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By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide 'pest' ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,' comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967

By Charles Waidner

IN response to many urgent requests for a concrete realization of a series of standard temperatures that would be available to any one anywhere for the standardization of pyrometers and the reproduction of the standard scale of temperature for use in laboratories and industrial works, the Bureau, in 1916, made arrangements with several manufacturers to prepare a series of- pure metals that could best serve this purpose. After the necessary preliminary work of chemical analysis, as a check on the purity, together with exact determinations of melting or freezing points, the Bureau began, in 1917, the issuing of melting -point standards of tin, zinc, aluminum, and copper. At the outset, it was decided to secure metals of the highest purity and of American manufacture, and this was accomplished in a more satisfactory manner than anticipated. In the preparation of these temperature standards, the Bureau has had the hearty cooperation of several American companies, which have succeeded in producing metals highly satisfactory for the purpose and of as high a state of purity as could have been obtained anywhere. Each company that undertook the responsibility of furnishing a metal for this series of standards exercised most painstaking care to produce the best possible product as to purity and uniformity. A representative of the Bureau witnessed the actual preparation of each metal. The 300 and 400-lb. (136 and 181-kg.) samples making up the first series were all used up, with the exception of the aluminum, early in 1919. The Bureau has taken steps to replenish its stocks of metals serving as pyrometric standards and to the list has been added lead. The copper and lead are being ordered this time in 1-ton lots and the zinc and tin in 300-lb. (136 kg.) lots as before. The wide dissemination of these samples will be appreciated when it is noted that the metals are distributed by the Bureau inn quantities of 50 cu. cm. each, at $2 a sample and accompanied by a certificate which gives the melting point as determined by samples from the same lot. The manufacture and detailed description of chemical analyses, physical measurements, and precautions in use of these pyrometric standards, are described in detail in the Bureau Circulcar No., 66.

Jan 8, 1919

By William Hall

THE product obtained by roasting stibnite is likely to contain some unoxidized antimony trisulphide and a mixture of antimony trioxide and antimony tetroxide. It was desired to determine, as accurately as possible, the condition of the antimony as well as the total quantity present. Attempts were made to separate the trisulphide and the two oxides by methods based upon their varying solubilities in different solvents, but no satisfactory results were obtained in this way. It was found, however, that by determining the total antimony content, the antimony present as trioxide, and the antimony present as trisulphide, a good idea of the chemical composition of the roasted product could be obtained. The total antimony was determined by dissolving the sample in concentrated hydrochloric acid, reducing the antimony entirely to the trivalent condition by means of hydriodic acid and eventually titrating the antimony back to the pentavalent condition by means of iodine in the presence of sodium bicarbonate.' The details of the procedure are as follows: Weigh out 0.25 gram of the roasted product into a trapped flask (Fig. 1), add 4 grams of powdered tartaric acid, 2 grams of potassium iodide and 40 c.c. of concentrated hydrochloric acid. Boil the solution gently for 5 min. and then cool to room temperature by shaking the flask while holding it under running water. Then, very carefully discharge the iodine color by the cautious addition of 0.05-normal sodium thiosulphate solution, adding a little starch toward the last. Nearly neutralize the acid with ammonia solution, but leave the solution distinctly acid. Pour the slightly acid solution into 200 c.c. of water con-

