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By P. Marier, T. R. lngraham

The kinetics of the sulfation of MnO,, MnzO3, and Mn3O4 in SO,, SO3, and O, mixtures was examined and the descending order of sulfation rates at temperatures near 400°C was found to be Mn,O3 > MnO, > Mn3O4. The respective activation energies for the thermal decomposition of MnO, and Mn,O, are 39 and 47 kcal. At 900°C, the thernzal decomposition of MnSO, to MnzO3 is slower than that to Mn3O4. The respective activation energies are 62 and 51 kcal, respectitely. MANGANESE is used to improve the hot workability of steel in the proportions of approximately 13.5 Ib of ferromanganese per ton of steel produced. This requirement accounts for about 95 pct of its large industrial market in North America. The remaining 5 pct is used in the battery and chemical industries. In most North American ores, the percentage of manganese and the manganese-to-iron ratio are not suitable for the direct production of ferromanganese. Hence, most of the North American requirements for manganese are satisfied by importing ore. Typically, many of the studies done on native low-grade manganese resources have been directed toward the production of ore substittes" and the recovery of manganese from open-hearth slags.3 Of the wide variety of processes which have been proposed, the most popular involve compounds in the Mn-S-O system. The thermodynamic properties of manganese and its compounds were reviewed by ah' in 1960 and, more recently, lngrahams discussed the thermodynamics of some of the reactions involved in the Mn-S-O system at normal roasting temperatures. The conditions for producing manganese sulfide during the reduction roasting of manganese sulfate are discussed by Fuller and Edlund.9 A novel scheme was proposed recently by zimmerley7 for utilizing waste sulfur dioxide from stack gases to recover the manganese from ocean-mined manganese nodules. Very little of the work published on manganese compounds has been related to reaction rates. Singleton et 1.' studied the rates of reaction on the MnO-C and Mn7C3-3MnO systems and observed linear and parabolic kinetics respectively in the systems. Tatievskaya et a1.' studied the low-temperature reduction of Mn&, MnO,, and Mn& in HZ and CO, and reported activation energies in the range 1628 kcal. In this paper, the rates of some of the decomposition and formation reactions involving MnSO4, MnOz, MnzO3, and Mn3O4 will be examined after the conditions for the thermodynamic stability of the individual compounds have been designated. CONDITIONS FOR STABILITY OF MnSO4, MnOz, MnZO3, AND Mn3O4 The areas of stability for h'hSO4, MnOz, MnzO3, and h3O4 were established from the data of Mah4 and Ingrahams and are shown in the predominance area diagram,10 logpq- logpsq, in Fig. 1. The diagram is drawn for two temperatures, 700°K, solid lines, and 1100°K, dotted lines. The sketch for the lower temperature includes the conditions likely to prevail in the Zimmerley patent7 when manganese nodules react with sulfur dioxide and that for the higher temperature indicates the conditions for recovering MnzO3 or Mn3O4 from MnSO4 during a roasting reaction. From the fact that the boundary between the areas of stability of MnOz and hSO4 at 700°K is parallel to the abscissa, it is evident that MnOz and SO2 should react together to produce MnSO4, irrespective of the oxygen pressure in the system. If the source of sulfur for sulfation were from waste flue gases, it is likely that the oxygen content of the gas stream would be more than sufficient to oxidize any MnsO4 to MnzO3, 107 atm of O2 required, or even to convert any Mnz03 to MnOz, 0.02 atm OZ required, prior to sulfation. At 1100°K, the diagram indicates that MnSO4 may be converted directly to either MnzO3 of Mn3O4, depending upon the prevailing partial pressure of oxygen. When the gas stream contains more than 1 pct Oz, logpq = -2, only MnzO3 would be recovered from an experiment done under equilibrium conditions. At oxygen partial pressures of less than 1 pct, one would expect to bring about a reversible exchange between MnSO4 and Mn3O4 by appropriate adjustment of the partial pressure of SOZ. These various reactions will be described in the subsequent kinetic experiments.

Jan 1, 1969

By William H. Spice

Drilling activities in South Central Texas for the year 1945 continued the steady increase over the past two years, while new fields discovered for the year included four new gas fields and one field extension. In the 30 counties included in this area, which comprises district No. 1, Oil and Gas Division, Railroad Commission of Texas, 141 exploratory wells were completed, compared with 61 drilled in 1944 and 29 drilled in 1943. Of these 141 tests, 55 were field well and 86 were wildcats; 38 were completed as oil wells, S as gas and gas-distillate producers, and 95 were abandoned as dry. Atascosa and McMullen Counties were the most active in the district, accounting for 73 of the wells drilled.

