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By A. A. Bauer

The ?-to-? transformation has been studied in zirconium alloys containing 22 to 70 wt pct U. In this range of compositions the ? phase can be retained by quenching. Transformation to ? occurs by a nucleation-and-growth process. The diffusion of atoms to preferred lattice sites to yield a partially ordered structure apparently controls the rate of reaction. Alpha uranium and a zirconium precipitate from the supersaturated E phase initially formed in alloys outside the equilibrium E phase composition limits. ZIRCONIUM-Uranium alloys have long been of interest for reactor-fuel applications because of the low thermal-neutron cross section of zirconium. Considerable information is available on the various properties and behavior of these alloys1 although there had been a number of areas where information was incomplete. As part of a program to provide more detailed knowledge in these areas, the presently reported investigation was undertaken. The constitutional diagram of the zirconium-uranium system is shown in Fig. 1.' The system is distinguished by a region of complete solid solubility between the body-centered cubic ß-zirconium and ? uranium phases and the existence of an intermediate phase in the vicinity of 50 wt pct U. This intermediate phase, designated as E, is reported3 to have a primitive hexagonal structure with a = 5.03 and c = 3.08A. The structure is partially ordered with zirconium atoms at the 0, 0, 0 position and zirconium and uranium atoms located randomly at the 1/3, 2/3, 1/2, and 2/3, 1/3, 1/2 positions. While the E phase may be nominally designated as of UZr2 stoichio-metry, the random distribution of uranium and zirconium atoms permit a considerable range in composition. Of interest in the research performed were alloys in the range from 20 wt pct (10 at. pct) to 70 wt pct (47 at. pct) U. In this range of compositions the body-centered-cubic ? phase can be retained either completely or partially on quenching. The nature and kinetics of transformation of the ? phase were the subject of study. Proceeding concurrently with the presently reported work was an investigation by Kearns4 which has since been reported. Kearns studied alloys containing 50 to 60 wt pct U prepared from sponge zirconium. While the work reported here is for alloys prepared from crystal-bar zirconium and the techniques of study are to some extent dissimilar to those employed by Kearns, general agreement so far as results and interpretation can be reported. Experimental Techniques—Alloys were prepared and the transformation of the ? phase studied during interrupted-quench and quench-and-temper isothermal heat treatments by means of hardness measurements and X-ray diffraction and metallographic techniques. The isothermal transformation of the ? phase on quenching and tempering was investigated further employing dynamic-modulus measurements. Electrical resistivity and limited Hall coefficient measurements were also obtained as part of the study. Alloy Preparation and Heat Treatment— Alloys containing 15, 20, 22, 30, 40, 45, 50, 55, 60, and 70 wt pct U were prepared from as-reduced uranium and crystal-bar zirconium. The alloys were double arc melted by consumable-electrode are-melting techniques. The final ingots were forged and rolled at temperatures between 790" and 840oC to 1/4-in. rod and 1/8-in. sheet. Chemical analyses of the fabricated alloys were

Jan 1, 1961

By V. F. Parry, J. B. Goodman

The low-rank coals containing 10 to 50 pet natural bed moisture represent over half of the tonnage reserve of the available solid fuels of the United States, but only about 2 pet of United States coal production is derived from these fuels. Increased utilization of these large reserves will result if the bed moisture can be removed at the mine in high-speed low-cost processes. This paper presents a theoretical and experimental study of the factors affecting high-speed drying of coal dusts. The time required to heat particles of coal is proportional to the square of their diameter, and it is calculated that the probable time in minutes is equal to 6D2. In other words, a 11 a in. coal particle should be heated to drying temperature in 1.5 to 2.0 sec. Likewise, 1/8 in. particles should be heated in about 6 sec. The net heat required to dry subbituminous coal and lignite varies from 240 to 375 Btu per pound, depending upon the moisture removed, and this heat can be obtained from 42 to 61 cu ft of hot gases at 600°F.

