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By Thomas Read

AMONG the large number of deep mines in the world there are several which do not differ much in depth. The St. John del Rey mine, in Brazil, has reached a vertical depth of 6726 ft. below the top of its shaft; miners enter it, however, through an adit which intersects the shaft 324 ft. below its top, wherefore it might be said that the mine is really only 6400 ft. deep. In the Kolar gold field of India there are a number of deep shafts, one of which reaches to a vertical depth of 6140 ft. below surface. In South Africa also there are a number of deep shafts, the Village Deep being 6100 ft. early in 1921. The City Deep, Ltd., proposes to sink to a depth of 7000 ft. but pre-sumably by the time it does so the St. John del Rey will be deeper than that, since it has been increasing in depth at an average rate of about 150 ft. per year. The deepest shaft in the United States, the Tamarack No. 5, although it is only 5308 ft. deep, actually approaches nearer to the center of the earth (4100 ft. below sea level, as against 3958 ft. , at St. John del Rey). The deepest workings in the Calumet & Hecla go down to 4600 ft. below sea level. The St. John del Rey is not only the deepest, mine in the world, but it also is worked by the oldest registered English mining company, which was organ-ized in 1830 to work a mine at a considerable dis-tance from this one. That mine proved unprofitable, and in 1837 operations were transferred to the. deposit now under discussion, where operations have been prac-tically continuous ever since.

Jan 6, 1923

Jan 1, 1936

By W. B. Mather

The object of this paper is to record and interpret data collected during the examination of over 250 barite deposits in the Central Mineral District of Missouri. In the course of this study, the origin of the deposits, which the author believes to be hydrothermal, has been given particular attention. Economic barite deposits occur in two main areas in Missouri: (I) in the Washington County District of Southeast Missouri, from which over 90 pct of the state's production is derived; and (2) in the Central Mineral District, which includes portions of 15 counties in Central Missouri (Fig I). Barite in the smaller Washington County District is mined from widespread low grade, relatively shallow residual deposits, whereas in the Central District, it is mined

Jan 1, 1948

By W. B. Mather

The object of this paper is to record and interpret data collected during the examination of over 250 barite deposits in the Central Mineral District of Missouri. In the course of this study, the origin of the deposits, which the author believes to be hydrothermal, has been given particular attention. Economic barite deposits occur in two main areas in Missouri: (I) in the Washington County District of Southeast Missouri, from which over 90 pct of the state's production is derived; and (2) in the Central Mineral District, which includes portions of 15 counties in Central Missouri (Fig I). Barite in the smaller Washington County District is mined from widespread low grade, relatively shallow residual deposits, whereas in the Central District, it is mined

Jan 1, 1948

By J. Elmer Thomas

The evolution of the oil business is one of the great industrial romances of modern times. First used as a medicine, then as a lubricant, then as an illuminant, and finally as a motor fuel, each change in its principal usage caused large increases in consumption. Producing Successes The producing branch of the industry responded ably to the demands made upon it. Never was there a famine, rarely any threat of scarcity, and stored inventories were gradually accumulated to form comfortable working stocks. Originally an erratic and hazardous undertaking, the discovery and development of oil fields has made such strides as to classify now as a science. When storage stocks were low, production in close balance with consumption, and demand trending sharply upward, considerable concern was expressed over future needs. Price was very responsive to fluctuations in supply under those conditions, and quotations for crude and refined oils exhibited wide swings. A very different situation exists today. Consideration of the statistics only since the war will show how recent has been this change. In the 10-year period from 1918 to 1927 inclusive, we produced in the United States 6,100,000,000 bbl. of crude and imported 900,000,000 bbl., our total supply being 7,000,000,000 bbl. The consumption was 6,600,000,000 bbl., thus adding to stocks 400,000,000 bbl., an accumulation of somewhat less than 6 per cent. of the total supply. During that period virtually every field was promptly developed as soon as discovered and nearly every well in the country was producing at full capacity. With the maximum production of the wells required to take care of the rapid increases in consumption, with storage stocks moderate and proven reserves very slight, the producing division of the industry acquired a tempo not needed now. Potential Surplus Today the situation is vastly different. The economic consumption is about 2,700,000 bbl., with current production slightly in excess of that.

