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By Louis A. Carapella, William E. Shaw

Magnesium and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitionai point has been set at 2 25°C by Schmidl for single crystals, and at 250°C by Morel1 and Hanawalt² for extruded magnesium metal. In a recent X-ray investigation on poly-crystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional tempelature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheet† over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig I. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Har-greaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Har-greaves constant S, was obtained by the integrated or intermittent loading procedure. The authors6 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformatione 1 loads. These findings have been applicd

Jan 1, 1947

By William E. Shaw, Louis A. Carapella

Magnesium and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitionai point has been set at 2 25°C by Schmidl for single crystals, and at 250°C by Morel1 and Hanawalt² for extruded magnesium metal. In a recent X-ray investigation on poly-crystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional tempelature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheet† over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig I. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Har-greaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Har-greaves constant S, was obtained by the integrated or intermittent loading procedure. The authors6 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformatione 1 loads. These findings have been applicd

Jan 1, 1947

By Warren E. Wilson

THE transportation of solids in pipe lines is a matter of deep concern in many fields of engineering. Much experimental and theoretical work has been done in an effort to devise means of designing pipe lines that will satisfactorily transport given solid loads, but there remain many unanswered questions in this field. The present discussion will be confined to a rather narrow portion of this field and will endeavor to point out certain factors that may well be considered when comparing the relative economy of various installations. The data have been presented previously but a new interpretation was prompted by a suggestion in a paper by Professor O'Brien,1 of the University of California, that the friction work per pound of dry material should be considered in determining the relative efficiency of various installations. This method of considering relative economy in various pipe lines leads to some rather unexpected conclusions, especially with reference to the economy of large pipe sizes. A previous suggestion by the writer3 concerning the economy of a rather peculiar type of installation is strengthened. It is not believed that the considerations set forth herein apply directly in the case of dredge lines, where economy is largely a matter of a high rate of pumping in order to reduce the unit overhead charge. However, it is believed that some value may be gained from these considerations in cases involving the disposal of a fixed amount of solids per unit time with a minimum expenditure of energy and at a low cost for replacement of worn pipes. Such situations are not uncommon in the disposal of mill tailings and the disposal of solids deposited from irrigation waters. It was found that data leading to general conclusions for various pipe sizes were not available but certain definite trends are indicated and methods of analyzing available data are presented in the hope that they may be of assistance in preparing engineering estimates on designs of pipe lines of the type described above. ENERGY. REQUIREMENTS Carrying out the idea contained in Professor O'Brien's paper concerning the method of computing energy required to transport solids, the following analysis leads to some rather interesting conclusions. Let us represent: [Solids load in terms of mass per unit time by W Ratio of mass of suspended solids to total mass of mixture flowing by p Volume rate of flow of mixture by Q Length of pipe by L Slope of energy grade line by s Mass per unit volume of solids by m, Mass per unit volume of liquid by ml Mass per unit volume of mixture by m,,, We then have as an expression for the solids load: W = pQm¬] The work done per unit mass, P, on the mixture to move it along the pipe the

Jan 1, 1945

By Robert M. Grogan, James C. Bradbury

The Illinois-Kentucky mining district has, since 1880, accounted for 80 per cent of all U.S. production of fluorspar. The ore deposits are of two types: vein deposits formed by fissure fillings along faults and bedding-replacement deposits formed by the replacement of strata at certain favored stratigraphic positions along minor faults and fractures. Fluorite is the chief valuable mineral in the deposits. Sphalerite and galena commonly are present in small amounts but, in some ore bodies, may form a substantial part of the valuable constituents of the ore. Calcite is the chief gangue mineral; quartz and barite Exposed strata range from Devonian are present in various amounts. through Pennsylvanian in age. Igneous intrusive rocks occur as mafic dikes and sills and intrusive breccia dikes and plugs. Structurally, the district is situated on a generally northwest- trending arch that has been sliced into a series of long, narrow blocks by normal faults that trend northeastward. The structural The localization of the ore deposits by faults and fractures, the association of fluorite mineralization with intrusive breccias, and various lines of petrographic and geochemical evidence indicate that the fluorite-zinc-lead deposits were epigenetic and deposited by solutions emanating from a deep alkalic magma.