Jan 1, 1916

By A. Gemperle

Electron diffraction and transmission electron microscopy on foils at room temperature were used to investigate the ordering of Fe-Si alloys containing 10 to 23 at. pct Si. A certain degree of DO3 order was found in all alloys. With the exception of the lowest silicon concentration for which the antiphase domains could not be clearly resolved, the alloys have a domain structure of two-domain type with boundaries having 1/4a01<111> displacement vectors for less than 12.3 at. pct Si and with boundaries having 1/2 a0<100> displacement vectors for more than 12.3 at. pct Si. The alloys with 12.3 at. pct Si have a domain structure consisting of fine domains with 1/2a&apos;o<100> boundaries within much larger domains with 1/4a&apos;o<111> boundaries. The development of these structures can be explained by transition of the alloy from the disordered state into the B2-type order and then into the D03-type order by the mechanism proposed previously for the FeSAl alloys. The existence of the B2 structure in the lower part of the investigated concentration range reported in some articles can be explained by fine domains with 1/2a&apos;o<100> boundaries formed by several disordered planes within large domains with 1/4a&apos;o<111> boundaries. The ordered structure predicted by the theory —with practically no domain boundaries —is found in the alloys having 12.3 at. pct Si where it develops in the B2 structure region. ORDERING in Fe-Si alloys was first studied by phragmenl who found that beginning with 13 at. pct Si the DO3 (Fe3Si) superlattice reflections appear in the diffraction patterns. The equilibrium diagrams constructed later by corson2 and Haughton3 from various measurements proposed the existence of a homogeneous solid solution (a phase) in the range from 0 to 25 at. pct Si. Jette and Greiner4 and Farquhar et al.5 measured the relation between lattice parameter and composition and they considered the break in the curve at 9 to 10 at. pct Si to be caused by the ordered solution a"(Fe3Si). Glaser and Ivanick6 Determined critical ordering temperatures of the alloys containing from 10.9 to 27.9 at. pct Si from the measurement of the electric resistivity of quenched samples. In all cases the critical temperature was lower than the melting point and it was highest for 25 at. pct Si. Lihl and Ebel7 measured the lattice parameter curves at various temperatures up to 1000°C. The region between two breaks on these curves, corresponding to 10 to 12.5 at. pct Si at room temperature, was considered by them to be two-phase (a + a"). They concluded by extrapolation of the measured values that a" in the alloy having 25 at. pct Si is stable up to the melting point. Davies8 studied superlattice reflections in the X-ray diffraction patterns of an alloy containing 8.7 at. pct Si. He found the B2 structure and short-range order in the slowly cooled samples and the DO3 A. GEMPERLE is Research Scientist, Institute of PhysicS, Czechoslovak Academy of Sciences, Prague, Czechoslovakia. __Manuscript submitted January 2, 1968. IMD structure in the quenched and annealed samples. This investigation first reports the presence of the B2 structure, phase a&apos;: in Fe-Si alloys. Meinhardt and krisement9,10 also found its existence in Fe-Si alloys by neutron diffraction. No order was detected by them in the alloy containing 8 at. pct Si. The onset of B2 order was observed at a composition of 9.2 at. pct Si. They found almost perfect B2-type order with partial DO3-type order at room temperature in the 10 to 12.5 at. pct Si range and almost perfect DO3-type order in the 12.5 to 25 at. pct Si range. They established the critical temperatures Tc of both the structures through measurement at higher temperatures. The critical temperature for the B2 structure was found to be always higher than the critical temperature for the DO3 structure of the same alloy. They extrapolated the curves of the critical temperatures and concluded that the alloys with more than 17 at. pct Si have the B2 structure up to the melting point and the alloys with more than 23 at. pct Si have the DO3 structure up to the melting point. The results of Meinhardt and krisement9,10 were confirmed by Dokken&apos;s measurement" of the temperature dependence of the electrical resistivity in the 10.8 to 15 at. pct Si range. On the other hand chessin12 detected by X-ray diffraction a considerably lower degree of order in the 12.7 at. pct Si alloy. ANTIPHASE DOMAIN STRUCTURE IN ALLOYS WITH B2- AND DO$-TYPE ORDER The ordered structures B2 and DO3 can be described in terms of a subdivision of the bcc lattice into four fcc sublattices with a parameter double that of the bcc lattice. Following Marcinkowski13 we will label them I. 11, 111, IV. The B2 structure in the AB alloy is formed by placing A atoms on sublattices I and II and B atoms on sublattices III and IV. In a non-stoichiometric perfectly ordered alloy having concentration (A) > (B), A atoms occupy sublattices I and 11. and A and B atoms distributed at random occupy sublattices III and IV. The DO3 structure in an A3B alloy is formed by placing A atoms on sublattices I, 11, and 111, and B atoms on sublattice IV. In a nonstoichiometric, perfectly ordered alloy having concentration (A)/3 > (B), A atoms occupy sublattices I, 11, and 111, and A and B atoms distributed at random occupy sublattice IV. As further shown in Ref. 13, two types of domains are possible in the B2 superlattice and the antiphase domain structure has associated with it boundaries with displacement vectors 1/4 a&apos;o<ll1> only. Four types of domains are possible in the DO3 superlattice and the antiphase domain structure has associated with it boundaries with displacement vectors 1/4a&apos;o<111> and 1/2a&apos;o<l00>. Bethe14 suggested on the basis of theoretical considerations that in a structure with two sublattices at low temperatures only one domain should be present in the whole crystal at equilibrium. Similarly Bragg15 concluded that at low temperatures the domain struc-