Jan 1, 1949

By Howard N. Eavenson

AN analysis of the bituminous coal situation by an authority who traces the production, mining, safety, markets and labor trends in comparison with other fuels. BEFORE 1918 the production of coal experienced a steady growth, with slight recessions in ouput in only twelve years (1837, 1841, 1852, 1855, 1861, 1874, 1876, 1889, 1894, 1905, 1909, 1914), and in each of these cases the loss was recovered in the following year and the increase continued. In each decade the output was doubled. Prices, while not high, allowed some profit. In 1918 during World War I, an output of 580 million tons was reached and with the exception of 1923 this total was not again reached until 1942, in World War 11. Losses of output in this period were much greater than ever before; in 1932 the total was 270 million tons less than in 1918 or 1923, and the loss after 1923 was not recovered until 1942. The greatest output was 631 million tons in 1947.

Jan 1, 1950

By C. H. Mathewson

MY treatment of the subject of "Metals of the Future" is imaginative rather than statistical or scientific, because reliable information concerning useful concentrations in the form of ore deposits of by far the majority of the elements does not exist and the chemical, physical, and mechanical properties of the unfamiliar metals are recorded only in fragmentary and uncertain form or not at all.

Jan 1, 1944

By W. L. Saunders

(Wilkes-Barre Meeting, June, 1911.) I. INTRODUCTION. IT is now generally admitted by experts that at least so far as rapid progress is concerned the Alpine system of tunnel-driving is superior to any other. This is perhaps natural in view of the record of experience in driving tunnels through the Alps. These great mountain-chains cannot be treated in the ordinary way by shaft-sinking and driving headings, thus multiplying the points of attack. The work must be done from the ends only, hence speed in driving is of the utmost importance; and, as necessity is the mother of invention, the concentration of effort to make progress has resulted in an organization and in mechanical appliances that have produced results so much in excess of the usual practice, even in America, that a discussion of the subject in detail should be of much value to the engineer and contractor. The first Alpine tunnel was the Mont Cenis, length 7.5 miles, driven with a progress that averaged about 7.75 ft. per day. Next came the Saint Gothard, 9.5 miles long, 18 ft. per day; Arlberg, 6.5 miles long, 27.25 ft. per day; Simplon, 12.25 miles long, 36 ft. per day. The figures represent progress when driving from two headings, so that by dividing them in two we get the daily single-heading progress. The latest of the Alpine tunnels is the Loetschberg, now being driven. In this work the world's record has been beaten by a single day's record in one heading of 36 ft. and by an average daily record in. one heading of 29.5 feet. The Alpine range forms a natural barrier between a large section of northern and southern Europe. This range extends from the southeast of France to the frontier of Hungary, between Italy and the plains of southern Germany. The contour

Jul 1, 1911

By R. B. Moore

IN 1914 the writer and K. L. Kithil announced, through Bulletin 70 of the U. S. Bureau of Mines, that the United States possessed the largest deposits of radium-bearing ore in the world. At that time a small amount of this ore was being, mined and shipped to Europe, and one company was preparing to start the extraction and recovery of radium in this country. The importance of our carnotite deposits in Colorado and Utah up to the publication of Bulletin 70 was not, however, appreciated by anyone.. At that time the total supply of radium in the world was about 10 g., calculated as element, and when I estimated that at least 100 g. of radium element, and probably 200 g., would be produced from our carnotite deposits, there was a considerable amount of skepticism. Up to the present time almost 200 g. have come from this ore, and some writers put this figure a little higher. Uranium ore was found in the copper mines of the Union Minière du Haut-Katanga at Luiswishi in 1913. Later discoveries were made at other places in the Belgian Congo, and the Katanga ores now represent the largest supply of radium-bearing ore in the world. In fact, since 1923 very little radium has been produced from American carnotite, the Katanga ore representing practically the world's supply of. radium since that date.

Jan 1, 1930

By PHILIP N. MOORE

THE development of the power of the Tennessee River at Muscle Shoals has become a matter of political interest as well as engineering possibility. The controversy over it has been so active that the facts have been obscured, the possibilities exaggerated. Although the members of the American Institute of Mining & Metallurgical Engineers are not generally specialists in hydroelectric development, those who visited Muscle Shoals in October, following the Birmingham meeting of the Institute, were interested, and many of them surprised to learn the actual conditions. These have long been familiar to those who have studied the matter through the reports of the U. S. Engineers on the subject. The approved plan contemplates three dams-No. 1, a low dam close to the City of Florence, planned in the interests of navigation, since the construction of the other dams has rendered impossible the use of the river without it. No. 2-named the Wilson Dam is now under construction. Concerning it political argumentation has waged. No. 3 Dam-much smaller, is planned to be erected several miles above No. 2.