Jan 1, 1968

By W. E. Ruder

It has been pointed out by Stead1 that grains of considerable coarseness may be developed in steels containing from 3 to 5 per cent. of silicon, and in a previous paper2 the present author has shown that under the proper conditions of annealing single grains having an area of 50 sq. cm. may be obtained. It is the purpose of this paper to discuss in more detail the conditions promoting the growth of these grains, in the hope that the experiments described may throw some additional light upon the general problem of grain growth in metals. These silicon steels lend themselves particularly' well to such experiments because of the ease with which the change in structure may be followed and because of the fact that the effect of the carbon present is largely obliterated by the high percentage of silicon. This forms a solid solution with the iron, which acts very much like a pure metal. This alloy has been found to have but one critical point, viz., Ar2. This point, determined by Roberts-Austen for Hadfield's 4 per cent. Si alloy, was found to lie at 703" C. Vigouroux3, in working with pure Fe-Si alloys, finds this point to rise from 750" C. for 0.5 per cent. Si to 860" for 6 per cent. alloy, with a flat region in the curve from 3 to 4 per cent. Si. No accurate determination of this point has been undertaken by the present author, but it has been roughly determined to lie between 730" and 750:. In the preliminary experiments, some of which have been described in a previous paper, it was found that practically all of these steels, when annealed to 1,200" C. or higher, showed grains of comparatively large size. These grains varied in size, however, from about 4 sq. mm. to 50 sq. cm. (see Figs. 1 and 2) under the same conditions of anneal, and it was for the purpose of determining the cause of this difference in size that the experiments herein described were undertaken. From a preliminary study of the chemical composition of the specimens

Jan 1, 1914

By Robert Stefanko

With passage of the Clean Streams Act of the Commonwealth of Pennsylvania and its impact on the coal industry, considerable research has been conducted to explore various approaches to the problem, including deep-well disposal. Available drillhole data from gas and oil wells were used to develop cross -sectional maps for various portions of the state and potential disposal zones were evaluated. Bethlehem Mines Corp., faced with a severe water problem at its Marianna operation in Washington County, cooperated with the Dept. of Mining at The Pennsylvania State University in establishing a 1500-ft well into the Salt Sands for the purpose of determining the feasibility of mine water disposal. The thickness, porosity, and permeability of the formation at the well site proved to be below what had been anticipated from drillhole data. Further, subsequent hydraulic fracturing did not improve the flow characteristics of the well; pumping pressures remained in the range of 1800-2000 psig for disposing of water at the rate of 150 gpm. The legal problems of disposal at the site were very formidable. When the Salt Sands proved to be less than satisfactory, permission could not be obtained to dispose in other promising formations. The paper details many of the problems associated with the experimental well and makes an assessment of the potential for deep-well disposal of mine water. The concept of disposing of liquid industrial wastes by deep-well injection is not a new one. Brines associated with crude oil long have been disposed of in this manner, with the additional benefit of aiding secondary oil recovery. More recently, with the expansion of nuclear energy, the lethal, highly radioactive wastes which are by-products of the fission process have created severe disposal problems. During the past ten years, a variety of industries have resorted to subsurface disposal, some of the details of which are given e1sewhere.l,2 The list reveals wide variations in injection rate, pumping pressure, cost, and waste disposition. Included are successful installations in Western Pennsylvania. Enactment of more restrictive clean-water legislation in Pennsylvania recently had a great impact on the coal industry. Among its provisions was the reclassifica-tion of most mine water as industrial waste whose dis-posal is prohibited in any stream of the Commonwealth. This had the effect of accelerating research in a variety of areas, although treatment methods still retained primary interest. When a feasibility study of deep-well disposal was proposed to the Pennsylvania Dept. of Mines and Mineral Industries, the Coal Research Board (CRB) approved it. This paper summarizes the efforts on this project. Acid mine water is a chemically complex liquid. having no definite quantitative relationship among its constituents. However, it is the iron disulfide (FeS2) associated with practically all coal seams that produces the objectionable products present in acid mine water when combined with air and water. The principal contaminants are sulfuric acid (H2SO,) and ferric hydroxide (Fe(OH)2. Ferric hydroxide is a rust-colored gelatinous precipitate that coats stream bottoms and destroys aquatic life. However, other ions and bacteria are present in acid mine water in varying amounts.

