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By E. T. Turkdogan, Klaus Schwerdtfeger, P. Grieveson

The rate of growth of "Fe4N" on a iron was measured by nitriding purified iron strips in flowing am -monia -hydrogen gas mixtures at 504" and 554°C. It is shown that a dense nitride layer is formed when a zone -refined iron is used in the experiments. With less pure iron, the nitride layer is found to be porous. Through theoretical treatment, the self-diffusivity of nitrogen is evaluated porn the parabolic rate constant, and found to be essentially independent of nitrogen actirlity, e.g., D* = 3.2 x l0-12 and 7.9x l0-12 sq cm per sec at 504" and 554?C. Some consideration is given to the mechanism of diffusion in the nitride phase. THERE is a great deal of background knowledge on the solubility and diffusivity of nitrogen in iron, and on the thermodynamics and crystallography of several phases in the Fe-N system. Although case-nitrided steels have many applications in practice, no work seems to have been done on the diffusivity of nitrogen in the iron nitride, ?', phase. The only work reported on the related subject of which the authors are aware is an investigation by Prenosil,1 who measured the growth rate of the e phase on iron by nitriding in ammonia-hydrogen gas mixtures. EXPERIMENTS Purified iron plates of approximate dimensions 1 by 0.5 by 0.03 cm were nitrided in flowing mixtures of ammonia and hydrogen, in a vertical furnace fitted with a gas-tight recrystallized alumina tube. After a specified time of reaction, the sample was cooled to room temperature by withdrawal to the water cooled top of the reaction tube. The furnace temperature was controlled electronically in the usual manner within *l°C; the temperature was measured using a calibrated Pt/Pt-10 pct Rh thermocouple. For each experiment the iron strip sample was cleaned with fine emery cloth and degreased with tri-chloroethylene prior to the experiment. The ammonia-hydrogen gas mixtures were prepared from anhydrous ammonia and purified hydrogen using constant pressure-head capillary flowmeters. The gas mixture flowed upward in the furnace with flow rate of 400 cc per min at stp. The composition of the gas mixture was checked by chemical analysis at regular intervals. In most cases, the compositions of the exit gas and metered input gas agreed within about 0.3 pct, indicating that cracking of ammonia did not pose a problem at the temperatures employed. Two series of experiments were carried out using two different types of purified iron samples. In the first series of experiments at 550°C, vacuum carbon deoxidized "Plastiron" was used. The main impurities present in this iron were, in ppm: 4043, 50-Cr, 20-Zr, 40-Mn, 20-P, 20-S, 20-C, 50-0, and 10-N. In these experiments the rate data were obtained by measuring the change in weight of the iron specimen suspended in the hot zone of the furnace by a platinum wire from a silica spring balance. The nitride layer formed in these experiments was found to be porous, particularly near the outer surface. In other experiments, high purity zone-refined iron (prepared in this laboratory) was used. The total impurity content of this iron was 30 ppm of which 20 ppm was Co + Ni, 4 ppm 0, other metallic impurities were less than 1 ppm. The zone-refined iron bar, -2.5 cm diam, was cold rolled to a thickness of about 0.03 cm and the specimens were prepared for the experiment as described earlier. After the nitriding experiment, the sample was copper plated electro-lytically and mounted in plastic for metallographic polishing. After polishing, the thickness of the ?' layer was measured using a metallographic microscope. The nitride layer formed on the zone-refined iron was essentially free of pores. RESULTS The different morphology of the nitride layers grown on "Plastiron" and zone-refined iron is shown in Fig. 1. Both samples were nitrided side by side for 55 hr. The holes in the less pure iron, Fig. l(a), are confined to a region about one half thickness from the outer surface. The dense layer grown on zone-refined iron, Fig. l(b), is thinner than the porous layer on the "Plastiron". The impurities in the iron are believed to be responsible for the formation of a porous nitride layer. The pore formation may be due to the high nitrogen pressures existing within the nitride layer, e.g., the equilibrium nitrogen pressure is 1.2 x l05 atm in the 38.6 pct NH3-61.4 pct H2 and 6.6 x l03 atm at the Fe-Fe4N interface at 554°C and 0.96 atm. It is possible that the oxide inclusions present in the electrolytic iron may facilitate the nuclea-tion of nitrogen gas bubbles within the nitride layer. Support for this reasoning is the fact that pores are only encountered in the outer range of the layer where nitrogen pressures are largest. The photomicrographs in Fig. 2 show the effect of reaction time on the thickness of the dense nitride layer formed on zone-refined iron. These sections are from samples nitrided in a stream of 29 pct NH3-71 pct H2 mixture at 554°C for 22, 70, and 255 hr. In all the sections examined the nitride-iron interface was noted to be rugged. These irregularities are be-

