Search Documents

By T. Rosenqvist

From the chemical, metallurgical, and mineralogical points of view, the importance of thermodynamic data for metal-sulphides and sulphur dissolved in molten metal has long been realized. Such data will give a basis for thermo-dynamic calculations of processes such as roasting and the distribution of sulphur between molten metal and slags. Furthermore, it will help us understand the chemical forces which tie sulphur to the metal and to the melt. Thermodynamic studies of solid sulphides and the equilibria between solid sulphides and metals have been carried out in a rather large number of cases by several investigators. An excellent review of this work is given by Kelley.1 On the other hand, very little is known about the thermodynamic properties of molten sulphides and of sulphur dissolved in molten metal. The only system which previously has been investigated in this respect is the iron/sulphur system. The purpose of the present investigation was primarily to obtain further data for metalisulphur melts and the system silver/sulphur was chosen, not because this system was expected to be of special interest in itself, but because the silver/sulphur system is a typical example of a metal/sulphur system. Because of the low melting temperatures, the work could be carried out without appreciable furnace and refractory difficulties. The sulphur in this system possesses a rather high escaping tendency compared to most other metal/sulphur systems. By the method employed (reaction with hydrogen to form hydrogen sulphide) this gives ratios Ph2s/Ph2 up to 0.30, which may be determined accurately. 'rhermodynamic investigations of the heterogeneous reaction Ag2S +H2 —+ 2Ag + H2S have previously been carried out by Pelabon,2 Keyes and Felsing,3 Jellineb and Zakowski,4 Wat-anabe,6 and Britzke and Kapustinsky.6 Their results are in rather poor agreement. Experimental Part PRINCIPLE In the present invehgation the escaping tendency of sulphur from the condensed phase was determined by the reaction: S + H2 = H2S The ratio Ph2s/Ph2 is at constant temperature, directly proportional to the escaping tendency of sulphur and to its chemical activity in the condensed phase. (This ratio will subsequently be denoted by H2S/H2.) From this ratio and its variation with temperature and with change in the com- position of the condensed phase, thermodyrlamic quantities such as free energy and heat of reaction can be derived. The apparatus used is shown in Fig 1. The silver/sulphur alloy was placed in a crucible inside a refractory tube and mounted inside the furnace to the left. The tube was a part of a closed, gas-tight system in which the gas mixture could circulate until equilibrium was established. Circulation was maintained by the glass propeller to the right, driven by an external magnet, and promoted by the chimney action of the furnace. The gas passed up through the furnace, down into the crucible where it came in contact with the alloy, passed rapidly up through a narrow tube and out of the hot zone. After equilibrium was established between the gas and the condensed phase, the composition of the gas mixture was determined from its density. In its circulation, the gas mixture passed through a chamber (lower right on Fig 1) containing a buoyancy-balance, where the density of the gas was determined by magnetic balancing. From the measured density,

Jan 1, 1950

THE Institute assembled on Tuesday evening, in the building of the University of Pennsylvania. In the absence of President Thomas, Vice-President Raymond occupied the chair. The Institute was welcomed in an eloquent and thoughtful address by Prof. J. P. Lesley, to which Mr. Raymond responded. Invitations were announced from the proprietors of Sellers' Tool Works, Whitney's Car-wheel Works, the Baldwin Locomotive Works, Lewis & Brothers' White Lead Works, the Southwark Foundry, Harrison's Boiler Factory, the University of Pennsylvania, and the Academy of Natural Sciences. The following gentlemen, being duly recommended by the Council as members and associates, were unanimously elected : Alexander, John S., . . . . . Philadelphia, Pa. Biddle, E. R., . New Pork. Britton, J.. Blodget, . . . . . Philadelphia, Pa. Brooks, Maj. T. B., . . . . . Marquette, Mich. Brown, D. P., . Pottsville, Pa. Canfield, Edw., . . . . . . Dover, N. J. Cogswell, W. B., . .Franklin IronW'ks, N. Y. Cornwall, Prof. H. B., . .New York. Edwards, Daniel, . . . . . . Danville, Pa. Estabrook, Juhn D., . . . . . Philadelphia, Pa. Firmstone, William, . . . . . Easton, Pa. Fritz, John, . . . . . . . Bethlehem, Pa. Gignoux, Charles, . . . . . . New Pork. Grant, E. M., . . . . . . . Tuskegee, Ala. Humphreys, A. W., . New York. Ingham, W. A,, . . . . . . Philadelphia, Pa. Keyes, W. S., . . . . . . Eureka, Nev. Kimball, Dr. J. P., . New Pork. Law, Charles, . Pittston, Pa. Neilson, W. O., . . . . . . Philadelphia, Pa. Newberry, Prof. J. S., . . . . . New York. Pearse, John B., . .Steel Works P. O., Pa. Ricketts, P. De P., . . . . . New Pork. Scranton, Col. Charles, . . . . . Ox ford, N. J. Sontag, Hugo, . . . . . . Cologne, Prussia. Steele, Thomas C., . .Summit, Pa. Wharton, Joseph, . . . . . . Philadelphia, Pa.