Jan 1, 1971

By J. W. R. Rayner

THE conventional method of making water gas involves individual plants for the separate carbonization of coal to coke and the subsequent gasification of coke with steam. The process demands lump coke, preferably made from the best quality of coking coals. The ash in the coke should have a high melting point and the gasification process suffers a loss of efficiency when cokes with low ash-melting points are used. In Britain, these coals are generally the most expensive and they are readily available only in certain localities. The coals not suitable for making lump coke, or yielding only poor quality coke, are much more widely available and are generally cheaper. DEVELOPMENT OF ALTERNATIVE PROCESSES In Germany, processes have been developed and operated commercially for the production of water gas from very low-rank coals such as brown coal and lignites, but much less effort has been spent on processes to use coals of intermediate rank, which are widely available in Britain. The brown-coal processes use coal in the form of either dust or briquettes. The most successful of the dust-gasification methods is the Winkler process, which made a substantial contribution to German oil production during the war. It uses coal in the size range 0 to 8 mm and the fuel bed is blown with a mixture of oxygen and steam at a rate high enough to give it a characteristic boiling motion or, in present-day phraseology, at a rate more than sufficient to fluidize it (Fig. 1). Air cannot be used to provide the heat required for gasification, for vari¬ous reasons. In the first place, to make the process continuous by mixing air and steam would involve the production of a lean gas containing much nitrogen. If a separate blow were used, a large amount of potential heat would be lost because the blow gas in such a process would contain a very high percentage of carbon monoxide. Oxygen is necessary therefore and oxygen remains relatively expensive for use in gasification. In the Winkler generator, formation of clinker caused by local overheating does not occur, because of the mobility and high heat transfer of a fluidized bed. These properties of fluidized dusts have been used most successfully.

Jan 1, 1953

By W. H. Bassett

THE ease and value of the application of spectrum analysis to industrial chemistry appears to be appreciated in few of the large works laboratories of this country. For 8 years, this analysis has been of great value to the authors in both analytical and metallurgical work. To the analyst the complete qualitative analysis of an unknown alloy, revealed by a spectrogram, is a sure basis for the planning of the most direct and rapid method of attack. As the determination of each element proceeds, the purity of precipitates may be checked as often as desired. The spectrograph proves invaluable in the recognition of impurities, the separation of which would entail a lengthy and difficult procedure, or when the weight of an unknown is less than is necessary to complete the desired determinations. A few hundredths of a gram will usually suffice for spectrographic analysis. In the separation of the rarer elements, the spectrograph will show, with precision, the point where each step has been successful. In zinc of certain classes, indium, gallium, and germanium have been isolated in this way; the presence of antimony in lake coppers has been proved; and bismuth has been detected in zinc and in alloys where the presence of a few thousandths of a per cent. would be harmful. An antimony precipitate in a delicate determination may contain a considerable proportion of tin or arsenic, both of which will be revealed. The spectrograph is consequently important to the metallurgist as well as to the analyst.

Jan 2, 1922

By Wilbur S. Burbank, Robert G. Leudke

The impressive western San Juan Mountains of Colorado were carved by Pleistocene and Recent erosion from a thick blanket of Tertiary volcanic rocks that rests upon a basement of metamorphic, sedimentary, and igneous rocks ranging in age from Precambrian to Tertiary. These rocks record a long, complex, and fairly complete sequence of geologic events that have affected the region through much of geologic time. The geologic history of the region includes several periods of deformation, erosion, and igneous activity; closely associated with two of these periods were two periods of mineralization. The older of these was related to Late Cretaceous-early Tertiary (Laramide) intrusive activity, and its deposits occur in the older sedimentary units. The younger, of later Tertiary age and related to the widespread middle Tertiary extrusive and intrusive activity, is the chief concern of this paper. Tertiary volcanism built a great plateau surrounding the San Juan volcanic depression, a complex of subsided crustal blocks in the vent areas. The Silverton and Lake City cauldrons, nested within the larger depression, were domed by resurgent magma that created keystone grabens along the distended crests of the domed floors and many postcauldron radial and concentric fractures, dikes, and intrusive plutons within and marginal to the cauldron sites. The postvolcanic evolution of large quantities of gases, chiefly carbon dioxide and water, propylitically altered the rocks in and around the volcanic depression prior to the younger period of ore deposition. The ore deposits, localized mainly in the radial and concentric fractures about the cauldrons and in the associated graben faults, include fissure veins, chimneys, replacements, and disseminations in volcanic and underlying basement rocks. Fissure veins, constituting the major economic source, yielded precious- and basemetal ores. Most veins are compound with sphalerite, galena, and chalcopyrite; some veins contain silver-bearing arsenical sulfosalts and free gold. These minerals occur in predominantly quartz gangue. However, gangues composed of several manganese silicates and carbonates and relatively· barren of metals are abundant locally and probably originated by alteration of rocks at roots of faults and fissures during evolution of carbonatic solutions. The bulk of the ores are hypogene and probably had their source in deep parent magmas of the shallow eruptive rocks. Total production since the early 1870's has exceeded half a billion dollars in recovered metals, with a ratio of precious- to base-metal values of about 3 to 2. Since 1930, improvements in metallurgical treatment and mining techniques have increased the base-metal yield.