Jan 1, 1946

By E. L. Vickers

Over the years, the pure theorist in economic analysis has accumulated a formidable array of facts in bringing his subject matter under control. Business managers and mining engineers are aware of the theorist's weapons, but the question of applying them to the mastery of practical problems seems hardly feasible, especially in view of the almost innumerable variables plaguing the everyday scene in the mining enterprise. One such sophisticated tool of long-standing in the theorist's arsenal is marginal analysis. Equally long-standing for the operating company and valuation engineer is the problem of defining the cut-off grade the point below which a mineral re- source ceases to be economically amenable to extraction. In other words, what part of a mineralized body of rock is ore and what is waste?

Jan 6, 1961

By R. F. Mehl, C. E. Birchenall

SINCE Maxwell1 first considered the self-diffusion process in 1872 its importance in the kinetic theory of matter has been recognized. Until the discovery of isotopes in 1913, a direct measurement of this quantity seemed impossible. The only information that could be gathered indirectly was for gaseous systems for which the kinetic theory was well developed. When methods of direct observation be-came available, investigations on self-diffusion were carried out in condensed phases. In metals these data are presumably of potential importance in the study of recovery, recrystallization, creep, sintering, and related phenomena. Following the pioneer work of Von Hevesy2 and his collaborators, who determined the rate of self-diffusion in lead with the naturally occurring thorium B isotope, several metals have been investigated. Pb, Ag³, Au.6,5, and Cu6,7,8,9 are examples of isotropic crystals existing in only one phase modification. Anisotropy of diffusion has been demonstrated in Bil6 and Znll. This paper is a study of a single metal in two allotropic forms and also of self-diffusion in a body-centered cubic lattice. Despite the fact that the measurements in each of the papers cited on self-diffusion in copper seem to be internally consistent to about 10 to 15 pet, the curves reported by different authors differ by factors of 2 to 4 at the same temperatures. This uncertainty may account, in part, for the failure to establish a successful correlation between the self-diffusion rates and other physical characteristics of the metals. No satisfactory theory of metallic self- diffusion has as yet been proposed to account for all the existing data and to permit estimation in other metals. Experimental Part: Two units of radioactive iron were used in these experiments, each a mixture of Fe53 and Fe59 (12). Fe53 decays by K electron capture and the emission of an X ray with a half life of about 4 years. Fe59 emits two beta spectra, one with a maximum energy of 0.26 Mev, the other 0.46 Mev, and gamma rays of 1.1 and 1.3 Mev, with a half life of about 44 days. They were present in nearly equal concentration initially. The composite half life started at about 50 days and increased as the Fe59 decayed, leaving Fe55 relatively more abundant. After aging a year, the half life was too long to measure significant decay in a month. The absorption properties also changed with time. Because of the importance of the absorption coefficient in the diffusion calculations, it was necessary to determine this quantity frequently over the period during which these experiments were carried out. This correction was unsuspected at the time of publication of notesl3 on this work and accounts for the discrepancy in alpha iron and for part of the discrepancy in gamma iron.* * The data in the present paper supersede those given in the notes entirely. In one note the scale of log D was inadvertently reversed. In addition to the correction for the drift in absorption coefficient, the D values for gamma iron at low temperatures were high owing to insuficient correction for diffusion occurring during heating and cooling through the high temperature part of the alpha range at a rate much slower than that employed in the runs reported here. The high temperature alpha rates are much higher than the low temperature gamma rates and correspond to large equivalent times at these temperatures. These experiments were discarded and new measurements taken. Independent experiments with the same activity units indicated a radioactive contaminant in the iron, but exhaustive attempts to isolate and identify it chemically failed. These experiments? indicate † These experiments will be discussed in a later publication from this laboratory. that the contaminant represented only a trace of little importance in the diffusion results. The active iron was plated from an iron chloride solution. Enough of the solution was dropped on a 1% in. square of filter paper to wet it thoroughly.