Jan 1, 1925

By J. J. Fritts, J. L. Patrick, T. L. Wright, C. O. Ensign, W. S. White, J. W. Trammell, J. C. Wright, D. J. Hathaway, R. J. Leone

The copper deposit at White Pine, Michigan, from which a little more than 5 per cent of United States primary copper currently is produced, is a large stratiform orebody, 4 to 25 feet thick and several miles across. The present ore column, containing about 1.2 per cent copper as chalcocite and native copper, is confined to the basal beds of the Nonesuch Shale. This upper Keweenawan (Upper Precambrian) formation is a distinctive gray siltstone unit, about 600 feet thick, overlying and overlain by thick red-bed sequences. All these rocks contain abundant volcanic debris, but the latest known igneous activity within 50 miles antedated the Nonesuch Shale. The rocks are unmetamorphosed and only moderately deformed, mainly by tilting and faults. Pyrite, presumably syngenetic, is the only prominent sulfide throughout most of the Nonesuch Shale. The basal beds of the formation, however, contain disseminated copper minerals instead of pyrite and constitute the cupriferous zone. On a regional scale, the top of the cupriferous zone cuts across bedding, and ranges from an inch or so above the base of the formation in some areas to more than 50 feet in others. However, within the cupriferous zone the distribution of copper shows remarkable stratigraphic control. Certain beds are copper-rich compared to the beds that lie between them and the differences persist throughout the White Pine region. Several darkgray thinly laminated beds in the lower 10 to 25 feet of the Nonesuch Shale are rich enough and sufficiently close enough together to constitute a mineable thickness where they lie within the cupriferous zone. Pyrite is the characteristic sulfide of the Nonesuch Shale as a whole. The principal sulfide mineral of the cupriferous zone at the base of the formation is chalcocite. The succession of minerals outward and upward from the center of the cupriferous zone is native copper-chalcocite-bornite-chalcopyrite- pyrite. The bornite and chalcopyrite are confined to a narrow fringe at the margin of the cupriferous zone. This pattern of mineral zones is believed to represent reaction between syngenetic pyrite and introduced copper. The main copper mineralization is independent of structure and apparently antedates deformation. Details of the geometry of the cupriferous zone indicate the possibility that copper was introduced from the underlying sandstone prior to lithification. The source of the mineralizing solutions and their copper is not known.

Jan 1, 1968

By John V. Beall

Early this year at the University of Arizona in Tucson, a survey was made of student opinion about the minerals industry. Over 100 of the three page questionnaires were completed and these were analyzed by the following categories: 40 Mining Engineering students, 20 Geological Engineering with 2 Geophysical Engineering students, 15 Geology students, 7 Metallurgical Engineering, 26 Underclassmen, 29 Graduate students and a composite of 84 total students. Not all of the results of the survey were predictable. After graduation there is a strong preference toward going to work in the mineral industries. The next most popular options, but trailing the first choice greatly, was graduate work or employment in another industry. A smattering of other choices were for teaching, government or research. None checked the box for drop out.

Jan 1, 1971

By J. D. A. Morrow

TO my mind the National Bituminous Coal Act so far has proved one of the unhappiest experiences that has ever befallen the bituminous coal operators of the United States. Viewed in the light of its ugly consequences everyone should recognize this measure for what it is -a weird thing as unreal as a page from "Alice in Wonderland." Indeed it might be another stanza to the tale of the Walrus and the Carpenter, with the coal operators in the role of the unfortunate oysters who were taken on that memorable ramble. It is time that coal producers open their eyes, jerk themselves out of any lingering hypnotic optimism about the price-fixing provisions of this law, demand the repeal of these corroding clauses, and then set about remedying as best they can the disastrous effects of this retromingent scheme to regulate the coal business.