Jan 1, 1968

By C. Crussard, R. Tamhankar

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers accord-ing to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Gerhurd Derge Carnegie Institute of Technology Schenley Park Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Staff Coordinator, James J. Burke THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chiprnan, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. W. Thornton, Chairman; Dennis Carney, John Chip-man, J. C. Fulton, J. H. Hollomon, H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: T. B. King, Chairman; S. J. Dickenson, R. P. Hermsdorf, R. Schuhmann, Jr., and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman, F. Lincoln Vogel, Jr., Vice-chairman, W. A. Backofen, R. W. Balluffi, J. H. Bechtold, M. B. Bever, R. S. Busk, C. G. Goetzel, Paul Gordon, C. D. Graham, .Jr., Robert F. Hehemonn, R. I. Jaffee, F. E. Jaumot, Jr., Irving R. Kramer, A. J. Lena, Harold Margolin, C. J. McHorgue, Russell A. Meussner, J. B. Newkirk, H. W. Paxton, G. E. Pellissier, I. S. Servi, Alan U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B. King, F. C. Langenberg, W. 0. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription $20 per year for non-AIME members in United States and North, South, and Central America; $25, foreign; $5 for AIME members. Single copies, $4.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed in its publications . . . Copyright 1958 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AIME New York ... Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts... Second class postage paid at New Yark, N. Y., and Ann Arbor, Mich. Volume 212, Number 6.

Jan 1, 1959

By F. W. Maclennan

The following is a list of members who died in 1929. It is compiled from reports to the Secretary's office. Biographical sketches published in Mining and Metallurgy are indicated in the last two columns. Issue Containing Year of Date of Biography Election Name Death 1929 Page 1922 Adams, Waldo Peck................................ June 2 September 435 1903 Argall, Joseph.................................... Nov. 1 1894 Austin, Leonard S................................. Oct. 30 December 580 1905 Bailed, Melbourne.........................Dec. 12 May* 280 1890 Barringer, Daniel M.............................. Nov. 30 February* 119 1895 Batchelleb, HENRr R.............................. Jan. 15 March 167 BINGHAM Charles E............................. 1923 Bibkett, E. H..................................... Apr. 23 August 394 1913 Bibbell, Robert W................................. Jan. 18 April 214 1926 Blackmar, Don C.................................. June 4 March* 189 1920 Bosworth, T. O.................................... Jan. 18 April 214 1894 Boucher, Arthur S..........................Jan. 6 May 257 1927 Brandenthaler, R. R.............................. Dec. 14 January* 64 1889 Bretherton, S. E............................... Oct. 4 December 581 1911 Brunton, F. K................ .. Aug. 17 1924 Brush, Charles F................................. June 15 September 436 1925 Cameron, Frank N........................May 16 July 349 1891 Chambers, Robert E.............................. May July 348 1908 Clark, J. Murray................................. Dec. 3 August* 407 1883 Clymer, edward T............................. Oct. 13 December 579 1914 Cofpey, George T................................. May 8 July 349 1901 Cooke, L. H....................................... Aug. 23 November 537 1915 Cousins, George W........................ June 30 February* 118 1886 Cowles, A. H...................................... Aug. 13 September 436 1892 Crane, Theron I............................. Nov. 2 December 579 1921 Crowell, Samuel B................................ Dec. 9 January* 64 1907 Curtis, Bracey.................................... Jan. 31 April 215 1895 de Batz, Rene........ ............... January March* 189 1928 Dines, Tyson S.................................... March May 257 1909 Dufourco, R. G............................. January November 537 1920 Ericsson, Eric A.................................. Apr. 4 April* 231 1920 Erlenborn, Willi....................... Nov. 10 March* 189 1888 Farish, John B.................................... Nov. 14 December 580 1891 Ferguson, Vincent........................... Mar. 8 May 257 1917 Finucane, T. R.................................... Mar. 22 February* 118 1921 Foch, Ferdinand................................... Mar. 20 1885 Foucar, Edouard I....................... Jan. 3 March 167 1880 Francklyn, Charles G............................. Jan. 11 April 214 1925 Friedl, Arthur J.............................. July 9 September 435 1894 Fuller, James W. Jr............................... April 4 1876 . Goodale, Charles W.............................. April 11 May 258 1912 Graybill, John..........................Dec. 11 June* 320 1887 Gritzner, F. A.................................. Mar. 26 July 394 1906 Gunther, C. Godfrey.............................. Deo. 26 February* 118 1900 Haggen, Edward A.............................. Apr. 22 October 488 1895 Hall, Benjamin M........................Nov. 19 March* 189 1913 Harper, Walter S................................. Feb. 15 August 394 1921 Hawley, William S................................ Apr. 20 June 298 1920 Herd, Walter ... . . . ..... Aug. 23 September 435 1889 Holt, Marmadtjke B............................... Dec. 26 February* 118 1928 Husk, Albert D .... ................June 9 December 580 1920 Hutchinson, S. Pemberton......................... Feb. 16 April 214 1926 Ivanoff, Constantine L............................ Mar. 7 June 298 1914 Jaeger, Frederick..... .............July 28 October 488 1891 Jennings, Robert E.......................Oct. 30 December 580 1922 Johnson, Homar L................................. Sept. 17 October 483 1927 Johnson, Homer H................................. Mar. 21 May 257 1918 Jones, Jesse L ..... ...............Jan. 22 April 214 1892 Jones, Thomas J................................... June 18 October 488 1883 JoOet, Cavalier H................................. Mar. 29 May 258 1881 Kennedy, John S . . . . ... ..........Apr. 22 August 394 1881 Kennedy,- Hugh.................................... May 23 September 435 1895 Kebvin, James H................................... September October 488 1926 Kkom, L. J........................................ Dec. 24 January* 64 1905 La Follette, Harvey M........................... Sept. 19 November 538 1920 MacDonald, Alexander............................ May August 394 1904 Marengo, Paolo................................... May 257 1925 Maxwell, Allison R............................... May 7 November 538