Jan 1, 1951

By Stephen G. Wright

Jan 1, 1985

By C. G. Bieber, J. R. Mihalisin, R. T. Grant

A growing demand for longer service life of gas turbines has placed increasingly rigorous requiret~rents upon superalloys employed for that application. Long-titne testing at high temperature has revealed that phase transformations occur in all superalloys. A common one of particular interest is o formation. Presented here are studies made to identify a and to characterize its formation and effect on properties in three cast nickel-base superalloys—IN 100 alloy, alloy 713C, and alloy 713LC. Methods are discussed by which o can be eliminated or inhibited in IN 100 alloy and alloy 713C. Evidence was obtained to indicate that some types of o may be more detrimental than others. Limitations in the electron vacancy approach to o prevention are pointed out, and it is shown how alternative approaches, such as reducing a complex superalloy matrix to the form of a pseudo-ternary system permitting equilibrium diagram treatment, lead to additional insights into the formation of in these alloys. AROUND 1960. Beiber1 developed IN 100 alloy, which still remains one of the strongest commercially available nickel-base superalloys. The principle used in the design of this alloy was to produce large quantities of y' phase in a y matrix through the use of copious amounts of aluminum and titanium. In 1963, ROSS' showed that when certain heats of this alloy were held for a long time at 1650°F they formed an acicular phase, subsequently identified as a.3 a is a hard and brittle phase first discovered in the Fe-Cr system by Bain and Griffiths.4 They termed it the "B" constituent. Subsequently this same phase was found in other systems, primarily those of the transition elements, and acquired the name "a" by which it is now known. The crystal structure of the a phase was first determined in the Fe-Cr system in 1950.5 It was shown to be tetragonal with a c/a ratio of about 0.52. as is the case with a found in other systems. This characteristic crystal structure is now the means by which a is identified. In superalloys, such as IN 100 alloy. large amounts of o impair the high-temperature creep strength and drastically reduce room-temperature tensile ductility. Discovery of o phase in some heats of IN 100 alloy quickly led to investigations of other superalloys for similar transformations. It was found that many of the stronger, more highly alloyed. super-alloys were indeed susceptible to o formation. This investigation has been concentrated on three commercial alloys: IN 100 alloy, alloy 713C, and alloy 713LC. J.R.MIHALISIN,MemberAIME, and C.G.BIEBER are with The International Nickel Co., Inc., Paul D. Merica Research Laboratory, Sterling Forest, Suffern, N. Y. R. T. GRANT, Member AIME, is with The International Nickel Co., Inc., Pittsburgh, Pa. Manuscript submitted May 22. 1968. IMD A detailed study has been made of the phase transformations and their relation to a formation along with a consideration of electron vacancy approaches for predicting a-forming propensity in these alloys. EXPERIMENTAL PROCEDURE Phase transformations were studied by light and electron microscopy, electron diffraction, microprobe investigations, and X-ray diffraction. Specimens for light micrographic examination were prepared by conventional grinding and polishing followed by etching with glyceregia (2:l HC1/HNO3 + 3 glycerine by volume). Photomicrographs of stress-rupture specimens were taken adjacent to the fracture unless otherwise noted in the text. Negative replicas for electron microscopy were taken from surfaces electropolished with a solution of 15 pct H2SO4 in methanol. For carbon extraction replication, a solution of 10 pct HC1 in methanol was used. A Siemens Elmiskop I was used for all electron microscopy. Selected-area diffraction studies were made at 80 kv using evaporated aluminum for standardizing the patterns. A nondispersive electron microprobe attachment was used to analyze the extracted precipitates chemically. The fluorescent X-rays were recorded using a flow counter containing P10 gas (90 pct Ar-10 pct methane) with a beryllium window and a single-channel pulse-height analyzer. The pulses from the analyzer were passed to a scaler-ratemeter and differential curves of counting rate vs pulse amplitude were obtained. The base line of the analyzer was driven with a synchronous motor at 0.5 v per min and a channel width of 0.5 v. The time for 105 counts was printed out for each 0.5-v increment. The microscope was operated at 80 kv with beam currents of 1 to 20 pa. This equipment detects elements from atomic number 13 to 40. X-ray diffraction studies were usually made on residues electrolytically extracted in 10 pct HC1 in H2O, although in one case a pattern was obtained from an etched surface of a metallographic specimen. A Siemens Crystalloflex IV was used with iron-filtered CoKa radiation. X-ray patterns were recorded using a goniometer speed of : deg per min. The scintillation counter and pulse-height analyzer operated at a channel height of 10 v and a channel width of 12 v. The equipment was calibrated with a powdered gold standard. The residues usually contained a number of phases. several of which could not be found in the ASTM card file. In addition, as is shown for the case of a phase in IN 100 alloy, other phases had a somewhat different lattice parameter from that reported in the ASTM card file, making it difficult to separate and identify constituents by comparison with ASTM d spacings. For these reasons, phases were identified on the basis of the lattice parameter obtained by indexing the ob-

Jan 1, 1969

By Mrs. V. J. DeCarlo, G. P. Salvo, H. W. Schadler, L. M. Osika

The lattice parameter of the inlerrnetallic compound Nb3Sn has been measured as a function of temperature from 80° to 1290°K. The results are compared with published data on the thermal ex- ThE recent interest in the intermetallic compound, Nb3Sn, as an engineering material for the production of superconducting devices has necessitated that certain engineering data be obtained. Because of the difficulty encountered in producing bulk pansion of niobium and indicate that the compound when made by diffusion of tin into niobium at 1000°C, would be subjected to a tensile strain of about 0.1 pct when cooled to room temperature. material which is single phase, the coefficient of thermal expansion has not been measured by dilata-tional methods. Therefore the lattice parameters of fine-grained samples of Nb3Sn produced on the surface of a niobium sheet by heating in molten tin at 950°C have been obtained as a function of temperature. The results are compared with published data on niobium2 and Nb3Sn3 and with lattice-parameter measurements made on small single crystals of Nb3Sn.