Jan 1, 1930

By T. C. Wilson, Gerald Edmunds, W. M. Peirce, E. A. Anderson

Thirty-six elements have been alloyed singly with cartridge brass. Ammonia and mercury stress-cracking tests have been conducted on the as-rolled and recrystallized strip. Ultra high purity cartridge brass has also been tested. Silicon improves stress- cracking behavior. High silicon (I per cent) cartridge brass quenched from high temperature (for example, 800 C.) annealing is exceptionally resistant to ammonia stress cracking. This improvement is not lost by subsequent cold working, but is greatly reduced by subsequent low temperature annealing. Phosphorus, arsenic, barium, cerium, magnesium, tellurium, tin, beryllium, and manganese benefit stress-corrosion resistance under some circumstances, but not others. The other alloying additions tried had no large effect on stress-cracking resistance. None of the elements added accelerated stress cracking. The impurities in commercial brass are not responsible for season cracking.

Jan 1, 1945

By Frederick Rhines

THE investigations of Wyman1 have demonstrated that copper deoxidized with several of the commonly used agents that confer immunity to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydro-gen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxy-gen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxi-dizing anneal, but beyond this the mecha-nism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subse-quently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves he reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the sub-scale may be complex compounds such, perhaps, as Si02-Cu20, which are partially reduced by hydrogen. These possibilities have been examined, and it has been con-cluded that the first three and possibly the fourth are operative collectively or indi-vidually under more or less predictable conditions.

Jan 1, 1940

By S. H. Brockunier

During the examination of a gold-property in Georgia, last summer, I had occasion to study the effect of different chemicals upon the ore; the object being to find a more economical method of extraction than chlorination, as practiced there, had proved to be. Some of my notes and results may be of interest to others. The country-rock consists of mica-schist, hornblende-schist and black slate. The vein-matter is quartzite and schist, containing some stringers of quartz, the whole forming a body from 20 to 50 ft. wide. All of the rocks in the vicinity have become disintegrated to a depth of from 50 to 75 ft., forming the so-called saprolite. I found the workings to represent two distinct classes : I. Open-cut surface-ore: very soft,oxidized and disintegrated; containing much alumina, silica and iron. Average value, $4 per ton. 11. Ore from lower levels : quartzites and schist; very hard ; containing much silica and manganese, some alumina, and from 2 to 10 per cent. of pyrites. Average value, $8 per ton. Class I. was soon dismissed. The only way to make it pay would have been by the use of steam-shovels and a large crushing-plant. The tendency to slime would be the principal difficulty.

Jan 1, 1902

By Wayne E. Tuomi

The mining industry is faced with a pressing problem; that is, to develop more efficient methods of extraction, handling and upgrading-techniques that will do the job faster and better than ever before. New techniques require new machines, or applications of new and improved materials that can be used to modify and improve existing machine and equipment designs. The traditional approach has been to increase productivity by increasing equipment size. Prognostication indicates that the trend toward larger equipment sizes and capacities will continue as one answer to the challenge imposed by future increases in mineral demands. But what is the limit on the continued growth of equipment size? Until about 1930, there was a very definite limit-a limit imposed by the strength of the steels and the power plants then available. The equipment engineer had come to an impasse: even though it was easily possible, for instance, to triple the size of a bucket, it had become impractical to correspondingly enlarge the boom, the counterweight, and the power plant.