What is experience worth? Representatives from the Mining, Metallurgy and Petroleum Societies discussed the question as part of the 1970 Annual AIME Meeting held in Denver, Colo. the week of February 15. Petroleum engineer-consultant, Michel T. Halbouty of Houston, Tex. offered his own clarification of present-day employer-employee relationships in engineering as a whole. "Longevity does not equal experience on the job. Further, when employees are considering salary increases and promotions, job performance is considered all the time; experience two- thirds of the time and length of employment one- half the time." He added, "worth is really what the employee can get for it and experience is essential to survival." Halbouty also noted that salary and responsibility is a function of man's value to his company and is about "as discrediting as grey hair." As far as the engineer is concerned, he reported, the company's ability to pay is, in large measure, not considered. From the company's viewpoint, however, the employee is expected to learn his first year on the job. His second year, he is expected to make his presence felt, Should he require three years to orient himself he might soon be looking for another job. The petroleum engineer pointed out that when the employee wants to know why the salary scale tends to plateau off in later years, most employers react by recognizing that employees "flatten themselves rather than the company flattening them."

Jan 1, 1970

M. AlbERtson, Chairman. Production Engineer, Shell Petroleum Corporation, Houston, Texas. R. P. McLaughlin, Associate Chairman. General Manager, Burnham Exploration Co., Los Angeles, Calif. Eugene A. Stephenson, Secretary-Treasurer. Professor of Petroleum Engineermg, Missouri School of Mines and Metallurgy, Rolla, Mo. Ezecutive Commillee M. Albertson, Chairman. C. E. Beecher, Empire Oil & Refining Co., Bartlesville, Okla. L. L. Foley, Petroleum Engineer and Geologist, Tulsa, Okla. R. B. Kelly, Division Manager, Pure Oil Co., Fort Worth, Texas. Hallan N. Marsh, Production Engineer, General Petroleum Corporation of California, Los Angeles, Calif. R. E. Somers, Geologist, The Gulf Companies, Pittsburgh, Pa. Production Engineering T. V. Moore, Vice-chairman. Charge Production Research Division, Technical Service and Development Dept., Humble Oil & Refining Co., Houston, Texas. Joseph Chalmers. De Bataafsche Pet. Maatschappij, The Hague, Netherlands. M. L. Haider, Petroleum Engineer, Carter Oil Co., Tulsa, Okla. Emile HUGUENIN, Deputy State Oil and Gas Supervisor, Los Angeles, Calif. Carl E. Reistle, Jr., Petroleum Engineering Dept. Humble Oil & Refining CO., Houston. Texas. Produclion J. Terry DUCE, Vice-chairman. Geologist, The Texas Company, New York, N. Y. Basil B. Zavoico, Associate Vice-chairman. Consulting Geologist, Houston, Texas. Engineering Research R. L. Huntington, Vice-chairman. Associate Professor, Petroleum Engineering, University of Oklahoma, Norman Okla. Economics Sidney A. Swensrud, Vice-chairman. Assistant to the President, Standard Oil CO., Cleveland, Ohio. Refinery Engineering Walter Miller, Vice-chairman. Vice-president, Continental Oil Co., Ponca City, Okla.