Jan 1, 1939

Remarks of Mr. Robert W. Hunt, General, Superintendent, Albany and Rensselaer Iron and Steel Company., Troy N. Y.—In discussing Dr. Dudley's two most interesting papers, I feel a natural hesitancy in disagreeing with conclusions formed after such careful and conscientious work. But I think he has made his deductions from too meagre premises. The analyses of but twenty-five samples are entirely too few to justify the establishment of so important a formula. When we consider that he indirectly proposes to regulate an interest amounting, even at the present low prices, to over $20,000,000 per annum, we may well hesitate before accepting a formula based upon the chemical and physical analyses of but twenty-five steel rails. Dr. Dudley touches the keynote in referring to the proposed labors of the Government Test Commission. They based their hopes of attaining success upon the chemical and physical analyses of a very large number of samples, and in the only branch of investigation which the short-sighted policy of Congress has allowed them to complete, i.e., chain cables, we find that a dozen, twenty-five or one hundred tests gave no satisfactory results. It was only after many hundreds that they were enabled to' draw conclusions. There are so many circumstances hearing upon the life of a rail, that the task of extracting a correct result seems herculean. I presume I am right in stating that in our Northern latitudes early winter and spring months witness the breaking of the greatest number of rails, thus seeming to prove that an unstable road-bed has much to answer for. Then, again, broken and flattened wheels must be taken into account, but I am convinced that more rails have been broken by the treatment which they received before leaving the rolling-mill

Jan 1, 1879

Remarks Of Mr. Robert W. Hunt, General Superintendent, Albany And Rensselaer Iron And Steel Company., Troy N. Y. - In discussing Dr. Dudley's two most interesting papers, I feel a natural hesitancy in disagreeing with conclusions formed after such careful and conscientious work. But I think he has made his deductions from too meagre premises. The analyses of but twenty-five samples are entirely too few to justify the establishment of so important a formula. When we consider that he indirectly proposes to regulate an interest amounting, even at the present low prices, to over $20,000,000 per annum, we may well hesitate before accepting a formula based upon the chemical and physical analyses of but twenty-five steel rails. Dr. Dudley touches the keynote in referring to the proposed labors of the Government Test Commission. They based their hopes of attaining success upon the chemical and physical analyses of a very large number of samples, and in the only branch of investigation which the short-sighted policy of Congress has allowed them to complete, i.e., chain cables, we find that a dozen, twenty-five or one hundred tests gave no satisfactory results. It was only after many hundreds that they were enabled to draw conclusions. There are so many circumstances bearing upon the life of a rail, that the task of extracting a correct result seems herculean. I presume I am right in stating that in our Northern latitudes early winter and spring months witness the breaking of the greatest number of rails, thus seeming to prove that an unstable road-bed has much to answer for. Then, again, broken and flattened wheels must be taken into account, but I am convinced that more rails have been broken by the treatment which they received before leaving the rolling-mill * The remarks of the participants in this debate have been written out by the speakers, and are here given without any attempt to retain the order of the dis¬cussion. While the report does not, therefore, preserve the vigor and spontaneity of the debate, it is believed that it gains in value by giving the matured views of the speakers. The continuation of this discussion at the Pittsburgh Meeting, May, 1879 (beginning with remarks of Mr. Cloud on page 401), is appended for convenience of reference.-T. M. D., Sec'y

Jan 1, 1879

By W. S. CAYPLESS, H. O. Hofman, E. E. HARRINGTON

1. INTRODUCTION. AT the Lake Superior meeting, September, 1904, Messrs. A. Gibb and R. C. Philp presented a paper entitled " The Constitution of Mattes Produced in Copper Smelting,)' in which they concluded that ferrous and cuprous sulphides formed the chemical compound, 5 Cu2S, fee. They arrived at this inference from the observed fact that a matte containing Cu2S, 90.4, and Fee, 9.6 per cent (or, in round figures, Cu2S, 90, and Fee, 10 per cent.), did not contain any metallic copper, while one with more than 10 per cent of FeS readily dissolved copper, and with less than this amount retained copper in mechanical suspension. Although they determined the melting-points of five mattes containing from 32.6 to 80.1 per cent of copper, they did not draw a freezing-point curve, as the necessary apparatus was not available. A microscopical examination of 11 polished samples, gave them a grayish-black field of very uniform appearance, except that 5 of the specimens showed the presence of metallic copper. The object of the present investigation was to supplement the above paper by drawing the freezing-point curve of the series ferrous sulphide cuprous sulphide, and to see how the constitution could be further, revealed by microscopical work. The results obtained lead to conclusions very different from those of Gibb and Philp. While their paper bears the date 1904, it was published only in 1906.2 In the meantime, Bolles3 had presented his paper, "The Concentration of Gold and Silver in Iron Bottoms." The raw material which formed the basis of the research was a matte containing Fe, 61.68, and Cu, 11.20