Jan 1, 1930

[Chairman ZAY JEFFRIES, Vice-chairman S. SKOWRONSKI, Chairman WILLIAM M, CORSE, Secretary Executive Committee J. R. FREEMAN, JR., Local Section G. E. JOHNSON R. S. ARCHER, Non-ferrous Data Sheets P. D. MERICA EDGAR C. BAIN, Journal Committee L. W. SPRING SAM TOUR, Papers Committee F. L. WOLF H. C. JENNISON, Membership Committee Local Section Committee J. R. FREEMAN, JR., Chairman R. J. ANDERSON, Cincinnati R L. DOWDELL, Minneapolis R. S. WILLIAMS, Boston G. H. CLAMER, Philadelphia W. A. SCHEUCH, Chicago R. F, Woon, New York Papers Committee S. SKOWRONSKI, Chairman F. H. DIx, JR.-Aluminum E. R. DARBY-Bronze C. S. WITH ERELL-Copper H. A. BEDWORTH-Brass W. K. FRANK-BRONZE F. W. HARRIS-Copper R. L. SUHL-Nickel H. M. ST. JOHN--Foundry Metallurgy R. S. DEAN-Theoretical Metallurgy]

Jan 1, 1928

By A. Spilners, M. Simnad

The rates of formation of the different oxides on molybdenum in pure oxygen at 1 atm pressure have been determined in the temperature range 500° to 770°C. The rate of vaporization of MOO, is linear with time, and the energy of activation for its vaporization is 53,000 cal per mol below 650°C and 89,600 cal per mol at temperatures above 650°C. The ratio Mo03(vapor.lzing)/MoOS3(suriace) increases in a complicated manner with time and temperature. There is a maximum in the total rate of oxidation at 6W°C. At temperatures below 600°C, an activation energy of 48,900 cal per mol for the formation of total MOO, on molybdenum has been evaluated. The suboxide Moo2 does not increase beyond a very small critical thickness. At temperatures above 725°C, catastrophic oxidation of an autocatalytic nature was encountered. Pronounced pitting of the metal was found to occur in the temperature range 550° to 650°C. Marker movement experiments indicate that the oxides on molybdenum grow almost entirely by diffusion of oxygen anions. USEFUL life of molybdenum in air at elevated temperatures is limited by the unprotective nature of its oxide which begins to volatilize at moderate temperatures. Although the oxide/metal volume ratio is greater than one, the protective nature of the oxide film is very limited. Gulbransen and Hickman' have shown, by means of electron diffraction studies, that the oxides formed during the oxidation of molybdenum are MOO, and MOO,. The dioxide is the one present next to the metal surface and the trioxide is formed by the oxidation of the dioxide. Molybdenum dioxide is a brownish-black oxide which can be reduced by hydrogen at about 500°C. Molybdenum trioxide has a colorless transparent rhombic crystal structure when sublimed, but on the metal surface it has a yellowish-white fibrous structure. It is reported to be volatile at temperatures above 500" and melts at 795°C. It is soluble in ammonia, which does not affect the dioxide or the metal. In his extensive and classic investigations of the oxidation of metals, Gulbransen2 has studied the formation of thin oxide films on molybdenum in the temperature range 250" to 523°C. These experiments were carried out in a vacuum microbalance, and the effect of pressure (in the range 10-6 yo 76 mm Hg), surface preparation, concentration of inert gas in the lattice, cycling procedures in temperature, and vacuum effect were studied. The oxidation was found to follow the parabolic law from 250" to 450°C and deviations started to occur at 450 °C. The rates of evaporation of a thick oxide film were also studied at temperatures of 474" to 523°C. In vacua of the order of 10- km Hg and at elevated temperatures, an oxidation process was observed, since the oxide that formed at these low pressures consisted of MOO, which has a protective action to further reaction in vacua at temperatures up to 1000°C. Electron diffraction studies showed that, as the film thickened in the low temperature range, MOO8 became predominant on the surface. Above 400°C MOO, was no longer observed, MOO, being the only oxide detected. The failure to detect MOO, on the surface of the film formed at the higher temperatures does not militate against the formation of this oxide, since according to free energy data MOO3, is stable up to much higher temperatures. At the low pressures employed, this oxide would