Jan 3, 1967

By Thomas G. Murdock

ETHIOPIA, the first country to be liberated from Axis domination, has recovered remarkably from the ravages of occupation and war. Mineral production has contributed significantly towards this recovery, as it has provided a means of obtaining foreign exchange and has given employment to hundreds of workmen whose maintenance otherwise would have presented a problem. Although primarily an agricultural country, never with a large mineral production, Ethiopia has within its borders a variety of minerals, both precious metals and nonmetallics. Some of these are important to the country as a national asset and others contribute greatly to local economy and can be expected to do so even to a greater extent in the future1 (Fig I). PHYSIOGRAPHY AND GEOLOGY The Empire of Ethiopia is essentially a mountainous and volcanic country, in northeast Africa, situated principally between latitude 4° and I5°N and longitude 34° and 44°E. It is bounded on the north by Eritrea, on the northeast by French Somaliland, on the southeast by Italian Somaliland, on the south by Kenya Colony, and on the west by Anglo-Egyptian Sudan. These European possessions thus completely surround the country. Its access to the Red Sea is through Eritrea; to the Gulf of Aden, through French or British Somaliland; and, to the Indian Ocean, via Italian Somaliland. These routes range in length from 40 to 250 miles. Ethiopia has an area of approximately 350,000 square miles, with a width from north to south of 625 miles, and a maximum length from east to west, along latitude 8°N, of about 875 miles. Physiographically the country is characterized by two very extensive sub-tabular plateaus: the Ethiopian Plateau to the northwest and the Somaliland Plateau to the southeast, separated by a long tectonic graben-the Rift Valley of the Galla Lakes and Danakil. The Ethiopian Plateau, deeply cut and notched by the drainage, slopes in a general northwest direction toward the Sudanese Plains and the valley of the Nile; the Somaliland Plateau slopes to the southeast, toward the Indian Ocean. The valley of the Galla Lakes and its extension to the northeast-the Awash River Valley, separates the plateaus, from Lake Rudolph to Danakil. This depression which constitutes a continuation or ramification of the Great Rift Valley of Central Africa joins in turn the trough of the Gulf of Aden and the Danakil-Eritrean Rift, continuations of the Red Sea and the Jordan Valley. The general basement of Ethiopia is made up of very old rocks, usually considered as Archaen.2 These rocks are represented by the metamorphic crystallines, such as gneisses, different kinds of schists, included lenses of crystalline limestone, and massive intrusives such as granites, diorites, and syenites, all cut by

Jan 1, 1947

By Alden B. Greninger, Alexander R. Troiano

Metallurgists have long believed that martensite in steel forms as plates along the octahedral {111} planes of austenite. Much has been written about mechanisms whereby units of the austenite lattice are pictured as transforming to martensite by shearing movements initiated along the octahedral planes of austenite, supposedly resulting in plates of martensite lying parallel to these planes of shear. A critical inspection of two or three photomicrographs of quenched hypereutectoid steel led us to the conclusion that the orientation habit of martensite, at least in hypereutectoid austenite, could not possibly be octahedral. Inasmuch as recent studies,30,31 of the martensite-type reaction in nonferrous alloy systems have established the irrational orientation habit as characteristic of this type of lattice transformation, the need for a thorough restudy of the crystallography of martensite formation in steel was evident. The present paper reports the results of such a study, extended to include both cementite and some of the products of constant-temperature decomposition of austenite. Also reported are a few of the results obtained from a microscopic and X-ray study of the austempering process in very high-carbon steel. I. The Martensite Transformation Previous Work Microstructure and Crystal Structure of Martensite.—Among the best series of published photomicrographs of quenched steels are those of Whitely,1 Robertson,2 Hanemann and Schrader,3 and Lucas.4 The crystal structure of martensite is body-centered tetragonal, with axial ratio varying from 1 near 0.0 per cent carbon to 1.08 for 1.75 per cent

Jan 1, 1940

By Alden B. Greninger, Alexander R. Troiano

Metallurgists have long believed that martensite in steel forms as plates along the octahedral {111} planes of austenite. Much has been written about mechanisms whereby units of the austenite lattice are pictured as transforming to martensite by shearing movements initiated along the octahedral planes of austenite, supposedly resulting in plates of martensite lying parallel to these planes of shear. A critical inspection of two or three photomicrographs of quenched hypereutectoid steel led us to the conclusion that the orientation habit of martensite, at least in hypereutectoid austenite, could not possibly be octahedral. Inasmuch as recent studies,30,31 of the martensite-type reaction in nonferrous alloy systems have established the irrational orientation habit as characteristic of this type of lattice transformation, the need for a thorough restudy of the crystallography of martensite formation in steel was evident. The present paper reports the results of such a study, extended to include both cementite and some of the products of constant-temperature decomposition of austenite. Also reported are a few of the results obtained from a microscopic and X-ray study of the austempering process in very high-carbon steel. I. The Martensite Transformation Previous Work Microstructure and Crystal Structure of Martensite.—Among the best series of published photomicrographs of quenched steels are those of Whitely,1 Robertson,2 Hanemann and Schrader,3 and Lucas.4 The crystal structure of martensite is body-centered tetragonal, with axial ratio varying from 1 near 0.0 per cent carbon to 1.08 for 1.75 per cent

