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By E. P. Klier, Taylor Lyman

THE structures formed when austenite is quenched to subcritical temperatures and allowed to transform isothermally have been the subject of intensive study since the work of Davenport and Bain.1 Isothermal transformation diagrams summarizing the results of many of these studies have become widely familiar to metallurgists. Of particular interest to metallographers are the dark-etching, acicular products of transformation formed by isothermal reaction below the temperature of maximum velocity of the austenite to pearlite reaction. These products, the bainite structures, can be formed in a wide variety of steels. However, the constitution of bainite is not well understood and divergent views have been expressed as to its mode of formation. In this investigation a combination of dilatometric, microscopic and X-ray methods has been brought to bear upon the problem in the hope of some elucidation of the bainite reaction as it occurs in hypoeutectoid steels. MECHANISM OF BAINITE FORMATION Davenport and Bain1 considered the mechanism of bainite formation to consist of two steps-an allotropic transformation followed by precipitation of carbide. The separation in time of the two processes was considered to be very slight in the upper temperature range and very marked at temperatures just above the martensite range. This concept has been restated by Vilella, Guellich and Bain2 in the form of a definition of the acicular mode of transformation as: The successive, abrupt formation of flat plates of supersaturated ferrite along certain crystallographic planes of the austenite grains; this supersaturated ferrite begins at once to reject carbide particles, (not lamellae), at a rate depending upon temperature. In effect, this is the acicular mode of transformation, even though the temperature be such as to limit the actual life of the quasi-martensite to millionths of a second. The investigation of isothermal decomposition of austenite in certain alloy steels (notably those containing chromium or molybdenum) has revealed that there may be a range of temperatures between the pearlite and bainite reactions in which the austenite decomposes at a relatively low rate.3-6 Further, it is characteristic that in the second region of fast reaction the decomposition of the austenite is incomplete by one reaction but goes to completion by a second reaction. These observations led Wever7 to a description of the bainite reaction as follows: I. The reaction takes place by initial precipitation of a martensitic intermediate structure. 2. In the upper temperature range this structure readily decomposes into ferrite and cementite. In the lower range carbon separates in an unknown form. 3. In the upper temperature range the precipitated carbide nucleates the precipitation

Jan 1, 1944

but, returning to South Africa, for the next two years he was assistant general manager of the Simmer Deep Gold Mining Co., at Johannesburg. In June, 1911, he returned to New Zealand as general manager and consulting engineer for the Consolidated Goldfields of New Zealand, at Reefton, which position he held at the time of his admission to the Institute in 1914. Early in September, 1915, he left New Zealand for active service in France. Corporal Sheppard B. Gordy Sheppard B. Gordy, born in Ansonia, Conn., in 1889, graduated from the Sheffield Scientific School in 1910 and with the degree of E. M. in 1912. He entered the employ of the Braden Copper Co. immediately on his graduation and remained with this company four years, working up through the various grades to assistant foreman and foreman to one of the individual mines. The last year he was in its employ, he acted as general mine foreman. He was for a short time with the Chile Exploration Co. and then went with the Andes Exploration Co. (Anaconda) and remained with the latter, doing mine exploration and development work, until he sailed for home in June, 1918, to give a more personal and active service to his country in her need. He declined a tender of induction into an officers' training camp, at the urgent request of Professor McClelland supplemented by Mr. Potter, because they demonstrated to his satisfaction that he could give more valuable service to his country in helping out with the aircraft production. Being within the draft age, in order to carry out this plan, it was necessary for him to be called by his Local Board and sent to camp. This call came Aug. 26. Two weeks before that time he had gone to Dayton, Ohio, to begin the study of aircraft production, and was sent by the Dayton Board to Camp Sherman, Chillicothe, Ohio, where he died of pneumonia on Oct. 9. Lieutenant Thomas Clarence Gorman Thomas C. Gorman, a lieutenant in the Second Tunnelling Company of the Canadian Engineers, was killed in France on Mar. 18, 1918. He was resting in his sleeping hut and was in the act of writing a letter when a bursting shell killed him.

Jan 1, 1920

but, returning to South Africa, for the next two years he was assistant general manager of the Simmer Deep Gold Mining Co., at Johannesburg. In June, 1911, he returned to New Zealand as general manager and consulting engineer for the Consolidated Goldfields of New Zealand, at Reefton, which position he held at the time of his admission to the 1nstitute in 1914. Early in September, 1915, he left New Zealand for active service in France. Corporal Sheppard B. Gordy Sheppard B. Gordy, born in Ansonia, Conn., in 1889, graduated from the Sheffield Scientific School in 1910 and with the degree of E. M. in 1912. He entered the employ of the Braden Copper Co. immediately on his graduation and remained with this company four years, working up through the various grades to assistant foreman and foreman to one of the individual mines. The last year he was in its employ, he acted as general mine foreman. He was for a short time with the Chile Exploration Co. and then went with the Andes Exploration Co. (Anaconda) and remained with the latter, doing mine exploration and development work, until he sailed for home in June, 1918, to give a more personal and active service to his country in her need. He declined a tender of induction into an officers' training camp, at the urgent request of Professor McClelland supplemented by Mr. Potter, because they demonstrated to his satisfaction that he could give more valuable service to his country in helping out with the aircraft production. Being within the draft age, in order to carry out this plan, it was necessary for him to be called by his Local Board and sent to camp. This call came Aug. 26. Two weeks before that time he had gone to Dayton, Ohio, to begin the study of aircraft production, and was sent by the Dayton Board to Camp Sherman, Chillicothe, Ohio, where he died of pneumonia on Oct. 9. Lieutenant Thomas Clarence Gorman Thomas C. Gorman, a lieutenant in the Second Tunnelling Company of the Canadian Engineers, was killed in France on Mar. 18, 1918. He was resting in his sleeping hut and was in the act of writing a letter when a bursting shell killed him.

