow. The consistency also changes towards, the bottom to a clay-like, sticky mass. The relative proportion of red and yellow ore is quite variable; in some places the yellow reaches close to the surface, while in others the red extends almost to the underlying serpentine. Fig. 1 is a map showing the Mayari division of the Spanish-American Iron Co. The ore lies on an irregular plateau about 15 miles long and 5 miles wide at the widest point, entirely covered with pine trees and brush, which grow directly on the ore. The elevation at the northern extremity, which is approached by the railroad, is about 1,700 ft. above sea-level. At the southern end the general elevation is about 2,000 ft. Ore is removed by means of scraper-bucket excavators and steam-shovels, these machines loading into special standard-guage, side-dump steel cars of 100,000 lb. capacity. A short haul

Aug 1, 1911

By A. S. Emanuel

A correlation has been developed for calculating the phase behavior of, gas-condensate systems at reservoir conditions. The correlation is based on the principle of corresponding states and has been coded for an IBM 7094. Experimental K-values were determined for several gas-condensate systems at reservoir conditions to evaluate various semi-empirical parameters of the correlation. The approximate range of application of the correlation is 150 to 300F and 1,500 to 6,000 psi. INTRODUCTION The rapid development of digital computers during the past several years has made feasible the calculation of hydrocarbon phase behavior by methods based on rigorous thermodynamic principles. Good correlationsl have been developed for low to moderate pressures, but these techniques have not yet been extended successfully to reservoir fluids at high pressures. Consequently, the determination of phase behavior of oil and gas systems at reservoir conditions is still based almost entirely on generalized data correlations or on experimental studies of the fluid in question. While these methods have been used successfully many times, they do have inherent limitations that restrict their applicability. Generalized correlations, such as the NGShlA K-charts, are limited to the range of pressure, temperature and components for which the data were determined. The accuracy of these correlations is often questionable because the effect of total system composition is not well defined. Experimental studies offer a reliable method for determining phase behavior, but usually the studies are costly and time consuming. Recently, Leland and co-workers presented a new approach to calculating phase behavior from the principles of corresponding states.6-8 Corresponding states methods determine the thermodynamics properties of a given system by comparison with a reference substance whose properties are known. The accuracy of this approach depends on close chemical and structural similarity between the reference substance and the system in question and between components within the system itself. For high accuracy, it is usually necessary to correct for chemical and structural dissimilarities. In principle, however, the corresponding states method should be no less accurate at high pressures than at low pressures, provided reference substance properties are known. This paper describes an empirical modification of the basic correlation proposed by Leland, et al.6 for the specific purpose of calculating the phase behavior of gas-condensate fluids at reservoir conditions. The modified correlation, which has been programmed for an IBM 7094, may be used for either approximate or precise determination of fluid behavior depending on the amount of analytical and, experimental data available for the system. BASIC THEORY The basic theory of the corresponding states phase equilibria correlation was first published by Leland, Chappelear and Gamson.6 Subsequently, Leland, Chappelear and Leach published methods for improving the accuracy of the original theory.7-9 The aim of the correlation is to calculate the K-value of each component of a given system as a function of pressure, temperature, and over-all composition, where Once the K-values are known, the phase behavior may be determined directly by an appropriate flash calculation. The basic equation for calculating component K-values was taken from the work of Joffe. 4 For any component i of a mixture, the K-value is given by

Jan 1, 1969

By R. F. Mehl, G. V. Smith

THE decomposition of austenite in steels, because of its immense practical importance, has been subjected to extensive study in recent years from the point of view of the mechanism of the process.1-3 Although much information has been acquired a number of questions, principally of theoretical interest, remain. One is that of the atomic-crystallographic mechanism by which each of the various reaction products forms. The isothermal reaction products of the eutectoid decomposition in plain carbon steels (to which this study is restricted) have conveniently been classified in three general groupings-pearlite, bainite, and martensite. Of these several products, pearlite and martensite have been studied extensively, but bainite has received only scant attention. As a result, the mechanism of the formation of pearlite and that of martensite are now fairly well understood while a great deal of uncertainty exists regarding bainite. PEARLITE Pearlite forms from austenite by the precipitation of alternate platelets of cementite and ferrite, which grow into the austenite matrix.2-5 The rate of reaction may be described in terms of a rate of nucleation and a rate of growth 2 3 Mehl and Smiths have attempted to determine the lattice relationships existing between the ferrite in pearlite and the parent austenite. Using a pole-figure method of analysis, it was found that a limited number of ferrite orientations resulted from the decomposition of a single grain of austenite; it was not possible,[ ]decide between two assumed ideal relationships, both of which appeared to account for the experimentally determined pole figure. It was definitely shown, however, that the relationship obtaining was quite different from that determined for the proeutectoid separation of ferrite.7 No attempt was made to determine the habit plane (matrix plane to which the precipitate lies parallel) of the pearlite lamellae. Belaiew8 earlier had stated that the number of directions assumed by the pearlite lamellae in a single grain of austenite was 12 (no details were given) and concluded wrongly, as Mehl and Smith' have pointed out, that the lamellae delineate the {210} planes of ferrite.* MARTENSITE It is known that martensite is a transitional constituent of body-centered tetrag-

Jan 1, 1942

Jan 1, 1882

In a straight caving system, the ore is first undercut and then broken down by its own weight or .by the weight of the overlying rock, or by a combination of both. Operations that involve the caving of the material overlying an orebody as an essential part of the work are also classed as caving, though practically all the ore is broken by drilling and blasting. Actually there are two distinct methods—sublevel caving and block caving, and modifications thereof. The mines described are Miami and Alaska Juneau.