Jan 1, 1969

By B. V. P. Rao, H. L. Lovell, G. Simkovich

In the study described here, flotation tests were conducted on pure CaF2, on CaF2 doped at several concentration levels with either NaF or YF3, and on natural fluorite samples containing various amounts of impurities in an effort to extend previous knowledge of the influence of crystalline point imperfections on the flotation properties of solids. The results of these tests showed that although recoveries generally decreased as impurities increased, the differences in recovery were not nearly as striking as those detected in earlier experiments. A number of experimentalists have shown an interest in the way in which crystalline point imperfections affect the flotation properties of solids. As long ago as 1953, Welch hypothesized that it might be possible to control surface imperfections and thereby also control the flotation of solids.&apos; A few years later, in some rather extensive work, Plaksin and his coworkers varied the surface imperfections of a number of compounds by oxidation or reduction processes and found that significant variations in flotation properties resulted.2-4 More recently, Simkovich showed that the recovery of both AgCl and PbS could be markedly varied by adding solid-solution impurities, which acted as doping agents, to these compounds.5 Then Mular studied the flotation of ZnO as a function of the doping agents Al2O3 and Li2O.6 Once again, it was found that these impurities, even in very low concentrations, had profound effects upon flotation recoveries. From an imperfection point of view, the defect structures of the compounds tested previously are as follows:7 PbS — amphoteric semiconductor with a Frenkel-type defect structure in the cation sub-lattice.8 AgCl - ionic conductor-Frenkel type defect structure? ZnO — n-type semiconductor, zinc ion interstitials and quasi-free electrons.10 All of these works undoubtedly bear some relation to the findings that the flotation properties of seemingly identical minerals from different ore deposits often exhibit extreme variation in flotation behavior, i.e., that small amounts of analytically undetectable impurities often have a great influence upon flotation

Jan 1, 1969

By Edward H. Robie

IN many ways, the Annual Meeting of the Institute in February was the most successful yet held. Attendance surpassed even that of the 75th Anniversary Meeting in 1947 with its international flavor. The number of technical sessions and the number and quality of papers presented almost certainly set a new record. The banquet was the best attended of any yet held even though the price reached a new high. Despite the demand for almost 1700 tickets to the banquet, some felt that the price-$13.50-was higher than they could afford. There are two points of view: One is that this is the big social event of the year for members and that it is worth from three to five dollars more to have it at the Waldorf and to have a luxury menu, as we did this year, with turtle soup, a fish course, guinea hen for the entree, and wild rice (which we understand is $3.50 per lb) for a vegetable. The other point of view is that a seven or eight dollar banquet of more simple food at the Commodore Hotel would more than make up in appeal, especially to the younger and less well-heeled members, what it would lack in glamour.