Jan 1, 1920

By H. DeWitt Smith

THE mine operated by the United Verde Copper Co. is situated near Jerome, Ariz., on the eastern flank of the Black Hills, at an elevation of approximately 5500 ft. (1676 m.) above sea level. The mine and the town of Jerome are located on a steep hillside, which slopes rapidly to the valley of the Verde River. The smelter town of Clarkdale is situated in the Verde valley 4.1 mi. (6.5 km.) distant in an air line from Jerome, and at an elevation of 3560 ft. The two towns are connected by the standard-gage railroad of the Verde Tunnel & Smelter R. R., a subsidiary of the United Verde Copper Co. This road is 11 mi. long and has a compensated 4 per cent. grade. At Clarkdale, it connects with the Verde Valley branch of the Santa Fe R. R. The narrow-gage (36-in.) line of the United Verde & Pacific Ry. was, until 1919, Jerome's only rail connection with a main trunk line. This road connects with a branch line of the Santa Fe system at Jerome Junction, after traversing 26 mi. of mountainous country. From the time of its location, in 1876, until its purchase by Senator W. A. Clark, of Montana, in 1889, the United Verde mine was worked on a small scale and shipments of high-grade gold-silver ore were made from the surface workings. Until 1894, when the narrow-gage railroad to

Jan 8, 1920

By Nicholas J. Grant, David S. Bloom

An investigation of the Cr-Ni system has revealed that there exists a eutectoid transformation at about 1180°C. 'The transformation in chromium implied by the eutectoid reaction was detected at about 100°C below its melting point. Associated with the eutectoid transformation, a metastable transition structure has been found. THE Cr-Ni phase diagram is shown in current literature to be a simple eutectic system in which the high chromium end of the diagram is incompletely determined, Fig. 1. The last investigation of this system was undertaken in 1936.' Because of limitations in metal purity, especially of chromium, and temperature measuring techniques, the diagram should be accepted with some reservations, as was indicated by Hansen.V or examwle.-, the wresence of the compound Cr²Ni, with a tetragonal structure," remains unverified and incompatible with the simple eutectic diagram. The work reported here began because of discrepancies that appeared in experimental studies in the binary alloys Cr-Ni and in the ternary system Cr-Mo-Ni. The existing binary Cr-Ni diagram failed to provide a complete explanation of observations made by microscope, X-ray, and thermal analyses. Experimental Methods The materials employed were of a higher degree of purity than were available to previous investigators. The Mond nickel used had a nominal purity of 99.87 pct, while the electrolytic chromium analyzed 99.03 pct with the major impurity being 0.5 to 0.7 pct oxygen with some iron. All alloys were melted in a vacuum furnace to remove dissolved gases, sufficient carbon was added to the charge to combine with all the oxygen as CO. Final analysis determined the carbon as about 0.02 pct and the oxygen around 0.06 pct or slightly more. Stabilized zirconia crucibles and thermocouple protection tips were used throughout and contributed no detectable impurity to the melts, as long as the oxygen in the chromium was kept low. Heats averaged about 250 g, which permitted about 2 in. of the thermocouple protection tips to be submerged. The temperature drop across the thermocouple protection tip was determined to be about 3°C, a minor source of error. The alloys, after removal from the vacuum furnace, were placed in a furnace operating in a purified argon atmosphere for the thermal analyses. An- nealed wolfram-molybdenum thermocouples provided the primary means of temperature determination, though a Pt-Pt-10 pct Rh couple was employed for a check when possible. A sensitive, high-speed Leeds and Northrup Speedomax recording potentiometer indicated the thermocouple output. X-ray diffraction patterns were obtained primarily on a Norelco unit, which permitted diffraction angles only up to 45" (28 = 90"). In general, either rotated or stationary solid samples were used, because it later evolved that many samples were susceptible to transformation resulting from the cold working involved in pulverizing. It was also noted that rotating a sample sometimes suppressed weak lines, so, usually, samples were not rotated. Later a high temperature camera was adapted for use at temperatures up to 1400 °C on the Norelco unit utilizing both solid and powdered samples. Unless otherwise noted, all X-ray patterns were made with a chromium tube and a vanadium filter. Further-