Jan 1, 1925

By Philip N. Adler, Harold Margolin

Univariant equilibria between the Ibcc, IIhcp, and UIfee phases of thallium have been determined and indicate a triple point at 110°C and 37 kbars. Calculated II —I transformation curves are compared with the experimental. Transformation volumes and/or enthalpies are calculated and enthalpies are compared with available data. ThE triple point of solid thallium has been reported by Bridgman as 153°C and 38 kbar.' More recently, Jayaraman et at.2 have reported the triple point as near 115°C and 39 kbars. Meyerhoff and Smith,3 assuming the elevated-pressure modification of thallium is fcc, as Kaufman suggested,4 and that it is continuous with the room-temperature fcc phase in the Tl-In system, have used pressure data up to 5 kbars to predict the triple point at 162°C and 35.8 kbars. Piermarini and weir5 have indeed found the elevated-pressure phase to be fcc. The effect of variations of pressure and temperature in the IIhCp — Ibcc transformation in thallium have also been reported by werner6 and more recently by Ponyatovskii.7 The work reported here is part of an investigation of the effects of temperature and pressure on the Tl-In system. I) EXPERIMENTAL PROCEDURE The onset and progress of transformation were determined by changes in resistance. A commercially available tetrahedral-type pressure apparatus was used. Specimens of 0.060 in. diam, representing 0.63 pct of the cell volume, were encased in AgCl and mounted in pyrophyllite, as shown schematically in Fig. 1. It can be seen that the specimen is in series with the graphite furnace. Resistance changes of 0.1 pct could be detected with a Kelvin bridge. Resistance of the sample was of the order of 1 milliohm. Other pertinent details in regard to calibration and cell-assembly design are given elsewhere.' Temperature calibration of the cell was carried out in two ways as a function of input wattage. Through a hole drilled in the graphite furnace, a chromel-alumel thermocouple was inserted into the AgCl to a point 0.010 in. from the sample, with the

Jan 1, 1964

By E. T. Turkdogan, L. S. Darken

Calcium ferrite melts were equilibrated with sulfur and oxygen-bearing gases at temperatures within the range 1290°C to 1620°C. The results show that at oxygen partial pressures below 10-4 atm the sulfide-reaction occurs and at higher oxygen pressures the sulfur dissolves in the melt principally as sulfate ion. It is also observed that when the product increases, sulfate ions are converted to pyrosulfate ions and the results permit the evaluation of the pyrosulfate/sulfate ratio. It is shown that the ratio y CaSO,/rCaO increases with decreasing concentration of calcium oxide in calcium ferrite, silicate and aluminate melts. Indications are that oxy-acids, e.g. silica, alumina and ferric oxide, increase yCaS0,. A few experiments were carried out within the sul-tide range and the results are in accord with those obtained by other investigators on aluminate and silicate melts. BECAUSE of the industrial importance and theoretical interest, many investigators have studied the reactions between molten oxides, silicates or alumi-nates, and gases containing oxygen and sulfur. The early work reviewed by Schenckl and studies made by Bardenheuer and Geller2 indicates that solution of gaseous sulfur in an oxide melt resulted in the replacement of the oxide ions by the sulfide ions. Measurements made by Grant and Chipman3 on the equilibrium partition of sulfur between molten iron and complex silicate melts also demonstrated that, for a given temperature and silicate composition, the distribution of sulfur between slag and metal increased with decreasing oxygen content of the metal. Fincham and Richardson4 studied the effects of temperature and partial pressures of sulfur and oxygen on the solubility of sulfur in simple silicate and alumino-silicate melts. They observed that at oxygen partial pressures below about 10-5 atm sulfur in the gas dissolved in the melt as sulfide ions, replacing an equal number of oxide ions of the melt. At oxygen partial pressures higher than 10-3 atm, sulfur entered the melt as sulfate ions. Similar studies were made by St. Pierre and Chipman5 using calcium ferrite and calcium silico-ferrite melts. The experimental data presented in this paper were obtained in this Laboratory about 10 years ago; this is the first formal presentation although a preliminary report was given previously.6 In each of these experiments, a pure synthetic CaO-Fe2O3 melt in a platinum crucible was equilibrated with a gas mixture (SO2-O2, SO,-air, SO2-CO, or SO2-CO2-CO) at a temperature ranging from 1296°to 1620°C. The experimental technique was essentially the same as that reported by Darken and Gurry,7 the main difference being that the atmosphere in the reaction chamber contained sulfur dioxide together with oxygen, or carbon dioxide-carbon monoxide

