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By Ottar Dragge, C. Danielsson, Bo Kalling

THE desulphurizing of pig iron has been accomplished with a number of different additions. The oldest and still most commonly used agent is soda, the extensive use of which commenced about 1925, when it was used principally for cupola furnace iron. More recent experience' seems to show that better results can be obtained with sodium hydroxide. The well-known desulphurizing properties of lime have also been exploited in different technical processes. Another material with even more powerful effect is calcium carbide.' The desulphurizing ability of manganese, when added to the ladle in sufficient quantity, should also be mentioned in this connection. During recent years increasing attention has been paid to the desulphurizing properties of metallic magnesium." An addition of a suitable alloy of magnesium is now in use purely for the purpose of sulphur elimination. Of the desulphurizing agents mentioned, lime is by far the cheapest, provided that the reaction can be brought about rapidly and completely. Therefore, a method that makes full use of the desulphurizing ability of lime may be able to compete with other processes. A method developed at the Dom-narfvet Iron and Steel Works (Sweden) will be described, which enables pig iron to be rapidly desulphurized to very low sulphur contents by using a burnt lime powder. as the desulphurizing agent. Lime in Older Processes In cases where lime has been used for the desul-phurization of pig iron, it has generally not been used alone, but mixed with other substances such as fluorspar, to obtain the formation of a molten slag during the process. This method has been tried by Tigerschiold,' who treated the iron with a lime-fluorspar mixture, the stirring of the iron being brought about inductively with low frequency alternating current. Very good results were obtained. A process of this type has also been suggested by R. P. Heuer, U. S. A. The principles of this method, which has been tested in Great Britain by Newell. Lanener. and Parsons." re that a mixture of lime and fluoispar is added to the hot metal in the ladle, while a powerful stream of nitrogen gas is blown into the bath to produce the required intermixing. The results of the tests were unsatisfactory, however. A similar process has been developed at The Steel Co. of Canada, according to a statement by H. M. Griffith.' Here the tests were carried out in a carbon-lined ladle provided with carbon tuyeres in the side wall for blowing nitrogen into the bath. The addition consisted of about 20 lb of a mixture of burnt lime and fluorspar per ton of pig iron. Good results appear to have been achieved. The sulphur content of the pig iron is stated to have been reduced from 0.025 to 0.050 pct down to 0.006 pct. Various methods of desulphurizing pig iron have been tried using lime powder without fluxing material for fusing. Eichholz and Behrendt7 have experimented with blowing a powdered limeicoke mixture with air into the ladle. Their results were, however, not conclusive and the experiments do not appear to have been continued. Similar experiments have been carried out at Domnarfvet, using nitrogen instead of air in order to avoid oxidation. But these attempts were not particularly successful. It appears to be difficult to achieve the required agitation by this means. The strong cooling effect of the gas on the iron is also a serious drawback. A method in many respects similar to that tried at Domnarfvet was tried by Eulenberg and Krus at the end of the 1930's. Here again desulphurization was carried out with lime alone, brought into contact with the molten iron in a rotary furnace. The temperature was kept at the required level, 1400" to 1500°C, by the introduction of a pulverized coal burner in one end of the furnace. The speed of rotating was not given. A paper by Bading and Krus states that, in one of the first experiments, the sulphur content in 56 tons of pig iron was brought down from 0.186 to 0.035 pct in 117 min, but that a considerable shortening of the time would be possible. According to later reports by Eichholz and Behrendt,' it should be possible by this process to achieve a desulphurization speed of 0.35 pct S per hr for a consumption of 6 to 10 pct limestone and 2 to 3 pct coke, as fuel exclusively. The final sulphur content is, however, not stated. Domnarfvet Method After a number of different procedures had been investigated, the tests at Domnarfvet were directed to desulphurization with lime in a rotary furnace. Before going into the practical details of the method, the theoretical aspects will be discussed briefly. If the pig iron does not contain alloying elements other than carbon, the reaction can be expressed most simply by the usual equation: FeS + CaO + C = Fe + CaS + CO [I] 4H,. ~ 34,000 cal That this reaction can be carried through to a very complete desulphurization of pig iron has been shown by OelsenD in a discussion in connection with the Eulenberg and Krus' method. He mentions two laboratory tests, in one of which the sulphur content in the pig iron at 1400°C was reduced from 0.540 to 0.006 pct after treating with 3.35 pct lime. The pig iron had a low manganese content, but other analysis is th. given. Mention also should be made of the recently published investigations by Fischer and Cohnen'" dealing with the influence of the carbon content of the iron on desulphurization with lime, although in this case fluorspar was added also. The tests show that efficient desulphurization is possible with lime in the steel bath, provided that the carbon content is sufficiently high. The temperature employed in these tests was considerably higher (1620") than that normal for treatment of pig iron. The author concludes that the product S% X C% - 0.011 at the temperature in question.