Jan 1, 1952

By D. G. Westlake

The electrical resistance of a series of V-H alloys (0 to 3.5 at. pct H) has been measured over the temperature range G° to 360°. Interstitial impurities made contributions to the residual resistivity, but not the ideal resistivity. The contribution of hydrogen in solid solution is expressed by Ap = 1.12 microhm-cm per at. pct H; but the contribution of precipitated hydride was negligible. A portion of the so1vu.s for the V-H phase diagram is presented. The solubility limit is given by In N (at. pct H) = (5.828 i 0.009) - (2933 i 44)/RT. Comparison of critical temperatures joy hydride precipitation and published critical temperatures for hydrogen embrittlement suggests the two are related. ThiS study was initiated as part of an investigation of the mechanism by which small concentrations of hydrogen embrittle the hydride-forming metals at low temperatures. It has already been shown that, in the case of hcp zirconium, a reduction in ductility accompanies the strengthening resulting from precipitation of a finely dispersed hydride phase.''' Our attempts to detect a similar precipitation of a second phase at low temperatures in V-H alloys by transmission electron microscopy have been thwarted because we have been unable to prepare thin foils that are representative of the bulk material with respect to hydrogen concentrati~n.~'~ The present investigation establishes the solvus of the V-H system at subambient temperatures. Subsequently, we hope to be able to determine whether the embrittlement temperature is related to the critical temperature for precipitation of the hydride in a given V-H alloy. veleckis5 has proposed a partial phase diagram for the V-H system based on extrapolations of the pressure-composition relations he measured at higher temperatures. Kofstad and wallace' conducted a similar study of single-phase alloys but did not attempt to establish the phase diagram. Zanowick and wallace' and ~aeland' have studied a portion of the phase diagram by X-ray diffraction, but they investigated no alloys in the hydrogen concentration range 0 to 3 at. pct, the range of interest to us. EXPERIMENTAL PROCEDURE The vanadium was obtained from the Bureau of Mines, Boulder City, Nev., in the form of electrolytic crystals. The analyses supplied with them listed 230 ppm by weight metallic impurities, 20 ppm C, 100 ppm N, and 290 ppm 0. The crystals were electron-beam-melted into an ingot that was rolled to 0.64 mm. Strips, 60 mm long and 4.2 mm wide, were cut from the sheet, and both rolled surfaces were ground on wet 600-grit Sic paper to produce specimens 0.4 mm thick. They were wrapped in molybdenum foil, vacuum-encapsulated in quartz, and annealed 4 hr at 1273°K. The specimens were annealed in a dynamic vacuum of 2X lo-' Torr for 30 min at 1073°K for dehydrogenation, and charged with the desired quantity of hydrogen by allowing reaction with hydrogen gas at 1073°K for 2 hr and cooling at 100°K per hr. Purified hydrogen was obtained by thermal decomposition of UH3. Sixteen specimens were studied: two contained no hydrogen and the others had hydrogen concentrations between 0.5 and 3.5 at. pct (hydrogen analyses were done by vacuum extraction at 1073°K). Electrical resistances were measured by the four-terminal-resistor method on an apparatus similar to the one described by Horak.~ The specimen holder was designed so that both current and potential leads made spring-loaded mechanical contact with the specimen. The potential leads were 30 mm apart, and the current leads were 55 mm apart. The current was 0.10000 amp. We used the following baths for the indicated temperature ranges: liquid nitrogen, 77°K; Freon 12, 120" to 230°K; Freon 11, 230" to 290°K; and ethanol, 290" to 340°K. Temperatures lower than 77°K were achieved by allowing the specimen to warm up after removal from liquid helium. Temperatures above 77°K were measured by a calibrated copper-constantan thermocouple (soldered to the specimen holder) and below 77°K by a calibrated carbon resistor. The temperature of the bath changed less than 0.l0K between duplicate measurements of the resistance. RESULTS AND DISCUSSION Typical plots of resistivity p vs temperature T are shown in Fig. 1. In the interest of clarity, only five curves are presented and the data points have been

Jan 1, 1968

By Edwin B. Eckel

This paper, based on brief field examination and on data supplied by the operators, records the condition of the Italian mercury industry as of March 1945, not long after Italy's collapse. Except for the once-Italian but now Yugoslavian Idria mine near Trieste, virtually all the known mercury deposits are in the Monte Amiata district in Siena and Grosseto Provinces, 75 miles north of Rome. This district contains the Abbadia San Salvatore. the Siele. the Argus, and the Cerreto Piano mines besides numerous prospects and unproductive mines. Under pressure from Germany the principal mines were highly productive during the early part of the war, but production fell off long before its end. All of the mines were damaged in some way at the German withdrawal but by September 1944 the Abbadia had resumed production and several others were only lacking power by the early spring of 1945. The Monte Amiata district is characterized geologically by a thick series of sedimentary rocks that range from Triassic to Eocene in age . and are surmounted on Monte Amiata itself by a thick cap of extrusive trachyte. Bodies of travertine and of landslide detritus, younger than the trachyte, are rather widespread. The structure is complex and little known but most of the ore deposits seem to lie along or near a major, north-trending fault or on associated cross-fractures. Cinnabar is the only important ore mineral and clay minerals are by far the most abundant products of hydrothermal alteration. A southward increase in the amount of stibnite, relative to cinnabar, suggests horizontal zoning. The grade of ore ranges from 0.60 to 3.0 Pet and the reserves, as compared with those in American mines, are enormous. Even in the face of war-time scarcities, the mines are remarkably self-sufficient and labor is plentiful, but the costs of production are estimated to be not greatly below those of the better American mines. Notes on the principal mines, on the mining and metallurgical methods, and on the manufacture of synthetic cinnabar are included in the paper. Introduction With but few brief interludes, Spain and Italy, including the Idria mine near Trieste, which has passed from Austrian to Italian to Yugoslavian hands in the Past 3 decades, have led the world in the production of mercury, or quicksilver, for many centuries. Despite their enviable position with respect to the supplies of a metal so essential in both war and peace, there is a notable lack of up-to-date information in America on the mercury industry of either country. Duschak and Schuette' and Schuettez,3 give by far the best summaries in English known to the writer, but the latest firsthand report cited by them on the Italian mines was published in 1915.' Having been deeply interested in the geology and economics of mercury for several years, the writer naturally felt most fortunate in being the to obtain enough firsthand information on the Italian industry to fill at least a few of the gaps in our knowledge. The opportunity came during the war, soon after this industry, together with the rest of Italy, had capitulated to the Allies. Many of the facts presented here are thus definitely "dated," but others are of less transitory nature, and even the dated facts should be of interest in showing the strength and