Jan 1, 1964

The following is an incomplete list of members and guests who called at Institute headquarters during the period July 11, 1918 to August 11, 1918. John Carter Anderson, Tucson, Ariz. Edson S. Pettis, San Francisco, Cal. Lieut. Frank A. Ayer, Tyrone, N. M. Wm. H. Rettie, Yonkers, N. Y. W. R. Canton, McGill, Nev. J. T. Robertson, Port Richmond, S. I. Alden Crankshaw, Palmerton, Pa. Harry O. Robinson, Margarita, John Davenport, W. Norfolk, Va. Venezuela. A. Faison Dickson. C. K. Seng, Gilbert, Minn. F. A. Fahrenwald, Cleveland, C). E. S. Sheffield. L. Hall Goodwin, New York. H. G. Smith. W. H. W. Hamilton, Baker, Ore. Harry M. Spoor. Floyd D. James, St. Louis, Mo. H. H. Stoek, Urbana, Ill. George A. Laird. Arthur L. Tuttle, Copperhill, Tenn. J. W. McBride, Spokane, Wash. Thor Warner, Phoenix, Ariz. Arthur Notman, Bisbee, Ariz. Christopher G. Atwater, Manager Agricultural Dept., The Barrett Co., is in Washington serving the U. S. Navy Bureau of ordnance in connection with the Navy nitrate plant recently authorized by Congress. Edward Ludlam Blossom announces his marriage to Mabel Townsend, daughter of Mr. and Mrs. George Comings Mills, on Wednesday, July 17, 1918, at New York City.

Jan 9, 1918

The following is an incomplete list of members and guests who called at Institute headquarters during the period Apr. 10, 1919, to May 10, 1919. Arthur K. Adams, Spencer, Mass. Ensign Floyd D. James, U. S. S. Fulton. W. T. Bates, New York City, N. Y. J. Harry Johns, Thorsden, Woking, A. D. Brokaw, Washington, D. C. England. E. H. Clausen, San Francisco, Calif. W. F. Jones, Rock Springs, Wyo. W. M. Corse, Mansfield, Ohio. E. L. Lasier, Washington, D. C. E. O. Daue, Philadelphia, Pa. John M. Lovejoy, New Rochelle, N. Y. G. D. Dub, Washington,, D. C. 2d Lieut. James F. Magee, Lancaster, S. B. Eaton, Dover, N. J. Pa., Sherman Eaton, Smethport, N. C. Ernest Marquardt, Casper, Wyo. J. A. Endweiss, La Jolla, Calif. Geo. B. Marshall, Abangarez, Costa Edgar W. Engle, North Chicago, Ill. Rica. 2d Lieut. Maxwell E. Erdofy, New York Benj. L. Miller, So. Bethlehem, Pa. City, N. Y. Major Desaix B. Myers, Camp Mills. Chas. A. Fellencer, Allentown, Pa. Edmund Newton, New York City, N. Y. Arthur Feust, Joplin, Mo. Seely B. Patterson, Jr., Allentown, Pa. Ensign Harold P. Ford, U. S. S. Radnor. Wm. R. Pearson, New York City, N. Y. A. D. R. Galloway, Accra, West Africa. Harold C. Price, Langeloth, Pa. R. C. Gosrow, Milwaukee, Wis. T. C. Roberts, East. Orange, N. J. C. A. Grabill, El Paso, Tex. P. H. Royster, Washington, D. C. Hobart A. Hanks, San Francisco, Calif. W. H. Staver, New York City, N. Y. John L. Henning, Lake Charles, La. N. L. Wimmler, Bangkok, Siam. 1st Lieut. J. Parke Hook, Philadelphia, Capt. Jay P. Wood, New York City, Pa. N. Y. An item in the May Bulletin made it appear that Frank W. DeWolf had just become connected with the State Geological Survey of Illinois. This was one of the inadvertences of war. Mr. De Wolf has been Director, or Chief, of the State Geological Survey for approximately ten years. Through the courtesy of the Governor of Illinois, lie was loaned to the Bureau of Mines for about seven months, after which period he resumed his former position.