Jan 1, 1952

PRESIDENT AND DIRECTOR DONALD B. GILLIES CLEVELAND, OHIO PAST PRESIDENTS AND DIRECTORS R. C. ALLEN CLEVELAND, OHIO D. C. TACKLING SAN FRANCISCO, CALIF. TREASURER AND DIRECTOR KARL EILERS NEW YORK, N. Y. VICE-PRESIDENTS AND DIRECTORS H. G. MOULTON NEW YORK, N. Y. HARVEY S. MUDD Los ANGELES, CALIF. PAUL -D. MERICA NEW YORK, N. Y. WILFRED SYKES CHICAGO, ILL. WILLIAM B. HEROY HOUSTON, TEXAS HENRY KRUMB NEW YORK, N. Y.

Jan 1, 1939

Following is the personnel of the various society and national committees on which the A I M E is officially represented United Engineering Society Officers of the Board, 1920 JOHN VIPOND DAVIES,, President CALVERT TOWNLEY, 1st Vice-president ALFRED D FLINN,, Secretary WALTER M McFARLAND, 2d Vice-president JOSEPH STRUTHERS, Treasurer Finance Committee House Committee WALTER M McFARLAND Chairman GEORGE H PEGRAM W L SAUNDERS

Jan 1, 1923

By S. Ramachandran, R. A. Walsh, J. C. Fulton

A method has been developed for calculating the oxygen content of commercially melted stainless steels. Application of thermodynamics to the de-oxidation reaction in straight chromium and Cr-Ni stainless steels has resulted in a set of equations DURING the past 30 years, many rewarding developments have resulted from the application of physical chemistry to steelmaking. A need still ex- which permits the calculation of oxygen contents. The model was programmed for computer calc~ilations. The validity of the method was demonstrated on routine oxygen samples from numerous commercially melted heats of stainless steel. ists for further progress in the use of thermodynamics to meet the more stringent requirements for cleaner steel. Current electric furnace practices have been developed around minimizing residual-oxygen content, one of the most important factors controlling the inclusion content of stainless steels. The residual oxygen is controlled by the use of deoxidizers during the finishing period and a number of empirical rules have been evolved. Although this feature of electric furnace practice has long been in use, only in recent years has funda-

Jan 1, 1963

By R. G. Robins, O. J. Kwok

The application of chemical thermodynamic theory to high temperature aqueous systems is discussed as a basis for the explanation of thermal precipitation. The derivation of high temperature potential/ pH diagrams is briefly outlined in order to show a temperature/pH relationship for hydrolytic precipitation, which is an effect that is caused simply by heating an aqueous solution. Various examples of thermal precipitation are given, with particular reference to separation of metal values from leach solutions. Metal sulphate solutions are shown to precipitate basic sulphates, hydrated sulphates , oxides, hydroxides, and oxydroxides of the metal depending largely on the pH, the concentration of metal ion, and the concentration of sulphate or bisulphate. The CuS04-H2S04-H20 system is treated in some detail, and the separation of copper from other metal ions is investigated. Other separations involving Fe, Ni, Zn, Cd, and Cr are considered. Other advantages of thermal precipitation, such as the formation of high purity, large particle size and easily filterable materials, are presented. The kinetics of thermal precipitation are also briefly examined.

Jan 1, 1973

By Marlin J. Veesaert

Urban quarries offer one of the greatest opportunities for profit in nonmetallic mining with limited financial risk-if properly evaluated, planned and developed to meet market needs. Location, with respect to market, is the prime consideration. Geologic considerations and quality of rock are nearly as important. Cost factors and return on investment (ROI) are the principal financial considerations. Risk of capital is determined by weighing all factors that should be considered and how well judgments are based on information acquired. It is a simple, true axiom of business that an investment must be founded on amount of capital required with its expected return plus profit, expertise required to operate, and time involved. Urban quarries generally offer excellent stone product market opportunities. Costs of land with mineral containment and processing operations are much greater than in rural areas. Environmental problems have become increasingly severe. Competition from other quarries in the market area is usually directly proportional to the profit attractiveness. Risk of capital (initial, developmental and operational) can be evaluated and reduced only by thorough analysis of the entire situation. Time and money expended on planning and preliminary investigations probably represent the most productive investment of available company resources. Basic Reasons to Establish a Limestone Quarry Profit Motive: Certainly the dominant and overriding motive must be that of attaining a reasonable profit. In certain situations a quarry firm may acquire land, necessary rezoning (if required), and satisfy all of the other prerequisites preparatory to beginning operations but delaying the actual development.

Jan 1, 1980

By Alfred H. Brooks

PetRoleUm seepages are known in Alaska at four localities, all on Pacific seaboard. These, named from east to west, are Yakataga, Katalla on Controller Bay, Iniskin Bay on Cook Inlet, and Cold Bay on the Alaska Peninsula. Besides these, a petroleum residue has been found near Smith Bay on the north Arctic coast of the Territory. At Katalla, Cold Bay, and Iniskin Bay there has been some drilling for oil, and in the first field several productive wells have been opened up. Alaskan petroleum, so far as its composition is known, is a refining oil, with paraffin base and low sulphur content. Most of what is known of the geology of Alaska oil fields is based on the investigations of Dr. George C. Martin, of the United States Geological Survey. A, G. Maddren, of the same service, has recently made a reconnaissance of the Yakataga oil field. The data to be here presented are chiefly taken from the following publications: G. C. Martin: The Petroleum Fields of the Pacific Coast of Alaska, with an account of the Bering River coal deposits, Bulletin No. 250, U. S. Geological Survey, pp. 9 to 27 (1905). G. C. Martin: Geology and Mineral Resources of the Controller Bay Region, Alaska, Bulletin No. 335, U. S. Geological Survey, pp. 112 to 130 (1908). G. C. Martin and F. J. Katz: A Geologic Reconnaissance of the Iliamna Region, Alaska, Bulletin No. 485, U. S. Geological Survey, pp. 126 to 130 (1912). A. G. Maddren: Mineral Deposits of the Yakataga District, Bulletin No. 592, U. S. Geological Survey, pp. 143 to 147 (1914). Katalla Field The Katalla field is marked by a series of seepages and gas springs occupying an east and west belt, about 25 miles in length and from 4 to 8 miles wide. (See Fig. 1.) This zone skirts the north shore of Con-