Jan 1, 1949

By Edwin B. Eckel

This paper, based on brief field examination and on data supplied by the operators, records the condition of the Italian mercury industry as of March 1945, not long after Italy's collapse. Except for the once-Italian but now Yugoslavian Idria mine near Trieste, virtually all the known mercury deposits are in the Monte Amiata district in Siena and Grosseto Provinces, 75 miles north of Rome. This district contains the Abbadia San Salvatore. the Siele. the Argus, and the Cerreto Piano mines besides numerous prospects and unproductive mines. Under pressure from Germany the principal mines were highly productive during the early part of the war, but production fell off long before its end. All of the mines were damaged in some way at the German withdrawal but by September 1944 the Abbadia had resumed production and several others were only lacking power by the early spring of 1945. The Monte Amiata district is characterized geologically by a thick series of sedimentary rocks that range from Triassic to Eocene in age . and are surmounted on Monte Amiata itself by a thick cap of extrusive trachyte. Bodies of travertine and of landslide detritus, younger than the trachyte, are rather widespread. The structure is complex and little known but most of the ore deposits seem to lie along or near a major, north-trending fault or on associated cross-fractures. Cinnabar is the only important ore mineral and clay minerals are by far the most abundant products of hydrothermal alteration. A southward increase in the amount of stibnite, relative to cinnabar, suggests horizontal zoning. The grade of ore ranges from 0.60 to 3.0 Pet and the reserves, as compared with those in American mines, are enormous. Even in the face of war-time scarcities, the mines are remarkably self-sufficient and labor is plentiful, but the costs of production are estimated to be not greatly below those of the better American mines. Notes on the principal mines, on the mining and metallurgical methods, and on the manufacture of synthetic cinnabar are included in the paper. Introduction With but few brief interludes, Spain and Italy, including the Idria mine near Trieste, which has passed from Austrian to Italian to Yugoslavian hands in the Past 3 decades, have led the world in the production of mercury, or quicksilver, for many centuries. Despite their enviable position with respect to the supplies of a metal so essential in both war and peace, there is a notable lack of up-to-date information in America on the mercury industry of either country. Duschak and Schuette' and Schuettez,3 give by far the best summaries in English known to the writer, but the latest firsthand report cited by them on the Italian mines was published in 1915.' Having been deeply interested in the geology and economics of mercury for several years, the writer naturally felt most fortunate in being the to obtain enough firsthand information on the Italian industry to fill at least a few of the gaps in our knowledge. The opportunity came during the war, soon after this industry, together with the rest of Italy, had capitulated to the Allies. Many of the facts presented here are thus definitely "dated," but others are of less transitory nature, and even the dated facts should be of interest in showing the strength and

Jan 1, 1949

By William Priestley

The author has shown, by .practical experiments, how the rate of cooling steel in the mold governs ingotism, segregation, the formation of dendrites, and the distribution of intergranular material; and the resulting effect these conditions have on the physical qualities of the steel before annealing, after annealing, and after forging. The paper also describes how the structure of steel is affected by the design of the mold and the method of pouring. It is shown that the various constituents of carbon steel segregate differently under different rates of cooling. For the classes of steel covered in this paper, it is concluded that the best physical structure and the most uniform chemical composition is obtained by pouring the steel at a low temperature and solidifying as rapidly as possible in the mold. MUCH time has been devoted, by metallurgists, to the study of steel after solidification and remarkable strides have been made in the heat treatment of steel, but less knowledge is available of the thermophysical, activity of the constituents of steel prior to solidification in the mold. It is known that certain elements added to steel produce marked changes in physical properties, also that other elements added to steel produce similar changes, but we have only meager knowledge as to how these elements combine in steel under different conditions of solidification. It is not sufficient to know, from chemical analysis, that a certain element is present in steel. We should know how this element is in combination with the other elements and whether the combination is such as will give the greatest physical properties. Certain elements go into solid solution with the iron, while others segregate to the grain boundaries and combine with the impurities collected there. Until it is known where an alloy produces the most beneficial effect and a means, is determined for controlling its physical location by altering solidification conditions, or otherwise, we will not obtain the maximum value from our alloys.

