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By R. B. Schluter, M. M. Fine

A process for winning copper from pelletized chalcocite concentrate without matte smelting and converting is under development at the Twin Cities Metallurgy Research Center of the U.S. Bureau of Mines. The new procedure includes a two-stage fluid-bed treatment in which the pelletized concentrate with 33% Cu and 7% S is first desulfurized to about 0.5% S in an oxidizing atmosphere, and then metallized by reduction with hydrogen. The reduced product is melted with flux to separate metallic copper from the gangue. The metal must be refined to remove residual sulfur and iron. The pelletizing of the fine concentrate into mini-pellets prior to fluid-bed treatment is an important feature of the process, because it permits shorter reaction time, decreases dusting, and facilitates subsequent processing.

Jan 1, 1972

By Samuel L. Hoyt

THIS paper gives a short account of plastic deformation as observed in single crystals of zinc, zinc having been selected for the experiments described herein because the phenomena are comparatively so simple and can be studied throughout such a wide range. It is hoped that the paper will serve to show the type of information which studies of single crystals afford and will contribute toward the solution of the general problem of metallic behavior. PRODUCTION OF ZINC SINGLE CRYSTALS The method of Czochralski,1 as modified by von Gomperz,2 was used to produce the crystals studied. The equipment is shown in Fig. 1. Molten zinc is held in a crucible at a temperature which is not far above its melting point, as measured by a pyrometer. A lava disk floats on ,the melt, and is provided with a central hole about 1 mm. in diameter. A glass tube, drawn into a capillary at the lower end, is suspended from a string which is wound up by an electric drive at the speed desired. At the start, the glass capillary is let down into the melt and the hoist is started.. The capillary brings up a small quantity of molten metal with it to a point just above the lava disk. At this point, a jet of hydrogen cools it and causes it to crystallize, with the result that a small crystal forms. As the hoisting is continued, more molten metal is drawn up, in turn to be solidified by the jet of hydrogen. This additional metal continues the growth of the crystal already formed, and a long, cylindrical crystal results. The speed of hoisting used was generally between 0.1 and 0.5 mm. per sec., and the crystals were from 4 to 6 in. long and about 1 mm. in diameter. By varying the conditions, crystals of quite different orientations were obtained and were used in the study of the phenomena to be described.

Jan 1, 1927

1910, hundreds of thousands of dollars of work and equipment in a 1500-foot shaft, crosscuts and pumping had found only copper-lean pyrite in two cross- cuts, and nothing in a third. Going aimlessly along the third crosscut one day, after looking at the barren face I happened to notice a dark spot in the white limestone, near the floor on one side. I picked, and found it was a little triangle of rich chalcopyrite. Next day I took Bill Gohring, then mine superintendent, in to see it. He said nothing else had succeeded so we might as well try that. The new drift broke into a full face of high grade copper ore in the first round, and continued in rich ore for 2200 feel broken only by a couple of short stretches of lean pyrite. The earlier crosscuts had happened to cut these lean areas. Q: Was there any single thing that called your attention to that little dark spot in the side of the Briggs crosscut, rather than to any other discolored spot? Joralemon: Nothing very definite. Maybe luck, maybe that indefinable subconscious thinking that