Jan 1, 1970

By F. Wald, A. J. Rosenberg

The general features of the constitution of the B-Pt system were determined using standard rnetal-lograph~c, thermoanalytic, and X-ray diffraction techniques. Three compound were found. Two of these, Pt3B and Pt,B, are formed by peritectic reactions at 523° and 890°C, respectively. The third, Pt3B,, is congruently melting with a flat maximum at 940°C but decomposes eutectoidally in to Pt,B ant1 boron nt - 600° to 650°C. THE low-temperature allomorph of boron (red, simple rhombohedra1 a boron) is of scientific and technological interest as an elemental semiconductor.' However, the studies of this material have been hampered by its reported instability above 1200"~ which precludes crystal growth from the melt (mp - 2200°C). Crystallization from platinum solutions has been suggested as an alternative crystal-growth technique, but has met with only limited success.' The technique depends upon the existence of a significant difference between the eutectic temperature and the transformation temperature of boron. In order to clarify the conditions for further crystal-growth experiments, we found it desirable to redetermine the main features of the B-Pt phase diagram since previous reports on the system1'5'6'7 are in marked disagreement. EXPERIMENTAL The experimental methods used were thermal analysis, metallography, X-ray analysis, and, to a lesser extent, measurements of microhardness. Most of the alloys were prepared from spectrograph-ically standardized boron obtained from Johnson-Matthey &Co., Ltd. (212 ppm impurities, exclusive of carbon and oxygen) and platinum powder obtained from F. Bishop & Co. (200 ppm impurities, mainly of other platinum group metals). Some alloys were also prepared with very high-purity, float-zone refined boron (99.9999 pct obtained from "Wacker Chemie" and extrahigh-purity platinum (99.999 pct) obtained from Johnson-Matthey & Co., Ltd. The reported results did not depend on the choices of these starting materials. Five-gram alloy specimens containing 10, 20, 25, 27.5, 30, 33.3, 34, 35, 37, 37.5, 38, 39, 40, 41, 42, 43, 45, 50, 55, 60, 70, and 80 at. pct B were made by melting the elements together in boron nitride crucibles using rf heating of a graphite susceptor, either in vacuum or under high-purity argon. All alloys were heated to at least 1800°C for -5 to 15 min. Most of the alloys did not wet the crucibles when the latter were outgassed by preheating under vacuum. In any event, no weight loss was detected after melting, and the nominal composition was assumed for all specimens. Thermal analysis on 2.5-g samples were carried out in boron-nitride crucibles under a vacuum of 5 x X torr. The apparatus was heated in a "Kan-thal A 1" wound furnace, which limited the maximum temperature to about 1100°C. The output of the indicator thermocouple was fed to a dc recorder with a 1-mv full-scale span and an adjustable zero. The apparatus was calibrated repeatedly, using the freezing points of high-purity aluminum, silver, and gold. The results justified the use of the NBS voltage vs temperature tables for Pt/Pt 10 pct Rh thermocouples. All thermal analyses were run at least twice and both the heating and cooling effects were recorded. Most of the alloys had a very strong tendency to supercool. However, the use of mechanical vibration permitted reproducibility within *5°C for all alloys, except in the region around 40 at. pct B. Only the cooling effects are plotted in Fig. 2, since they appear to be more reliable. For metallography, the alloys were cut with a diamond cutting wheel, cast in a polymethacrylate resin, ground and polished with diamond paste, and etched with dilute aqua regia, a common etch for platinum alloys. Both copper and molybdenum radiation were employed to obtain X-ray diffraction data using Debye-Scherrer cameras and a "Norelco" diffractometer Diffractometry with high scanning speeds (1 deg per min) using nickel filtered CuK, radiation was used to identify the main regions of the diagram. However, molybdenum radiation was used for the detection of boron, since the latter showed very strong absorption and fluorescence effects with CuK, radiation. RESULTS AND DISCUSSION Three intermediate compounds, corresponding to the compositions Pt3B, Pt2B, and Pt3B2, were found in the system. Fig. 1 reproduces their X-ray diffraction spectra, together with those of pure boron and pure platinum. As can be seen from the thermal-analysis data in Fig. 2, Pt3B and Pt2B are formed by

Jan 1, 1965

Sykes, W. P.-Effect of Temperature, Deformation, Grain Size, and Rate of Loading on Mechanical Properties of Metals. Discussed by Zay Jeffries, W. H. Bassett, F. E. Carter 3 Evans, Geo. Watkin.-Alaskan Coal Fields. Discussed by P. N. Moore, H. H. Stoek, G. S. Rice, H. Emerson 4 Eavenson, Howard N.-Run-off and Mine Drainage. Discussed by J. R. Campbell, Andrew B. Crichton, J. B. Warriner, R. V. Norris, H. G. Moulton, H. B. Wright 7 Andrews, Allen, and Garcia, John A.-Skip Hoisting for Coal Mines. Discussed by R. V. Norris, Geo. S. Rice, H. N. Eavenson, E. A. Holbrook, Robert Obert, Andrews Allen, T. M. Chance 12 Rice, Geo. S.-Coal-pillar Drawing Methods in Europe. Discussed by Carl Scholz, D. Harrington; H. 1. Smith 16 Knapp, Arthur.-Modified Oil .well Depletion Curves. Discussed by Roswell H. Johnson 21 Alvey, Glenn H., and Alden W. Foster.-Barrel-day Values. Discussed by Roswell H. Johnson 22 Matteson, W. G.-Secondary Intrusive Origin of Gulf Coastal Plain Salt Domes. Discussed by Eugene Coste, E. W. Shaw, Joseph E. Pogue, F. G. Clapp, E. DeGoIyer, W. G. Matteson, H. W. Hixon, R. Van A. Mills 23 Reger, David B,-Carbon Ratio of Coals in West Virginia Oil Fields. Discussed by J. T. Singewald, Jr 33