Jan 2, 1924

By Frank W. Dickson, George Tunell

Five hot spring areas of the western United States show evidences of present day deposition of HgS; two also show evidences of accompanying Sb2S3 deposition. Sulfide minerals are depositing at or near the surface from hot waters that differ for each spring ai:ea in amount and kinds of dissolved matter. All the springs contain dissolved substances that act as buffering agents and that cause increased alkalinity with increasing temperature. Transport of Sb2S3 is possible in H2O and in boron and sulfide solutions. Increasing alkalinity and temperature enhance stibnite solubility. Quantitatively important transport of HgS appears restricted to alkaline sulfide solutions that contain HgS2=. Elemental mercury probably forms in deep hot waters because HgS breaks down into mercury and sulfur above 200°C, and free S is removed by reaction with water. Elemental mercury should accompany HgS2= in solutions that were at 200°C or higher. Cinnabar deposits from saturated alkaline sulfide solutions because of combinations of temperature decrease, dilution, oxidation, and reactions with wall rock: Amedee Hot Springs, Boiling Springs, and Coso Hot Springs are areas in which HgS is the only sulfide deposited. Hot waters at Amedee and Boiling Springs are supersaturated with HgS or transport colloidal HgS. Steamboat Springs waters deposit mainly silica and stibnite, but they have deposited HgS recently. Sulphur Bank waters deposit mostly stibnite and some HgS. The hot-spring waters of all springs represent highly modified deep water. Field and laboratory studies support the concept of transport of HgS in moderately alkaline sulfide solutions as HgS2=. Fluctuating deposition of stibnite and cinnabar reflects availability of sulfide or variations in deep-source HgS and Sb,S,. Silica and HgS dissolve mutually in alkaline sulfide solutions, and cinnabar and quartz would be expected to deposit simultaneously. Free mercury given off by hot-spring waters would impregnate country rocks.

Jan 1, 1968

By J. W. Spretnak, V. Kandarpa, G. W. Powell, R. A. Erickson

Neutron-diffraction pattens were obtained at room temperature from two austenitic manganese steels, oxc wth n carbon content of 1.23 zct PC/ and the olher 0.63 wt pct. Analysis of the data showed that the curOan atols (ions) occupy tile octaheadral site. any of the cavbon is in the tetahedral site, tile concentration is too strzall lo be detecled by tzeulr-on d$facton. AS part of a long-range investigation of eutectoid decomposition, a study of the structure of austenite has been undertaken in order to characterize as best as possible the parent phase in the Fe-C system. Austenite is a solid solution of carbon atoms in fcc iron, the carbon atoms being located in interstitial positions. Of the two kinds of interstitial sites, octahedral (0, +, +) and tetrahedral (4, a, $), in this lattice, the larger octahedral sites are usually considered as the probable position of carbon. The strain energy involved in pytting a neutral carbon atom (covalent di; ameter 1.54)' into a tetrahedral site (diameter 0.56A) is considerably greater than that associated with p2tting carbon into the octahedral site (diameter 1.08A). Dayal and arkeen' observed the migration of carbon in iron under the influence of an electric field indicating tha tye carbon is ionized. pe ionic radius of C'4 is 0.15A and that of C" is 0.29. Consequently, it is conceivable that carbon ions could occupy the tetrahedral sites if one considers only the strain energy. Size considerations alone do not provide a complete explanation for the formation of the interstitial solid solutions, however. because metals such as copper, zinc, and cadmium do not appear to form interstitial solid solutions in spite of their large interstitial sites. Evidence which suggests partial ioni-zation of the carbon in austenite has also been obtained by Speiser, Spretnak, and alor who derived formu- lae relating the observed change in lattice parameter to the effective diameter of the solute atom. Assuming the carbon occupies the octahedral site. they computed the effective diameter of carbon to be 1.33A whereas the covalent diameter is 1.54A. petch5 concluded from powder X-ray diffraction experiments that carbon atoms occupy the octahedral sites. His conclusion was based on the general trend observed in the intensity of the diffraction lines as the carbon content of the austenite was increased. However, the major difficulty associated with application of X-ray diffraction to this particular problem is the relatively poor scattering power of carbon. Williamson and smallman' utilized X-ray diffraction to study the line broadening caused by the strain field about carbon atoms inferrite: these investigators concluded that at least 85 pct of the carbon in ferrite occupies the octahedral (0: 3, B) site rather than the larger