volatilize off as soon as it was formed. Its vapor pressure is relatively high and is given by the equations" log p(mm iig) = -16,140 T-1 -5.53 log T + 30.69 (25°C—melting point) log p(mm He) = -14,560 T-1 -7.04 log T+1 + 34.07 (melting-boiling point). Lustman4 has reported some results on the scaling of molybdenum in air which indicate a discontinuity at the melting point of MOO, (795°C). Above the melting point of MOO,, oxidation is accompanied by loss of weight, since the oxide formed flows off the surface as soon as it is formed.5,6 Qathenau and Meijering7 point out that the eutectic MOO2-MOO3 melts at 778C, and they ascribe the catastrophic oxidation of alloys of high molybdenum content to the formation of low melting point eutectics of MOO3 with the oxides of the melts present. Fontana and Leslie -explain the same phenomenon in terms of the volatility of MOO,, which leads to the formation of a porous scale. Recent unpublished work by Speiser9 n the oxidation of molybdenum in air at temperatures between 480" and 960°C shows that the rate of weight change of molybdenum is controlled by the relationship between the rates of formation and evaporation of MOO,. They have measured the rates of evaporation of Moo3 in air at different temperatures and estimated an activation energy of 46,900 cal. This compares with the value of 50,800 cal per mol obtained by Gulbransen for the rate of sublimation of MOO, into a vacuum.

Jan 1, 1956

By F. Petkovich, M. P. Sudbury

Development of a new method of treating flotation concentrates for the preparation of feed suitable for direct charging to blast furnaces or converters is described. The method takes advantage of the fact that pyrrhotite contained in the concentrates can be made to undergo exothermic reactions which, under properly controlled conditions, result information of oxidation products that serve to cement the concentrate particles together. Thus green concentrates either in the form of pellets or briquettes containing 5 to 8 pct moisture not only were hardened, but also completely dried autogenously by continuous countercu,vrent shaft treatment with air. The process was developed through pilot plant operations ranging from 35 1b per hr to 2.5 tph, culminating in products evaluation tests on a railway-car scale. Falconbridge Nickel Mines Ltd., Falconbridge, Ont., have practised sintering, on a travelling grate machine, for many years to prepare a pyr-rhotite-bearing Cu-Ni sulfide flotation concentrate for blast furnace smelting. In recent years the development of new mines, and the construction of concentration plants some 40 miles from the smelter has increased the quantity of concentrate shipped, and encouraged the search for a method of producing dry, hard pellets or briquettes suitable for direct charging to a blast furnace or converter, and capable of withstanding considerable handling. The cementing properties of pyrrhotite oxidation products were discovered during a search for a suitable agglomeration method for sulfide concentrates, and were exploited in a process subsequently developed for autogenously drying and hardening pellets and briquettes of pyrrhotite-bearing Cu-Ni sulfide flotation concentrate. EARLY TEST WORK The production of hard, dry pellets of concentrate filter cake was attempted in the drying plant of one of the new concentrators. While soft pellets were produced containing 5 pct moisture, attempts at further drying resulted in disintegration of the pellets and intolerable dusting. The plant therefore was controlled to produce a concentrate containing about 6 pct moisture. The partially dried concentrate, which was shipped to Falconbridge for sintering, tended to heat spontaneously in transit. An at- tempt to briquette the moist concentrate at Falconbridge, in a plant incorporating a muller, a 20-in. roll briquetting press, and a steam-heated travelling grate oven, was more successful, although the equipment corroded rapidly due to the acid nature of the concentrate after spontaneous heating had occurred. LABORATORY STUDIES OF SPONTANEOUS HEATING OF CONCENTRATE The spontaneous heating of partially dried concentrate was studied in the laboratory. Moist concen-

