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By J. F. Radavich

Many heats of steel of low carbon value have been known to produce brittle pieces of steel. The brittleness is believed to be due to the impurities located within the grain boundaries. Such brittle steels have been examined with an optical microscope to ascertain the nature and the amount of the impurities present at the grain boundaries. Due to the relatively low resolving power of the optical microscope, the impurities are not visible in fine detail. The writer obtained some sheet steel and proceeded to determine the location of the impurities and to show the application of the electron microscope to the study of grain boundaries. One sample was known to be capable of becoming embrittled, whereas another sample was believed to be much less susceptible to embrittlement. Treatment of Specimens The specimens were embrittled by annealing above the A3 point under mildly oxidizing conditions. One piece of ingot iron could not withstand a 90" bend, whereas another piece of ingot iron was not affected and could withstand a 90" bend. The brittle piece was then annealed at a high temperature in a hydrogen atmosphere. The annealed ingot iron was termed cured and could withstand a 90" bend very easily. The three specimens examined will be designated as brittle, good. and cured in the discussion that follows. Procedure The sizes of the specimens were as follows: one piece of brittle ingot iron-3/8 by 35 in.; one piece of good ingot iron-96 by 1/8 in.; one piece of cured ingot iron-36 by 54 in. The specimens were too small to be polished by hand and therefore were mounted in bakelite. The polishing procedure was carried out in the conventional manner with the use of 1/0 through 3/0 papers, and the final polish was done with alumina on a billiard cloth. The specimens were then etched in a 4 pct solution of picral in alcohol, and then they were examined through an optical microscope. An area was chosen that showed distinct grain boundaries, and an effort was made to keep near this area when pulling the replicas REPLICA TECHNIQIJE The replica technique used in the preparation of the replicas for examination under the electron microscope is described in Electron Metallography.' It consists essentially of the following steps: 1. Obtaining a suitably etched specimen. 2. Applying a swab of ethylene di-chloride on the surface. 3. Applying a formvar solution on the surface. 4. Placing a screen on any desired spot. 5. Breathing on the fornivar layer. 6. Applying scotch tape on the screen and film. 7. Pulling the film and the screen up with the Scotch tape. 8. Separating the screen from the Scotch tape. This replica technique is very similar to the one described by Harker and Shaefer. However, with the added step, the percentage of replicas removed is very much higher regardless of the length of the time from the etching of the specimen to the actual pulling of the replica. The replicas were then shadow cast with manganese at a filament height to replica distance ratio of 1 1/2:7. This produced a very high contrast replica for use in the electron microscope. One of the dificulties encountered with this study was the restricted area of the specimen. The width of the specimens was the same as that of the 200 mesh nickel supporting screen. In order to increase the effective area, the screens were cut down as shown in Fig 1. The arrow indicates the direction in which the replica was pulled. This operation made it possible to obtain a large percentage of good replicas. Fig 3 shows an electron micrograph of a brittle piece of ingot iron and a grain boundary that was polished mechanically. The surface is very rough probably due to the incomplete removal of the flowed layer by the picral etchant. The grain boundary does show evidence of impurities. It was decided to electropolish the specimens to obtain a much smoother surface than the one obtained by mechanical polishing. ELECTROPOLISHING The specimens were cut in half to expose the metal on the back side. The exposed metal had sufficient area to make good electrical contact and electropolishing was carried out easily. The conditions for electropolishing were 0.9 amp, 35 volts, and 25 sec. in an electrolyte composed of 850 cc of ethyl alcohol, 100 cc distilled water, and 50 cc of perchloric acid. The polished specimens were then etched in the 4 pct picral solution for a shorter time than was necessary for