Jan 1, 1940

By George Watkin Evans

During the past ten or twelve years, the average reader of newspaper and magazine articles has been led to believe that enormous deposits of high-grade coal exist in the northland and that these can be mined for practically nothing. But much of the reputed glitter and attractiveness of Alaskan coals disappears when viewed at close range. Many areas of coal-bearing rocks are widely distributed geographically from Cape Lisburne, on Bering Sea, to Admiralty Island, south of Juneau. Bituminous coal is found at Cape Lisburne, on the Bering Sea, at Five Finger Rapids on the upper Yukon, and at Herendeen Bay and Chignik Bay; lignite is found on the Kobuck River, along the Yukon River from points near the mouth to Tonakat, near Rampart, at Dawson, on the east shore of Cook Inlet, and in the Tanana Valley, 50 mi. south of Nenana. The Susitna and Matanuska Valleys contain coal ranging from lignite to anthracite, and in the Bering Lake district, there are coals ranging from semi-bituminous to anthracite. No effort will be made to describe all of these fields, but the writer will confine himself to the four principal fields, namely, the Nenana field! in the interior of Alaska, tributary to the Fairbanks district; the Matanuska field, in the Matanuska Valley; the Kachemak Bay field on the east shore of Cook Inlet; and the Bering River field, east of the mouth of Copper River. Nenana Coal Field The Nenana field occupies an area east of the Nenana River 70 mi. (112 km.) southwest of Fairbanks and approximately 50 mi, from the town of Nenana, which is located at the junction of the Alaskan Railway and the Tanana River. It is on the northern flank of the Alaskan Range and occurs within the foothills of that district. The elevations range from 1000 to 4000 ft. (304 to 1219 m.). Future developments may prove the field to extend from a considerable distance west of the Nenana River to the headwaters of the Tanana River. The coal measures are of Tertiary age and are probably Eocene. They are not badly deformed by folding, but portions of the field show

Jan 1, 1922

A small group of members of the Institute headed by W. H. Shockley, has insistently demanded that the Institute submit to the members for letter ballot the question of our using in our publications and corre-spondence certain so-called "simplified spellings." The principal argu-ment in favor of this proposal is written by Mr. Shockley and will be submitted in full to the membership for ballot. It rests chiefly on the desirability of saving the time of school children in the learning of the spelling of the English language. A sample of correspondence had with one of the gentlemen on this subject is given herewith in order that members may see what the correspondence and publications of the Institute would look like if we adopted the proposals. This sample was chosen at random: "Onse I condemd the report ov a president of the Institute. He did not pruve his case even on paper-"a hot air profet," I sed. Time has pruved he was." "I rote yu about the muvement to better the spelling in the Institute Bulletin, etc., neglecting to say some things that I mite hav said and things hav happened since which no member ov a democratically governed society shoud stand without protest."

Jan 12, 1919

By Charles Austin

IN a recent paper the authors1 discussed the reactions to tempering of hypereutectoid steels quenched from 1000° C., as revealed by studies on changes in hardness, electrical resistivity, coercive force and metallo-graphic characteristics. The data, which related specifically to temper-ing temperatures of 550°, 650° and 710° C., for varying periods up to 125 hr., permitted the following important conclusions: 1. The rate of softening of the steels at the temperatures examined differed markedly although the steels were of "similar" general chemi-cal composition. 2. The temperature of maximum softening spread over a range from about 650° C. to the eutectoid inversion. 3. The divergence in behavior was ascribed, at least in part, to a profound difference in tendency to graphitization on annealing at sub-eutectoid temperatures. 4. The mode of spheroidization of the cementite, as revealed by metallographic studies, also varied considerably in the different steels. The purpose of the present investigation is to pursue further the study of the difference in behavior of the steels on tempering over a wider range of temperature. To this end the following features have received particular attention: 1. Comparison of temperatures of maximum softening of the various steels when the quenched samples were tempered for 5 hr. and for 75 hr. followed by furnace cooling and by quenching in water. 2. Determination of the effect of quenching temperature, prior to tempering, on the rate of softening. Quenching temperatures of 1000° and 850° C. were used in the investigations. 3. Examination of the microstructures obtained with the various heat-treatments employed.

