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By O. F. Kammerer, W. E. Miller, D. H. Gurinsky, J. Sadofsky, J. R. Weeks

Zirconium and titanium inhibit solution mass transfer of steels by liquid bismuth, mercury, and lead. It is shown that in bismuth and mercury, these adsorb on the surface of the steels and subsequently react with nitrogen and possibly carbon from the steels to form inert, adherent surface layers of ZrN, TiN, or TiN + Tic. Data are presented which describe the condition under which thase deposits form. These inhibitors decrease the solution rate of iron into bismuth, and require a higher supersaturation for precipitation of iron from bismuth. USE of the low-melting heavy metals (bismuth, lead, mercury, and their alloys) as coolants has been limited because solution mass transfer of steels occurs in these liquids; i. e., iron dissolves in the hot sections of the heat transfer circuit and deposits in the colder sections. The rate of solution of iron and the temperature coefficient of solubility are sufficiently great to cause complete or partial stoppage by the deposition in the coldest section of a closed circuit in finite time, even though the actual solubilities are extremely low. In the development of the mercury vapor turbine by the General Electric Co., Nerad and his associates1 discovered that the addition of as little as 1 ppm Ti or Zr to magnesium-deoxidized mercury reduced the mass transfer of ferrous alloys by mercury to a negligible amount. Reid2 reported that titanium was detected chemically on the surface of steels contacted with this mercury alloy in amounts varying from 2.0 to 2.6 mg per sq in., the greatest amount being found in the hottest portion of the circuit. Reid stated that the titanium forms the intermetallic compound Fe2Ti by reaction with iron on the surface of the steels. This compound was presumed to be highly insoluble in mercury. More recently, El-gert and Egan3 have reported a greater than 100-fold reduction in the rate of mass transfer of a 5 pet Cr steel by liquid bismuth upon the addition of titanium (in excess of 50 ppm) and magnesium (350 ppm) in the liquid metal, during experiments performed in thermal convection loops* over the temperature differential 700° to 615° C. Also, Shep-ard and his associates' have reported that the addition of titanium to liquid bismuth and Pb-Bi eutec-tic produced a marked decrease in the rates of solution of both iron and chromium from type 410 steel capsules under static conditions. This inhibiting effect increased with repeated reuse of the capsules. Tests performed in this laboratory under carefully controlled conditions have shown that the addition of zirconium and magnesium, or titanium and magnesium, to liquid bismuth or lead greatly reduces the rate of mass transfer of chromium alloy steels and carbon steels in thermal convection loops with a maximum temperature of 550°C.5-9 The present paper will review the data obtained to date at this laboratory on the behavior of iron and steels in contact with liquid bismuth alloys containing titanium or zirconium, and will attempt to explain the role of the above additives in reducing solution mass transfer. Reaction between the Zirconium or Titanium Dissolved In Liquid Bismuth and an Iron or Steel Surface Reaction between Zirconium Dissolved in Bismuth and the Surface of Pure Iron-—A small pure iron crucible (analyzed by the supplier to contain 0.8 ppm N was contacted with bismuth containing approximately 0.1 pet Mg and varying amounts of a radioactive zirconium tracer. The crucible was then inverted at the temperature of contact. The thin residual layer of adherent bismuth was dissolved in cold, concentrated nitric acid. The crucible surface and the solidified bismuth were then analyzed for radioactive zirconium. An analysis of the activity loss on the crucible surface and the weight loss of the crucible during the nitric acid treatment showed that the acid treatment removed the zirconium that had originally been dissolved in the adherent bismuth, but not any zirconium that may have reacted with the crucible surface. The crucible was then pickled in warm aqua regia to remove all surface activity, hydrogen-fired at 600°C, and recontacted with a new liquid alloy. The results of the experiments contacted 1 hr at 450°C show, Fig. 1, a Langmuir-type adsorption with an adsorption free energy of approximately 17 keal per g atom Zr.5 This deposit was estimated to contain 1 atom of zirconium for each 7 to 8 iron atoms on the crucible surface, assuming a surface roughness factor of the pickled crucibles to be five. Increasing the temperature to 520°C caused consi-