Jan 9, 1964

By H. Kahata, I. Iwasaki, Y. Takahasi

A combined process of segregation roasting-flota-tion or magnetic separation was developed to recover nickel from lateritic iron ores and oxidized nickel ores. An ore was mixed with a halide, such as sodium or calcium chloride, and a solid reductant, and roasted, whereby the nickel content was segregated out as discrete metallic particles. Either by magnetic separation, or by flotation using a sulfhydryl collector together with a heavy metal salt as an activator, the metallic nickel could be concentrated, Effects of such variables as the types and amounts of the halide and solid reductant addition and of the roasting conditions were extensively investigated. The concentration results on several types of ores from Japan, the Philippines, and New Caledonia are presented. Laterite is a residual product of rock decay in tropical and subtropical regions, and consists mainly of hydrated oxides of iron and alumina. Those derived from serpentine sometimes become enriched in nickel, cobalt, and chromium contents. Oxidized nickel ores are of the similar origin, but their nickel as well as silica contents are higher due to gamierite-type silicates. Apparently, nickel enrichment is more pronounced in the transition region between the surface layer of iron laterite and the underlying serpentine. Iron laterites often contain over 50% iron, and their reserve is reported to exceed 22 billion tons, corresponding approximately to 20% of the world iron ore reserve.1 It is readily apparent, therefore, why the iron laterites have attracted much attention of the steel industry as a potential source of iron ores. Numerous attempts to remove nickel and chromium as byproducts, have been reported in literature.' Worldwide discoveries of high-grade iron ore deposits in recent years have inevitably lessened the interests in iron laterites. However, in view of the tremendous potential for their gross value and supplies of nickel, cobalt, chromium, and alumina along with iron, the problem remains as a challenge. Much of the chromium in laterites is present in the form of relatively coarse particles of chromite, and various classification methods have successfully been applied for its removal.2,3 The nickel, however, is intimately associated with limonite, and ordinary concentration techniques are totally ineffective. Much attention has, therefore, been given to hydro-metallurgical or pyrometallurgical means. Yet, all the known processes appear to have limitations either economically or for the use of products as iron raw materials due to a high residual content of nickel. Some attempts have been made to pre-roast laterites or oxidized nickel ores, particularly with sulfidizing agents, and to remove nickel either by magnetic separation,' or by flotation.4 It is apparent that any such concentration process would require grain growth of nickel during roasting for effective separation. Oxidized copper ores are reported to be concentrated by the segregation roasting-flotation process,5 in which the ores are roasted with a chloridizing agent and a carbonaceous reductant in order to promote the growth of metallic copper through repeated cycles of copper chloride volatilization and its reduction on the solid reductant surfaces. Examination of a vapor pressure-temperature diagram of various metal chlorides indicates that a separation of nickel from iron may be effected by a similar process. In fact, the segregation roasting of laterites was reported to increase the extraction of nickel by the ammonia leach process, as compared to the ordinary reduction roasting.6 In the present article some of the preliminary experimental results of the segregation roasting, followed by either flotation or magnetic separation, on laterites and oxidized nickel ores are reported. The effects of various parameters in the roasting as well as in the concentration steps are discussed. MATERIALS AND METHODS An oxidized nickel ore from Thio, New Caledonia, and three laterites from Homonhon, the Philippines, Wakasa and Miyagawa, Japan, were selected for the

Jan 1, 1967

By Robert Glass Cleland

IN gathering material for this book, I have made extensive use of the archives of Phelps Dodge, contemporary news- papers, and a wide range of secondary sources. Two manuscripts-one on the history of Phelps Dodge by Arthur Train, Jr., and John L. Lawler, the other a biography of William E. Dodge by Richard Lowitt-have been of the greatest value. I owe a particular debt to the authors whose names I have just mentioned. I have also gathered important information and obtained revealing points of view from conversations with many people. Personal visits to the company's mines and plants added knowledge and understanding that nothing else was able to supply. I am greatly obligated to the officers of the company, especially to Mr. Louis S. Cates, chairman of the board of directors, Mr. Robert G. Page, president, Mr. George R. Drysdale, vice-president of Phelps Dodge Corporation, and Mr. Walter C. Bennett, president of Phelps Dodge Refining Corporation, for their co-operation and assistance. Mr. Wylie Brown, former president of Phelps Dodge Copper Products Corporation, also supplied valuable data and deeply appreciated hospitality. In my visits to the Phelps Dodge properties, company representatives extended every hospitality and placed at

Jan 1, 1952

By Robert E. Sorenson

EXPLORATION for deep-seated orebodies in the Silver Belt area of the Coeur d'Alene mining district is complicated by meager surface expressions of diagnostic criteria, lack of knowledge of the significance of specific alteration phenomena, and the great expense involved in the exploration for ore shoots, the tops of which often occur near sea level elevation or below and as much as 4000 ft or more below the surface. Except for the early studies of Ransome and Calkins in 1903 and 1904,[1] little geological work was done in the Coeur d'Alene district for many years, and it is only during the last 15 to 20 years that complete and careful geological mapping has been applied to most of the mines in the area. Much early information, which now would prove invaluable, is lost in hundreds of miles of caved and inaccessible mine openings not mapped by mining geologists. In more recent years mining geology has become a tool of greater use in the district, and some measurable progress is being made in the accumulation of observations that are adding gradually to the knowledge of ore deposits in the district.