Jan 1, 1937

By Frederick Laist

F. N. FLYNN, Clifton, Ariz.-I would like to ask Mr. Mathewson what percentage of his leaching liquor is wasted at this time? It has a bearing on the question in connection with the New Cornelia, and I think it is a very important question. E. P. MATHEWSON, Anaconda, Mont.-I am not sure what the percentage is now, but we don't discard the strong liquors. Something like 25 per cent. of the wash water taken out each day is sent over a special set of scrap iron tanks, and the copper recovered there. We had a little trouble at first. We did not proceed to use the sponge iron for the reason that the plant we originally contemplated was abandoned for flotation. Our original idea was to use a leaching process on all the tailings of the mill, but we found it would take a great deal of time to build a plant; and the cost of operating the plant we estimated to be about the same and the recovery the same. It was a question of time with us, and we decided to adopt flotation. That changed our plans. We now have the leaching plant, treating the tailings of the old dump, and the flotation applied to the current tailings. The sponge iron was figured for the large plant. We can get all the scrap iron necessary for the small plant-plenty from the scrap produced in the main plant of the smelter.

Jan 12, 1916

By F. S. McNicholas, R. L. Healy

NOTEWORTHY because of the amount of explosives used, the tonnage broken, and the wide range involved both vertically and laterally, was a large underground blast fired last November at the Hidden Creek mine, Anyox, B. C. Stoping methods and mining prac¬tices at the Hidden Creek mine have previously been described in the technical press. Earlier mining methods employed included shrinkage stoping, glory-holing, and "spiral" stoping. The latter especially has been a practice peculiar to the Granby company, having been used for years at its Phoenix mines and later at the Anyox property where conditions as to size of orebodies and strength of ground both in the ore and walls were similar. These methods all leave tremendous excavations supported at key points by pillars and braces that may only be safely mined by big blasts.

Jan 1, 1935

By E. W. Davis

THE large iron-ore producers on the Mesabi Range are able to maintain the silica in their shipping products at from 8 to 10 per cent by mixing ores of various grades, some assaying 4 per cent silica and some as high as 18 per cent silica. For each ton of 4 per cent silica ore mined, a ton of 14 per cent silica ore can be mined and mixed with it and the average grade maintained at 9 per cent. This mixing operation has made possible the utilization of large cluantities of ore too lean to be used alone. and herein lies the advantage of the producers who operate a number of mines at the same time. As the grade of the ore from one of the properties falls off, a little high-grade ore from another property can be mixed with it and the average maintained, while if one property alone were being operated all of the ore below grade would be left behind.

Jan 1, 1930

By Henry M. Bates, Roscoe Pound

Mr. Chairman and Gentlemen: I accepted your Chairman's invitation to speak to a group of experts in this field with the greatest hesitation, because I know little or nothing about it. Certainly I can make no detailed suggestions, or suggest planning along very definite lines. You cannot do that sort of thing in a vacuum, and as I have suggested, my knowledge of the whole oil problem is next to nothing. It is possible that as a student of our public law, constitutional law particularly, for a number of years, I have acquired a perspective that may enable me to offer, for what they are worth, some general thoughts on these problems. I think that nothing in the whole field of law requires more definitely and clearly the functional approach than does the problem of a sound legal solution of the difficulties of the oil and gas industry. The industry is dealing with substances that are peculiar, and one must know how those substances act and what has been the history of the industry, to undertake to make anything like specific suggestions. I certainly am not qualified.

Jan 1, 1935

By Walter W. Bradley, OLAF P. JENKINS

IN April of this year the California State Division of Mines (formerly known as the State Mining Bureau) observed its 50th anniversary. The Division serves as a bureau of information and, an encyclopaedia of California's economic minerals. Its primary function is to make economic surveys of the mineral resources of California, their development and utilization. Geological studies also constitute a related part of the work as being necessary in tracing and out- lining ore deposits and the most likely areas in which to find them. The results of the Bureau's data-gathering are published in the form of annual reports of the State Mineralogist, and in bulletins on specific substances. The Division is just completing a series of reports on the mineral resources of the State arranged by counties.. It is now starting .a new series of reports arranged according to substances particularly the so-called non- metallic commercial groups. Of these the following are now available: clays, barite, and mineral paint. These will be followed by reports on feldspar and silica, diatomaceous earth, limestone and others