Jan 1, 1961

By R. Salter, C. K. Chase

Although Asarco's Silver Bell Unit, 40 miles west of Tucson, Ariz., is known primarily for copper production, molybdenite is also produced as a byproduct in the 8000 tpd flotation mill. The Silver Bell ore comes from two pits approximately two miles apart. Copper mineralization is essentially chalcocite resulting from two to three-fold secondary enrichment in a highly altered zone. A typical porphyry copper deposit, Silver Bell ore is of medium hardness. The ore consists of about one part molybdenum to 65 parts of copper. In the copper concentrate which is the starting point for separate molybdenum recovery, the ratio is also one part molybdenum to 65 of copper. Molybdenum mineralization is primary. Enrichment is not evident but it is notable that the molybdenite is more common in the more siliceous, harder rocks. The actual molybdenite occurs as diversely oriented flakes of fairly constant grain size, mostly in fractures associated with quartz veins. Most of the mineral appears unoxidized; secondary coatings on the molybdenite flakes are fortunately rare. In May 1962 a modified, improved version of the molybdenite circuit was put into operation.

Jan 7, 1964

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

A. U. Seybolt (General Electric Research Laboratory)—The authors should be commended for adding some important information to our knowledge of the solubility of interstitial elements in metals. It is becoming increasingly evident that the effect of even traces of such elements have very far-reaching effects upon the mechanical properties of the body centered cubic metals. Those who have worked in this area know that the accurate determination of the small solid solubility limits in systems of the type reported by the authors is a quite difficult task, and it is therefore not surprising that frequently the results of different workers are not in agreement. It is instructive, and usually helpful, to plot the solubility results on log weight or atomic percent -1/T coordinates to find out if a straight line is obtained. A straight line is expected because in systems displaying solubilities of the order of 1 to 3 at. pet or less, Henry's law is usually obeyed—or at least well enough obeyed so that the deviation from linearity is not very appreciable. If Henry's law is obeyed, one canthen use the Van't Hoff Equation in the form In N = ?H/RT + C, where N is mole fraction, at. pet, or wt pet for small values, and AH is the partial molal heat of solution of the solute. R and T have the usual significance, and C is an integration constant. If one plots the reported nitrogen solubility values as indicated above, the three points fall reasonably well on a straight line. The oxygen values for the two upper temperatures fall very closely to the nitrogen values as shown in the authors' Fig. 15. However, the value at 500°C departs widely from the straight line established by the data at 1500" and 1000°C. It is, of course, true that one cannot place too much emphasis on the significance of a line established by only three points, but in the absence of reasons for anticipating deviations, data exhibiting wide departures from linearity should at least be examined closely. Fig. 16 shows the log at. pct -1/T plots for the authors Ta-O and Ta-Ndata including a solid circle point at 500°C and 1.8 at. pet for Ta-O, which is simply extrapolated from the two higher temperature points. In addition, the data of R. P. Elliott9 for Nb-O are shown. These points were picked off his curve and are not very exact, but as can be seen they line up well on a straight line. It is interesting, and probably significant, that the slope of Elliott's results is not far from those of Vaughn, et al. This is probably to be expected because one would anticipate that the partial molal heats of solution of oxyten in these two very similar metals should be not too far apart. AH for Ta-O is about -1900 cal per mol, while for Nb-O it is near -2300 cal per mol. Hence, this lends some support to the thesis that the point at 500°C for Ta-O is much too high. The data of Gebhardt and Preisedanz10 are also plotted, and it is seen that their data while lying on a linear plot, have an appreciably steeper slope. The possible reasons for this will not be discussed here except to point out that their pressure-composition data show anomalies which suggest that they may have been dealing with a different equilibrium from that being discussed. There is another consideration which would also suggest that the solubility at 500°C is lower than shown. The solubility values were obtained by the classic method of first establishing a lattice parameter-composition curve. This the authors did, and there is probably little doubt that it is quite accurate. Such a plot is generally almost error-free because it has a self-correcting feature in that any deviation from linearity makes a data point immediately suspect, and subject to confirmation. Unfortunately, this is not true with respect to the actual solubility values. These are obtained ordinarily by taking an alloy containing more solute than is soluble at some temperature and then thermally