Jan 7, 1951

By D. B. RUSHJIORE

(New York -Meeting, February, 1912.) TORCHES were used by the early Romans for mine-lighting, and these were followed by open lamps or earthen jars filled with tallow or oil, and later by candles. In early coal-mining, explosive gases seldom occurred, and, if they were encountered, the danger of explosion was materially diminished by the absence of any ventilating-system and the consequent insufficient circulation of air to form with the methane an explosive mixture. As the art advanced, the danger of fire-damp became more apparent, and methods for testing the air were resorted to as early as in the fifteenth century. The method of testing consisted in lowering a clog in a, basket down the shaft. As soon as he encountered fire-damp he would commence to howl, after which he was withdrawn, and a leafy bush was fastened to the end of the rope and run rapidly up and clown the shaft. This so disturbed the accumulation of gas as to cause it to rise out of the shaft. Later this odd method of testing was improved upon through the discovery that a light inserted in a body of fire-dam p would produce a blue flame. Candles were used for this purpose, and, when fire-damp was thus discovered, brushing or some other primitive method of fanning was resorted to for driving out the gas. In some instances the gas was burned away, regardless of the danger thereby incurred. A man, wearing a well-moistened coat and a mask with glass spectacles, descended in the mine a few hours before each shift. With a long stick, to which was fastened a burning torch or candle, lie would crawl on the floor with the stick so raised that the light would sweep the roof and ignite the gas which it encountered. In this position the flame of the explosion would pass over him, after which he would retreat from the gases resulting from the combustion. The occurrence of serious accidents resulted in

Jul 1, 1912

By N. B. Davis

I. Introduction. II. Definition of Plasticity. III. Theories of Plasticity. A. Structure of the clay particles. (1) Fineness of grain. (2) Plate structure. (3) Interlocking particles. (4) Sponge structure of particles. B. Presence of hydrous aluminum silicates. C. Molecular attraction between particles. D. Presence of colloidal gelatinous matter. (1) Review of theory of colloids. (a) Suspension colloids. (b) Emulsion colloids. (2) Experiments. IV. The Formation of Clays. A. Residual clays. B. Transported clays. V. Summary. VI. Conclusion. I. IntRodUction While working with a number of very sticky cracking clays from western Canada the writer became interested in a study of the cause of the excessive plasticity. This led to a review of the rather bulky literature on the subject and the finding that plasticity still remains to be satisfactorily explained. Most of these investigations seem to have been carried on solely from the chemical viewpoint, the geologic aspects having been ignored. In nearly every case, the investigators have worked with the higher-grade clays of low to medium plasticity, such as the kaolins, the excessively plastic ones having generally been neglected, partly because of their limited application, yet the author believes that these are

Jan 1, 1915

By Arthur Bell

(San Francisco Meeting, September, 1915) . PRIOR to 1908 the oil production in the State of California, had been almost entirely a heavy fuel, oil, with a high flash point, hut changed within a-short period to a large percentage of refining oil with a low flash, by reason of the coming in of the Santa Maria field, the Midway field, and the increased production of the Fullerton field. This is clearly shown in the following tabulation of California's production: Year Barrels . Below -20° Be, Above 20° Be,, Per Cent_ Per Cent. 1905 48,307,000 90 10 1910 77,698,000 SO 20 1912 90,075,000 6o 31 1914 10:3,600,000 47 53 The bringing in of these high percentage's of light oil with their dangerous low flash and the increasing demand for the refined products necessitated the devising of some cheap and efficient means of quickly separating the lighter elements either in the field or at the main distributing points; also it became necessary to remove the excessive percentage of water which many of the light oils carried in emulsion.

Jan 9, 1915

By W. L. Honnold

AS BOTH South Africa and diamond mining are unfamiliar subjects it seems best that on such an occasion as this I should endeavor to reflect the atmosphere of the place and to picture the mines from an industrial rather than from a technical standpoint and, because of long absence, my remarks must necessarily be sketchy and in some particulars not up to date. The preferable route to South Africa is via England, direct steamers from America being inferior as to service and effecting no saving of time. The newer boats are of about 20,000 tons capacity and very comfortable. Seventeen days are required for the voyage and only one stop is made-that at the island of Madiera, three days out. Between Southampton, the port of departure, and Madiera the weather may be warm or cold and the