Jan 1, 1915

By W. Rostoker

Single isothermal sections were constructed for the titonium-rich corners of the systems Ti-Fe-O, Ti-Cr-O, and Ti-Ni-0 with a view to locating the shape and disposition of the ternary intermediate-phase fields for the compounds isomorphous with Fe3W3C. IN a previous note,' it was reported that a group of ternary intermediate phases existed which occurred in the general composition range Ti,X,O-Ti&O where X was one of the following elements: copper, nickel, cobalt, iron, or manganese. In two instances, binary intermediate phases occurred (Ti²Cu and Ti²Ni) which appeared to be isomorphous. The X-ray diffraction patterns of the phases could be indexed on a cubic lattice whose cell edge was of the order of 11 kX. Karlsson2 stated that the line extinctions and line intensities indicated that these phases were isomorphous with Fe³W³C and therefore belonged to the space group Oh. This author also noted that no unique phase of this type occurred at the composition Ti,Cr,O. This latter statement was accepted as true at the time the previous technical note was written.' However, work continued along these lines and that reported here has shown that a phase isomorphous with Fe³W³C does exist in the vicinity of the composition Ti³Cr³O but not at or near Ti4 Cr²O. The lattice parameter of this phase was found to be 13.01 kX. Metallographic examination of both as-cast and annealed specimens of these supposed ternary oxide phases disclosed structures which were far from single phase in many instances. It was considered a point of some interest to locate more positively the composition coordinates of the single-phase fields. To this end, single isothermal sections for the systems Ti-Fe-O (1000°C), Ti-Cr-0 (1000°C), and Ti-Ni-0 (900"C) were constructed. Phase relationships were studied by both X-ray diffraction and metallotrra~hic methods. Allovs were prepared as 10 g buttons by melting in a noncon-sumable electrode, water-cooled copper crucible arc-melting furnace using a helium atmosphere. Oxygen was introduced quantitatively by the use of weighed amounts of TiO² or TiO. Iodide titanium and the purest available alloying metals were used. All results are discussed in terms of the nominal composition of the melts. Previous experience with making oxygen-rich alloys had shown that oxygen losses were not significant if a homogeneous melt was produced. Weight-loss measurements were used to check loss in metallics during melting. Anneals were conducted in evacuated Vycor bulbs, and annealing times ranged from 24 hr at 1000 °C to 48 hr at 900°C. To achieve equilibrium in certain sluggish alloys, seven-day anneals were used. Debye-Scherrer powder patterns were taken in a 14 cm diam camera using filtered CuK radiation (K² = 1.541232 kX; K., = 1.53739 kX). Specimens were prepared by crushing and screening previously annealed buttons. In general, the X-ray diffraction results were used to identify the major phases, while the metallographic examinations were more useful in indicating the number of phases present. By the use of the combined results and general fundamental rules governing ternary equilibrium, it was possible to construct isothermal sections in good detail. In some instances where auxiliary lattice-parameter data were available, it was possible to lay down tie lines and to locate more positively corners of three-phase fields. Isothermal Section of the System Ti-Fe-O at 1000°C The binary systems Ti-O³ and Ti-Fe4 have been published. Binary phases, TiO, TiFe, and TiFe2, are likely to be encountered in the titanium-rich corner of the system. The structures are NaCl (Bl), CsCl (B2), and MgZn, (C14) types, respectively. Although preliminary X-ray diffraction studies indicated the presence of a ternary phase in the composition range Ti,Fe,O-TiJ?e,O, metallographic examination of two specimens at these compositions revealed the presence of other phases. Thirty-eight alloys were used to delineate the phase boundaries of the isothermal section illustrated in Fig. 1. The five almost single-phase ter-