Jan 5, 1921

By M. T. Hepworth, R. Schuhmann

Hydrogen solubility measurements were made on a series of Ti-O alloys, and a portion of the 800°C isotherm for the Ti-O-H system was determined. Activities of oxygen and titanium were calculated from the experimentally measured activities of hydrogen, using ternary Gibbs-Duhem integrations. The data were extrapolated to obtain thermo-dynamic properties of binary Ti-O solutions. The thermodynamic properties of a Ti-0 solid solutions thus determined were compared with properties predicted from interstitial models. The Gibbs-Duhem equation, long used to calculate activities in binary systems, has been extended. recently to ternary systems.1"3 When the activity of one component in a ternary system is known as a function of composition, the activities of the other two components can be calculated from that of the first by an integration procedure, provided certain restrictions are observed on the path of integration. Often the activity of one component in a ternary system can be measured readily, while the activities of the other two components are difficult to measure. Gibbs-Duhem calculations are especially applicable to such systems. The further possibility arises of developing a new and indirect approach to activity measurement in binary systems. The proposed new method for binary systems consists of adding varying amounts of a third component whose thermodynamic behavior is easily measured. The activity of this added component is determined experimentally as a function of composition. Then the activities of the two components of the original binary system are calculated by Gibbs-Duhem integrations and extrapolations. For the work to be described in this paper, the Ti-0-H system was selected as a promising system for evaluating this approach. Investigations of the Ti-H system have shown that the activity of hydrogen can be measured precisely with little difficulty. Pure titanium transforms from a low-temperature a form (hcp) to a higher-temperature /3 firm (bcc) at 882.5"~ The phase transformation occurs in a temperature range where hydrogen pressures are easily measured. Also, the diffusivity of hydrogen at temperatures above 600" or 700"~ is large enough that equilibrium can be reached within a reasonable time.

Jan 1, 1962

By Carl Floe

A NUMBER of proposals have been made for the hydrometallurgical recovery of copper from flotation concentrates, but as yet no process has been developed that has demonstrated an ability to compete with the present smelting methods under ordinary conditions. The treat-ment of copper concentrates by hydrometallurgical methods is in general similar to that used in the present electrolytic zinc process and involves roasting, leaching with H2S04 solution, separation of solutions, control of impurities and electrodeposition. While many of these steps are simpler and more readily carried out for copper than for zinc, a number of inherent difficulties have prevented the general adoption of the process. To compete with smelting, the following problems must still be con-fronted, although many solutions for their have been proposed: (1) con-duction of the roast in such a way that leaching will give an extraction of copper comparable to that obtained by smelting; (2) regulation of the ferric iron content of the solutions during electrolysis; (3) disposal of the excess acid regenerated from the sulphates formed in roasting; (4) eco-nomical recovery of the precious metals from the leach residues. The roasting problem is largely one of preventing the formation of copper ferrites, CuO.Fe2O, and Cu20.Fe2O3, which are quite insoluble in dilute sulphuric acid. These ferrites are apparently formed' to a small extent even at low temperatures and above 650° C. their formation is rapid1. While it is possible to carry out laboratory roasts in such a way that less than 5 per cent of the total copper is present in the insoluble ferrite form, a closer temperature control is required than can readily be obtained in industrial furnaces. The flash" roasting effects and consequent high temperatures that occur as the calcine falls from hearth to hearth in the ordinary multiple-hearth roaster are probably largely responsible for the inevitable formation of some ferrites. The result is that in a commercial plant the extraction of copper would not average more than 90 per cent in a single 10 per cent H2SO4 leach. This is

Jan 1, 1937

By H. Kenworthy, M. M. Fine

The progress made to date in the mineral dressing of complex Arkansas titanium ores is reported in this paper. Concentrates of rutile, a dioxide of titanium, were produced by treating a submarginal ore from the Magnet Cove Rutile Co., Inc., Magnet, Ark. The rutile recovery at present is 45 to 50 pct of the total TiO2 with the possibility of increased recovery with additional research. The work reported herein is part of a general study which will later include results of investigation of other titanium ore bodies in the Magnet, Ark., area. The fragile character of the rutile minerals, the softness of the gangue, the occurrence of pyrite and leucoxene, and the considerable proportion of extremely small size rutile in the presence of montmorillonite- and illite- type clays in the Magnet Cove open-pit mine are the important factors in the mineral dressing of this submarginal rutile ore.

Jan 1, 1949

By Charles Eichrodt

THE ore that is being treated by the present plant lies between the leached zone, or capping, and the mixed sulfide and oxide zone. The principal copper minerals are chalcanthite (CuSO4.5H20), brochantite (CuS04 3Cu (OH)2) and atacarnite, (CuC12.3Cu (OH)2). There are, in addition, some other minerals such as cuprite and kröhnkite (CuSO4. Na2SO4.2H20). These minerals, with many others, occur in a greatly crushed granodiorite rock. Most of the copper-bearing minerals occur in the cracks and veinlets, but there are disseminated values and it is probably the relative proportion of these that accounts for some otherwise unexplainable variations in extraction. The entire mineralization of the ore is complex and varies with depth. This variation, the problems presented thereby, and the effect of various constituents of the ore will be taken up in detail. An analysis of an unweighted composite of the ore treated during 1927 follows:

Jan 1, 1930

By W. R. Hibbard

The increased strength of a polycrystal-line metallic aggregate compared with that of its individual crystals generally has been associated with complex stress distributions at the grain boundaries resulting from atomic irregularity between grains. This disregistry, together with the necessity for adjacent crystals to deform compatibly regardless of the single crystal crystallo-graphic strain mechanism, complicates this mechanism so as to increase the metal's resistance to deformation. Although Taylor1 has shown from purely mechanical considerations the requirement for at least five active slip systems to absorb the complexities during the homogeneous deformation of polycrystalline face-centered cubic metals, experimental studies by Barrett and Levenson2 indicate that this is feasible only in a qualitative sense because of deviations from homogeneous deformation. Seitz and Read in their review3 state: " Unfortunately . . . present knowledge of the grain boundary influence is not sufficient to complement the work in single crystals and provide us with a good foundation for treating polycrystals." The purpose of this investigation was to attempt to clarify the gap between single crystals and crystalline aggregates by an analysis of the effects of dcformational stresses. Some of the results were described by C. H. Mathewson in his 1943 Campbell Memorial Lecture.zl Previous Investigations Since the performance of single crystals deformed under pure stresses has been relatively thoroughly investigated, the most significant researches are concerned primarily with deviations from single crystal behavior of large grained specimens. Qualitative grain boundary effects involving the observed amount of slip werc reported by Carpenter and Elam5 in 1921. Individual crystals in a two or three grained aluminum specimen deformed by tension acted in the normal manner described by Taylor and Elarn4 except for marked modifications at the grain boundaries. There the power to withstand deformation was considerably increased, leaving a ridge on the specimen where decreased slip occurred, often noticeable yi in. from the boundary. Adcock,6 Yamaguchi,' Seumel, Hirstg and others have also reported this phenomenon as a qualitative trend. Yet attempts by O'Neill'o and Ljunggrenll to measure a difference in hardness at grain boundaries in undeformed specimens were unsuccessful. Miller12 measured quantitatively the reduction in slip near the boundary between the single crystal and polycrystalline areas of zinc specimens. These effects consisted of two parts: I. Next to the polycrystalline interface thc distribution of stresses was so altered

Jan 1, 1949

By W. T. lsbell

HERCULANEUM, MO., about thirty miles south of St. Louis on the Mississippi River, is the site of the lead smelter of the St. Joseph Lead Co. The lead concentrates come by rail from the Flat River district and from three properties in Madison County, Missouri; from the Balmat division in St. Lawrence County, New York; a small tonnage from the Tri-State district; and occasionally from the Aguilar property in Argentina. The average grade is 67 to 68 percent lead and 1 to 3 oz of silver. The bulk of the material is flotation concentrate, with some gravity or table concentrate. No secondary metals, outside drosses, or any materials high in bismuth, arsenic, or antimony are treated. All concentrate is received in box-caps and is unloaded directly from a trestle into the concentrate bins at the roaster plant. Flux, coke, and any miscellaneous lead-bearing material is either unloaded directly into bins or unloaded with a locomotive crane. All moving and switching of cars is done with two thirty-ton steam locomotives. Shipping facilities for the plant are provided by the Missouri-Illinois Railroad. Water for the plant and for fire protection is obtained from a dam built in a near-by creek. Drinking water both for plant and town is obtained from

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

ONE of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film A comprehensive program has been undertaken to study these phenomena This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C Before the introduction of the electron diffraction technique, it «as necessary to use either direct chemical analyses or X-ray diffraction analyses to determine the nature of the oxide film formed on the metal or alloy Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry In special cases the information obtained may be identical, but in general both view-points are necessary Much of, the early work was carried out on the oxidation of bulk samples where thick films were obtained The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses Although much useful information has been obtained in this manner, little could be learned about the character of the protective oxides during the period when the films were actually protective Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective LITERATURE The oxidation of iron has been extensively investigated by X-ray and electron diffraction Jackson and Quarrell1 found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe304, between 515° and 900°C the stable film was FeO Above the upper change point of iron the oxide was found to be Fe304 prom 400° to 515°C , FeO, Fe304 or a mixture of the two oxides was found Recrystallization of the air-formed film below 400° and above 900°C led to the formation of Fe304 In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described

Jan 1, 1946

By Sweetser, Ralph A

AT the fall meeting of the Iron and Steel Division, Oct. 4, 1934, in New York, a symposium was held on Slag Control in the Making of Iron and Steel. The chairman was J. H. Nead and the vice chairman, G. B. Waterhouse. The latter presided at both morning and afternoon sessions. The papers and discussions were presented in the order in which they appear on the following pages. To meet space requirements, much of this material has been considerably condensed. CONTENTS Slag Control and the Blast Furnace. By Ralph H. Sweetser. (With dis¬ cussion.) I Slag Control in Rimming Steel. By L. F. Reinartz 5 Slag Control Applied to Low-carbon Steel. By Frank G. Norris 9 Discussion on both papers 11 Slag Control for Basic Open-hearth High-carbon Steel. By W. J. Reagan. (With discussion.) 14 Slag Control for Recarburized Rail Steel. By A. P. Miller and T. S. Washburn. (With discussion.) 18 Slag Control for Alloy Forging Steel. By A. L. Feild. (With discussion.). . . 24 Slag Control for Alloy Forging Steel. By R. C. Good 27 Slag Control in Acid Open-hearth Steel. By Francis B. Foley. (With dis¬cussion.) 29 Slag Control for Basic Electric-furnace Steel. By H. F. Walther. (With discussion.) 31 Physical Testing of Slag. By A. B. Kinzel. . 40 General Discussion 41