Jan 1, 1952

By G. W. Toop

In a recent publication,31 Darken has derived an equation to describe thermodynamic behavior in ternary metallic solutions with compositions near pure component 1: Eq. [I] is understood to be a general equation, consistent with the ternary Gibbs-Duhem equation, which is proposed as a logical formalism in view of observed behavior in some binary metallic solutions31&apos;32 rich In Eq. and am are constants obtainable from the 1-2 and 1-3 binaries. The parameter 023 may be determined from measurements on the ternary The purpose of this discussion is to compare Eq. [I) or [3] with other ternary formulations involving binary terms, within the regions of validity of Eqs. [I], [2], and [3]. First, the ternary point is considered to be at the intersection of two composition paths, one with constant N1 and another with constant N2/N3 as shown in Fig. 10. The terms in Eq. [3] may be related to the binary points shown by multiplying the first term on the right-hand side of Eq. [3] by N2 (1) /l -N1, the second term by the third term by and the fourth term by each multiplier being unity: It should be noted here that no suggestion has been made that either the binary or the ternary systems form regular solutions. However, Eq. [5] and hence Eq. [3] shows that the contribution made to the ternary excess free energy from the 1-2 and 1-3 binaries has the same form as for a regular ternary system.1 Before considering the term a23 for the above case, a second geometrical relationship is examined with the ternary point at the intersect ion of three composition paths with constant N1/N2, N2/N3, and Nl/N3, respectively, as shown in Fig. 11. For this geometry, ternary values of NZ and N3 in terms of the binary values shown may be substituted into Eq. [I]. Then by making use of identities of the form Eq. [6] contains terms that are similar to those in a ternary regular solution formulation34 based on the geometry shown in Fig. 11. Although at finite concentrations, unless the 1-2 and 1-3 binaries form

Jan 1, 1968

OFFICERS AND COMMITTEES OF LOCAL SECTIONS AIME Committee on Local Section Affairs Roger Pierce, Chairman Carleton C Long Thomas C Frick AIME Committee on Student Chapter Affairs John P Nielson, Chairman John C Calhoun, Jr J R Van Pelt, Jr Council of Section Delegates A A Burr, Chairman (Hudson-Mohawk) Ralph A Watson, Vice-Chairman (North Pacific) L G Neely, Secretary (West Central Texas) INTERIM COMMITTEE M O Langham (East Texas), Fulton J Olivier (Delta), L W Smith (Niagara Frontier), G R Spindler (Central Appalachian) LOCAL SECTIONS (There are 78 Local Sections in the United States, 9 Foreign) ADIRONDACK Established June 18, 1952 Official year begins in April Meets fourth Saturday monthly, April through October Seven meetings annually Local Section Dues AIME Members $2, Nonmembers $3 Charles F Dievendorf, Chairman Severn P Brown, Vice-Chairman George E Erdman, Secretary-Treasurer Gouverneur Talc Co , Inc Gouverneur, N Y Malcolm V Lowry, &apos;60, Section Delegate Committees Membership David J Crawford, Chairman Program Brower Dellinger, Chairman Student Affairs Eugene A Eastman, Chairman

Jan 1, 1959

By J. M. Lohr

A COMMERCIAL development requiring a suitable alloy or alloys for sealing into various grades of glass made it desirable to have a more exact knowledge of the expansion characteristics of the nickel-iron alloys than appeared in the published literature. The expansion of the more common. FIG. I.-EXPANSION CURVES OF SEVERAL FIG. 2.-EXPANSION CURVES OF TWO TYPES OF GLASS. (Courtesy of R. C. A.) TYPES OF GLASS. (Courtesy of R. C. A.) types of glass under consideration varies from 2.7 to 10.4 X 10-6 per degree Centigrade, over the range 20° to 400° C. For reference, the thermal expansion curves f several types of glass used for sealing by the lamp and tube industries are given (Figs. 1 and 2). This paper covers a detailed investigation of the thermal expansion of a series of nickel-iron alloys in which the nickel content varies from 30 to 70 per cent. Particular stress is laid on the alloys that contain between 40 and 55 per cent Ni.