Jan 1, 1930

By Charles Behre

THIS paper deals with recent geologic studies in the slate belt of Northampton, Lehigh and Berks counties, Pennsylvania. The work was conducted under the auspices of the Pennsylvania Topographic and Geologic Survey. Three years have now been spent in detailed consideration of the economic geology of this region. In the field, particular attention was paid to the bearing of geology on quarry development and property valuation and the object of this paper is to summarize the results from that viewpoint. Excellent studies of a somewhat similar nature have already been carried out by Bowles,1 but with the emphasis upon the details of quarrying and fabricating methods, rather than upon the geologic relations. THE NORTHAMPTON-LEHIGH-BERKS DISTRICT Location The region here discussed lies in east-central Pennsylvania and extends southwestward from Delaware River, on the New Jersey line, to the Schuylkill in north-central Berks County. It is an elongated belt occupying the northern sections of the three counties mentioned and lying along the southern edge of Blue Mountain. Its length is about 50 miles and its average width five or six, though in places it attains a maximum of 10 miles.

Jan 1, 1928

By AIME AIME

TWENTY-TWO sections and all four of the divisions sent delegates to the annual meeting. They became so interested in the wide ranging dis6ussion of old and yet ever-new problems of Institute affairs that three instead of two sessions scheduled were necessary. Monday morning the meeting assembled with President Bassett presiding in the absence of President-elect Tally, who had been called to Baltimore by the serious illness of a brother. Thursday morning Vice-president Turner presided until Mr. Tally appeared after which the latter guided the sessions. Since reports from all of the active sections save one had been mimeographed and sent in advance to the delegates, detailed reports from each were dispensed with. The discussions dealt largely with membership problems, both local and national, with financing, speakers and programs, visits from national officers, and the conduct of the annual meeting. Many interesting and constructive suggestions were made and will be reported back to the sections by the delegates.

Jan 1, 1931

By AUGUSTUS J. MONKS, Norman L. Weiss

THE Santa Barbara Unit of the Compania Minera Asarco, of which the San Diego mill is a part, is in the Parral District of southern Chihuahua. Although the concentration of sulfide ores has been practised in Santa Barbara since 1900, the San Diego mill, completed in 1921, was the first plant in northern Mexico to attempt the treatment of oxidized lead ores. From the milling point of view the many ores that have been treated at San Diego are very similar, the differences among them being rather of degree than type. Since 1921 the number of ores from different sources treated simultaneously has varied from four to eleven; in no case have any distinctive characteristics warranted the separate treatment of any of these. The zone of oxidation, source of the ores milled at San Diego, extends to a depth of 300 to 400 ft. below the surface. These ores carry more gold and less silver, lead, copper, and zinc than the underlying sulfide ores; the gangue minerals appear comparatively unchanged by oxidation and leaching. Lead occurs in diverse minerals, chiefly in cerussite, galena, and angle-site, the proportion of the lead in galena varying considerably in the different mines. An average of the feed to the mill would show the following approximate distribution of the lead content:

Jan 1, 1930

By E. C. IBBOTSON

THIS process was reported upon by the Canadian Commission in 1904, and much detailed information was also given in a paper by Chief Engineer V. Engelhardt.1 Believing that some of the latest particulars of the process will be of interest, I submit the following data. At Gysinge in Sweden during the year ending May 31, 1906, from a fixed furnace giving 1 ton (2,240 lb.) of steel per tap, there were produced 950 tons of tool-steel and special steel ingots. . In carbon and iron tool-steels all the usual tempers were made. The bulk of this steel was made from charges composed of about 80 per cent of Swedish white pig-iron and 20 per cent. of steel-scrap. The percentage of carbon was regulated by the addition of briquettes. Other charges were made from Swedish white iron and steel-scrap. The average time taken per charge, for the year, when adding briquettes, was 7* hr., and the electric energy consumed was 1,128 units (kilowatt-hours) per ton. The average time per charge for white-iron and scrap charges was 5.5 hr., and the electric energy consumed was 886 units per ton. These consumptions include all time and energy lost from various causes, such as bad water-supply, ice, etc. It is quite ordinary practice to complete the charges with briquettes in 6.5 hr., and without briquettes in 5 hr., as shown by the following typical charges White pig-iron, 1,457; steel-scrap, 439; briquettes, 220; ferrosilicon (50 per cent. of silicon), 17 ; ferromanganese (80 per cent. of manganese), 15 lb. ; and aluminum, 1 oz.=