Jan 1, 1950

The Library of the above-named Societies is open from 9 A.M. to 9 P.M. on all week-clays, except holidays, from September 1 to June 30, and from 9 A.M. to 6 P.M. during July and August. The Library contains about 55,000 volumes, including sets of technical periodicals and the publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend a portion of their time in localities isolated from sources of information. To these the Library can render valuable service through correspondence; letters requesting information will receive special attention. The Library is prepared to furnish references and copies of articles on mining and metallurgical subjects; to determine the existence of mining-maps, and to furnish general information as to the geology and mineral resources of all countries. All communications should be made as definite as possible so that the information received may be what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable shape. The members of the Institute can be of service to the Library by forwarding copies of mining-reports, maps privately issued, and similar material, which will be classified, indexed, and made available to other members. Suggestions for additions to the Library, either by purchase or personal solicitation as gifts, will be welcomed. It is hoped that members while in the city will use the Library freely, and assurance is given that most careful service will be rendered to them.

Jan 4, 1913

By Cyril Wells, Robert F. Mehl

The two earlier papers in this series1,2 presented data on the rate of diffusion of carbon and of manganese in gamma iron. Apart from their scientific interest, these data are needed chiefly in order to treat data on carburization, on rate of formation of pearlite, and on rate of austenit-izing in a quantitative way.1'2'9'10 In the present investigation rates of diffusion of nickel in ?-Fe over wide temperature and concentration ranges have been determined, and the effects of carbon, of im- purities, and of grain size on these rates have been studied. Claussen,3 using the data of Fry,4 has calculated the diffusion coefficient of nickel in y-Fe as 9.2 X 10-11 sq. cm. per sec. at 1200ºC., but had no data from which to calculate the variation of D with concentration, temperature, and percentage of carbon. Method and Materials Method.—Nickel was diffused along the axis of a cylindrical specimen across a concentration gradient, concentration-penetration curves were determined and D values calculated from Grube or Matano solutions.5 Details of the method are given

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The two earlier papers in this series1,2 presented data on the rate of diffusion of carbon and of manganese in gamma iron. Apart from their scientific interest, these data are needed chiefly in order to treat data on carburization, on rate of formation of pearlite, and on rate of austenit-izing in a quantitative way.1'2'9'10 In the present investigation rates of diffusion of nickel in ?-Fe over wide temperature and concentration ranges have been determined, and the effects of carbon, of im- purities, and of grain size on these rates have been studied. Claussen,3 using the data of Fry,4 has calculated the diffusion coefficient of nickel in y-Fe as 9.2 X 10-11 sq. cm. per sec. at 1200ºC., but had no data from which to calculate the variation of D with concentration, temperature, and percentage of carbon. Method and Materials Method.—Nickel was diffused along the axis of a cylindrical specimen across a concentration gradient, concentration-penetration curves were determined and D values calculated from Grube or Matano solutions.5 Details of the method are given

Jan 1, 1941

By Henry B. Smith, S. Paul Lindau

ThREe years ago it was decided by the management to granulate the matte that is produced in the smelter of the St. Joseph Lead Co. at Hereulaneum, Mo., thereby doing away with a large amount of labor in handling the matte and in subsequent crushing. On Mar. 1, 1915, the granulator was put in operation and up to Jan. 1, 1916, 18,735 tons had been granulated. The four blast furnaces have a daily output of about 280 tons of pig lead and 100 tons of matte assaying about 11.0 per cent. Pb. It is expected that projected improvements in roasting methods will eliminate more sulphur from the charge, and cut down the matte-fall to about one-half of the present figure. The blast furnaces are tapped into movable forehearths or settlers, 6 ft. by 4 ft. by 22 in., the slag overflowing into 27-cu. ft. slag cars which are hauled to the dump by electric locomotives. Previous to the adoption of granulation, the matte was tapped from the forehearths into small slag pots which were dumped after cooling. The matte cakes were broken with sledges, and transported to the crushing plant for fine crushing and screening. Here the matte was reduced to 1/4-in. size before being fed to the roaster bins. A Wedge and a Holthoff mechanical furnace are used for preroasting before sintering on the Dwight and Lloyd machines. The matte is returned to the furnaces as an iron flux until the gradually accumulating copper content reaches about 7 per cent., after which it is put aside to be concentrated in a small copper blast furnace, the resultant high-grade matte being sold. When the matte does not settle readily from the slag, two settling devices are often used, the second one being a large catch-pot, which gathers any matte that may overflow from the forehearth, the slag then overflowing from the catch-pot into the slag cars. When full of matte, the catch-pot is removed, allowed to cool, and the contents broken and crushed. a With the present plan of granulating, the matte is tapped into 6-cu. ft. iron ladles. These are transported to the granulating plant by a 5-ton