Jan 1, 1959

By L. R. Shoenberger

Boron has been used to produce nonaging low-carbon sheet steel. Retention of the necessary minimum amount of about 0.006 pet partially killed the steel. Amounts exceeding about 0.012 pet increased the degree of deoxidotion, piping tendencies, and possibility of hot tearing in primary rolling. Semikilled practice resulted in good ingot yields and satisfactory surface quality. Aluminum added with the boron provided a protective de-oxidizer. Good drawobility was indicated by performances of the steel in a limited number of deep-drawing trials. Some problems with hot-tearing and boron-analysis procedures were overcome. Metal lographically, the boron semikilled steels revealed some structures not usually found in plain low-carbon steels. IN 1943 Low and Gensamer1 reported that strain aging, which hardens and embrittles ordinary low-carbon rimmed steel, was due to nitrogen and carbon, and that oxygen played a relatively unimportant role. Since then, many investigators have substantiated their findings and indicated that nitrogen is particularly potent. Commercially, today's most widely produced non-aging sheet steels for deep drawing are either aluminum killed or vanadium rimmed types. The difference in deoxidation practice, alone, is evidence that oxygen is apparently not an important consideration in control of strain aging. The fact that nitrogen is important is apparent in the consideration that has been given, knowingly or unknowingly, to the amount combined with aluminum and vanadium. Patents were granted to Hayes and Griffis2 for the processing of aluminum-killed steel, and to Epstein" for the manufacture of vanadium rimmed material. Certain prescribed steps in producing these steels can be correlated with the formation of the respective nitrides within certain temperature ranges below the usual hot-finishing temperatures. The potential nonaging properties of either type can be reduced or suppressed by cooling too rapidly to permit the aluminum or vanadium to combine with nitrogen. Subsequent suberitical annealing of the cold-rolled strip, however, normally forms the nitrides and produces the resistance to strain aging. Titanium-killed nonaging steel, described by Comstock,1 forms a nitride in the molten state and is essentially nonaging throughout its processing. Zirconium-killed steel, which was investigated briefly by the author,* appeared to have similar nitride- forming characteristics. It is known" that chromium can produce nonaging rimmed steel, but relatively little is known of the potentialities of some of the other nitride-forming elements such as boron, silicon, columbium, and cerium. In attempting to develop a new nonaging cold-rolled sheet steel with good drawability, the following factors were considered pertinent. Such a steel would necessarily have a low carbon content and therefore have a relatively high degree of oxidation when made in a basic open-hearth furnace. If the denitriding element were also a deoxidizer, a part of the addition would be lost as oxide. The degree of deoxidation would determine whether the steel is rimmed, semikilled or killed, and also could be expected to have an important bearing on ingot yields and ultimate surface quality. Assuming that the pattern for the production of cold-rolled sheets would not be changed to any great extent, the nitride must form in the molten steel, in hot rolling, in subsequent cooling, or in annealing. The nitride, once formed, should resist dissociation and be stable in the final product. Usually an excess of the nitride-forming element is required to combine with sufficient nitrogen. If the element used is a strong ferrite strengthener, a small excess may markedly decrease drawability. With aluminum and vanadium, about 0.03 to 0.05 pct in the steel is preferred. Epstein has said" that about 0.30 pct chromium is required. Titanium nonaging steels are hard unless a sufficient amount (about 0.30 pct) is added also to combine with the carbon. The cost of the necessary amounts of these latter two elements discourages commercial acceptance. Silicon was considered as a possible nitride former, but since amounts up to 0.10 pct in rimmed and semikilled steels do not induce marked resistance to strain aging, larger amounts are apparently required, which would tend to harden and strengthen the ferrite. Of the other elements mentioned, all but boron are expensive heavy-metal elements. Stoichi-ometrically, almost an equal weight of boron would be required to combine with the nitrogen—-ordinarily about 0.003 to 0.006 pct in scrap-practice open-hearth steels. Boron is a slightly stronger deoxidizer than carbon but is less powerful than zirconium, aluminum, or titanium. Thus a rimmed-steel practice might be possible. There is much in the technical literature concerning the hardenability effects of minute amounts of boron in killed steels but very little about its behavior in low-carbon material—particularly as a ferrite strengthener. The available data indicated a need for better information concerning the effects of boron in low-carbon strip steels. Experimental Work Development of a Boron-Treated Nonaging Strip Steel—Initial attempts to produce a boron-rimmed strip steel employed 3-ton basic open-hearth heats which could be teemed into molds large enough to sustain a normal rimming action. Boron as ferro-boron was added to the ladle in small amounts because of the reported hot-short character of aluminum-killed heat-treating grades containing more than about 0.005 pct boron. Actually, the amounts used, i.e., 1/8 and 1/4 lb per ton, would be large for