Jan 1, 1956

By W. W. Vaughn, R. H. Barnett, E. E. Wilson

Soon after the search for uranium ores on the Colorado Plateau began in earnest, thousands of feet of drill core ranging from 1 1/8 to 2 1/8 in. diam became available for study. Although significant advances had been made in the technique of quantitative gamma-ray borehole logging, instrumentation was in the development stage, and complete reliance could not be placed on gamma-ray logs alone to interpret quantitatively the meaning of radioactivity in a drillhole. A method that would be faster than chemical analysis and still give reproducible and reliable results for various drill core sizes was desirable to provide additional information on the enormous footage of drill core being accumulated. A solid phosphor scintillation drill core scanner was designed and constructed. Basically the instrument was developed to measure radiation from a drill core which would not be clearly recorded by a gamma-ray logger using a Geiger tube as the sensitive element. Such data would be beneficial in constructing isorad maps to delineate ore-bearing zones. A calibration in the range 0.01 to 0.1 pct eU3O8 was provided; above 0.1 pct eU3O8 gamma-ray logs were available and were being used to calculate grade and tonnage of ore reserves. The core scanner, however, has been used to estimate equivalent uranium content of ore-grade materials containing as much as 2.2 pct eU308 with an accuracy of ±10 pct, the sample being in the form of a BX drill core. Actually, an apparent calibration of eU308 vs counts per unit time is a straight line with a slope that is a function of the sensitive element and the geometry of the counting assembly. A true calibration that will show the expected departure from a straight line is due principally to the random nature of the pulse from a radiation source and the nonlinearity of the electron circuitry.

Jan 6, 1959

By L. S. Castleman, L. L. Seigle

IN a recently reported investigation, J. B. Clark and F. N. Rhines1 used a diffusion couple technique to determine the number of intermetallic phases which should be present in the Al-Mg equilibrium phase diagram. Their method was an application of the following generally accepted principle. If a diffusion couple made up of two metals is annealed at a given temperature for a long time, all the phases of the binary system which exist under equilibrium conditions at the diffusion temperature will form intermetallic layers. It is important that the diffusion temperature be high enough and the diffusion time be long enough to permit the nuclea-tion of all thermodynamically stable phases at the interface of the couples and their growth to observable thicknesses. These simple time-temperature criteria are at times difficult to satisfy, and it is the purpose of this note to point out a situation in which this is the case. The authors are currently studying diffusion bonding in the Al-Ni system." It is well established

Jan 1, 1958

By J. W. Downey, S. T. Zegler

A study has been made of the occurrence of Phases having the Cr30-type structure in ternary alloys having the general composition where B cept for iron and copper all the B components are known to form binary compounds having the type structure. The occurrence of the struc-ture type in the ternary alloys was investigated using optical and X-ray metallography. The results indicate that iron can replace virtually none of the cobalt in at 900°C, but substitutes for nickel in up to the approximate composition tually insoluble in V3Ni and 2) and exhibit complete solubility. At 100 nickel can be substituted for cobalt in VSCo up to the composition solubility; and 3) in the system , two solid solutions having the type structure occur. At the same temperature, 1000°C, V3Si exhibits limited solubility for V3Co but is completely mis-cible with V3Ga. Lattice parameters have been determined for all the binary and ternary phases. The solid solutions are discussed in terms of the atomic size and electronic factors which are thought to influence the occurrence of Cr30-type phases. The binary compounds V3Co and V3Ni were found to form peritectoidally from o phases and a vanadium, the former compound at a temperature between 1000" and 1050°C, the latter between 800°and 900°C. The substitutions of nickel and rhodium for cobalt in V3Co were determined not to raise the superconducting transition of VSCo to a temperature as high as 2°K. The occurrence and stability of binary intermediate phases having the Cr30- or A15-type structure (space group o;, Pm3n) have been discussed in several recent papers . Vanadium forms the struc -ture at or near V3B stoichiometry with all the mem -bers of the cobalt and nickel groups in the periodic table and also with Au, Ga, Si, Ge, Sn, P, As, and Sb. This paper describes a survey of the occurrence of the CrsO-type structure in ternary alloys having the general composition V3(B, B') where B and B' are Fe, Co, Ni, Cu, Rh, Ir, Si, and Ga. The purpose of the survey was to clarify the connection between the position of the B partner in the periodic table and its CrsO-type phase-forming tenden~y.~,~ The survey is part of a broader program concerned with the influence of B-partner substitutions on the superconducting transition temperatures of CrsO-type compounds. The transition temperatures, Tc, of some of the ternary Cr,O-type phases found in the survey are also discussed in this paper. EXPERIMENTAL PROCEDURE The alloys were prepared by arc-melting in an A-He atmosphere and were in the form of buttons, weighing approximately 3 g. The metals used in their preparation were received from commercial sources and were in all cases 99.9+ pct pure. The vanadium was spectrochemically pure except for 800 ppm of Si, 200 ppm of Fe, and 200 ppm of Al. For study of each pseudobinary system at least seven alloys were prepared having the general compositions case of alloys containing gallium, melting losses were small, usually less than 0.3 pct of the total weight of the metals charged for melting. Melting losses were somewhat greater for gallium alloys, ranging in general from 0.9 to 5.0 pct. Ternary V-Si-Ga alloys were chemically analyzed and the results are given in Table I. The analyses show most alloys to be within 2 at. pct of the intended composition. Throughout the balance of the paper the intended compositions are used in discussing the alloys. The cast buttons were annealed within evacuated quartz capsules for times ranging from 3 to 6 weeks at temperatures between 800" and 1000°C and water-quenched. The phases present in the annealed and quenched alloys were identified by optical and X-ray metallography. X-ray diffraction photograms were made with powders prepared from the bulk specimens, by the use of a 114.6-mm-diam powder camera with copper irradiation. The lattice parameter of CrsO-type phases and their standard errors