Jan 1, 1917

By Rainer Kahrger

During the last decade, advances were made in solvent extraction/electrowinning (SX/EW) technologies. Combined with heap leaching, these technologies made it viable to exploit large, low-grade oxide copper deposits. The El Abra Mine is a good example for such a deposit. The deposit is situated in northern Chile at an elevation of about 4,000 m (14,000ft), 70 km (45 miles) north of Calama. Codelco sold 51% of the El Abra to Cyprus Minerals in June 1994, with Codelco retaining the balance. In 1993, Cyprus and the engineer on the project began discussions withinternational companies regarding the materials-handling system requiredfor the project. These early discussions were considered critical for this fast-track project.

Jan 1, 1996

By Dennis C. Martin

Construction of the Cerro Colorado on-off leach pad in northern Chile required about 3 Mm2 (32.3 million sq ft) of fill over an area of about 600,000 m2 (6.5 million sq ft) in irregular terrain with relief of up to 40 m (130 ft). Earthwork construction was completed in about six months using mine waste, placed in 4 to 6 m (13 to 20 ft) lifts with mine haul trucks. The lift thickness was reduced and the compactive effort increased in the upper 10 m (33 ft). This was done to develop a mat for additional resistance to possible differential settlements due to the modest density of the fill and dynamic (earthquake) conditions. A single 2-mm (80-mil) high-density polyethylene (HDPE) liner was used below the leach pads. This was protected from the loading and unloading equipment by bedding and cover systems. It consisted of screened sand, gravel and silt as the bedding and cover layers and a heel of screened gravel and primary crushed low-grade ore.

Jan 1, 1995

By S. Kashani-Nejad

The kinetics of the thermal decomposition of samples of Mg2(OH)3Cl.2H2O that were obtained by a novel leaching technique applied to a commercial magnesium electrolysis feed were investigated under ambient atmosphere. Thermogravimetric (TG) Analysis showed that decomposition of Mg2(OH)3Cl.2H2O exhibited a single intermediate stage wherein crystalline water was lost at roughly 108 °C. Conversion of the resulting Mg2(OH)3Cl to MgO, HCl and 1120 occurred at temperatures above 398 °C. Thermal decomposition of anhydrous Mg2(OH)3Cl was seen to be consist of two stages. Both stages exhibit first order kinetics with respect to the weight percent of Mg2(OH)3Cl remaining in the sample. However, the rates of decomposition in the two stages were significantly different. Detailed analysis of the kinetic data suggested that the rate of decomposition of Mg2(OH)3C1 was controlled by the rate of removal of the gases released. The change in decomposition rate during the course of the experiments was explained by HCI being released in stage 1 and followed by release of H2O in stage 2.

Jan 1, 2004

By C. M. Bartley

Canada has been a producer of sulphur in various forms for about 100 years, Pyrites, as a source of sulphur dioxide for the manufacture of sulphuric acid, were being mined in the 1860's. Smelter gas, for the same purpose, has been recovered since 1928. Between 1935 and 1943, and from 1952 to the present, elemental sulphur has been produced in Canada from two raw material sources and by several methods. This paper attempts to present a view of the current status of the elemental sulphur industry in Canada based on the sour gas fields of Alberta and British Columbia. Production from this source has increased rapidly in the past 12 years to make Canada one of the major sulphur producers of the world. The present industry in Canada relies mainly on sour gas sulphur and it is expected that it will continue to grow in the future. However, before describing current activity relating to sour gas it may be of interest to outline briefly the early pyrite activities, the roots of the sulphur industry in Canada.