Jan 1, 1967

By E. A. Peretti

BEFORE embarking on a detailed investigation of the system indium-antimony-bismuth, experiments were carried out to determine the existence of quasi-binary sections. The bordering binary systems are known1 and show the occurrence of three intermetallic binary species corresponding closely to InSb, InBi and In2Bi. Attention was focused on the low-indium end of the ternary diagram where the possible quasi-binary sections, excluding ternary compound formation, would involve the pairs: InSb-Bi, InBi-Sb and InSb-InBi. The latter pair revealed itself as a true quasi-binary, so it was investigated fully by thermal analysis, x-ray and microscopic examinations. All compositions were made by proper combination of three elements involved. The indium had a guaranteed purity of 99.97 pet; the antimony contained 99.99 pet Sb, and the bismuth had a purity of 99.99 pet. Alloys were made by melting together antimony, bismuth and indium in evacuated, sealed pyrex-glass tubes at a temperature of 600°C with vigorous agitation. The melts, weighing about 80 grams, were allowed to freeze in the sealed tubes and finally were transferred to glass tubes for the taking of cooling and heating curves. A protective atmosphere of helium was used, and the melts were stirred mechanically while cooling at rates of from 0.5 to 3°C per min. Temperatures were measured with a calibrated chromel-alumel thermocouple and were recorded graphically on a Minneapolis-Honeywell extended-range recorder working in conjunction with a Leeds and Northrup type K-2 potentiometer. Conventional polishing techniques gave satisfactory results in preparing specimens for microscopic examination. Etching was carried out with Vilella's reagent or aqueous mixtures of chromic oxide with either nitric acid or sulfuric acid plus dichromate. Conclusions deduced from the thermal analysis and microscopic examinations were confirmed by X-ray photograms using Co-K alpha radiation. The phase diagram is shown in Fig. 1. The liqui-dus consists of an uninterrupted line running from the freezing point of InSb (525°C) to a eutectic point experimentally indistinguishable from the freezing point of InBi (110°C). X-ray patterns of the InSb show a slight expansion of the lattice with the addition of InBi, and microscopic work indicated the solid solubility of InBi in InSb to be less than 0.5 pet at room temperature. Acknowledgment We wish to thank the Indium Corporation of America for the loan of the indium used in this investigation. References 1 E. A. Peretti and S. C. Carapella, Jr.: Trans. ASM., 1949, vol. 41, P. 947. T. S. Liu and E. A. Peretti: Trans. ASM, 1952, vol. 44, p. 539. Metals Reference Book, vol. 1, 2nd ed., AIME, p. 345.

Jan 1, 1959

COUNCIL OF EDUCATION OF AIME (Formerly Mineral Industry Education Division) Established as a Division January 15, 1932 Established as a Council February 26, 1957 John C Calhoun, Jr, Chairman 0 Cutler Shepard, Vice-Chairman Thomas A Read, Secretary-Treasurer Dept of Mining & Metallurgical Engrg University of Illinois Urbana, Illinois COUNCIL OF ECONOMICS OF AIME (Formerly Mineral Economics Division) Established as a Division December 15, 1948 Established as a Council February 26, 1957 Louis C Raymond, Chairman Lorin A Cranson, Vice-Chairman Henry T Mudd, Vice-Chairman Adam K Stricker, Jr, Vice-Chairman Paul F Yopes, Secretary-Treasurer U S Bureau of Mines Albany, Oregon

Jan 1, 1957

Organization Place Date 1917 American Electro-Chemical Society Detroit; Mich. May 2-5 American Waterworks Association Richmond, Va. May 7-11 American Institute of Electrical Engineers New York City May 18 America' Society of, Mechanical Engineers Cincinnati, Ohio May 22-25 American Iron and Steel Institute New York City May 25-26 ' Interstate Oil Mill Superintendents Association. Augusta, Ga. May (last wk.) Electric Power Club Hot Springs, Va. June 11-14 Society for the Promotion of Engineering Education .... Evansville, Ind. June 19-22. American Institute of Electrical Engineers Hot Springs, Va. June 25 American Society for Testing Materials Atlantic City, N. J. June 26-30

Jan 5, 1917

By Jack A. Kanz, Samuel R. Shortes, E. C. Wurst

Zinc diffusion into GaAs from the vapor phase through reactively sputtered SiO, films Izas been inrestigated for various zinc pressures at 1000"C. Diffusions were carried out in evacuated quartz ampules with elemental zinc and with various Zn-Ga alloys. Sputtered films have proved effective in lowering surface concentrations and preventing surface deterioration during diffusion. Approxin.ate complenzentary error-function impurity distributions were found when surface concentrations were reduced to approximately 3 -—4 x 10" atoms cm'3 or less with dilute zinc sources or by diffusion through SiO, films. Zinc difhsions in GaAs tlzrough SiO, films produced more planar diffusion fronts than were observed with uncoated zuafers under identical conditions. A) Surface Deterioration During Diffusion. Device technolorn-- in compound semiconductors has been hampered by several difficult problems not normally encountered with silicon and germanium. 111-V and 11-VI compound semiconductors generally have volatile constituents at temperatures used for diffusion. To achieve specific junction depths in reasonable lengths of time, or to obtain particular impurity distributions and doping levels, it is often necessary to use temperatures which cause surface deterioration and erosion of the wafer. The resultant surfaces are generally unsuitable for devices. The type and extent of surface damage depends to varying degrees on the particular environment of diffusion and on the particular impurity in question. The most common type of deterioration results from simple dissociation of the gallium and the arsenic during diffusin.' The deterioration process is significantly enhanced by thermal gradients in the diffusion zone, usually resulting in vapor transport and condensation at the cooler portion of the system. The resulting damage sometimes appears as a general haziness over the surface or an array of pyramidal etch pits characteristic of the particular orientation. Occasionally, erosion of the surface occurs uniformly over the wafer so that surface loss is not readily apparent. Workers in GaAs usually resort to the sealed-ampule type of diffusion system3"5 rather than the more conventional open system used for silicon and germanium. Another type of deterioration results from direct interaction of the impurity with the surface. The form of deterioration may vary from surface alloying, as in the case of zinc, to direct chemical attack and vapor transport of the reaction products, as in the case of sulfur. Surface alloying with zinc occurs at higher temperatures and source vapor pressures.4 The process is largely controlled by the amount of free gallium on the surface of the wafer in equilibrium with the arsenic lost to the system. The group-VI elements, sulfur, selenium, and tellurium, are commonly used donor impurities for gallium arsenide. These elements are characterized by high vapor pressures and high chemical