Jan 1, 1938

The University of Chicago Press, 5750 Ellis Ave , Chicago, Ill This Press publishes books on a wide variety of subjects of scientific interest, as well as several journals Only a few books on geology have been published, however, and the Journal of Geology. The Journal of Geology: A semiquarterly standard American publication in the geological field. $6 per year, single copies, $1, back numbers, within the past five years, $6 per volume Books on geology: The origin of the earth, by T. C Chamberlin, $2 50, Two solar families, by T. C Chamberlin, $2 50, Quantitative classification of igneous rocks, by W. Cross, J. Iddings, L V Pirsson and H. S Washington, $1.75; Studies in minor folds, by C. E. Decker, $1 50; An introduction to the study of ore deposits, by F. H Hatch, $3, A descriptive petrography of the igneous rocks, by A. Johannsen, $4 50, Essentials for the microscopical determination of rock¬forming minerals and rocks, by A. Johannsen (revised ed ) $3, Outlines of geologic history, with special reference to North America, edited by R D. Salisbury, 8150

Jan 1, 1933

By Roswell P. Angier, Herbert S. Kalish, Henry H. Hausner

POWDER metallurgical methods as applied to zirconium are of great interest because they permit not only the fabrication of parts directly to shape with a minimum loss of material but also the utilization of scrap, and the metal may be processed at temperatures well below the melting point. There are two difficulties involved in the melting of zirconium: 1—High vacuum is necessary for melting, and 2—zirconium reduces nearly all oxides so that it is difficult to find a suitable crucible material. The purest material, zirconium crystal bar, is expensive, and the methods of subsequent fabrication are limited. Cold rolling or extrusion of zirconium crystal bar is suitable for making certain shaped parts, but where melting is involved, the purity of the metal is invariably decreased, and a method of casting to a definite shape does not seem to be feasible. Where it is necessary to hot roll, zirconium must be covered with a steel or copper jacket to protect it from the air. This is necessarily a costly operation. Where annealing of zirconium is necessary it must be conducted in a high vacuum. In an investigation of powder metallurgical methods for zirconium, the zirconium powder used should be characterized by the following properties: 1— Highest degree of purity, 2—uniformity in particle shape and particle size distribution, 3—low compression ratio, and 4—satisfactory strength of the compacted powder (green strength). Zirconium powders have been made by two methods: By the reduction of zirconium tetrachloride (ZrC1,) with sodium,2&apos; *•B "nd by the reduction of zirconium oxide with calcium and calcium chloride." The first method represents one of the earliest attempts to make pure zirconium metal, and the sintered product from this powder is extremely brittle. The second method of making zirconium powder is far more successful, but the powder made in this way has an extremely low apparent density and, therefore, a high compression ratio which makes it difficult to use it for powder metallurgical purposes. For these reasons the above-mentioned zirconium powders were not used in this investigation. To obtain sintered zirconium compacts of highest &apos;purity and good ductility, it was first necessary to produce a suitable powder. Pure zirconium has been made chiefly by two methods. The iodide method, from which the product is "crystal bar" zirconium, was developed first.&apos;." By this purification process very soft, pure, and ductile zirconium metal can be produced. The second method, developed by the U. S. Bureau of Mines, is the reduction of zirconium chloride with magnesium." The sponge zirconium thus produced is also soft, pure, and ductile.