Jan 1, 1938

By Petri Bryk, John Ryselin, Rolf Malmstrom, Jorma Honkasalo

THE theoretical possibilities for the realization of flash smelting have been known for a long time. Calculations concerning the same can be found in previously published literature,1 and suggestions for its accomplishment in practice are described in patents on the subject. Likewise a smaller number of practical test results are known. Autogenous smelting is closely connected with flash smelting, since in flash smelting techniques it is possible to use the heat evolved by oxidation of the sulfides for the smelting process to such an extent that under certain conditions smelting can proceed without additional fuel. However, in the event that insufficient heat is available from the oxidation of the sulfide concentrates, then additional heat may be supplied by preheating the air, using oxygen enriched air, on burning additional fuel with the concentrate.

Jan 6, 1958

I AM sure, that you understand that of all the things created by the most high God Himself or by Nature at His command, not one-even though it be an atom or the smallest worm-has been produced without some particular gift. And if we do not always discern this in every thing, the cause lies in our defective vision, in our little knowledge, and in our lack of careful thought concerning the necessity of seeking hidden things. Certainly those things that have such inner powers, like herbs, fruits, roots, animals, precious stones, metals, or other stones, can be understood only through oft-repeated experience. [37] Others do not need so much knowledge and belief for their, powers are obvious and shown to us at all times by their effects. They reveal themselves to us through the sense of sight by their splendor and variety of colors, through the sense of smell by their odors, through the sense of hearing by the melody of the harmonious or unpleasantly discordant repercussions. of the air. They likewise manifest themselves by. their softness or harshness. As you see, all those things, according to. their limits, are conveyed .by the ordinary senses to the mind, by whose distinctions all their species, both harmful and beneficial, are discerned. Then they are reviewed by the judgment in all their degrees of perfection and imperfection, so that whoever seeks them with careful study or with experience often finds them. Now, in order to shorten this discourse, since I wished to speak to you of lodestone and its properties, I tell you that it is one of those things that show their apparent effects to our sight by a particular virtue hidden in such a way that its cause, as far as I know, has never been known to the very wise natural speculators who have spoken on every other subject. Thus one who considers its actions carefully must surely marvel, for it appears that Nature has put into this stone a certain spirit of vivacity, so that it seems to have-I would like to say-hands, although they are not seen. For I see that it not only attracts iron but also takes hold of it and keeps it attached to itself. This action is certainly great enough to bear certain witness to the virtues possessed by other created things that do not manifest their powers to the external senses. In order not to prolong this discussion, I tell you the following. This stone is found in various places and of different colors and properties. The