Jan 1, 1963

By E. S. Machlin, Morris Cohen

The martensite reaction in single crystals and polycrystals of 70 pct Fe-30 pct Ni alloys is shown to be autocatalytic in nature, producing bursts of transformation during cooling. The temperature of the first burst of transformation, called Mb, occurs below M, in these alloys. Experiments were devised to test the athermal embryo and strain embryo theories of martensite nucleation. The results indicate that internal strains, either within the virgin austenite or around existing martensitic plates, control the nucleation process in these alloys. Furthermore, the growth of martensitic plates is not limited by the attainment of an elastic balance with the austenitic matrix, but by the occurrence of plastic deformation at the martensite boundaries which interferes with the propagation mechanism. IN an investigation of the martensitic habit in single crystals of a 69 pct Fe-31 pct Ni alloy,' it was observed that about 25 pct of the austenite transformed during subatmospheric cooling within the time-interval of an audible click. This event proved quite spectacular: The shock wave sent out from the specimen freely suspended on a thread in the refrigerating liquid was occasionally sufficiently intense to shatter the Dewar container and to separate the toluene column in the immersed thermometer. The Present investigation was undertaken to determine- the kinetics and mechanism of this "burst" type of martensitic reaction. The analyses of the alloys studied are given in Table I. The composition of the single crystal specimens is designated by alloy A, while the polycrystal-line specimens were made of alloys B and C as noted in the text. The single crystals were prepared in a vacuum furnace, using a modified Bridgman technique. Most of these crystals were homogenized by holding for 24 hr at about 1300°C just after solidification. However, it may be emphasized here that the degree of homogenization was not a controlling factor in the subsequent experiments, inasmuch as specimens having different degrees of homogenization yielded the same results. All of the single crystals were fully austenitic as slowly cooled to room temperature. An illustration of the burst phenomenon is given in Fig. 1, which shows oscillograms of electrical resistivity and temperature vs. time during the continuous quenching of 1/16 in. wire specimens (alloy B) in a dry ice and acetone bath at —77°C. There are at least two observable bursts in this case, as indicated by the sharp decreases of resistance accompanying the sudden formation of substantial quantities of martensite. The thermal arrest during the quench probably corresponds to the larger burst. Usually the bursts are followed by more or less progressive transformation during continuous cooling. It will also be noted that the resistance continues to decrease after the specimen has reached the bath temperature. This isothermal change denotes the formation of martensite at constant temperature, and will be the subject of another paper. Examination of fiducial scratches on the surface of a transformed single crystal has shown2 that the scratches in adjoining nonparallel martensitic plates are usually bent in opposite directions, as though one plate forms in such a way as to relieve the matrix stresses set up by the adjacent plate. This, together with some of the results described in ref. 1, Table I. Compositions of Alloys Studied, in Percent Alloy Ni C N Mn Si P S Cr A 31±0.3 0.048 0.027 0.003 0.56 0.007 0.002 B 29.5±0.2 0.036 0.02 0.19 0.09 0.008 0.006 C 19.99 0.52 0.37 0.47 0.010 0.015 0.04 led to the tentative concept that a cooperative action exists which provides the impetus for much of the transformation that appears during the burst. The following series of experiments were performed in order to test this idea. Cooperative Nature of the Burst Two adjacent disks, Va in. thick x % in. diam, were cut from a single austenite crystal of alloy A using a jeweler's saw. One of the disks was then cut into 15 parts. Then 12 of the latter pieces and the second disk were austenitized (stress relieved) at 600°C for 30 min and water quenched to room temperature. The temperatures at which the first burst of transformation appeared were determined for

Jan 1, 1952

By ALFRED D. FLINN

ENGINEERING COUNCIL has passed, not out, but upward! Therefore, its recent wake was conducted by itself as a joyful occasion somewhat in advance of its official demise. Council held its last meeting in Washington, Dec. 16, 1920. Business was transacted with dignified gravity in the forenoon. During the afternoon calls were made upon the chiefs of technical bureaus of the Government: the Chief of Engineers, U. S. Army; Chief of Yards and Docks of the Navy Department; Director of U. S. Reclamation Service; Director of U. S. Geological Survey; Director of Bureau of Mines. The Council pronounced them, each and all, able men and true. But what of the evening? Well, there was a dinner at the Washington Hotel. Twenty-six men gathered around a flower-strewn table-not a casket. As guests, there graced the festive board the hosts of the afternoon calls, and a number of members of the new American Engineering Council. The body about to be apotheosized-otherwise known as Engineering Council-was both jocular and reminiscent. Rewards were bestowed and appreciations expressed. To the man who had for three long years borne the burden of chairmanship and whose financial recklessness made possible the Washington office and the movement for a National Public Works Department, the following "note," duly engrossed and signed, was given, accompanied by "The Song of the Council Crew."