Jan 6, 1919

By C. Wagner

When an alloy solidifies and the composition of the solid differs from the composition of the liquid, atoms of the alloying elements rejected at the solid-liquid interface have to diffuse toward the bulk liquid. Diffusion may be supported by convection. Theoretical calculations have been made for a liquid without convection, for a liquid involving natural convection, and for solidification of a liquid alloy at the surface of a rotating disk as an example of forced convection. WHEN an alloy solidifies, the equilibrium composition of the originating solid phase differs in general from the composition of the liquid phase. Thus, segregation may take place, i.e., the composition of the solid phase formed at different times differs from the bulk composition. The degree of segregation depends on several factors such as the partition ratio of the alloying elements between the liquid and the solid phase, the rate of solidification, and convection. To clarify, a theoretical analysis has been worked out. The following presuppositions are made: 1—Calculations are confined to the solidification of binary alloys in which the concentration of component A (solvent) is much greater than that of component B (solute). 2—The equilibrium concentration of the alloying element B is assumed to be lower in the solid phase than in the coexisting liquid phase. 3—At the solid-liquid interface, partition equilibrium is assumed. 4—The dependence of the partition ratio of the solute between the liquid and the solid phase on concentration and temperature is disregarded since only small concentrations of the solute are considered. 5—The concentration of the alloying element B in the solid phase is supposed to be lower than the saturation concentration for the formation of a second solid phase. 6—diffusion in the solid phase is disregarded, since diffusion rates in the solid state are comparatively low. When the partition ratio of the solute between the liquid and the solid phase is greater than unity, a part of the solute is rejected at the solid-liquid inter- face and has to diffuse toward the bulk liquid. Thus there is necessarily a concentration difference in the liquid between the solid-liquid interface and the bulk liquid as has been pointed out by Hayes and Chipman,' Rutter and Chalmers,' Tiller, Jackson, Rutter, and Chalmers, and others (see Fig. 1). In view of the concentration gradient in the liquid phase, the ratio of the concentration of the solute in the solid phase to that in the bulk liquid differs from the equilibrium ratio, although at the solid-liquid interface, partition equilibrium is assumed. Under certain limiting conditions, the solid may even have virtually the composition of the bulk liquid as is shown below. General Equations Let u be the linear crystallization velocity in cm per sec, D the diffusion coefficient of component B in the liquid phase in cm2 sec-', c',, and c", the concentrations of component B in the liquid and the solid phase, respectively, in mol per cm", and s the distance from the solid-liquid interface toward the bulk liquid at a given time t. The partition ratio is assumed to be equal to a partition constant K. Thus. The difference in the specific volume between the liquid and the solid phase may be disregarded. In view of the discontinuity of the concentration of the solute at the interface according to Eq. 1, u(c', — c",), , , = tic', (S = 0)(1 — K) gram-atoms B per unit area per unit time are rejected at the interface and have to diffuse toward the bulk liquid. From Fick's first law it follows that uc',,(s = 0) (1 ~K) == - D(dc',,/?>s). _-„. [2] The concentration profile in the liquid near the interface depends on the interplay of diffusion and convection as is discussed in the following sections. A schematic concentration profile is shown in Fig. 1. The "effective thickness of the diffusion boundary

Jan 1, 1955

By E. Peters

As in other fields of Extractive Metallurgy, Hydrometallurgy is preoccupied with separation processes and with oxidation-reduction processes. The physical chemistry of each type of process can be described in terms of thermodynamic equilibria and in terms of reaction kinetics. Reaction kinetics are much more important at the low temperatures limiting hydrometallurgical processes than in com- parable pyrometallurgical operations and the number of cases in which the kinetics can be described by simple liquid-phase mass-transfer models are sharply limited. It is convenient to subdivide the applicable rate phenomena into processes in which (a) interface reactions control the rate,(b) mass transfer processes control the rate, (c) solid state process affect the rate, (d) thermodynamically predicted phase changes or molecular reactions fail to take place, (d) metastable substances or supersaturated phases persist, and (elchomogeneous reactions in solution affect the chemistry and the kinetics. Examples are drawn from the unit steps of leaching, cementation, hydrogen reduction, and electrowinning.

Jan 1, 1973

By Mayumi Someno, Kazuhiro Goto, Masahiro Kawakami

The apparent rates of decarburization of liquid alloys of Fe-C, Fe-C-S, Ni-C, and Co-C systems and the rate of oxidation of solid graphite with pure carbon dioxide gas and with gas mixtures of carbon monoxide and carbon dioxide have been measured in the temperature range of 1000° to 1600°C. The cotnposition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells with the ZrO,-CaO solid electrolyte. 1) The apparent rates of the carbon removal are essentially the same for all the cases of solid graphite, Fe-C, Fe-C-S, Ni-C, and Co-C systems under the same experimental conditions. 2) The apparent rates are independent of the carbon content in the high carbon concentration range but very much affected by the flow rate and the gas composition of the CO-CO2 reactant gas mixture. The ratio of the gas consumed by the reaction to the total quantity of the supplied gas is very large under the present experi~nental conditions. 3) There is a concentration gradient of' carbon dioxide in the vicinity of the reaction surface and the content of CO, becomes extremely small at the reaction surface. 4) A large time fluc-tuation of the gas composition was observed. This jluctuation implies the presence of unstable flow in the gas phase in the vicinity of the reaction surface. THE decarburization of molten steel by an oxidizing gas or by slag may be one of the most important chemical reactions in steelmaking processes. Nevertheless, the kinetics of this heterogeneous chemical reaction do not seem to be well-solved even with the previous studies. Although the conditions for the reaction in steelmaking processes are quite different from those in the laboratory scale, some critical experiments may give information on the mechanism of the decarburization. From the previous work,'-' it is known that the rate of the decarburization is independent of the carbon content in liquid iron with more than about 0.2 wt pct C when the oxidizing gases are supplied to the surface of liquid Fe-C alloys on a laboratory scale. Two rate-controlling steps have been proposed for the decarburization of liquid iron with the high carbon content: one is the surface reaction control proposed by Swisher and Turkdogan;' the other is that the rate is controlled by the gaseous diffusion through the gaseous stagnant layer. proposed by Baker. Warner, and Jenkins.7 and also by .Ito and Sano.2 In the present study, some experiments have been carried out for the evaluation of these rate-controlling steps in the decarburization of liquid iron with high carbon content. The apparent rate of decarburization of liquid iron has been compared with the rates of carbon removal of liquid Ni-C, Co-C, and solid graphite under the same experimental conditions. The composition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells. I) EXPERIMENTAL PROCEDURE Fig. 1 shows the schematic diagram of the reaction chamber. Solid graphite and liquid metals were contained in an alumina or magnesia crucible of 32 mm ID and 35 mm in height. The samples were heated by high-frequency induction and the temperature was measured by the calibrated optical pyrometer. The temperature was held constant to within 10°C. The re-actant gases were supplied to the surface of the samples through the quartz tube of 8.0 mm ID. The distance from the end of the quartz tube to the surface was 20 mm. The block of high-purity graphite was cut and shaped to the inner profile of the crucible. The height of the shaped graphite was 18 mm, which corresponded to the depth of the liquid iron of 100 g. About 100 g of Fe-C alloy (4.20 to 4.40 pct C), Ni-C alloy (1.84 pct C), Co-C alloy (1.85 pct C), and Fe-C-s alloy (4.35 pct c, 0.5 or 1.0 pct S) were melted in the crucible. The reactant gases were pure CO, and gas mixtures of CO-CO,: the flow rates were controlled by capillary flowmeters with bleeders.