Jan 1, 1964

By F. M. d’Heurle

Films of molybdenum have been prepared by sputtering onto oxidized silicon substrates. The resistivity. lattice parameter, orientation, and grain size were studied as a function of substrate temperature and substrate bias. Under normal sputtering conditions, the resistivity of the films was found to be quite high (600 x 10 ohm-crn). However, with the use of the negative substrate bias of 100 v and a substrate temperature of 350°C, films weve produced with a resistivity of ahout twice that of bulk molybdenum. The lattice parameters measured in a direction nornzal to the surface of the films weve found to be gveatev than the bulk value. This was interpreted as being at least partly due to the presence of compressive stresses. The effects of annealing in an Ar-H atmosphere were studied in terms of diffraction line width, lattice parameter, and resistivity. BECAUSE of its relatively low bulk resistivity (5.6 x 106 ohm-cm)' molybdenum is potentially interesting as a thin-film conductor in integrated circuits. An additional feature which makes it attractive for this purpose is its low coefficient of expansion (5.6 x KT6 per "c),' which is fairly well matched to that of silicon (3.2 x 10 per c). It is possible to deposit molybdenum films by evaporation but generally films produced in this manner have a high resistivity. In order to achieve resistivities close to bulk value, Holmwood and Glang found it necessary to operate in a vacuum of about 107 Torr and to maintain the substrates at 600 C during film deposition. Sputtered molybdenum films have been examined by Belser et a1.7 and, recently, by Glang et al.' This paper describes the results of an attempt to extend some of that work and examine the effects of annealing and getter sputtering on the physical and structural properties of the films produced. SPUTTERING APPARATUS AND PROCEDURE The apparatus used for most of the film sputtering work described here consisted of two "fingers" serving as anode and cathode, respectively, which were mounted within an 18-in.-diam glass chamber. A liquid nitrogen-trapped 6-in. diffusion-pump system was used to achieve a vacuum of about 1 x 107 Torr within the chamber prior to sputtering. The essential features of the equipment are shown in Fig. 1. Cathode and anode fingers are stainless-steel tubes isolated from the top and bottom plates by Teflon collars. In order to limit the discharge to the space between anode and cathode, each finger is surrounded by an aluminum hield, at ground potential, having an internal diameter 18 in. larger than the outside diameter of the finger. The cathode and anode fingers are 6 and 4 in. in diam, respectively. A 116-in.-thick sheet of molybdenum is brazed with a 10 pct Pd, 58 pct Ag, 32 pct Cu alloy to a copper disc which is mounted by means of screws and a large 0 ring onto the lower end of the cathode finger. The disc is cooled during sputtering by water circulation inside the finger. The use of several feet of plastic tubing for the water input and outputg reduces leakage to ground to less than 1 ma when the cathode potential is raised to 5 kv. The upper end of the anode finger is terminated by a brazed-on copper block. A variety of specimen holders can be easily mounted on the upper face of this block. Substrate heating or cooling is achieved by use of an appropriate unit attached to the lower face of the same block. Heating is achieved by means of cartridge-type heaters and cooling by copper coils fed with forming gas under pressure. The inner chamber of the specimen finger constitutes a small vacuum chamber of its own which is evacuated by an auxiliary mechanical pump in order to limit heating element oxidation and heat transfer by convection currents. An advantage of the finger arrangement is the absence of cooling and heating coils and wires within the main chamber. The stain less-steel shutter is useful to establish a discharge for cleaning the cathode at the beginning of each sputtering run. Water cooling of the shutter reduces heating and the out-gassing of impurities which might condense on the nearby substrates. Unless otherwise specified, the substrates used in these experiments were 1-in.-diam oxidized silicon wafe:s, 0.007 in. thick, having an oxide thickness of 6000A. The substrate holders were large copper discs onto the surface of which a number of molybdenum discs, 116 in. thick and 78 in. in diam, were brazed. The wafers were clamped to the molybdenum discs