Nov 1, 1906

By T. L. Johnston

MUCH has been said and written about deep mine shafts and deep drill holes as man in his search for mineral wealth digs deeper into the earth's crust. Each year some new extra depth is heralded as a record, but with unlimited possibilities of going still deeper. In contrast to "digging deep," "mining high" is limited by the height of the mountains (Mt. Everest being the maximum with its 29,000-ft. elevation) and also by the extent of human endurance. An ex- ample of what might be called near- stratosphere mining in what is probably the highest mine worked by compressed air in the world is seen in a recent project in the Andes mountains of southwestern Bolivia.

Jan 1, 1939

By William H. Shockley

[SECRETARY'S ]NOTE.-The following notes, arranged and edited in this office, but not yet revised by the author, were placed at my disposal with much modest hesitation (due to their incomplete and fragmentary character), upon my earnest request, and my argument that such recent and trustworthy data concerning a new and important mining industry ought not to be withheld from our Transactions, simply because they are not sufficient to constitute a, complete academic treatise on the subject. This argument is recommended to the attention of many other members, who are waiting for the opportunity to contribute something "monumental" to our Transactions. In a number of instances, death has nulli¬fied this ambition, and the intended "monumental" contribution has turned out to be an obituary notice by the Secretary, instead of a valuable record of the professional experience thus hopelessly lost to the world.-R. W. R.] The official publications of the the Russian Government give fairly complete statistics of the dredges operated in the Empire; and in a recent English bluebook, Mr. Cook's report on Siberian Trade presents a brief account of dredging in Siberia. The data in Table I. (not given by Mr. Cook) have been taken from the Gold Mining Messenger (Russian) for July, 1905. These interesting statistics, though incomplete, show that the Yenisei dredges are working on poor ground and yield small returns. According to report, but few yield a profit exceeding 10 per cent. per annum on the capital invested. In the summers of 1904 and 1905, I traveled in the Urals as far north as lat. 61° N., long. 61° E., on the the Lozva river, a part of the vast system of the 01) river. This clear-water stream starts from the summits of the Urals at an altitude of 4,000 ft., and flows through a flat country, densely wooded with larch, spruce, pine, fir, birch and poplar. The river is full of fish, and is navigable for good-sized steamers as far as Ivdell. Winter lasts from early November to late April, the temperature rang¬ing from -60° F. to a summer maximum of 90° F. The rain¬fall is 20 in.. The climate is healthy, although mosquitoes,

Jul 1, 1906

By E. G. Banks

THIS paper is presented in the belief that metallurgists and chemists will be interested in the practice of grinding in tube-mills in connection with stamps, especially since the records of working here given extend over a lengthy period of time (since May, 1905). The ore from the Waihi mine-more especially that produced in the upper levels-contains a large proportion of hard, chalcedonic quartz, and the gold exists in an exceedingly fine state, conditions which necessitate very fine crushing in order to ob¬tain a high extraction of the precious metal. Before the introduction of tube-mills at the 90-stamp Waihi mill, it was found necessary to stamp through 40-mesh (1,600 holes per sq. in.) woven wire-screens, having a fairly high discharge. The pulp then graded

Jan 1, 1907

By E. W. Pehrson, J. W. Furness

NONMETALLIC MINERALS, exclusive of fuels, may be divided into three groups: Building materials, fertilizer minerals, and miscellaneous minerals. Building materials, such as sand, gravel, slone, lime, and the ingredients of cement and clay products, occur widely in nature and are thus available near consuming centers at relatively low prices. Cost of transportation over great distances deters any' substantial movement in world trade. On the other hand, fertilizer minerals, such as phosphate rock, potash, nitrates, sulfur, and pyrite, and the miscellaneous nonmetallic minerals, such as long-fiber asbestos, mica, graphite, fluorspar, and china clay, do not have such widespread occurrence and consequently contribute the major part of the world's commerce in such minerals. The U. S. Bureau of Mines has prepared charts showing the inter-