Jan 1, 1962

By AIME AIME

THIS year the Petroleum Division holds its fall meeting at Houston, Texas, Oct. 2 and 3, with head- quarters at the Lamar Hotel. Technical sessions will be held in the morning and afternoon of both days. A smoker on Friday afternoon will afford an opportunity to get together socially. Saturday evening is left free for private parties to the beach at Galveston, where a wide variety of entertainment is available. On Oct. 4 there will be an excursion to Sugarland oil field, with luncheon at Boling and a visit to Boling sulfur mine and plant in the afternoon. There are nine technical papers on the program for Friday. Saturday morning will be devoted to oil production control and it is planned to make the discussion more

Jan 1, 1931

By Stanislaus Skowronski

OVERPOLED copper, as commonly defined, is copper which has been excessively reduced during the poling period of the refining process. Owing to its porosity, such copper is unfit for commercial purposes. The cause of this phenomenon is undoubtedly the lack of oxides in the copper, yet this does not completely explain it. Refined copper of the same "pitch" and "set" varies considerably in oxygen contents, and analyses of overpoled bars also show similar wide differences; moreover, it is possible to melt copper in crucibles so as to obtain bars that are practically free from oxygen although they show a "tough pitch" and "level set" surface. Frederick Johnson advances the following theory: The regulation of the quantity of oxygen in copper is the keynote of all copper refining. It is the presence of a Well defined proportion of oxygen in the form of cuprous oxide, forming a copper-cuprous oxide eutectic, Which enables copper to be cast free from blowholes. It seems that When oxygen is present, other gases are less soluble in molten copper; When oxygen is absent, or is present in insufficient quantity, the copper dissolves other gases, such as hydrogen and carbon monoxide, Which are insoluble in the copper when solid, and, being rejected during the process of solidification, causes internal porosity and external ridges and excrescences.1 The "level set" of Wire bars, etc., is entirely the result of a compromise between the occluded gases and cuprous oxide. With excess of the former the metal would be "overpitch" and spongy, While an excess of the latter would result in the metal being "underpitch" and brittle.2 The result of the absorption and subsequent expulsion of reducing gases, carbon monoxide and hydrogen, and the effect of this action. on the overpoling of copper are in dispute; the literature on the subject is full of contradictory statements and will continue to be so until better analytical methods have been developed. Sulphur, however, is tangible. The refiner can see it in his button sample and consequently attributes to it any trouble that may happen during the melting of the copper.

Jan 3, 1918

By V. F. Parry, J. B. Goodman

The low-rank coals containing 10 to 50 pet natural bed moisture represent over half of the tonnage reserve of the available solid fuels of the United States, but only about 2 pet of United States coal production is derived from these fuels. Increased utilization of these large reserves will result if the bed moisture can be removed at the mine in high-speed low-cost processes. This paper presents a theoretical and experimental study of the factors affecting high-speed drying of coal dusts. The time required to heat particles of coal is proportional to the square of their diameter, and it is calculated that the probable time in minutes is equal to 6D2. In other words, a 11 a in. coal particle should be heated to drying temperature in 1.5 to 2.0 sec. Likewise, 1/8 in. particles should be heated in about 6 sec. The net heat required to dry subbituminous coal and lignite varies from 240 to 375 Btu per pound, depending upon the moisture removed, and this heat can be obtained from 42 to 61 cu ft of hot gases at 600°F.

Jan 1, 1949

By F. F. Aplan

Mineral processing engineers have recorded an- other year of active research and development work. Most gratifying was the broadly based attendance at the Mineral Processing Fundamental (formerly Basic Science) Committee sessions at the 1968 Annual Meeting of the AIME. Because of the availability of good papers, the active discussion and the growing attendance, sessions have grown from one to three at the annual meeting. Prof. M. C. Fuerstenau of the University of Utah will chair the Mineral Processing Fundamentals Committee for the next two years and we may thus be assured of continued active leadership. The name change from "Basic Science Committee" to the more descriptive "Mineral Processing Fundamentals Committee" approved by the MBD executive council is a welcome improvement. Our profession continues to attract the interest and cooperation of those in other professional groups. The 1968 Engineering Foundation Particulate Matter Conference, under the chairmanship of John Karpinski of Bethlehem Steel, was devoted exclusively to comminution this year. It attracted conferees from five continents and served as a particularly stimulating source of interchange of knowledge from many technical fields. Next year's conference will be under the chairmanship of Professor L,. G. Austin of The Pennsylvania State University. This conference plus the Symposium on Wettability and Flotation to be held at the annual American Chemical Society meeting in Minneapolis in April indicates the success achieved in the inter-disciplinary approach to problems. Other evidence of this spirit of professional cooperation is the forth- coming book on Size Reduction edited by D. W. Fuerstenau. This is the outgrowth of an AIChE symposium on size reduction held in 1965.

Jan 2, 1969