Jan 1, 1925

By Harry L. Washburn, Robert L. Llewellyn, W. J. Halvorsen

Many of the problems that occur in the preparation plant originate from practices in the mine. Impurities in raw coal can be in the seam itself or from extraneous material taken in mining from the roof or bottom. In the case of underground mines, the choice of mining equipment will affect the size consist and the amount of extraneous material included with the coal. Also, governmental regulations concerning the degree of rock dusting, gobbing underground, and cleanup have increased the dirt in raw coal. Sulfur dioxide emission standards, on the other hand, are pressuring the coal industry to clean coal more thoroughly. Coal supplied for coking purposes is nearly all upgraded by washing, while for the largest market, electric power generation, a high proportion is shipped as a raw product with processing, in whole or in part, only necessary when excess impurities are mined with the coal. This chapter will deal primarily with plants that process or wash coal to some extent (Fig. 1) and only incidentally with mines shipping raw run-of-mine coal crushed to a top size of, usually, 51 to 102 mm (2 to 4 in.), with little, if any, other treatment. JUSTIFICATION FOR COAL PREPARATION During the past decade, major changes have occurred affecting the market, profit, and long-range planning of the coal industry. Mining companies have become "partners" with consumers at many new and some old mines, both for steam and metallurgical coals. Coal properties have become "assigned" tonnages at mutually agreed upon conditions and prices. Lower unit-train tariffs have been instrumental in helping coal markets to compete against oil and nuclear energy. Coal prices for power plants are still on a Btu (British thermal unit)

Jan 1, 1981

By P. W. George

THE rapid increase in cost of discovering new orebodies by churn drilling in the Tri-State district has led to some attempts to lessen the expense by using geophysical methods. Electrical prospecting was tried three or four years ago, but no successful results were recorded. In 1926, the Federal Mining and Smelting Co. engaged the North American Exploration Co., of Houston, Texas, to make some tests with the torsion, balance. At first, it was thought that the most favorable conditions for discovery of ore deposits with the torsion balance would be in locations where the ore was known to occur at rather shallow depths, FIG. 1.-CROSS-SECTION OF DUENWEG LEASE. therefore the first trial was made at Duenweg, east of Joplin, where some zinc ore had been developed at a depth of 130 ft. The gravity gradients at 61 stations on a tract of about seventeen acres indicated plainly one large zone of maximum gravity and a smaller narrow zone of minimum gravity. Fourteen churn-drill holes, half of which struck .ore, show that all the ore found was located outside the zones of maximum and minimum gravity. In the zone of maximum, gravity the limestone beds were closest to the surface, and the first chert beds encountered were at the greatest depth. The results (shown in Table 1) indicated that the gravity of the limestone was greater than the gravity of the fractured chert together with its orebodies, and probably also greater than the bouldery soil and clay on top of the limestone. A cross-section of the Duenweg lease is shown in Fig. 1.

Jan 1, 1928

By E. E. Schumacher

IN a laboratory devoted to the furtherance of the science of communication, the breadth and variety of the problems encountered are challenging to a metallurgist. In my own long association with the Bell Telephone Laboratories, our metallurgical group has dealt with a vast number of alloys, both ferrous and nonferrous, and with many materials in the border range of metallic properties., The objectives of our design engineers embrace every phase of telephony, and the properties they desire in metals are generally unusual, frequently unique, and often conflicting. Commercial alloys have not always been available with properties to meet a special requirement in the telephone plant, and many alloys have had, therefore, to be custom-made. Anyone who has had the opportunity to observe the results of tests of all types on numerous such alloys, both commercially and specially produced, or who has taken part in the development of an alloy of some necessary, but new or unusual combination of properties, could not fail to be impressed by the frequency with which a desired goal has been reached or adequately approached through the presence of decimal quantities of alloying elements. Nor could One fail to be struck by the occasions when, conversely, of a minute amount Of impurity element has rendered an alloy useful. It is no exaggeration to state that the content be- hind the decimal point often spells success or fail-ure, and the critical content is sometimes far to the right of the decimal point as I shall later illustrate. The great effects of small additions have long been recognized and have, in fact, been described by many investigators. The importance of the minute, however, cannot be overemphasized. Therefore, in this discussion, I propose to illustrate for you some of the startling instances, drawn primarily from our own experiences, wherein small, even vanishingly small, proportions of stranger elements in otherwise common aggregates have com-pletely changed the customary pattern of behavior. No one property has a monopoly as to being dis-proportionately affected by minor elements. Nearly all properties are affected, but there is time here to include only a selected few. I have chosen, there-fore, three of general interest: strength, magnetic, and electrical properties. I shall inquire into both the mechanisms and consequences of these disproportionate effects and try to share with you the fascination and challenge of this field. Strength Properties of Lead and Lead Alloys To illustrate the effect of the minute on strength properties I have selected lead and its alloys, with which we have worked extensively for many years. Lead has the advantages of being available in quantity in a state of high purity and of being fairly easy to melt and fabricate without contamination to any extent detectable by the spectrograph. It has the interesting disadvantages of recovery and recrystallization at room temperature. Whether I