Jan 1, 1907

By Richard J. Lund

Stock piling-and by that I mean well-organized stock piling on a substantial scale-is almost as old as the hills themselves. It was back in early Biblical times, as recounted in the Book of Genesis, that Joseph was charged by Pharaoh with the responsibility of stock piling food during the seven years of plenty to guard against the seven subsequent years of famine that were revealed by the Pharaoh's dream. And this same policy of storing up food or materials to provide for future anticipated emergencies can be traced repeatedly down through the ages. So our own efforts are anything but new. Our modern concept of stock piling-the purchase and storage of strategic materials to assure supplies needed in time of some future war- stems from our experience in World War I. In 1920, the War Department was charged by Congress with the responsibility of procuring all War Department supplies and mobilizing industry in the event of another war. During the two decades that followed there were many authoritative studies made of our deficient mineral problem, all of which pointed out the urgent necessity of stock piling certain strategic materials as a reserve against future war. One such study, made in 1925 through the combined efforts of the Mining and Metallurgical Society and the AIME, was done at the ex- press request of the War Department. Eight years later another more de-

Jan 1, 1949

By T. H. Oxnam

INTRODUCTION. THE predominating value of the ores now being treated by the Palmarejo and Mexican Gold Fields, Ltd., is silver, although some gold is also carried. The present method of treatment consists of wet-crushing and concentrating, followed by the cyanidation of the unroasted sands and slimes. The sands are treated by leaching and the so-called accumulated slimes by a system of agitation and decantation. It is only within very recent years that the cyanidation of unroasted silver-ores has been commercially successful. In fact, at the time operations were begun at the cyanide-plant at Chinipas, February, 1902, I knew of no other leaching-plant treating similar ores successfully. The cyanide treatment of the Palmarejo ores differs but little from the ordinary practice in cyaniding gold-ores; and perhaps but little, if any, new information concerning the metallurgy of silver is to be gleaned from it. PALMAREJO MINE. The Palmarejo mines are located in the southwestern part of the State of Chihuahua, Mexico, on the foothills of the Sierra Madre mountains, at an elevation of 3,200 feet. The mills, 12. miles distant, are situated on the Chinipas river, near the town of Chinipas, which is about 150 miles northeast of Agiabampo, on the Gulf of California. Supplies are shipped via this port as this route is the best and most direct to the property. The ore-bodies in the Palmarejo mines have been deposited. along a series of rock-fractures, caused by an intrusion of eruptive rock. The most important of these fractures or fissures, both in width and value, are the Prieta and Blanca veins, which.

Jul 1, 1905

[Pumps: oil-well: plunger: essential parts, G26, 130; 74, 828 improved type, 74, 846 leakage, 74, 837 operating cycle, 74, 833 Uren design, G26, 145 sucker-rod failures, G26, 136 sucker-rod stress, 74, 835 sucker rods, 74, 830, 832 tubing, 74, 833 tubing difficulties, G25, 138; 74, 836 Olivite, 73, 337 valve and seats, 74, 832 Punching: Monel metal, 78, 86 nickel, 78, 86 Punjab. See Indian Empire. PUPIN, M. L biography, M26, 113 John Fritz medalist, 1931, M81, 499 recipient of Washington Award, M28, 155 PURDY, R.: Discussions: on Relative Efficiencies of Domestic Fuels in Relation to Their Costs and Their Advantages 108, 353 on Uses on Coal in the Ceramic Industry, 108,389,398]