Jan 1, 1935

By E. C. Harder, D. F. Hewitt

Since early in 1916, when it became apparent that the steel industry of the United States could not depend for the duration of the war on several important foreign sources of manganese and might have to depend entirely on domestic ores, the U. S. Geological Survey, with the assistance of several cooperating organizations, has made a comprehensive investigation of domestic manganese resources. The work has included field studies in a number of states well as annual, quarterly, and monthly canvasses among operators concerning current and future production. In order that the interested public might have access to the important results of the studies, preliminary reports concerning the field work as well as periodic summaries of production were issued as promptly as possible. Although numerous summaries of production l2, l3, l4 have been prepared from time to time for the use of the several boards and committees responsible for the conduct of the war, it has been thought for some months that those engaged in the industry, as well as others, might be interested in a preliminary summary of the accumulated geologic and production data. The cessation of hostilities, in November, 1918, probably detracts from the usefulness of much of the material that is here presented, but apart from the historic interest in the performance of an important industry in war time, there is a possibility that some of the conclusions may be helpful to those who continue to exploit domestic deposits, as well as to those who wish to measure the country's independence in mineral supplies. Appropriate final geologic reports are being prepared by the geologists who did the field work. The present authors, having done but a small part of the recent field work, acknowledge with great appreciation the use of preliminary and unpublished reports and the cordial informal cooperation of the following geologists in the preparation of this paper: F. L. Ransome, G. W. Stose, F. C. Schrader, J. T. Pardee, E. L. Jones, Jr., H. D. Miser, Laurence LaForge, J. B. Umpleby, Arthur Keith, F. J. Katz, and E. S. Larsen, of the U. S. Geological Survey. Field work in Virginia was carried out in cooperation with the Virginia Geological Survey, T. L. Watson, State Geologist; in Georgia, with the Georgia

Jan 1, 1920

By G. R. Speich

A cellular precipitation reaction in which cells consisting of an Ni3Ti (DO24) phase and austenite are formed has been studied in an austenitic Fe-30 Ni-6 Ti alloy. The variation of the growth rate and interlamellar spacing of the Ni3Ti cells with temperature has been determined m the range 400" to 975°C; the interlamellar spacing is proportional to the degree of undercooling; the growth rate can be expressed by an equation of the form G = K?T)2 exp(-Q/RT). The habit of the Ni3Ti lamellae is (001)Ni3Ti (111)y;[010]Ni3T2 [010]y. An almost perfectly coherent interface is formed between Ni3Ti lamellae with this orientation rela -tionship and the intervening austenite. This first Ni3Ti cellular product is subsequently consumed by a second cellular reaction of much coarser spacing. CELLULAR precipitation reactions have been studied in copper-base,1,2 Au-Ni,3 pb-sn,4 and iron-base ferritic5,6 solid solutions, and this mode of precipitation has been treated theoretically by smith," Turnbull,8,9 cahn,10 and more recently by bohm.11 In the case of substitutional austenitic iron-base alloys little or no data are available, Cellular precipitation reactions are well known in austenitic nickel-base alloys12,13 but usually these reactions do not proceed to completion because of general precipitation occurring in the matrix, and they have not been studied in detail. Precipitation from an austenitic Fe-30 Ni-6 Ti alloy was studied as part of a larger investigation of the mechanisms of precipitation from substitutional iron-base alloys. This alloy, austenitic at high temperatures, decomposes at lower temperatures by a double cellular precipitation reaction. The first decomposition product consists of alternate lamellae of an Ni3Ti(DO24) phase and austenite. The reaction proceeds to completion, consuming all of the original austenite. This first cellular product is subsequently consumed by a second cellular reaction of much coarser spacing. The first cellular reaction was studied in detail by light and electron microscopy, hardness measurements, and by X-ray and electron diffraction. Interlamellar spacings and growth rates were measured during isothermal aging in the range 400" to 975°C. The orientation relationship between the Ni3Ti and austenite lamellae was determined and indicates that an almost perfectly coherent interface exists between the two phases. This first Ni3Ti cellular reaction is of particular interest because it occurs over such a wide temperature interval. This allows cellular growth rates and interlamellar spacing data to be obtained for much larger degrees of undercooling than reported hitherto. MATERIALS AND EXPERIMENTAL PROCEDURE The Fe-30 Ni-6 Ti alloy was prepared from electrolytic iron, Mond nickel shot, and sponge-purity titanium* by vacuum melting in a zirconia crucible