Jan 1, 1921

By R. Taggart, D. H. Polonis, W. C. Gallaugher

In the Ti-Cu system, the a' phase can be produced over a wide range of alloy composition witJwut the retention of measurable amounts of the ß or ? phases. This paper reports on the decomposition of this hexagonal martensite phase front the standpoint of solute corzcentratiorz, tempering temperature, and coherency strain condition. The mechanism of precipitation during tempering comprises localized precipitation which is followed by discontinuous precipitation if sufficient coherency strains are present. The localized precipitation process in hypoeutectoid alloys is described by the generalized Johnson-hiehl equation and an activation energy of 46,000 cal per mole. In hypereutectoid alloys the corresponcEing activation energy is 51,000 cal per mole. The rate-controlling process has been proposed as the difision of copper along a' platelet interfnces. SEVERAL investigations have been reported concerning the kinetics of decomposition of the mar-tensitic a' phase in titanium binary alloys.' In the Ti-Mo system,' two modes of a' decomposition have been observed in the presence of /3 phase; one of these involves the precipitation of fine a from a', and the other involves diffusion across the a'-ß interface. In studies of the Ti-Cr system, Rostoker2 did not detect the formation of TiCr2 during tempering. In Ti-Ni alloys,3 the intermediate phase Ti2Ni has been found to precipitate directly from a' along the interfaces between plates. With the exception of the study of Ti-Ni alloys the previous investigations of tempering phenomena in substitutional martensites are mainly qualitative and do not present a detailed description of the precipitation processes. The following limitations restrict the correlation of the microstruc-tural processes and reaction kinetics during tempering in most binary-alloy systems. 1) A mixture of at least two phases characterizes the constitution of quenched alloys. 2) Difficulties have been encountered in obtaining uniform structures throughout quenched samples. 3) The reaction products, and in particular their morphology. have not been clearly resolved. 4) The martensitic a' phase forms over only a limited composition range for most titanium-base binary alloys. Gomez and polonis4 showed that the Ti-Cu system provides an excellent basis for investigating the tempering of a' over a range of composition without the complication of retained P or the transition w phase. In the present work the effects of solute concentration, tempering temperature, and coherency strain conditions are considered with reference to the over-all precipitation process in quenched alloys of the Ti-Cu system. Both microstructural observations and kinetic data are correlated to define the rate-controlling processes which govern the observed localized and discontinuous precipitation reactions. An earlier paper5 was devoted to a discussion of the modes of heterogeneous nucleation of Ti2Cu from the martensitic a' structure. The present paper will therefore emphasize the progress of the tempering reaction beyond the initial stages. EXPERIMENTAL METHODS The Ti-Cu alloys for this study were prepared by conventional arc-melting procedures. Chemical analysis revealed that the alloy buttons contained approximately 0.02 wt pct 0, 0.04 wt pct N, and within 0.1 wt pct of the intended copper concentration. The progress of the tempering reaction was followed by means of electrical-resistance measurements utilizing a Kelvin double bridge, microhard-ness readings with a 400-g load, and X-ray dif-fractometry patterns to reveal line-broadening effects. Metallographic specimens examined at magnifications greater than X1000 were shadowed with germanium to reveal fine structural details. Direct carbon replicas were prepared for the electron-microscopy studies. EXPERIMENTAL RESULTS Property Changes. The changes of microhardness that accompany the precipitation of Ti2Cu from a' are shown in Figs. 1 and 2. As the solute concentration increases the peak hardness, for a given tempering temperature, increases. In alloys of given composition the time to reach the peak hardness agreed with the time to attain maximum X-ray diffraction peak breadth, as shown in Fig. 3. The maximum hardness and the maximum line breadth increased with lower tempering temperatures, and the time to reach the maximum also increased. The a' peaks broadened during the initial stages of tem-

Jan 1, 1965

By M. N. Shetty

LARGE copper whiskers were grown from cuprous iodide by reduction with hydrogen at about 500°C. Carefully selected single-crystal whiskers of [loo], [110], and [Ill] orientations were used and the whisker shapes and cross sections are shown in Fig. 1. Spec-trographic analysis of a typical batch of whiskers showed that the composition was better than 99.9 pct with iron and silicon as the major impurities. The test specimens varied from about 70 to 400 u in diam and they did not show a conspicuous yield drop as observed in very fine whiskers (diam <25 u), tested by Brenner.1 The characteristics of the stress-strain curves were similar to those of bulk single crystals, even though the maximum flow stresses reached in some orientations were comparable to the yield stresses observed in fine whiskers. Mechanical properties of whiskers of different materials and copper whiskers up to about 100 u in diam have been reviewed,&apos; and a mechanism of slip band propagation in fine whiskers has been recently suggested.3 Whiskers in this work were tested in a floor-model Instron testing machine using low strain rates. (Details of the testing procedure, diameter dependence of the yield stress, and the characteristics of the load elongation and stress-strain curves have appeared esewhere.4) Due to the extensive deformation, >50

Jan 1, 1970

PROF RICHARD ÅKERMAN Stockholm, Sweden ANDREW CARNEGIR New York, N.Y. DR. JAMES DOUGLAS New York, N.Y. PROF HATON DE LA GOUPILLIERE Paris, France R.A. HADFIELD Sheffield England PROF HANS HOEFER Leoben, Austria PROF HENRI LOUIS LE CHATELIER Paris France M FLORIS OSMOND Paris, France JOHN E. STEAD Middlesborugh, England PROF DIMITRY CONSTANTIN TSCHERNOFF St Petersburg, Russia CHARLES D WALCOT Washingtion D.C. PROF DR HERMANN WEDDING Berlin, Germany