Jan 1, 1951

Body Hoists A complete new line of hydraulic dump truck body hoists and bodies featuring many outstanding design improvements has just been announced by St Paul Hydraulic Hoist Fourteen models of this new hoist are available in a selection of capacities from 6 to 25 tons The new body hoist features low standard mounting height, advanced lifting point, new low operating oil pres [ ] sures, a new Uniflex subframe, friction-free roller bearing drive mechanism, including pump and power takeoff, to insure quiet operation and long trouble-free life A stress-eliminating design feature of the new hoists absorbs dumping shocks and permits use of a new principle in hoist design a flexible subframe which ends tendency of rigid hoists to crack or bend when flexed Circle No. 1 Combination Drill A new combination drill offering all three methods rotary, auger, and percussion drilling on the same rig is the revolutionary feature of the latest drill rig designed by Mobile Drilling Inc The B-36 drill is larger, more powerful and versatile than previous models built by this company This new drill has a hydraulic feed of approximately 8000 lb pressure The hydraulic feed cylinder is located directly over the rotary turn table The carriage of the drill is of tubular construction The drill mast, also of tubular construction, nests in the tube members of the drill carriage for cross-country travel with a maximum overall height of 10 ft The drill mast telescopes together with the feed cylinder hydraulically to an operating height of 16 ft The drill can be furnished with an auxiliary cat head, sand reel, and special high pressure water pump The B-36 maximum depth for auger drilling without water is approximately 150 ft, depth for rotary drilling with water is in excess of 300 ft Circle No 2

Jan 1, 1952

By B. M. Blake, R. S. Reppert, A. F. Keiser, E. J. Trinkle

The southern West Virginia coalfield was formed in a rapidly subsiding depositional basin associated with deep-seated growth faults. Subsidence began to the southeast during deposition of the Pocahontas Formation, and then shifted to the northwest during deposition of the New River, Kanawha, and Allegheny Formations. Rocks of all the coal-bearing formations grade into massive sandstones to the northwest. For the No. 3 Pocahontas, Sewell, Campbells Creek, and No. 5 Block coals discussed in this study, the overall sulfur and ash values of each coal seam increase gradually toward the northwest. The thickness of each coal tends to increase toward the southeast. These trends are partly a reflection of the differential subsidence of the coal basin along with varying degrees of peat accumulation and degradation. The northwest side of the coal swamps underwent relatively less subsidence and, thus, more degradation due to increased aerial exposure, with a resulting increase in the sulfur and ash values of the coals, and a decrease in the thickness. The open sea existed to the west of the coal swamps, and this marine environment also contributed to the higher sulfur values to the northwest. Coals of the Pottsville Group in the southern West Virginia coalfield generally have sulfur values between 0.6-1.0% with some as high as 2-3% on the northwest edge of the coal basin.

Jan 1, 1983

By Wayne Loel

THE application of aerial photographs to all phases of geologic mapping is set forth, indicating the advantages to be gained in different types of country and under varying climatic conditions, Methods of field and office procedure are given from a geological point of view, as well as suggestions regarding the best methods of aerial mapping for different uses and under varying field conditions, including the study of submarine geology. Aerial photographs with accompanying geologic maps are shown to illus-trate the appearance from the air of different geologic features under varying climatic and topographic conditions.

Jan 1, 1938

By C. W. Davis

THE name fuller's earth, which was derived from its early use in "fulling" or removing grease from woolen goods, is a term that is generally considered to designate mineral matter, containing hydrous aluminum silicates of the clay group, which has a high capacity for removing colors from oils, whether of animal, vegetable, or mineral origin. Fuller's earths are usually dried and may be "tempered" by heating or may be treated with water or reagents to improve their efficiency. For our purpose the term "acid-treated earths" will include those products from the partial decomposition of mineral water -by acid which are equal to or more efficient than an untreated fuller's earth from Quincy, Fla., when used in bleaching mineral oil by the "contact" process. In general, the contact process for treating oils consists of heating and agitating a mixture of oil and finely divided adsorbent, the latter being subsequently removed by filtration. The term "adsorbent" is used because, although there has been a great deal of controversy over the mechanism of removal of impurities from oils by mineral matter, there is no doubt that adsorption, which involves the surface of the solid, plays a major part.1 The properties that make fuller's earth useful in the treatment of petroleum products by "percolation" and in the purification of edible oils by the contact process have long been studied, but the comparatively recent adaptation of the contact process to the bleaching of petroleum products has made desirable the further investigation of fuller's earth and other, adsorbent earths.