Jan 1, 1970

By C. D. Starr

IT is well known that the martensite reaction can be induced to occur isothermally above the M, temperature by plastic deformation of an alloy in its austenitic state, and also that as the test temperature is increased above the M. temperature, plastic deformation under a given set of conditions merely causes additional slip with a corresponding tendency toward the formation of less martensite per unit of strain. Thus it appears that a maximum temperature exists above which martensite cannot be formed isothermally by plastic deformation. This temperature is commonly designated as the equilibrium temperature Te. Attempts to determine experimentally the equilibrium temperature have indicated that a critical temperature is observed, under a given set of conditions, above which martensite cannot be formed isothermally by plastic deformation. But the observation of a "so called" critical temperature, Te, should not be confused with the equilibrium temperature, Te. In order to clarify this anomaly, true stress-strain curves were obtained for a series of type 304 stainless steel specimens (manufacturer's analysis, 0.08 pct C, 18 to 20 pct Cr, 8 to 10 pct Ni, balance Fe) over the temperature range 67" to 300°K.' Since martensite is magnetic, a quantitative measure of the amount of martensite that was produced by plastic deformation was obtained by determining the magnetic permeability as a function of strain. The results of these tests are given in Fig. 1. They appear to indicate that a plastic critical point does exist at about 240°K for the stainless steel under investigation here. But that 240 °K is not the equilibrium temperature nor even a true plastic critical temperature can be seen from Fig. 2 wherein the permeability of the same material is shown to increase with cold rolling at 293 OK. Consequently the observation of a "so called" plastic critical temperature is dependent on the mode of deformation and has no theoretical significance. Acknowledgment This work was sponsored by the Office of Naval Research. Permission to publish this note is gratefully acknowledged.

Jan 1, 1954

By J. C. METCALF

MORE than 80 per cent. of the iron produced in the United States and over 30 per cent. of the world's annual production is obtained in the Lake Superior district. Though iron ore was discovered on the Marquette range in 1844, the poor transportation facilities retarded the development of this region for many years. The structure of the Lake Superior basin is essentially an east-west synclinorium with steep dips on the south side of the lake and considerably flatter ones on the north and west. The Upper Huronian series, which -is the iron-bearing one of the formation, on the south side of the lake dips north from 55' to 80°, and on the north side dips south from 8" to 200. The series has been subjected to local folding and faulting, which have influenced the development of the mining systems used.