Jan 1, 1963

By F. G. Jones, R. D. Pehlke, H. E. Gardner

The solubility of nitrogen in liquid Fe-18 pct Cr-8 pct Ni-0. 7 to 2.3 pct A1 alloys has been measured up to the solubility limit for the formation of aluminum nitride in the temperature range 1600° to 1700°C uszng the Sieverts' method. The solubility of nitrogen in 18-8 stainless steel increases with increasing aluminum content. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from the elements dissolved in liquid 18-8 stainless-steel alloys has been determined to be: ?G° = -42,500 + 20. IT in the range from 1600° to 1700° C. EVANS and pehlke1 have measured the equilibrium conditions for the formation of aluminum nitride, AlN, in liquid Fe-A1 alloys. The present study extends that work to the more complex solvent, liquid 18 pct Cr-8 pct Ni (18-8) stainless steel. Recent work by Small and pehlke2 has dealt with the effect of fourth-element additions on the solubility of nitrogen in 18-8 base alloys. They found the effect of aluminum additions, up to 0.74 pct, on the solubility of nitrogen to be small. The present study covered the range from 0.74 to 2.28 pct aluminum, and by extending the composition range may be used to better define the effect of aluminum on the nitrogen solubility in these alloys. EXPERIMENTAL PROCEDURE The Sieverts' method was used to measure the equilibrium solubility of nitrogen gas in liquid 18-8 stainless steel alloys containing 0.74, 1.49, 1.93, and 2.28 pct Al. The solubility was measured as a function of the nitrogen gas pressure at temperatures of 1600°, 1650°, and 1700°C. The apparatus used is the same as described by Small and Pehlke.2 The 100-g melts were made from Ferrovac-E high-purity iron, Crucible Steel Co.; 99.95 pct Cr, Union Carbide Corp.; 99.9 pct Ni, International Nickel Co.; and 99.99+ pct Al, Aluminum Co. of America. The aluminum was charged at the bottom of the crucible, surrounded by nickel and iron. The chromium was packed into the interstices to minimize vapor transport of the aluminum during initial melting. The hot volume of the system, measured for each melt with argon, ranged from 45 to 55 standard cu cm with a temperature coefficient of —8 x 10-3 cu cm per °C. The melt temperature was measured with a Leeds and Northrup disappearing-filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature calibration of the system by Small and pehlke2 was assumed. Two problems are involved in determining the solubility product of a solid, metal nitride phase in liquid iron alloys. These are: 1) establishing the point of departure from Henrian behavior at the solubility limit of the metal nitride phase; and 2) determining the composition of the solid nitride which is precipitated. Determination of the solubility product of AlN was made by admitting small amounts of nitrogen into the reaction bulb until the deviation from Sieverts' law was clearly evident in the form of a pressure halt. To obtain the solubility product at several temperatures during one run the following procedure was used: 1) add increments of nitrogen to determine the Sieverts' law line at the lowest desired temperature; 2) continue to add nitrogen to precipitate a small amount of the nitride phase; 3) increase the melt temperature 50°C to dissolve the precipitated nitride; 4) repeat step 2 until either a nitride formed or the system reached ambient pressure; if a nitride formed at 1650°C, the sequence was repeated at 1700°C. The composition of the precipitated phase was checked by an X-ray diffraction pattern obtained from powder scraped from the surface of the solidified 1.93 pct A1 melt. RESULTS AND DISCUSSlON Solubility Measurements. Fig. 1 is a typical nitrogen-absorption curve obtained from measurements on a 1.93 pct A1 alloy. Since the initial absorption of nitrogen follows Sieverts' law the nitrogen solubility is plotted as a function of the square root of the pressure of nitrogen gas in the reaction bulb. The results of the solubility measurements for all alloys studied are summarized in Table I. The slope of the Sieverts' law line for each alloy was determined. Since this is also the solubility of nitrogen at 1 atm pressure of nitrogen gas, the latter designation is used for the data. It should be noted. however, that in most cases the value lies above the solubility limit for AlN. Fig. 2 shows the effect of aluminum on the solubility of nitrogen at this reference pressure and as a function of melt temperature. The solid portions of the lines represent attainable solutions; the dashed regions lie above the limit for precipitation of AlN.

Jan 1, 1969

By George D. Graffin.