Jan 1, 1936

By Richard H. Olson

"Rarely in our technological society does the discovery of a new class of inorganic materials result in such a wide scientific interest and kaleidoscopic development of applications as has happened with the zeolite molecular sieves." That opening sentence in a landmark volume on zeolite molecular sieves by D. W. Breck (1974), is, if anything, an understatement. Zeolites were recognized as a new group of minerals in the 1750s, but it was not until 1930 that the first analysis of the crystal structure of a zeolite mineral was made. In the late 1940s research workers at Union Carbide Corp. began a program of zeolite synthesis and study which has resulted in one of the major research achievements of all time. Naturally, with the vast research and development efforts devoted to the synthetic molecular sieves, Union Carbide became concerned in the mid-1950s about its position should minable deposits of natural analogues be discovered. Zeolite minerals have diverse origins, and even a brief discussion of these is beyond the scope of this paper. The early work on zeolites was confined to igneous rock occurrences (e.g., amygdules and veins) which were formed by "space-filling;" these crystals tend to be euhedral, thereby rendering them appealing to both mineralogists and collectors. During the first year or so of Union Carbide's exploration (which began in mid-1957) attention was devoted solely to such igneous, occurrences. A landmark paper by Bramlette and Posnjak (1933) heralded the potential significance of the occurrence of zeolite minerals as alteration products of vitric ash and similar materials. In the summer of 1958, full attention was directed by Union Carbide to the search for deposits of this type in the western United States. Since then, such exploration has been continuous by both commercial firms and private parties. The future economic potential for natural zeolite deposits seems to be restricted to those of the "open-and-closed system" types as described by Sheppard (this chapter). Therefore, this and the following discussions will concentrate upon these types; the other types of zeolites in sedimentary rocks (e.g., deep-sea sediments, burial metamorphic, and hydrothermal) will be, for the most part, ignored. Despite the relative cheapness of natural zeolite deposits as compared with the cost of synthetic molecular sieves, there has been minimal development of zeolite mining in the US over the past 25 years or so. Mumpton (this chapter) discusses the present commercial utilization of natural zeolites and their future potential in detail, but perhaps the following will serve as useful background. In the early days of synthetic molecular sieve research and production, the efforts were concentrated largely upon such high-value applications as physical separation of components in a stream (based upon molecular size and geometry) and in catalysis. Due to a number of reasons (some of which are difficult for an outsider to understand), natural zeolite ores (beneficiated or not) have not made substantial inroads upon the use of the higher-priced synthetic molecular sieves for the foregoing applications, but this is not to say that such a condition will exist forever. Furthermore, in view of the many other uses which are now known, or which loom in the future, the competitive position of the natural zeolites vs. the more expensive

Jan 1, 1983

By H. M. Davis, T. S. Jones

A methodfor accelerating the reduction of a metal oxide by carbon monoxide is to incorporate in the reduction system a nonreducible oxide which has a strong affinity for carbon dioxide and will remove it from the product gases. The effectiveness of this method was investigated by veduction experiments on specially prepared powder mixtures of SrO-ZnO ("active'.) and SrCO3-ZnO (reference). Measurements at 750o and 677°C showed that the rate of reduction of ZnO by CO was as much as an order of magnitude greater in the presence of SrO. Under the experimental conditions at least as much CO2 as generated by veduction was absorbed when SrO was present. Enlzancernent of the veduction rate by SvO resulted from modification of' gaseous djfitsion processes. THE specific question posed in this investigation was whether the reduction reaction CO + ZnO - Zn(g) + COa [1] could be accelerated by incorporating strontium oxide into the oxide charge undergoing reduction. Provided the strontium oxide was active enough, it could remove carbon dioxide from the product gases of ( 11 and form strontium carbonate, thus modifying Reaction [ 1] to CO + ZnO + SrO = Zn(g) + SrCO3 [ 2] This study of the comparative rates of Reactions [ I] and [2] can be considered as a particular case of a general scheme for increasing the rates of reduction of metal oxides by carbon monoxide. The limits of applicability of this scheme are indicated in the simple thermodynamic analysis presented in the appendix. This analysis primarily dictated the choice of the system, CO-ZnO-SrO, employed in this investigation. In addition, it was thought that a study of this scheme by use of the CO-ZnO-SrO reaction system would be of special interest in view of indications in the literature1-3 that the gaseous reduction of zinc oxide is prone to rate control by diffusion in the gas phase. The distinction should be pointed out between this and other efforts to increase the rates of reduction reactions through the use of addition agents. Additions of a wide range of chemicals have been tried with de- grees of apparent success varying from slightly negative to highly positive. The reasons for making additions have included the use of salts to produce effects akin to catalysis,4, 5 the alteration of the microstruc-tural details of the reduction process (including solid-state diffusion),6-8 and the conversion of an en-dothermic reaction into one that is exothermic or autogenous.9-12 The means used to attempt alteration of the enthalpy change has commonly been to incorporate lime into the charge, so that heat is generated by reaction with either of the reaction products, carbon dioxide or water. The use of lime in this way makes endeavors such as that of Edstrom and Wiberg similar to the present one. Furthermore, the basic principle behind the present work has previously been set forth.13 However, a detailed investigation of the type of reaction described in this work does not appear to have been conducted. EXPERIMENTAL PROCEDURE From both conceptual and physical standpoints, Reaction [2] is to be considered as the sum of two reactions:

Jan 1, 1968

By Clark L. Corey, Bogdan Lisowsky

Electrical resistivity, X-ray line positions, degree of order, and microstructures have been investigated for Ni-A1 alloys near the Ni3Al composition. The results indicate that Ni3Al undergoes disordering between 1250oC and the mp; also supersaturated y, produced in y + y' alloys by gas quenching, is extensively ordered prior to y' (Ni3Al) phase separation. The latter reaction, if not both, must follow the cooperative phenomena model. Shifts in line position as a function of quench-indulced super satulration are shown. Lattice pavarneters of equilibriunz and nonequilibrium phases are given. THE objective of this investigation was to determine the mechanism and kinetics of the reactions which occur in Ni3A1 and hypostoichiometric Ni3A1 alloys. The results are of particular significance relative to pre-precipitation phenomena. Early work on Ni-A1 binary compositions near the Ni3A1 composition (13.6 wt pct Al) has been adequately reviewed by Hanssen,1 whose phase diagram is presented in Fig. 1. williams2 verified the suggestion made by Taylor and Floyd3 and others4 that y', Ni3A1, may precipitate coherently on (100) planes of the y phase (see Fig. 1 for phase nomenclature); he further suggested a two-step precipitation mechanism consisting initially of probably short-range ordering followed by actual precipitation of y'. The precipitation stage in low-aluminum hypo-eutectic compositions has been studied by a number of investigators;*"7 short-range order or "zone" formation have been suggested as explanations for various diffuse X-ray scattering effects. The ordering reaction in Ni3A1 alloys is characterized by a) a very rapid rate of ordering in nonstoi-chiometric compositions, b) absence of a disordered phase region for the stoichiometric compound, y', or Ni3A1, c) precipitation phenomena as a dominant aspect in hypoeutectic alloys, and d) an increase in elec-trical resistivity on ordering.' The latter two factors were found by Newkirk to characterize ordering in Co-Pt, for which an extensive and detailed analysis was made.' An electrical-resistivity increase on ordering has also been reported for cuAu3.10 PROCEDURE Ni-A1 alloys in the form of 1300-g chill-cast ingots were prepared by vacuum melting electrolytic nickel and high-purity (99.99 pct) aluminum. Very small heats prepared from high-purity carbonyl nickel, supplied through the courtesy of Dr. Goff of the Naval Research Laboratory, were used for comparison with the larger ingots and no differences were noted. The cast material was homogenized in purified argon for a minimum of 72 hr at 1200°C and water-quenched from 1350°C. Compositions studied are given in Table I. The 10 pct A1 alloy was both hot- and cold-rolled. X-ray superlattice line intensities and peak positions were obtained from -270 mesh filings, using CuK, radiation with a LiF crystal monochromat adjusted to receive both 01 and a2. One-degree slits and a 1/8 deg per min scan rate were used to record line traces. A standard tungsten powder, obtained through the courtesy of G.E. Research Laboratory, was used to calibrate line positions.

Jan 1, 1968