Jan 1, 1952

By E. H. Hamilton, H. C. Vacher

The limiting concentrations of carbon and oxygen which may CO-exist at equilibrium in liquid iron are important in determining the degree to which liquid steel may be refined before it is deoxidized. Most refining processes depend upon the oxidation of a highly carburized iron which invariably results in contaminating the steel with oxygen. The oxygen thus introduced presents many problems to the refiner, who in turn has attempted to rid the steel of this impurity by deoxidation witch elements such as manganese, silicon and aluminum. The importance of the limiting concentrations of carbon and oxygen is accentuated in view of a number of recent researches which have indicated in many instances the existence of relations between oxide inclusions and dissolved oxygen and physical properties and chemical behavior of steel. The determination of the equilibrium concentrations of carbon and oxygen existing in iron under steelmaking conditions is obviously of fundamental importance. It has been generally assumed that the product of the equilibrium concentrations of carbon and oxygen in liquid iron is a constant and that this product is directly proportional to the carbon monoxide pressure in equilibrium with the liquid iron. Hertyl.2 has computed values for this product based on open-hearth data which are all in the neighborhood of 0.01 to 0.03 (per cent. FeO X per cent. C) for temperatures in the vicinity of 1550" to 1600" C. and one atmosphere pressure. Kinzel and Egan % have attempted to determine the value of this product by exposing liquid iron to carbon monoxide at one atmosphere pressure. The value reported by them was 0.0005 at 1550" C. In order to apply certain equations to the rate of carbon elimination in the open-hearth process, Feild4 found it necessary to assume a value of 0.0102 at 1580" C. for this

Jan 1, 1931

By C. Z. Serpan, L. J. Wittenberg

The density of liquid plutonium was determined, by a pycnometm&apos;c technique, from 664 to 788°C and exhibited a temperature dependence, which could be expressed as:. P= C17.63 - 1.52 x 10-"t] +0.04 g per cc where t = OC. These density values compare favorably with the values previously obtained by a technique utilizing Archimedes&apos; principle. The apparatus and method were evaluated when the densities 0.f molten tin and bismuth were measured and found to be in agreement with accepted literature values. PLUTONIUM or an alloy of plutonium in the liquid state has been proposed as a fuel for a fast-breeder type nuclear power plant.&apos; Since knowledge of the liquid density of plutonium is required for the proper design of such a system, this study was undertaken. In addition, the density and volume expansion coefficient of liquid plutonium are of interest for comparison with these same properties of the six allotropic modifications of the solid metal. Comstock and GibneyZ were first to report a value for the density of liquid plutonium. The value for only one temperature, 665"C, was calculated from data obtained by the radiography of the meniscus, Fig. 3. Recently, the density at a series of temperatures has been reported by Knight,3 who obtained his values by using a differential volumeter, and by 01-sen, Sandenaw, and Herrik, who obtained their values from measurements of the loss in weight of a tungsten bob immersed in the liquid. The density of liquid plutonium reported here was determined by a vacuum pycnometer method. In an evacuated system, the tips of calibrated tantalum pycnometers were lowered beneath the liquid sur-

Jan 1, 1962

For the year ending February, 1919 PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS NEW YORK, N. Y. PHILIP N. MOORE ST. Louis, Mo. FIRST VICE-PRESIDENT C. W. GOODALE BUTTE, MONT. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 12, 1918

For the year ending February, 1919 PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS NEW YORK, N. Y. PHILIP N. MOORE ST. Louis, MO. FIRST VICE-PRESIDENT C. W. GOODALE BUTTE, MONT. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 4, 1918