The first use of graphite is lost in the mists of time. It was used by primitive man to make drawings on the walls of caves and by the Egyptians to decorate pottery. As early as 1400 A.D. graphite crucibles were being made in the Haffnerzell district of Bavaria. Through the Middle Ages graphite was confused with other minerals, especially galena and molybdenite. Two common names that are still used for the mineral are "Plumbago," meaning leadlike, and "Black Lead." The latter name implied that graphite is either composed of lead or at least contains a large percentage of it. Gessner is credited with having recognized it as a separate mineral in 1565, but its composition was not determined until 1779, when Scheele demonstrated that graphite oxidized to carbon dioxide, thus proving its carbon constitution. In 1789, Werner named it "graphite" from the Greek word "graphein," meaning to write. The United States has long relied on foreign countries for its graphite supplies. This reliance has been due more to the lack of suitable domestic graphites than to any particular preference for buying minerals overseas. Ceylon (now Sri Lanka) graphites were imported as early as 1820, and Madagascar graphites have been imported since the properties on that island were opened up about a hundred years later. Mexico has long supplied the United States with most of its requirements for amorphous graphite. Physical Properties and Classification Graphite is found in laminated, flaky aggregates disseminated in schistose rocks. It also occurs in veins and exhibits a foliated or fibrous structure. Graphite is a black lustrous mineral that crystallizes in the hexagonal system, with rhombohedral symmetry. The crystals have tabular form and are six-sided; the faces are commonly striated. The flakes have perfect basal cleavage and are opaque. When well crystallized, the flakes have a black metallic luster while the amorphous material is black and earthy, with a microcrystalline compactness. The flakes feel greasy. Graphite is an excellent conductor of heat and electricity. It melts at approximately 3550°C at a triple point under 1250 psi. It sublimes between 3300-3500°C at 14.7 psi. At 3726°C a second triple point occurs at approximately 100,000 atmospheres. Thermal oxidation in the presence of oxygen begins at 300°C and the rate increases with temperature. The three forms of carbon (charcoal, graphite, and diamond) are distinguished by chemical and physical tests. The specific gravity of charcoal is 1.3 to 1.9, of graphite 2.266 g/ cm3 (crystal density), and of diamond 3.5. Graphite has a hardness of 1 to 2 (Mohs' scale). Natural graphite can be divided into three classes: disseminated flake, crystalline vein (fibrous or columnar), and amorphous. Flake graphite is a lamellar form found in metamorphic rocks, such as marble, gneiss, and schist. Each flake is separate, having crystallized as such in the rock. Crystalline vein graphite is found in the form of well defined veins or as pocket accumulations along the intrusive contacts of pegmatites with limestones. The graphite of such deposits is of two types, foliated and columnar. The important Sri Lanka (Ceylon) deposits are vein type. Amorphous graphite is commonly found as minute microcrystalline particles more or less uniformly distributed in feebly metamorphic rocks, such as slates and shales, or in beds consisting practically entirely of graphite. The latter usually are metamorphosed coal seams and carry as much as 80-85% graphitic carbon, while the former, being altered carbonaceous sediments, commonly range from 25 to 60%

Jan 1, 1983

By Charles H. Foreman

IN JUNE 1921, the Sullivan &lining Co., owned jointly by the Bunker Hill and Sullivan Mining & Concentrating Co. and the Hecla Mining Co, started work on the development of the Star Mine. The development work contemplated called for a crosscut from the Hecla workings on the 2000 level to the Star ledge. The length of crosscut necessary to encounter the Star ledge was approximately 8900 ft. from the Hecla shaft. By using workings formerly made by the Hecla Mining Co., only about 8100 ft. of actual crosscutting was necessary. This crosscut has a direction of S 20° W and would have a tendency to crosscut any ledges in the intervening ground.

Jan 1, 1924

By G. K. Manning, E. R. Stein, E. E. Underwood

Columbium, carbon. and nickel additions were made to iron-base alloys with 20 pct CY. The effects on microstructure, precipitation-hardening characteristics, and High-temperature properties were investigated by means of metallographic, hot-hardness, and magnetic measurements. An austenitic alloy consistilzg of Fe-20Cr-14Ni-0.8C-2.5Cb had higher hot-lzaciness at 1700°F than the other alloys investigated. Its favorable standing is attributed to an enhanced interaction of Cb and Cr4C particles dispersed within a stable austenitic matrix. FOR the past 20 years, cobalt- and nickel-base alloys have been used for the more stringent high-temperature applications because of their excellent creep resistance. Although their performance is quite satisfactory, other base materials must be considered for large tonnage, low-cost applications such as for the automotive gas turbine. Iron-base alloys are also used extensively, but at somewhat lower temperatures, primarily because of the instability of particles or because precipitation occurs at relatively low temperatures. Since unusual stability has been reported for Fe-Cb and Cb-C compounds.1-3 it was hoped that effective amounts of these compounds could be taken into solution at temperatures just below the melting range, then precipitated upon reheating. Actually, strengthening was found to occur by both precipitation hardening in some alloys and by phase transformations in others. Among the alloys investigated, that with the best high-temperature properties owes its strengthening to a combination of carbide particle interaction and a relatively stable austenitic matrix. EXPERIMENTAL PROCEDURES Small preliminary melts of about 100 g were made in a vertical Glotube furnace, using alundum crucibles and an argon atmosphere. Alloys weighing 35 lb were melted in a basic-lined induction furnace, also under argon. The compositions of the alloys are given in Table I. The nickel-free alloys were usually ferritic, while those containing nickel were generally austenitic. Depending upon the particular heat treatments, or the combination of alloying elements, two-phase alloys of ferrite and austenite could be obtained. In the following text, however, the nickel-free or nickel-bearing alloys are referred to simply as either ferritic or austenitic alloys respectively. The small ingots were swaged at 2000°F, in steps, to rods of approximately 3/16-in. diam. The large ingots were forged at 2100°F to 1-in. sq bars. No difficulties were encountered in swaging or forging any of the alloys to as much as 90 pct reduction in area. For heat treating at temperatures above 2000°F, specimens were sealed in quartz tubes under a partial pressure of helium. No special precautions were found to be necessary at lower temperatures. Intermetallic compounds in the preliminary alloys were identified by means of X-ray diffraction measurements. Correlation of these results with micro-structural characteristics (such as color, shape, size, and location) of the compounds aided in their identification. Magnetic susceptibilities were also obtained at room temperature with a Magne Gage instrument after the various heat treatments. To