Jan 1, 1936

By Cornelius F. Kelley

EVERY man connected with the mining industry should take a significant pride in the fact that he belongs to an industry and to a profession that, from the beginning, has been constructive. The miner digs his ore and he gives the metal to art, to industry, and to commerce. The nature of our business is destructive only in that we deal with a wasting asset. That should be a source of great pride to those who belong to the profession. But unfortunately, the product of our mines, our smelters, and our re- fineries does not always go to constructive purposes. There are times when, in the administration of the affairs of men, our product chiefly goes to purposes which are destructive. When we look upon the panorama of horror that is being enacted throughout the world today, we wonder whether any effort toward the development of civilization and culture and education and well-being has been worthwhile. We are appalled to see the things that have been developed, through the application of science, toward progress and efficiency, now used for the catastrophic destruction of those things which are the most valuable that man has built. We must find hope that this is but an episodic thing; that it must, in the infinite wisdom of the Almighty, usher in a period of peace and progress, of civilization and development that will make man's existence upon earth worthwhile.

Jan 1, 1941

By R. C. Neavel

One of the most important requirements to be met by any coal producer is delivery of size consists tailored to specific applications. Generally these specifications include a minimum as well as a maximum size limit. The customers of a major Indiana coal producer noticed that some shipments of sized coal contained a large proportion of undersize pieces. Also, in these shipments, the pieces which remained within the specified limits were cracked and, when handled, crumbled readily. The producer, certain that these shipments had been properly sized at the tipple, suspected that degradation had occurred in transit. The Indiana Geological Survey was requested to examine the coal from one of these shipments to attempt to determine the cause of breakage. Two basic facts about coal and coal seams led to the employment of petrographic techniques in this investigation. First, all coal seams consist of accumulations of diverse organic and inorganic constituents; and second, most coal breakage, either desirable or undesirable, can be attributed to the inherent weakness of some of these constituents or to poor adhesion between certain constituents. Analyses of degraded coal Sampling: Samples were secured from 2 stock piles of 2-by 4-inch coal in a dealer's yard. The coal in both piles had received the same treatment from mining to storage, although it had been mined and shipped on two different days. The size consist of one pile, however, appeared smaller than that of the other. The sample from the degraded pile is referred to as the slack sample, and the other is called the unslack sample. Size analyses: In order to determine the actual size consist, the samples were screened, with a minimum of rough handling, on square 2-inch, 1-inch, 1/2-inch, and 12-mesh screens. It is assumed that 100 percent of the 2-by 4-inch coal is retained on a 2-inch round screen at the tipple. Analyses of several loads at the tipple indicate that approximately 26 percent of the 2- by 4-inch coal, 100 percent of which was assumed held on a 2-inch round screen, passed through a 2-inch square screen. Twenty-six percent may be taken as the normal difference between round and square screens. Results of the analyses of stockpile coal are shown in Table 1. Cumulative percent versus size are plotted on a Rosin-Rammler chart as Figure 1. Both samples approximately follow normal size distribution; this indicates that breakage is not size preferential and also that the samples are representative of the stockpiles. Although both samples exhibit the same general size distribution, the median size of the slack sample is considerably smaller than that of the unslack sample. Fifty-five percent of the unslack sample was undersize (29 percent greater than the normal 26 percent difference), and 83 percent of the slack sample was undersize (57 percent greater than the normal 26 percent difference). Both piles contained a greater percentage than normal of undersize coal; this indicates that they were both affected by degradation, but to a different degree. Bedding-plane analyses: Coal, because of its laminated nature, will break preferentially along bedding planes, especially where adjacent constituents are poorly cemented to each other. Subsequent breakage perpendicular to the

Jan 1, 1961

By Open-Hearth Steel

I received a telegram yesterday from Mr. J. H. Nead saying that he regretted circumstances had come up which prevent his attending the meeting, but that arrangements have been made and Mr. T. S. Washburn, of Inland Steel, will act as the Co-Chairman in his stead. We are sorry, of course, that he cannot be here at this conference. We have, therefore, asked Mr. James J. Bowden, chief metallurgist of Republic Steel Corporation, Cleveland, to act as Chairman and Mr. Tom Washburn to act as Co-Chairman. I will turn the meeting over to these gentlemen at this time.

Jan 1, 1940

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult's law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult's law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.' One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys' revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult's law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.' Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957