Jan 1, 1929

By FRED T. WILLIANS

INTRODUCTION. THE Park City mining-district is distinctively a camp of few properties, 5,000 acres, or one-third of the entire district, being under the management of but three companies. As a rule, the ore-bodies lie deep, with no outcrop, except where erosion has formed the deeper canyons and gulches. Ontario canyon exposed the famous Ontario ledge, and Woodside gulch showed the first ore of the Silver King Coalition mine. The Quincy ore-bodies were first brought to light in upper Empire canyon, and Thaynes canyon was instrumental in aiding the prospector during the early days of the camp. There are 22 shafts which have reached a depth of at least 500 ft., ten a depth of 1,000 ft., five a depth of 1,300 ft., and two a depth of 2,000 ft. The amount of lateral development has been proportionally extensive, including six long tunnels, four of which are in 3 miles, with a fifth now being driven. The Ontario lower drain-tunnel is now more than 4 miles long. The formations are sedimentary, dipping about 30° NW. and N., and traversed by many fissures, dikes, and faults. The principal ore-bodies are found associated either with the contact of the basal Ontario quartzite and the overlying limes, or on a quartzite stratum within the limes, or in the fissures, or along some of the porphyry dikes. The district covers the intersection of the Uintah and Wasatch ranges, which explains the existence of large folds and faults, and fissures of great length, width, and depth. In a general way, the geology of the district consists of a basal quartzite dome, which has been exposed by erosion at the Ontario property. The Ontario fissure lies entirely within this formation. Flanking this dome on the west, north, and east lie

Jun 1, 1911

By G. R. Love, M. L. Picklesirner

THE use of color adds a new beauty, power, and versatility to metallography. This has been amply demonstrated in a number of public exhibits and on the walls of corporate, government, and university metallographic laboratories around the world. Indeed, in a number of cases, the color not only is of esthetic value but is scientifically essential to the competent examination of particular samples and systems. Optical strain analysis,' determination of true grain size in U-A1 alloys: phase identification in Nb-base alloys,3 analysis of transformation rates in heat-treated Nb-Zr alloys,4 measurement of solidification segregation in cast Nb-Zr alloys,' study of the intermediate phases in Nb/Sn diffusion couples,6 investigation of the oxidation kinetics at various surface orientations in single crystals,7'8 and a number of other research efforts9'10 would have been vastly more difficult without the extra clarity and distinction introduced by color—either the colors resulting from particular polarized light techniques or the interference colors obtained by oxidation. It is unfortunate that the beauty of colored micro-structures cannot be shared more widely, but the economics of publishing a technical magazine apparently prohibits color plates except under extraordinary circumstances. It is doubly unfortunate that no convenient, general method exists for communicating the information available in colored microstructures to the scientific community. True, in some instances the color changes observed are dramatic enough that direct black and white photography is adequate. In photoelastic stress analysis, several orders of interference fringes may be produced and it is frequently desirable to suppress the color effects (use monochromatic light) to simplify interpretation. On the other hand, relatively minute color variations may be readily detectable by eye, be of considerable assistance in interpreting a structure, and yet be enormously difficult to reduce to an unambiguous black and white print. In order to illustrate a possible compromise or solution to the above problems, we wish to show three black and white photographs of the same region of an Nb/Sn diffusion couple whose interpretation depends heavily upon use of color techniques. These micro-structures were obtained from a section through a rod consisting of commercial-purity niobium tubing filled with 99.995 pct Sn (melt-filled in 10"6 Torr vacuum). The composite rod, measuring 500 mm long, was bent into a hairpin shape and inserted into water-cooled copper grips in a vacuum high-temperature furnace. The rod was outgassed for 2 hr at a furnace temperature of 800°C and was further heated by self-resistance using a 2.2-kva ac power supply. The rod was raised to 1910°C over a 4+-hr period, held for 15 min, slow-cooled to 1500°C over a -hr period, and free-cooled to room temperature (all temperatures were measured with W5Re/W26Re thermocouple). Throughout the heat treatment the ambient pressure was kept below 8 x lo-' Torr. Metallographic preparation of the sample was completely conventional except that it was necessary to extend the grinding steps to remove damage in the brittle NbsSn phase introduced by sectioning. No satisfactory chemical or electrochemical etch has been found for these diffusion couples; of those which have been tried, any that attack the niobium-rich phases at all attack the tin-rich phases disastrously. However, the final polishing steps did produce a slight relief effect and this, coupled with anodizing, yielded excellent clarity in the microstructures for direct observation. The anodizing voltage was chosen to give maximum change in color per unit change in composition. In this case, indeed normally, this maximum sensitivity occurred in the blue-to-red color range. The pure niobium tube wall anodized to a relatively bright blue