Jan 1, 1962

By T. B. Counselman

"C" VERYONE who has to calculate cyanide circuits, -¦-' using either thickeners, filters or both, realizes the headaches involved in solving a set of simultaneous equations. When you calculate a large number of these, based on experimental data, trying to arrive at the best flowsheet, you can spend days at the task. T. B. COUNSELMAN, Member AIME, is Manager, FluoSolids Division, The Dorr CO., Stamford, Conn. AIME New York Meeting, Feb. 1950. TP 2783 B. Discussion (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Aug. 23, 1949. Herewith is presented a short method, equally accurate with the standard simultaneous equation method, and much quicker. Here for instance is the standard simultaneous equation method, for 100 tons per day of $10 ore, with the conditions assumed as below (fig. 1). Conditions Assumed a. 100 tons of ore per day crushed in cyanide solution. b. Discharge from all thickeners with 50 pct moisture. c. $10 value dissolved per ton of ore. d. 50 pct in mill and 50 pct in agitators. e. 400 tons of solution from thickener V precipitated to $0.02. f. Agitation with a dilution of 2 of solution to 1 of solids. g. Let V, W, X, Y and Z represent value in dollars per ton of solution discharged from the resvective thickeners. Equating Out of and Into Each Thickener 1. lOOVplus 400V = 500W plus (0.50 X $10 X 100) 2. 1OOWplus 600W= 500X plus lOOW plus (0.50 X $10 X 100) plus lOOV 3. lOOXplus 500X = 1OOWplus 500Y 4. 1OOY plus 500Y = 1002 plus 1OOX plus (400 X 0.02) 5. 100 Zplus l00Z = l00Y plus 100 tons of water (value $0.00) Simplifying: 1. v = W plus 1.00 2. W = X plus 1.20 3. X = Y plus 0.24 4. Y = 0.2Zvlus 0.064 5. 2Z= Y

Jan 1, 1951

By T. B. Counselman

"C" VERYONE who has to calculate cyanide circuits, -¦-' using either thickeners, filters or both, realizes the headaches involved in solving a set of simultaneous equations. When you calculate a large number of these, based on experimental data, trying to arrive at the best flowsheet, you can spend days at the task. T. B. COUNSELMAN, Member AIME, is Manager, FluoSolids Division, The Dorr CO., Stamford, Conn. AIME New York Meeting, Feb. 1950. TP 2783 B. Discussion (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Aug. 23, 1949. Herewith is presented a short method, equally accurate with the standard simultaneous equation method, and much quicker. Here for instance is the standard simultaneous equation method, for 100 tons per day of $10 ore, with the conditions assumed as below (fig. 1). Conditions Assumed a. 100 tons of ore per day crushed in cyanide solution. b. Discharge from all thickeners with 50 pct moisture. c. $10 value dissolved per ton of ore. d. 50 pct in mill and 50 pct in agitators. e. 400 tons of solution from thickener V precipitated to $0.02. f. Agitation with a dilution of 2 of solution to 1 of solids. g. Let V, W, X, Y and Z represent value in dollars per ton of solution discharged from the resvective thickeners. Equating Out of and Into Each Thickener 1. lOOVplus 400V = 500W plus (0.50 X $10 X 100) 2. 1OOWplus 600W= 500X plus lOOW plus (0.50 X $10 X 100) plus lOOV 3. lOOXplus 500X = 1OOWplus 500Y 4. 1OOY plus 500Y = 1002 plus 1OOX plus (400 X 0.02) 5. 100 Zplus l00Z = l00Y plus 100 tons of water (value $0.00) Simplifying: 1. v = W plus 1.00 2. W = X plus 1.20 3. X = Y plus 0.24 4. Y = 0.2Zvlus 0.064 5. 2Z= Y

Jan 1, 1951

By H. I. Aaronson, H. A. Domian

ELectvon-probe analgsis has been used to in7:estigatr the partition ot alloying- elements between aus-tenite and proeutectoid ferrite (or the Jerritic component of bainite) in high-purity Fe-C-X alloys, lsuully at tzco levels of carbon content fca 0.1 and 0.4 pct in ntost steels) at temperatures between the M, and the Ae3 in Si, mn, Ni, mo, Co, Al, Cr, Cu, and PI steels. No partition ous found during the early stages of transformation at any temperature studied in the Si, ,mo. Co, Al, Cr, and Cu steels. Partition did take place, Jrowel'er, in Ihe Mn, ATi, and Pt steels, occurring in lewtperature. regions below the Ae3 of ca 130°, 65", UNDERSTANDING the mechanisms through which alloying elements influence the kinetics of austenite decomposition reactions which proceed by nucleation and 35c respectively. A break was discovered in the TTT curve for the initiation oj the proeutectoid ferrite reaction in the latter steels at the temperature at which partition began. The alloy content in ferrite at the a:y bondavy remained at constart lecels, shown experimentally to be significantly above those corresponding to eqiilib+iu??l, e'en at the longest reaction times investigated (ca 1o6sec). The partition and the TTT curve observations foere rationalized on the basis of the thermodynamic treatment developed in an accompany ing paper. and diffusional growth has been a major research objective of physical metallurgy since the latter part of the 19th century. The measurements made on the dif-fusivities of carbon and of substitutional alloying elements in austenite during the 1930's and 1940's seemed to provide a useful clue as to the nature of these mechanisms. These measurements showed that the diffu-sivity of carbon is several orders of magnitude higher than that of the alloying elements at a given tempera-

Jan 1, 1967