Jan 1, 1942

By M. J. Pool, P. J. Spencer, R. V. Miner

The partial molar heat of solution of rhodiunz in liquid lin and Rh-Sn alloys has been measured as a function of rhodium concentration at 700" , 725" , 750" , and 775°K. The values at infinite dilution are very exo thermic, ranging from -29,950 to -28,260 cal per g-atom Rh at 700" and 775"K, respectively. At the solubility limit the heat of solution becomes sharply nzore exothermic and has permitted the liquidus boundary to be accurately established at each temperature. From the measurements in the two-phase region of liquid Plus RhSn, the heat of formation of RhSn,has been determined. A large increase in the heat of formation between 725" and 750°K suggests the possibility of a phase transformation in this compound. V ERY few measurements have been made of the heats of solution of transition metals in liquid tin; yet those values that are available are of great interest because of their very large exothermic nature. For example, the heat of solution at infinite dilution of palladium in tin has been measured as about -26,000 cal per g-atom (625" to 800°~),' while the heat of solution at infinite dilution of platinum is even more exothermic at -28,591 cal per g-atom (914°K).' These values are of the same order of magnitude as the heat of formation of many intermetallic compounds and as such clearly indicate that very strong bonding must exist between the solute and tin atoms in the liquid solutions. Rhodium might be expected to display similar solution characteristics in tin in view of its close electronic resemblance to palladium and platinum. Since no thermodynamic data are available for Rh-Sn alloys, rhodium was chosen as an appropriate solute for further investigation of transition-metal systems with highly exothermic heats of solution at infinite dilution. EXPERIMENTAL The heat of solution of rhodium in dilute Rh-Sn liquid solutions was measured as a functlon of rhodium concentration at 700°, 725", 750°, and 775°K. The liquid-metal solution calorimeter used in this work has been fully described elsewhere. At the start of each series of measurements, the solvent bath consisted of about 0.5 g-atoms of 99.9+ pct pure tin. To this was made a number of small rhodium additions, about 0.0005 g-atoms each, and the heat of solution was measured for each. Rhodium of 99.9+ pct purity in powder form was used in order to promote rapid dissolution in the liquid tin. The powder specimens were contained in tin foil stated to be purified (lead-free). This foil was found to have no measurable heat of solution in pure tin so the effect of any impurities could be neglected. The energy equivalent of the calorimeter was experi- mentally determined by dropping tungsten and/or tin specimens at intervals during each series of rhodium drops. The tungsten and tin used were 99.95 and 99.999+ pct pure, respectively. The only heat effect due to a tungsten drop, or a tin drop at low rhodium concentrations in the bath, is the sensible heat of the specimen. The heat content of these materials is well-established and is presented in the compilation of Hultgren et al. 4 As the rhodium concentration in the tin bath increases a small heat effect arises from the reaction: Sn (liquid, T) — & (soln, T) where T is the temperature of the tin bath. Where necessary, this heat of solution of tin was determined by Gibbs-Duhem integration, and corrections were made to the heat effect of the tin calibration specimens and the tin foil containing the rhodium specimens. RESULTS AND DISCUSSION The calculated values of the heat of solution of rhodium in dilute Rh-Sn alloys as a function of composition are shown graphically in Fig. 1. The values have been corrected for the sensible heat of the specimens, initially at 273"K, and apply to the reaction:

Jan 1, 1969

By Hugh M. Roberts, R. D. Longyear

Introduction ............................ 27 GEnERal Geology........................... 29 The ORebodY in Western Falco~ridgI TownsRip........... 31 Quartzite-Graywacke Formation................... 33 Greenstone............................ 33 Norite ............................. 33 Metamorphism.......................... 35 The Orebody........................... 36 Mineralogy ........................... 37 Grade of Ore........................... 42 Genesis oF tEe Ores . :....................... 43 Summary of Various Hypotheses.................. 44 Magmatic Segregation by Crystallization of Sulphides........ 44 Gravitational Segregation of Molten Sulphides at the Base of the Magma 45 Intrusion of Molten Sulphides after the Consolidation of 'he Nurite.. 45 Deposition by Hydrothermal Solutions.............. 46 Magmatic Segregation by Extraction from Crystallizing Norite... SO The Relationship between the Exploration and Theories of Origin .... 50 Volume Relations of Norite and Sulphides............... 62 Intimate Association of Norite and Sulphides............. 53 Granitic Material........................ 54 Uniform Content........................ 54 Sulphides in Walls......................... 54 Absence of Typical Hydrothermal Minerals.............. 55 SUmmaRY................................ 56 Introduction During 1916 and 1917. the E. J. Longyear Co. of Minneapolis. Minn., carried out a campaign of exploration for nickel-copper ore in the Sudbury District of Ontario. The work was initiated by W. E. Smith. a resident of Sudbury. who called the attention of W. J. Mead. Chief Geologist