Jan 1, 1910

By F. A. Forward, V. N. Mackiw

The paper relates to the laboratory and pilot plant studies that have been carried out by Sherritt Gordon Mines Ltd., Metallurgical Research Div., in developing the ammonia pressure leach process for extracting copper, nickel, cobalt, and sulphur from high grade nickel concentrate produced from Lynn Lake ores, and describes in some detail the chemistry of the process. IT is well known&apos;.&apos; 2 that copper, nickel, cobalt, zinc, ferrous iron, and a number of other metals combine with ammonia in aqueous solution to form complex ions of the form [Me(NH,)x]"+. The stability and solubility of these ions depend on the concentration of the metal ion in solution, on the amount of NH, present, and on the amount and type of anions present, e.g., OH-, C0;-, NO,, C1-, SO;-. If ammonia is partially or completely removed from such solutions, for example by boiling, the soluble ammines tend to decompose and the metals precipitate as basic salts. These properties of metal ammines have found practical application in the commercial recovery of copper, nickel, and cobalt from a variety of ores. In an operation formerly conducted at Kennecott"" the mill tailing containing 0.80 pct Cu as copper carbonate was leached by percolation with an ammonia-ammonium carbonate solution to dissolve the copper as the ammine. At Calumet and Hecla0-" With a mill tailing containing about 0.4 pct Cu as metallic copper, it has been found necessary to aerate the ammonia-ammonium carbonate leach solutions between stages to oxidize the solubilized copper. At Nicarol"-" where nickel and cobalt occur as oxides and silicates which are not soluble in ammonia, the ore is heated to decompose silicates and to selectively reduce the nickel and cobalt to metal, leaving the iron as Fe,O,, and is then leached with ammonia-ammonium carbonate solution accompanied by aeration to dissolve nickel and cobalt as ammines. In each of these leaching operations, the anion present is CO, and the metals can be precipitated from the leach solution as oxide (copper) or hydroxide and carbonate (nickel and cobalt) by boil- ing off NH, and C02 both of which are recycled to treat a subsequent ore charge. The products-—oxide, hydroxide, or carbonate—can be treated by conventional smelting, calcining, or electrolytic methods to convert them to refined metals. Thus the procedures mentioned utilize the properties of the ammines to extract copper, nickel, and cobalt from nonsulphide ores and separate them from the leach solutions. These processes have the advantage that they can be carried out in closed vessels at atmospheric pressure, that the leaching solutions are specific for the desired metals, that the metals can be recovered as relatively pure compounds by the boiling operation, and that the NH, and CO, can be recycled. Also, as the leach solutions after boiling and filtration are substantially free of metals, NH,, and CO,, they can be discarded, thus facilitating the control of the water balance in the leaching circuit. When, as is the case with Sherritt Gordon concentrates, sulphides are treated with ammonia solution in the presence of oxygen, the leach solution contains SO,--, and an entirely different set of conditions is encountered. The ammine sulphates (of nickel, for example) are more soluble than the carbonates and can be only partially decomposed by boiling. The SO, and NH, in the solutions can not be recovered by boiling. Thus, despite the more favorable leaching conditions resulting from high solubility of the ammine sulphates, the recovery of metals, NH,, and SO, from the solutions must be effected by other means. Sherritt Gordon Nickel Concentrate Treatment The Ni-Cu-Co flotation concentrate produced at Lynn Lake&apos;" contains 12 to 16 pct Ni, 1 to 2 pct Cu, 0.2 to 0.5 pct Co, 33 to 40 pct Fe, 28 to 34 pct S, 8 to 20 pct insoluble, and less than 0.02 oz per ton precious metals. The nickel is present chiefly as pentlandite, the copper as chalcopyrite, and the iron as pyrrhotite and pyrite. Most of the cobalt is thought to be present in pentlandite, although it is known that a small amount occurs as Co-Ni-pyrite.

Jan 1, 1956

By H. M. Beatty, T. L. Joseph, Gust Bitsianes

SUCCESSFUL blast-furnace operation depends upon securing an optimum balance between a number of important variables. This balance will vary somewhat from furnace to furnace in the same plant and with raw materials available in different plants. It is difficult to isolate the effect of any one variable unless it has a rather pronounced effect upon the efficiency of operation. The physical properties of iron ore and coke are known to affect the process, yet it is difficult to set up any definite yardstick by which these differences can be appraised. In recent years, whenever practicable, operators have taken steps to obtain better control over the absolute size and uniformity of size of the ore and coke. The size and physical character of the stone, however, have received comparatively little attention, emphasis being placed upon chemical composition, fluxing efficiency, and action as a desulphurizing agent. Since the stone occupies only about 10 per cent of the volume of the stock column, its influence upon permeability is less than that of the ore and the coke. The large pieces now used have a tendency to roll to the center and thus increase the permeability of this part of the stock column. Smaller pieces would be more effective in promoting the permeability of denser portions of the stock. The size and physical properties of blast- furnace stone are important also for reasons best understood by considering the results obtained by the crushing and the sizing of iron ore. Crushing ore to about 2 in. at Provo, Utah, and to about I in. in Alabama produced material somewhat less permeable to gases, even though sized. In spite of some sacrifice in permeability, the efficiency of the process was improved by crushing and sizing the ore, as indicated by a substantial saving in fuel and increased output. This saving in fuel is due in large measure to more thorough reduction of ore in the upper part of the furnace and to a corresponding decrease in the amount of carbon consumed prematurely above the tuyeres by the reaction CO2 + C = 2CO ? 70,080 B.t.u. [I] The physical properties of stone, its size and rate of calcination are important because they influence the rate at which C02 is released and the completeness of calcination before reaching a level in the furnace where the temperature does not exceed 1050°C. (1920°F.). Briefly, carbon dioxide from the limestone or from the reduction of ore may cause premature com- bustion of carbon above the tuyeres. Assuming that 1000 lb. of limestone is used per ton of pig iron, about 435 lb. of C02 will be liberated during calcination of a good grade of stone. If all this CO2 from the stone were to oxidize carbon prematurely, about 120 lb. would be consumed above the tuyeres in a heat-absorbing reaction. The amount of carbon thus consumed when a