By Paul Rhedey

Various commercial pelroleum cokes were heat-1,reated at temperatures between 500° and 1500°C, in a nitrogen atmosphere, in laboratovy induction furnaces. The rate of tenlperature rise was varied betzveen 10" and 300°C per min, or the green cokes were flash-calcined, orv a combination of heating rates was used. Changes in the rate of heating had only negligible effects on the degree of&apos; calcination as characterized by mean crystallite thickness and the chemical properties of the calcined coke. The physical structure of the cake was however significantly affected when rate of heating during calcination exceeded 50°C per min over the temperature range of 600° to 900°C. Surface-accessible porosily increased with the .rate of temperature rise, and this was accompanied by a change in pore size distribution. Source and properties of the green coke also had an influence on the structure of the calcined coke. The evidence presented suggests a similar mechanism of porosity development in petroleuiiz coke during calcination in industvial equiplnenl, such as rotary kilns. An increase in surface accessible povosity incveased the pitch binder requirement when the coke was used as aggregate in Soderberg paste. A correlation was established between calcined coke porosity and paste binder requiremenl. ManY results have been published on the changes of properties of petroleum coke during calcination, such as chemical composition, real density, electrical resistivity, crystallite and pore structure. The correlation of these properties with temperature of calcination and time at maximum temperature has been rather well established in both laboratory and pilot plant experiments. Surprisingly little attention has been given however to the effect of calcination conditions, such as rate of temperature rise or furnace atmosphere, on the chemical and structural properties of the calcined coke. It has been observed that petroleum coke, when calcined in industrial equipment, acquires higher porosity and lower real density than those attainable in laboratory furnaces at apparently identical calcina- tion temperature and soaking time. This paper describes a study of the effect of rate of heating during calcination on calcined coke properties using green petroleum cokes of different volatile matter, hydrogen, and sulfur content. An attempt was made to correlate the changes in coke structure with the flowability of anode paste of the type normally used in aluminum reduction cells. EXPERIMENTAL Petroleum Cokes Used. In the study of release of volatile matter and sulfur during calcination and the effect of rate of heating on calcined coke properties two delayed cokes of different sulfur contents were used. The results of analysis of the green cokes are given in Table I. In the study of the effect of flash calcination thirty-six commercial petroleum cokes from twelve different refineries were used with a range of properties shown in Table 11. Calcination Conditions. Calcination experiments were carried out in a laboratory induction furnace. In each run a 200-g sample of dry green coke sized to 10 by 65 Tyler mesh was calcined in a graphite crucible. The crucible containing the sample was placed in the middle of a stack of eight others filled with metallurgical coke to reduce temperature gradients within the sample. Temperature was measured by two Pt, Pt-10 pct Rh thermocouples and controlled by a Celectray instrument. The two couples generally agreed within 5°C. In the study of volatile matter and sulfur release the samples were heated to temperatures in the range of 500" to 1500°C at a rate of 10°C per min in a nitrogen atmosphere and held at the final temperatures for 30 min. In the study of the effect of heating rate on calcined coke properties the desired rates between 10&apos; and 300°C per min were obtained by manually adjusting the power input. Flash calcination was carried out by dropping 100 g of the green coke into the graphite dish preheated to the calcination temperature. Because of the small heat capacity of the furnace the coke was introduced in 20-g portions at a time. For this purpose a 2-in.-long nipple between two 1-in. gate valves installed on the top flange of the furnace served to provide a gas seal while feeding coke to the furnace. It was estimated that the temperature of the coke reached that of the furnace at a rate of approximately 1000°C per min. Holding time at final temperature was also 30 min. Calcined Coke Proper- Determined. Porosity was determined on 20 by 35 Tyler mesh samples using an Aminco-Winslow mercury pressure porosimeter with an operating range of 1.8 to 3000 psi absolute pressure (100 to 0.05 p pore diameter range).&apos; Apparent density was obtained by the mercury poro-simeter. It represents a particle density of the 20 by

Jan 1, 1968

By E. S. Grumell

THE correct sampling of coal and coke is becoming important to an ever increasing number of producers and consumers. This, therefore, may be an opportune moment to examine where we stand with regard to existing and proposed methods. In this paper an attempt will be made to review, as briefly as possible, some of the considerable amount of painstaking research which has been done in the last 10 years, and which has unquestionably led to a much better understanding of the subject. In so doing we shall try, on the one hand, to make clear where substantial progress has been made, and on the other hand, to draw attention to points that require further investigation. The paper is divided into sections in order to emphasize the major divisions of the subject; further, in order to retain this emphasis, detailed consideration of some of the points has been relegated to appendixes. No attempt has been made to give a complete survey of the literature, as this has already been done by L. A. Bushell.2 The following abbrevia-tions will be used: A.E., average error; P.E., probable error; S.W.R., size-weight ratio; B.S.I., British Standards Institution.