Jan 1, 1918

By P. R. Sahm, T. V. Pruss

Mixtures of fine GaSb and Gds as well as preal-loyed GaSbl,As, powders were hot-pressed at 690°C and 25,000 psi. Dense alloys with compositional gradients of less than 5 pct were obtained from mixtures containing about 20 mol pct GaAs. For x < 0.2, there were increasing compositional gradients, and for x > 0.2 a GaAs-rich second phase appeared in the microstructure. Densification as well as alloying wlechanisms were enhanced by dissociation and, possibly, oxidation reactions of the powders. Densification of coarse prealloyed material, however, primarily depended on plastic flow phenomena and required temperatures just below solidus and pressures of 50,000 psi Thermal and electrical properties were measured. Although in no case was the figure of merit of melt growth materials approached closer than to within 25 pct, the better overall thermoelectric properties were found in coarse-grained, prealloyed materzals which had been compacted to near theoretical density and where grain regrowth had been induced. Similar results are believed to hold in other binary 111-V compound systems if processed under similar conditions. The densification of unalloyed GaSb powders during pressure sintering (= hot pressing) was shown to depend strongly on powder particle size.&apos; Fine powders displayed a "liquid skin effect" that enhanced compaction through the presence of liquid gallium, whereas coarse powders compacted predominantly by plastic flow. The liquid skin effect, in particular, appeared attractive for alloying GaSb with other, higher-melting, III-V compounds, and to densify these in a one-step operation. This is of special interest in the case of III-V compound alloys as the conventional techniques of melt growth or long-time annealing of powders2 is very time-consuming, especially in cases where a large separation of liquidus and solidus can be expected, such as in GaSbl alloys.2 It was felt that experimentation with this system, a particularly unfavorable example, would allow us to extrapolate to several other, more favorable, cases. Uses of Ill-V alloys are most evident in thermoelectric energy conversion devices.&apos; For this reason certain thermal and electrical properties were measured and compared to those of melt-grown material and to hot-pressed prealloyed powders. EXPERIMENTAL PROCEDURE The pressure-sintering apparatus has been previously described.&apos; Using this equipment, both powder mixtures of GaSb with GaAs and prealloyed GaSbl-,As, powders were hot-pressed. The mixtures were pre- pared from cast GaSb and melt-grown GaAs. The prealloyed material was obtained from stoichiometric melts, initially heated to 1200°C in an evacuated quartz ampoule, and then annealed in the solidus-liquidus interval. A typical annealing cycle consisted of a heating to 850°C (1 hr), extended successive annealing at 750°C (65 hr), and slow stepwise cooling (25 hr) to below solidus. The GaSb, GaAs, and GaSbl-,As, materials were ground in a vibrational mill to particle sizes below 500 . A jet mill reduced these further where necessary. Fine powders were analyzed by Coulter counting for their size distribution. Average sizes by volume were calculated from the data. Mixing of the powders, where necessary, was carried out through rapid vibrational motion. The hot-pressing operation consisted of a degassing period of 15 hr, in most cases at 690°C, followed by several hours of compression, normally 25,000 psi at 690°C for powder mixtures and 50,000 psi at 710°C for prealloyed powders. The chemical compositions were confirmed by X-ray fluorescence analysis. To estimate the degree of solid solution achieved, lattice parameters were determined and interpreted according to Vegard&apos;s rule. In addition, optical microscopy helped to correlate the relative amounts of the phases present as well as the degree of porosity to the measured density. To reveal grain boundaries, polished surfaces were etched4 with H 2 O:H 2 O:HCl = 2:l:l. In several cases microscopic concentration gradients were monitored by electron-probe analysis-. RESULTS AND DISCUSSION Alloying and Densification of GaSn-GaAs Powder Mixtures. After preliminary experiments showed that no appreciable alloying took place in mixtures of coarse GaSb (22.5 p) and fine GaAs (2.5 p) powders, hot pressing of mixtures was confined to fine powders only (3.1 and 2.4 p, respectively). Alloying and densification apparently occurred simultaneously with a grain regrowth mechanism which depended on the presence of a liquid phase.&apos; The liquid phase was provided by the dissociation of GasbS particles into liquid gallium and antimony above 555°C. This not only enhanced grain regrowth and densification, as in unalloyed GaSb,&apos; but took on additional importance here for the alloying process. Alloying was speeded up by the resulting liquid-solid interaction as compared to the very slow solid-state diffusion process normally expected at these temperatures.&apos; The results obtained with a series of powder mixtures have been compiled in Table I. It is seen that for mixtures with less than 20 mol pct GaAs, x < 0.2, the compositional ranges increased and for x > 0.2 a GaAs-rich phase and free antimony appeared in the microstructure in sizable amounts.

Jan 1, 1968