Jan 1, 1942

By F. E. Harris

It has been said that carbon is "ubiquitous" with reference to iron alloys. Certainly at temperatures where carbon and iron form the solid solution, austenite, it may be readily added to, or removed from, steel surfaces. Differences in concentration potential are the sole requirements for carbon flow. To measure the rate of carbon flow, a proportionality factor, D, is arbitrarily expressed in units of (length)2 X (time)-&apos;. If the term used for carbon concentration is weight Pet C, as is customary, then a factor must be found, changing this term to One of weight Per unit volume when the diffusion coeficient, D, is used in flow formulae. The determination of D values for carbon is complicated since D varies with the concentration itself. The Matano method has often been employed for systems involving a variant D. This method expresses all evaluation of unsteady flow whereby D is given a relationship with the numerical value of C-x slopes. The author contends that this solution is incorrect, except when D is invariant. The primary purpose of this paper is to support this contention. Here diffusion is controlled under two conditions of flow. The first part deals with the steady state; the second part considers unsteady flow under definite restrictions. Beginning with the fundamental concept, the development is continued until equations for C-x curves are obtained. The solution is then subjected to experimental data. It is realized that a great amount of reliable data is required for a rigorous proof. KO such research is claimed. Instead an attempt is made to set forth the physical significance of the diffusion mechanism, and particularly to express the factors which influence the flow of carbon in austenite. Of equal significance is the implication that gaseous media may be employed with reasonable accuracy in making these determinations. The Steady State Diffusion of Carbon in Au~tenite The fundamental experiment defining diffusion in solid metals may be readily performed for carbon in gamma iron.&apos; For this experiment a thin plate of medium carbon steel is chosen. The surfaces of this plate may be taken as two parallel planes which may be considered infinite for points well in the Center of the planes. These two planes are held at different concentrations of carbon at a constant temperature. This temperature, 1700°F for example, is one where the single phase: carbon in solution with gamma iron, exists. When these conditions are held for a sufficient time the concentration of carbon of the different points of the solid ment down towards its steady state value. At points well removed from the ends, the concentration will remain the Same along planes parallel to the surfaces of the plate.

Jan 1, 1948

By F. E. Harris

It has been said that carbon is "ubiquitous" with reference to iron alloys. Certainly at temperatures where carbon and iron form the solid solution, austenite, it may be readily added to, or removed from, steel surfaces. Differences in concentration potential are the sole requirements for carbon flow. To measure the rate of carbon flow, a proportionality factor, D, is arbitrarily expressed in units of (length)2 X (time)-&apos;. If the term used for carbon concentration is weight Pet C, as is customary, then a factor must be found, changing this term to One of weight Per unit volume when the diffusion coeficient, D, is used in flow formulae. The determination of D values for carbon is complicated since D varies with the concentration itself. The Matano method has often been employed for systems involving a variant D. This method expresses all evaluation of unsteady flow whereby D is given a relationship with the numerical value of C-x slopes. The author contends that this solution is incorrect, except when D is invariant. The primary purpose of this paper is to support this contention. Here diffusion is controlled under two conditions of flow. The first part deals with the steady state; the second part considers unsteady flow under definite restrictions. Beginning with the fundamental concept, the development is continued until equations for C-x curves are obtained. The solution is then subjected to experimental data. It is realized that a great amount of reliable data is required for a rigorous proof. KO such research is claimed. Instead an attempt is made to set forth the physical significance of the diffusion mechanism, and particularly to express the factors which influence the flow of carbon in austenite. Of equal significance is the implication that gaseous media may be employed with reasonable accuracy in making these determinations. The Steady State Diffusion of Carbon in Au~tenite The fundamental experiment defining diffusion in solid metals may be readily performed for carbon in gamma iron.&apos; For this experiment a thin plate of medium carbon steel is chosen. The surfaces of this plate may be taken as two parallel planes which may be considered infinite for points well in the Center of the planes. These two planes are held at different concentrations of carbon at a constant temperature. This temperature, 1700°F for example, is one where the single phase: carbon in solution with gamma iron, exists. When these conditions are held for a sufficient time the concentration of carbon of the different points of the solid ment down towards its steady state value. At points well removed from the ends, the concentration will remain the Same along planes parallel to the surfaces of the plate.

Jan 1, 1948