Jan 1, 1962

By William L. Fink, H. R. Freche

This is the thirteenth paper of a series from the laboratories of the Aluminurrl Company of America presenting the results of investigations of equilibrium relations in aluminum-base alloys prepared from electro-lytically refined aluminum. The ninth paper, on The Constitution of High-purity Aluminum-titanium Alloys,' presented a type of system that had not previously been encountered in aluminum alloys. Subsequent work has shown that there are several similar binary aluminum diagrams including that of aluminum and chromium. The present investigation was limited to the cxtreme alnminum end of the aluminum-chromium system. The first systematic investigation of the aluminum-chromium equilibrium diagram was carried out by Hindrichs.? The resulting equilibrium diagram with some imaginary additions suggested by Guillet3 is shown in Fig. 1. Recently Goto and D6gane4 investigated the constitution of aluminum alloys containing up to 32 per cent chromium, and presented the diagram that is reproduced in Fig. 2. Wide discrepancies in the two diagrams are evident. The following intermetallic compounds have been reported in the literature: A1Crl5,6 AlloCrlzSi,5 AlCr4,6 AlCr3,7 AlaCr.8 Preparation of Alloys and Chemical Analyses With the exception of sample Y4206, which will be described under Determination of Hyperperitectic Liquidus, the alloys were prepared from electrolytically refined alurninum% Of which the analysis is given in

Jan 1, 1933

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By Benjamin Smith Lyman

It has seemed that it might be a highly useful contribution to the study of structural geology to assemble, in as compact a form and on as large a scale as practicable, a great number of

Jan 1, 1896

By William M. Baldwin, T. S. Howald, A. W. Ross

EXPLORATORY WORK THE related subjects of preferred orientation, directionality in physical properties, and earing tendencies of wrought metal [ ] strip have attracted the attention of metallurgists to such an extent that in the past 20 years hundreds of researches have been published on this one general problem. The anisotropy of tensile strength and elongation have been exhaustively studied in their relationship to the occurrence of ears in cups drawn from strips-20.29 and, to a lesser extent, yield strength7,11,17 and stress-strain curves" have been investigated. Despite the tremendous fund of knowledge thus accrued, no simple quantitative correlation of directionality and earing tendencies has yet been found. In a sense, this is not surprising. The formation of ears in a drawn cup clearly is a special phase of the general study of metal flow; in particular (as will be brought out in the course of this paper), ears are due to anistropy in the rates of deformation of the metal in the radial, circumferential, and "thickness" directions of the original blank. It would be difficult to effect a correlation between earing tendency and a property that may be completely independent of the flow of metal, or at best related to metal flow in an exceedingly complex fashion. Yet, it is this correlation that has been attempted; tensile strength and elongation are attributes of metal rupture, a phenomenon that has quite admirably been shown to be distinct from the phenomenon of metal flow,21 while yield strength and stress-strain

Jan 1, 1945

By H. I. Aaronson, H. A. Domian

ELectvon-probe analgsis has been used to in7:estigatr the partition ot alloying- elements between aus-tenite and proeutectoid ferrite (or the Jerritic component of bainite) in high-purity Fe-C-X alloys, lsuully at tzco levels of carbon content fca 0.1 and 0.4 pct in ntost steels) at temperatures between the M, and the Ae3 in Si, mn, Ni, mo, Co, Al, Cr, Cu, and PI steels. No partition ous found during the early stages of transformation at any temperature studied in the Si, ,mo. Co, Al, Cr, and Cu steels. Partition did take place, Jrowel'er, in Ihe Mn, ATi, and Pt steels, occurring in lewtperature. regions below the Ae3 of ca 130°, 65", UNDERSTANDING the mechanisms through which alloying elements influence the kinetics of austenite decomposition reactions which proceed by nucleation and 35c respectively. A break was discovered in the TTT curve for the initiation oj the proeutectoid ferrite reaction in the latter steels at the temperature at which partition began. The alloy content in ferrite at the a:y bondavy remained at constart lecels, shown experimentally to be significantly above those corresponding to eqiilib+iu??l, e'en at the longest reaction times investigated (ca 1o6sec). The partition and the TTT curve observations foere rationalized on the basis of the thermodynamic treatment developed in an accompany ing paper. and diffusional growth has been a major research objective of physical metallurgy since the latter part of the 19th century. The measurements made on the dif-fusivities of carbon and of substitutional alloying elements in austenite during the 1930's and 1940's seemed to provide a useful clue as to the nature of these mechanisms. These measurements showed that the diffu-sivity of carbon is several orders of magnitude higher than that of the alloying elements at a given tempera-

Jan 1, 1967