Jan 1, 1964

The Library of .the above-named Societies is open from 9 A.M. to 9 P.M. on all week-days; except holidays, from September 1 to June 30, and from 9 A.M. to 6 P.M. during July and August. The Library contains about 55,000 volumes, including sets of technical periodicals and the publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend a portion of their time in localities isolated from sources of information. To these the Library can render valuable service through correspondence; letters requesting information will receive special attention. The Library is prepared to furnish references and copies of articles on mining and metallurgical subjects; to determine the existence of mining-maps, and to furnish general information as to the geology and mineral resources of all countries. All communications should be made as definite as possible so that the information received may he what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable shape. The members of the Institute can be of service to the Library by forwarding copies of mining-reports, maps privately issued, and similar material, which will be classified, indexed, and made available to other members. Suggestions for additions to the Library, either by purchase or personal solicitation as gifts, will be welcomed. It is hoped that members while in the city will use the Library freely, and assurance is given that most careful service will be rendered to them.

Jan 6, 1913

The words ""Uncertainty"" and ""Risk"" pervade every discussion about mining exploration and investment. Perhaps these terms are subjectively understood by industry professionals, but objective portrayal of these concepts outside the industry is a woefully undeveloped science. This paper addresses current industry understanding and practice regarding quantitative risk assessment techniques, and provides examples of the application of three of these techniques. Probabilistic techniques for financial risk assessment are valuable adjuncts to conventional financial analysis, and address a range of issues not assessable by any other means. The value of whole-of-project probabilistic risk assessment is currently debatable for decision-making purposes, but is seen as important as a mechanism to focus attention to the critical issues that ultimately impact on project success. The dissection of project capital into risk and non-risk components provides valuable insights into risk characteristics not readily quantifiable in any other way. This technique also provides a framework for more objective ""what if?"" scenario evaluation and for the capital structure of resource projects. Finally, mechanisms for the valuation of undeveloped reserves are examined, and guidelines suggested. The importance of reliability in production cost estimates is highlighted and the impact of early development on reserve valuations is discussed. The importance of economics throughout all stages of the evaluation process is fundamental.

Jan 1, 1994

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly, subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fume less fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003

By R. M. Santmyers

Umber and sienna, like ocher, are naturally occurring mineral pig- ments composed largely of clay permeated with hydrated iron (ferric oxide), but they differ from ocher in that they also contain hydrated manganese oxide. The presence of manganese accounts for their browner color. In addition to silica and alumina (clay) and the coloring oxides of iron and manganese, these pigments often contain lime, barium, and other metallic salts as impurities. Sienna most nearly approaches ocher in chemical composition, and the chief distinction is its physical character. It grades into ocher with de- creasing iron content and into umber with increasing manganese content. Sienna is translucent rather than opaque and is more of a stain than a pigment; as the iron oxide content is rather high (often 60 to 80 per cent), the color is strong and rich and varies from pure brown to reddish brown. This pigment raw sienna, terra di Siena, and Italian earth. is known under several names: Burnt sienna is a pigment of an orange-brown tint made by cautionsly calcining raw sienna. It is divided into two grades; American, and Italian burnt sienna. American burnt sienna is a reddish-brown pigment containing from 25 to 60 per cent iron oxide (Fe2O3). One grade, found in Pennsylvania, analyses as high as 80 per cent and is mown as double strength sienna. Italian burnt sienna is a pigment generally containing more iron than the American product, averaging 60 to 75 per cent iron oxide.3 American pig- ments of the same iron content differ materially in shade, having a Havana- brown color, whereas the Italian is more of a maroon. Italian siennas when tinted with 20 per cent of white, show a bluish tint, whereas American siennas yield a brownish or yellowish hue. Raw umber, also known as Turkey umber, Levant umber, and terra ombra, is a greenish to yellowish brown siliceous and ferruginous earth, containing a considerable proportion of one or other of the higher oxides of manganese, Mng04 and MnO2." It is similar in many respects to raw sienna except that it is much coarser and contains more manganese oxide. All umbers contain over 5 per cent of manganese dioxide. Like sienna, umber is a permanent pigment, not being injured by light or by impure atmospheres. Burnt umber (velvet brown, chestnut brown, etc.), results from the calcination of raw umber. The color is much richer and warmer than that of the raw umber. The colors are equally permanent and can be used in conjunc- tion with all other durable pigments.