Jan 1, 1921

By Waldemar Lindgren

Discussion of the paper of WALDEMAR LINDGREN and CLYDE P. Ross, presented at the New York meeting, February, 1916, and printed in Bulletin No. 106, October, 1915, pp. 2171 to 2190. WALDEMAR LINDGREN, Boston, Mass.-I happened to go down to Cuba rather unexpectedly in the winter of 1914, and spent a few very interesting days at Daiquiri and Mayari. To C. F. Rand and his associates I am greatly indebted for permission to visit the mines and for many courtesies received. A few months after that, I met Professor Kemp who informed me that he had just returned from a geological study of Daiquiri. We talked over what to do in a case like that. We both liked to publish our opinions, and so finally agreed to write two papers entirely separately, I not knowing any of Professor Kemp's conclusions,1 and vice versa. We were rather interested in seeing what would happen. Of course, as might be expected, we disagreed on some points; not, of course, that we ordinarily disagree, but simply because when two men work in the same field and with different ideas, probably they are apt to vary slightly in their conclusions. Some years ago A. C. Spencer went down there for the military interim government and published the results of his study. His view of the origin of the deposit differed from that of Professor Kemp and from mine. So here are three different results obtained by three different geologists. Such differences in opinion on obscure subjects sometimes tend to bring geology into disrepute. It is perhaps not surprising that different opinions have been expressed, for this occurrence of iron ore is one of the most difficult to explain that I have ever seen. MAX ROESLER, Great Neck, L. I.-I had the opportunity this summer of spending about two months down at the Juragua deposits, and studied them with the idea of writing a paper on them, which I hope will come out later. The interpretation of the occurrence at Ocania Mine is the thing which particularly struck me, in the last paper. At the Ocania Mine we may have these large blocks of limestone which have been utterly and entirely altered, to a remarkable extent.

Jan 5, 1916

By Paul E. Rosten

Introduction This papers describes some of the latest improvements that have been incorporated or planned by the Cleveland-Cliffs Iron Co. to reduce operating costs and improve pellet quality. The Cleveland-Cliffs Iron Co. operates and manages mining, beneficiation, and pelletizing operations in Michigan, Canada, and western Australia. This paper deals with the grate-kiln pelletizing operations at Republic, Humboldt, Tilden, Empire, and Pioneer in Michigan, and the Adams and Sherman in Ontario, Canada. Table I characterizes each operation in regard to location, ore type, pellet capacity and date that pellets were first produced. All of the operations with the exception of Pioneer and Tilden, utilize downdraft-two-pass grate cycles of drying followed by preheating. Pioneer utilizes an all-downdraft, three-pass grate cycle which consists of three drying zones followed by the preheat zone. The Pioneer and Tilden cycles have been described previously (Lindroos and Koski, 1966; Villar and Dawe, 1975; Koski, 1977). Tilden utilizes a three-pass grate cycle with a stage of updraft drying, followed by two downdraft drying stages. Recuperation systems which supply hot gases to a drying zone from second stage cooling were designed and fur¬nished for Tilden I. Tilden II will be identical. Empire IV will also be furnished with a recuperation system. The Adams grate¬kiln system was retrofitted with a recuperation system. This paper will summarize some of the efforts that are in effect or planned for grate-kiln pelletizing systems to: (1) reduce operating and maintenance costs, (2) reduce energy requirements, (3) improve product quality, and (4) meet environmental standards.

Jan 1, 1981

By D. E. Mikkola, G. E. Poquette

X-ray diffraction was used to study the growth of antiphase domains in quenched (or "disordered&apos;? Cu3Au annealed in the range 300" to 385°C. Measurements of the long-range order parameter indicate that a high degree of order is established rapidly at these annealing temperatures. Average domain sizes obtained by Fourier analysis of the superlattice peak profiles show that antiphase domain growth is analogous to classical metallurgical grain growth (i.e.,fol-lows a D2 US kt relation). The activation energy for the growth process, 44 kcal per mole, indicates diffusion control. The anisotropy in the observed effective domain sizes from seven different superlattice peaks can be best accounted for by a configuration involving antiphase domain boundaries on {100 } and (111 ) planes, where the (100) boundary is the low-energy type, {lOO} Type I. The disappearance of the (111) antiphase domain boundary during domain growth is dif-fusion-controlled with an activation energy of 48.5 kcal per mole. On the other hand, the behavior of the parameter representing the amount of (100) Type I boundary indicates that there may be a conversion of the higher-energy boundary types to (100) Type I boundary during the growth process. THE order-disorder transformation in the alloy Cu3Au has been the subject of numerous experimental investigations over the past 40 years, most of which have involved measurements of convenient physical properties such as resistivity and hardness as a function of heat treatment. The interpretation of these data is difficult because measurements of this type have the disadvantage that they yield total changes resulting from several different atomic processes which may be occurring simultaneously. The present study was undertaken to establish by means of X-ray diffraction the kinetic behavior of one of these atomic processes, namely antiphase domain growth. In the completely ordered state Cu3Au has an L12 structure which can be described as an fcc type arrangement of atoms in which the gold atoms occupy the corner sites and copper atoms the face-centered sites. Three other equivalent unit cells can be formed by allowing two gold atoms to occupy opposite face-centered sites and copper atoms to occupy the remaining corner and face-centered sites. These four different unit cells are crystallographically related by a shift of 1/2<110>. Quenching from above the critical temperature (392°C) to room temperature retains the "disordered" structure-a "random" arrangement of copper and gold atoms having the fcc structure. Annealing the disordered alloy below the critical temperature causes ordering to occur through the nucleation and growth of ordered regions at different points throughout the crystal. These small ordered regions, each based on one of the four types of unit cell, grow by consuming the disordered material until they impinge to form a domain structure in which the domains are antiphase by a shift of 4(110). The boundaries between domains are called antiphase domain boundaries (APDB) and they have been found to lie primarily on &apos; {100} planes in highly ordered Cu3Au. Two types of APDB can occur on ( 100) planes. An example of an (001)1/2[110] shear type APDB is shown in Fig. I. Because of the layer of copper atoms separating the domains in this case, there are no near-neighbor violations across the boundary and it has a low surface ener This type of APDB will be referred to as {lOO} Type I. Fig. 2 shows an (001): [011] climb type APDB, (100) Type 11. This type of APDB can be described as resulting from removal of a (200) plane followed by a shift of 1/2<110> to bring the separated regions together. Near-neighbor violations across (100) Type I1 APDB make it a high-energy boundary. There are numerous other possible APDB configurations; however, it is only worth noting that shear type APDB can be produced on the (111) plane by motion of a normal fcc dislocation with Burgers vector 1/2<110> through the ordered structure. A (111); [110] shear type APDB is shown in Fig. 3. Again, because of the near-neighbor violations this type of APDB has a higher energy than the (100) Type I APDB.