Jan 1, 1967

By P. Shahinian, H. H. Smith, M. R. Achter

Crack growth rates are measured at elevated temperature in a resonant fatigue machine from vibration frequency decreases calibrated in terms of crack depth. Crack growth rates in Type 316 stainless steel at 500º and 800°C show a sharp increase with oxygen pressure in an intermediate pressure range and little or no change at high and low pressures. At 500°c, I torr of oxygen reduces the fatigue life by almost a factor of 100 in comparison to that in vacuum and raises the growth rate of shallow cracks by the same At At 800°C the effects are smaller. Changes in slope in the crack growth rate curves are discussed in terms of a model in which rates of surface production and of surface coverage by gas are compared. The use of a calculation method in which the surface exposure time is equal to X/v, where x is the interatomic spacing and v is the growth rate, makes it possible to obtain order of magnitude agreement at 500°C between the observed pressure and the predicted pressure at these slope changes. At 800°C oxidation becomes a .factor and the data cannot be treated by simple adsorption theory. THE decrease in the fatigue life of metals as a function of gas pressure usually follows a stepped curve with virtually all of the decrease concentrated in a sharp drop in a transition zone at intermediate pressures and little or no change at low and high ranges. A number of models, differing in the details of the mechanism, have been offered to explain the shape of the curve. Measurements of crack growth in aluminum as a function of gas pressure by Bradshaw and Wheeler' and Hordon2 demonstrated opportunities for quantitative comparison to evaluate the proposed models. Since comparable data were lacking at high temperatures, in the present work rates of crack propagation were measured in Type 316 stainless steel at 500" and 800°C as a function of oxygen pressure. Choice of this material was dictated by two considerations; it is stiff enough at these elevated temperatures to resonate with the regenerative drive on our fatigue machine and it is known to display a large effect of environment. A new method of calculation is described to predict the gas pressure at the critical point. EXPERIMENTAL PROCEDURE Because of the difficulty of measuring crack depths directly at high temperatures, an indirect method was developed based on the decrease in the resonant frequency with the growth of a crack. A reversed bending, constant amplitude fatigue machine, described previously,3 vibrates a specimen at its resonant frequency, automatically records any changes in it and shuts itself off after it has reached a preset value of frequency decrease. The record of frequency change is used to determine the rate of crack growth. Sheet type specimens of Type 316 stainless steel, Fig. 1, incorporated a sharp, shallow notch to localize the formation of a single crack. After machining, they were annealed in a vacuum of l0-6 torr either at 1066" (lot A) or 871°C (lot B) and then electropolished in an acetic-chromic acid solution. Bending strains were measured at 500" and 800°C by an optical technique4 and reported as total strain without correction for the notch. At 500°C, the 0.141 pct strain was 0.085 pct elastic and the remainder plastic. At 800°C the 0.062 pct strain was all elastic. To convert frequency decrease to crack length, calibration curves were obtained by interrupting the vibration at stated intervals of frequency decrease. The crack depth was measured microscopically at a magnification of X400 and reported as the average of the measurement on each edge. Some specimens were sectioned for crack measurement while others were returned to the machine and fatigued further. There was good agreement between the two methods. Before beginning the vibration, the vacuum chamber was first evacuated cold to 1 x 1O-6 torr, then heated to the operating temperature and held there until the pressure was again reduced to 1 x10-6 torr at which time oxygen was introduced to the desired pressure. In this investigation the vibration frequency was nominally 10 cps and a decrease of 0.6 cps was taken as the failure point. The choice of the frequency decrease to represent failure has no appreciable effect on the fatigue life because the crack is growing very fast at this point.

Jan 1, 1970

By M. D. Hassiallis

The claim is made in a number of patents1'2'3'4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S2-R' (where x = 1,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using diphenyl sulphide, ditolyl disulphide and dinapthyl disul-phide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed. was that of Moses, Hess, and Perkins. A sample of ore weighing 500 • grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65-mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a a-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8:I. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of I2:I. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. Contact-angle Tests In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcodte, chalco-pyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By M. D. Hassiallis

The claim is made in a number of patents1'2'3'4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S2-R' (where x = 1,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using diphenyl sulphide, ditolyl disulphide and dinapthyl disul-phide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed. was that of Moses, Hess, and Perkins. A sample of ore weighing 500 • grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65-mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a a-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8:I. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of I2:I. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. Contact-angle Tests In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcodte, chalco-pyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By Raymond E. Birch, Oscar M. Wicken

THE mineral magnesite, formerly the source of nearly all magnesia, now shares this role with brucite, dolomite, and the world's natural and artificial brines. The mineral magnesite is the normal carbonate of magnesium, MgCO3, composed when pure of 47.6 pct MgO and 52.4 pct CO2. It is one of the calcite (CaCO3) group of rhombohedra1 car- bonates, which also includes dolomite, CaCO3.MgCO3, and siderite, FeCO3. Magnesite does not form an isomorphous series with calcite or dolomite; consequently, these lime-bearing carbonates commonly present in magnesite deposits are there only as mechanical mixtures. Magnesite and iron carbonates form a continuous isomorphous series and therefore are inseparable mechanically. The variety of magnesite known as breunnerite is an isomorphous mixture of iron and magnesium carbonates. Magnesite may be either crystalline or amorphous (cryptocrystalline). The former, which includes breunnerite, is often termed spathic magnesite. Crystalline magnesite varies from finely to coarsely crystal- line in texture and has a hardness of 3.5 to 4. The color is white, yellowish, blue-gray to drab, red, pink, black, or mottled. It is seldom found pure but usually contains variable amounts of iron, lime, silica, and sometimes manganese. The color cannot be used as an index of purity. The cryptocrystalline variety is perhaps the more common type but the crystalline variety usually occurs in larger deposits. The amorphous type is fine grained and compact, showing no cleavage. It is usually snow white but sometimes is light to pale orange yellow or buff, owing to impurities. The fracture is conchoidal to uneven and the hardness 3.5 to 5. Silica may be present as inclusions of serpentine, quartz, chalcedony, or other minerals. The lime and iron contents are usually low. In general, amorphous magnesite is somewhat purer than the crystalline variety. The specific gravity of cryptocrystalline magnesite is 2.90 to 3.00. Pure crystalline magnesite has shown a specific gravity of 3.02 but iron

Jan 1, 1949