Sep 1, 1931

By W. H. Eddy

The Bureau of Mines conducted laboratory batch-and small-scale continuous flotation processing tests on waste granite fines from Georgia, to determine the feasibility of recovering usable feldspar and quartz products by flotation. Two flotation methods were utilized for the removal of biotite and other iron-bearing minerals: One was in an acid-cationic circuit, and the other in an alkaline-anionic-cationic circuit. Feldspar was recovered using an acid-cationic method. To produce commercial-grade feldspar and quartz products it was necessary to employ either two sequential froth flotation circuits or one froth flotation circuit supplemented by wet-magnetic separation techniques to remove iron contaminants. Continuous flotation processing yielded a commercial-grade feldspar concentrate containing, in percent, 3.8 Na20, 5.4 K20, and 1.10 CaO, with recoveries of 77.8, 70.3, and 64.4, respectively. The feldspar tailing was high-quality glass sand containing 98.2 percent SiO2 and 0.024 percent Fe2O3. About 42 percent of the quartz was recovered at glass sand specifications. An effective separation of, potash feldspar from the bulk feldspar concentrate was achieved by batch flotation in a mineral separation cell.

Jan 1, 1974

By C. D. Adams, R. T. Tuenge, C. N. King, J. A. Samuels, B. F. Espinoza, R. C. Dye, C. F. Schaus, D. C. Smith, N. M. Peachey

"Recently, doped calcium thiogallate (CaGa2S4) phosphors have been investigated for use in electroluminescent flat panel displays. The current technique used for the deposition of thin film calcium thiogallate is sputtering. Unfortunately, this requires a high temperature annealing process to provide the desired crystallinity of the phosphor. Recent efforts have focused on the possible use of metal-organic chemical vapor deposition (MOCVD) to produce the CaGa2S4 layer. The use of MOCVD provides an attractive alternative to sputtering since it does not require heating above the strain point temperatures of the glass substrates used for the display panels. To accomplish this, the deposition of both Ga2S3 and CaS is investigated as these compounds are intermediate steps in the development of the phosphor deposition. Uniform, crystalline films of both Ga2S3 and CaS were deposited and the process shows promise for successful deposition of the CaGa2S4 phosphor.IntroductionThe lack of a satisfactory blue phosphor having sufficiently high luminances at low power has hampered the development of high resolution flat panel displays. Recently, a new series of blue emitting materials have been investigated for use in thin film electroluminescent (TFEL) devices. l ,2,3 These phosphors are based on a series of alkaline earth thiogallate host materials of the form MGa2S4:RE where M can be either calcium, strontium, zinc, or barium and RE is a rare earth ion. A full-color VGA TFEL panel using CaGa2S4:Ce as the blue phosphor has recently been fabricated and tested. l This FPD provided a luminance of 10 cdlm2 at 60 Hz. The enhanced blue in this display allowed its color capabilities to approach those of the conventional CRT.The method of depositing the phosphor onto the display panels in these test devices has been sputtering. Unfortunately the phosphor as deposited does not possess the crystalline properties required for optimum luminance. The crystalline structure is achieved by subsequent annealing of the deposited material. Although this post deposition anneal provides the desired crystal structure, it occurs above the strain point temperature of ordinary glass. Consequently, the implementation of these phosphors requires the use of glasses capable of withstanding high temperatures, adding to the cost of the final display unit."