Jan 1, 1967

By E. A. Gulbransen, K. F. Andrew

Thermodynamic information on the solubility of hydrogen in exothermic metals is limited. Thus, the overall solubility decreased as the temperature rose, which suggests the heat of solution of hydrogen in the metal is negative; yet the terminal solubility in the metal phase increased, which suggests an endothermic reaction. A thermodynamic analysis, therefore, was made of the several equilibria involved when hydrogen dissolved in the metal. Equations were derived expressing the solubility, terminal solubility, and decomposition pressures of hydrogen in terms of the heat, entropy, and free energy of solution of hydrogen in the given phase. The relations between the thermodynamic functions for the a-zirconium and 8-hydride phase were developed. The thermodynamic quantities were determined experimentally by the measurement of the decomposition pressures over a broad composition and temperature range. Two new methods of analyzing the experimental data were developed for determination of the terminal solubility. STUDIES', ' of the impact strength of zirconium at room temperature indicated that small quantities of hydrogen, of the order of 10 parts per million, embrittles the metal. Micrographic' and X-ray diffraction' studies showed this embrittlement to result from the precipitation of a second phase upon slow cooling. These studies suggested that the terminal solubility of hydrogen in the metal phase increased with increase of temperature. This behavior appeared to contradict the effect of temperature on exothermic hydrogen occluders such as zirconium. For these metals, the solubility of hydrogen should decrease with increase of temperature. Before these facts could be understood, a thorough analysis of the several equilibria was essential. It was the purpose of this paper to consider the several equilibria involved when hydrogen was reacted with zirconium from both the theoretical and experimental points of view. Since the overall solubility of hydrogen in the metal has been considered by a number of workers, it was proposed to study the composition range 0 to 6 atomic pct H in detail. Literature Schwartz and Mallett' determined the terminal solubilities of hydrogen in the metallic phase from diffusion studies. They extrapolated concentration-penetration curves to the boundary between the solid solution phase and the hydride phase at the surface. Their results showed values of 2.6 atomic pct at 400°C and 5.2 atomic pct at 500°C. Extrapolations of the data to room temperature suggested very low values for the terminal solubilities. This study confirmed the hydrogen embrittlement results and indicated that the terminal solubilities increased as the temperature was raised. The solution of hydrogen in zirconium over the complete concentration range was studied by Hall, Martin, and Rees3 and by others. The results showed that hydrogen was absorbed up to a maximum composition of 66 atomic pct or ZrH This composition represented the t-hydride phase. The maximum amount of hydrogen absorbed increased with pressure and decreased with temperature. Due to this temperature behavior, zirconium was classed as an exothermic occluder." In 1930 Hägg studied the crystal structures of the Zr-H alloys over a broad composition range. Four hydride phases were found. However, the range of homogeneity of the several phases was not studied. Gulbransen and Andrew" recently studied the phase diagram of this system by X-ray diffraction methods and by a thermodynamic method based on decomposition pressure measurements. The results showed that only two hydride phases existed for low temperatures, the 6 and the .-phases of Hagg.' Both phases had broad regions of homogeneity. The lower limit of the two-phase region of a and d-phases suggested a terminal solubility of 4 atomic pct at 500°C. This value was in agreement with the results of Schwartz and Mallett.' To avoid hydrogen embrittlement at low temperatures, it was necessary to heat the metal in high vacuum at elevated temperatures. To choose the conditions of temperature and high vacuum, it was

Jan 1, 1956