Jan 1, 1939

By W Lindlief, Cyril Stanley Smith

Several investigators, mainly concerned with the mechanical properties of the alloys, have studied the so-called aluminum bronzes after various quenching and reheating treatments. Of these works, perhaps the most complete is that of Bouldoires, who studied changes of length, electrical conductivity, thermoelectric force, hardness and micro-structure on tempering quenched alloys containing 5 to 20 per cent of aluminum, although the work of Carpenter and Edwards,² Curry13 Greenwood,4 Braesco,5 Matsuda,67 Grard8 and others has added much to our knowledge of the changes occurring during tempering. The so-called acicular ß decomposes on tempering at temperatures between 350" C. and the eutectoid, giving rise to a Widmanstätten structure of a needles in a matrix of 6 or fine a + 6, associated with an increase in hardness and almost complete loss of ductility. Matsuda studied the eutectoid transformation by means of dilatation and electrical conductivity measurements during cooling at different rates. He found that on cooling at the rate of 10" C. per minute there was a decrease in electrical resistance and in length instead of the usual increase which occurred with slow rates of cooling. On tempering the rapidly cooled samples, the increase commenced at about 400" C. and at 520" C. the resistance and length had reached the equilibrium values. These peculiarities he accounted for as being due to a transitional phase ß&apos; being formed, ß&apos; having an electrical resistance and volume less than either ß or a + 6. Obinata9 published some electrical conductivity curves for copper-aluminum alloys showing a double break at the eutectoid temperature,

Jan 1, 1933

By Carle R. Hayward

This work was first undertaken in the metallurgical laboratory of the Massachusetts Institute of Technology in 1907 by L. A. Dickinson, E. Phelps, and V. S. Rood, under the author&apos;s direction. They attempted to determine the diagram for the system Cu2S-MiS, but several inexplicable results were obtained. The following year, P. H. Mayer with Mr. Dickinson carried on some experiments with nickel sulphide and found that the molten material slowly lost sulphur until it reached a composition corresponding to the compound Ni3S2, established by Bornemann.l At this point the composition remained stable. The freezing points of the mixtures gradually fell off with the loss of sulphur. Since the above facts seemed to explain the erratic results obtained in the first experiments, Mr. Mayer with F. Jaeger attempted in 1910 to establish a correct equilibrium diagram for the Cu2S-Ni3S2 series. They prepared pure Cu2S and Ni3S2 and determined the cooling curves for various mixtures. The fusions were made in a platinum resistance furnace and the temperatures were measured with a platinum-iridium thermocouple connected with a Sullivan galvanometer. The curve was established for mixtures containing more than 40 per cent. Cu2S, but they were unable to determine certainly the direction of the curve beyond that point. Nothing further was attempted with this series until the present year, when the work was carried to a successful conclusion with the assistance of A. Butts, Jr., and E. H. Weil. The results of this work are given in the following pages. Preparation of Cu2S.—A piece of cathode&apos; copper from the Buffalo plant of the Calumet & Hecla Co. was cut into shavings by a shaper and converted into sulphide by heating in boiling sulphur. A porcelain casserole was used for the purpose, the heat being furnished by a Bunsen burner. It was found that after boiling in the sulphur for an hour the copper shavings were completely converted into sulphide. The liquid sulphur was then poured off, leaving the solid sulphide in the casserole in

Jan 1, 1915

EUGENE McAULIFFE, * St. Louis, Mo.-The method employed by the Engineer&apos;s Committee in arriving at a proper selling price for coal and coke represents hard painstaking effort based on a thoroughly scientific foundation; and the United States Fuel Administration can well point with pride to the work of this committee. The results so obtained placed

Jan 12, 1918