Jan 1, 1994

By Chuck Edwards

Whatever your opinion of the validity of the scientific case for global warming, or of the wisdom of the Kyoto Protocol, it would seem judicious to err on the side of caution and try to sensibly minimize global climate change. To this end, we should take prudent steps to minimize our emission of greenhouse gases. Cameco is the world's leading supplier of uranium for use as fuel in nuclear power plants. Cameco’s uranium production fuels nuclear power plants in 16 countries. Nuclear power plants generate clean electricity without greenhouse gas emissions. This presentation describes the role that uranium and nuclear power can have in meeting the growing demand for electricity and at the same time combating global climate change.

Jan 1, 2004

NEW MEMBERS The following list comprises the names of those persons who became members during the period Apr. 10, 1919, to May 10, 1919. BEAVER, JAMES J., Supt., Mech. Ore Loaders, Tennessee Coal, Iron & R.R. Co., Box 62, Bessemer, Ala. BLACKWELDER, ELIOT Geol. & Prof. of Geol., Univ. of Ill., Urbana, Ill. BRAECKE, GUSTAVE E., -Min. Engr., Mgr., Societe Curas et Soldado, La Carolina, Spain. BRINK, CYRIL GORDON, Reduction Officer, Charge of Reduction Works. Fairview Devonian Montrose Gold Mines, Ltd., P. O. Sheba, Transvaal, So. Africa. COMERFORD, JOSEPH S., Chief Chem. & Met., American Manganese Steel Co., New Castle, Delaware. DROSDOWSKI, N. C. V., Asst. Supt.,, The Spassky Copper Mine, Ltd., Karagandy, Akmolinsk, Oblast, Siberia. DUNGLINSON, GEORGE, JR., Asst. to Gen'l Mgr., Norfolk & Western Railroad, Bluefield, W. Va. FARAGHER, PAUL VANCE, Research Fellow on Light Metals, Mellon Institute, Pittsburgh, Pa.

Jan 6, 1919

A comprehensive understanding of the effects of autoclave configuration (batch, semi-batch, continuous) on the residence time necessary to achieve a target conversion is a prerequisite for design of commercial scale autoclaves. Particle size distribution, mineral and reagent concentrations, temperature and mixing also influence the conversion. This paper outlines the bases of using test data to predict performance of commercial scale autoclaves. Recommendations for coordinating test program design with selection of scale-up method are provided. Examples are given to illustrate the different levels of engineering effort needed to meet corresponding levels of design optimization and accuracy.

Jan 1, 1998

By S. A. N. Sheya

Many gold-bearing ores in the Western United States also contain small amounts of mercury. The presence of mercury creates potential pollution and health hazards during several steps in gold processing. An investigation was undertaken by the Bureau of Mines to develop techniques for removing mercury from cyanide mill solutions by selective electrowinning to reduce the potential hazards. Sixty-five percent of the mercury was selectively electrowon from synthetic carbon strip solution at applied potentials of 1.00 to 1.50 V when using a mercury-coated platinum or copper plate cathode. Increasing the active surface area by using mercury-coated copper wool resulted in up to % pct of the mercury being electrowon from mill carbon strip solutions that contained 1.9 to 20 ppm Hg, 20 to 345 ppm Au, and 0.35 to 39.5 ppm Ag. About 98 pct of the silver was electrowon with the mercury onto the mercury cathode. Gold extraction ranged between 0 and 20 pet. Results of the investigation showed that choice of cathode material was critical to the success of the process. Selectivity was not achieved using uncoated steel wool cathodes.