Jan 1, 1970

By W. Evans, C. E. Ells

The agglomeration of hydrogen in pure aluminum and A1-Mg alloys has been studied through use of hydrogen introduced into the metal by cyclotron proton irradiation. Both the growth and dispersal of the agglomerates have been followed by metal-lographic techniques. During the cyclotron irradiation, agglomeration occurs at temperatures i 100°C for hydrogen concentrations as low as 1 ppm. On heating at elevated temperatures, 300°C to 600°C, intragranular agglomerates first coarsen and then disperse. The agglomerates formed at grain boundaries are much larger than the intragranular agglomerates; with hydrogen concentra- tions > 10 PPm, heating for 1 hr at 500°C results in extensive grain-boundary cracking. The hydrogen agglomerates have been shown to inhibit grain growth, but no inhibition of recrystallization has been observed. The ability of hydrogen to enter aluminum at a free surface, combined with its high-diffusion rate at elevated temperatures, accounts both for growth and dispersal of the agglomerates. Irradiations at elevated temperatures give results consistent with the explanation proposed for agglomerate behavior on post-irradiation heating. 1 HE formation of hydrogen-filled bubbles, or blisters. in aluminum and its alloys has been studied for over&apos; thirty years. The work up to 1952 has been reviewed by Kostron&apos; and since then Ransley and

Jan 1, 1963

By R. D. Nelson, D. H. Polonis

ThE eutectoid decomposition of 6 phase in the Cu-Sn system (32.53 wt pct Sn) has been studied by several investigators.1-6 On the basis of X-ray work, Iball and 0wen1 reported complete decomposition of 6 in powder specimens after 7 days at 300°C. Wang and Hansen followed the micro-structural changes during heat treatment of lump specimens and estimated 5 pct decomposition after 63 days at 300°C. Wang and Hansen suggested that the discrepancy between the decomposition rates of powder and lump specimens might be due to the excess surface free energy of powders. The present work involved 6 decomposition in copper-tin alloy powders containing 32.6 wt pct Sn. Alloy lump specimens exhibited entirely 6 phase after fairly slow cooling (air cooling) from above 350°C and were so brittle that they could be easily crushed to-200 mesh in a percussion mortar. X-ray diffraction study of the as-crushed powders (-200 mesh) revealed 100 pct 6 phase with very slight line broadening effects due to strain introduced by crushing. Only 6 phase was detected by X-ray diffraction in powders which were heat treated 4 hr at 450°C and air cooled to room tem-

Jan 1, 1960

By Paul C. Merritt

Chrysotile asbestos producers in Quebec may soon experience a unique situation-i.e., strong competition from American ore sources for the short fiber market west of the Mississippi River. This com- petition will be forthcoming from Copperopolis and Coalinga, two deposits now being developed on opposite flanks of the San Joaquin Valley in central California. The combined output now planned from both deposits is 100,000 tons annually, equivalent to about 50% of the annual market demand in the western, central and Gulf States, and more than twice the tonnage sold in 1960 by all other American asbestos producers combined. The principal companies involved in these new undertakings are Jefferson Lake Asbestos Corp. (subsidiary of Jefferson Lake Sulphur Co.), Hidden Splendor Mining Co., Coalinga Asbestos Co. (Johns- Manville Corp. in conjunction with Kern County Land Co.), Union Carbide Corp., and Asbestos Corp. Ltd. Jefferson Lake&apos;s principal interest is at Copperopolis where the company&apos;s new 70,000-ton per yr mill recently went on stream. The company also holds some claims at Coalinga, but this latter area is better known as the site where Hidden Splendor, Coalinga Asbestos Co. and Todd Industries (a local company) have established operating mines and mills capable of turning out 30,000 tons of fiber each year. Coalinga is also the site of exploration by Union Carbide Nuclear and Asbestos Corp. Ltd.

Jan 9, 1962