Jan 1, 1988

By Harry C. Gatos, Frank J. Bachner

It was shown through high-pressure experiments that tin loss by volatilizatim is necessary for the degrada-tion of the superconducting transition temperature of Nb,Sn associated with high-temperature annealing. Crystallochemical analysis of the degraded Nb3Sn showed that it constitutes a new phase with ordered niobium-site vacancies, created by the migration of niobium atoms to vaccnt tin sites. This new phase was found to form when 4 pct Nb-site vacancies were present. It has a transition temperature of 6'K and a lattice parameter of 5.283A. A similar degradation effect was observed in Nb,Al. Its superconducting transition temperature dropped from 16.5" to 8" K following a high-temperature annealing. The superconducting temperature degradation in these 0-tungsten structure compounds is attributed to the disruption of the interchain d bonding by the periodic interruption of the niobium atom chains. By annealing the degraded Nb, Sn at 1000 C in nitrogen its normal superconducting behavior is restored most likely due to the incorporation of nitrogen atoms causing the elimination of the ordered vacancies. HANAK et al.' have observed low superconducting transition-temperature values (T, - 9"K) in some NbsSn samples deposited from the vapor phase. They attributed such low T, values to disorder in the 0-tung-sten structure. Much lower T values (down to 5.6"K) were reported by Reed et al.zC for NbsSn samples annealed at high temperatures. These authors also attributed this degradation effect to disorder (random occupation of the A and B sites by niobium and tin) but pointed out that such disorder could be brought about (by high-temperature treatment) only in samples containing niobium in excess of the stoichiometric composition NbsSn. Both groups reported that the normal superconductivity behavior could be rever-sibly restored by appropriate heat treatment. Courtney et al., also found that degradation in NbsSn requires excess niobium brought about by the loss of tin during the treatment. However, these investigators proposed that the degradation is due to niobium-site vacancies resulting from the migration of the niobium atoms to the vacated tin atom sites. They did not consider the reversibility of the effect. The present study attempts to establish the nature of the above degradation phenomenon. EXPERIMENTAL PROCEDURES All compounds prepared for this investigation were made from the powders or filings of the elements which were intimately mixed, cold-pressed into a cylindrical pellet at approximately 50,000 lb per sq in., and then submitted to the desired heat treatment. The samples annealed under high pressure were placed in a MgO sample container which was mounted in a pyrophyllite tetrahedron designed for a tetra-hedral-anvil press. Details of the experimental arrangement are given elsewhere. This setup allowed heating at 1800°C or above under pressures in excess of 30kbars for 3 hr. The samples annealed in a vacuum were prepared in a high-temperature vacuum furnace which could reach temperatures up to 2400°C under a pressure of 2 x lo-' Torr. For annealing in a reactive atmosphere, a quartz tube was placed in a clamshell furnace and the desired gas ambient passed through the tube. Lattice parameters were determined using a Debye-Scherer 114.6-mm camera. Cohen's method, programmed for the IBM 7094 computer, was used to calculate the lattice parameter from the measured d spacings. X-ray integrated intensity measurements were made on several samples. These samples were ground to -400 mesh and the powder mixed with a solution of collodion in amyl acetate. The mixture was poured into a depression milled in a bakelite disc. When the mixture dried, the surface of the disc was ground flat leaving a diffraction surface defined by the face of the disc. The disc was mounted in a Philips rotating specimen holder which allowed the rotation of the sample in the plane of the diffraction surface and the integrated intensity measured using a scintillation counter and a pulse-height analysis sys-tem. The superconducting transition temperatures were determined by means of self-inductance techniques.' EXPERIMENTAL RESULTS AND DISCUSSION The Role of Tin Loss in the Degradation of Super-conductivity. The loss of tin during high-temperature annealing can be effectively suppressed by annealing under high hydrostatic pressures. Accordingly, a series of experiments were performed under pressures of approximately 30kbars. This pressure was the minimum under which high-temperature experiments could be safely performed in the particular pressure apparatus employed. Experiments were also designed to test high-pressure effects on the superconductivity behavior of NbJSn. The results of the high-pressure annealing experi-ments are summarized in Table I. All samples were prepared as described earlier. They were reacted and homogenized at 1000°C for 24 hr under argon at-

Jan 1, 1967