Jan 1, 1959

By J. F. Martin, J. E. Friedline, L. M. Melnick, G. E. Pellissier

A method has been developed for determining gases in steel in which the gases are extracted by vacuum fusion and analyzed by mass spectrometry. This method is especially applicable for determining small amounts of oxygen and nitrogen. The lower limit of detection for both oxygen and nitrogen is 0.0001 pct with an average deviation of about 0.0001 pct for oxygen and 0.00008 pct for nitrogen. Hydrogen analyses by this method are in good agreement with analyses by vacuum tin-fusion. A complete analysis of all gases extracted from a steel sample can be accomplished in 40 min. It has long been known that certain of the gaseous elements exert particular effects on the physical and mechanical properties of steel. With the recent advent of new experimental steelmaking practices it is now possible to obtain steels with extremely low contents of such elements as oxygen and nitrogen. Present methods for determining these two gases are of insufficient sensitivity as applied to steels made by these newer practices, and therefore a new technique was considered necessary. A review of the literature showed that the conventional vacuum-fusion method1 was the procedure most suitable for modification to obtain a sensitive method for determining the gaseous elements present in steel simultaneously. However, for trace amounts of gases it is impractical to increase the sample size because of the physical limitations of the apparatus and the increased degassing time which would be necessary. Also, when only one of the desired gases is present in trace amounts, quantitative separation by conventional vacuum fusion is almost impossible. Since small analytical mass spectrometers are now commercially available, it was decided to use this instrument in conjunction with conventional vacuum fusion for both qualitative examination and quantitative determinations of the gaseous elements in steel. This technique has already been used with success for the analysis of copper and lanthanum.2"4 APPARATUS A vacuum-fusion unit was first designed and built, Fig. 1. This unit was designed especially for the determination of small amounts of nitrogen and/or oxygen in steel since an acceptable method (vacuum tin-fusion)5 was already in use for the determination of hydrogen in steel. The vacuum system was con- structed of Pyrex glass throughout. Mercury check valves were used in place of stopcocks in the high-vacuum section of the system. Ferromagnetic samples are normally introduced into the vacuum system through a mercury lift. In case of a break in the lift, the mercury is prevented from entering the furnace by a self-locking, mercury safety check valve, Fig. 2. This check valve, developed at our laboratory, is a modified T/S ball-and-socket joint placed in the sample inlet system between the mercury and the furnace. A sudden entry of mercury or air pushes this valve into the closed position, completely blocking the top of the mercury lift. The check valve is held in the closed position by the vacuum of the apparatus. A separate entrance tube also was placed in the system, so that samples which would amalgamate with mercury, or which are nonmagnetic, could be introduced into the furnace. A slightly modified Guldner-Beach furnace is used in this system.8 The optical flat was connected to the system by a ground-glass joint to facilitate cleaning, a quartz delivery tube was substituted for Pyrex, and the crucible was used uncovered. Fusion takes place in a high-purity graphite crucible insulated by — 200-mesh high-purity graphite powder. The crucible set (crucible and funnel) is suspended in a quartz crucible. The furnace envelope and the sample inlet system are exhausted by 2 single-stage, mercury-diffusion pumps in series. The first of these is a high-speed pump, which will work only with a very low backing pressure. This pump is used to exhaust the gases from the furnace as rapidly as possible. The second mercury-diffusion pump is used as a backing pump for the first; the capacity of this pump is much lower. However, it will work efficiently against a back pressure of 3 mm of mercury. To assure positive pumping, a modified Naughton and Uhlig condenser7 is used. With the use of proper valving the second pump is also used as a circulation pump in the catalyst system.

Jan 1, 1959

By J. Chipman, N. J. Grant, H. L. Bishop

Lime and dicalcium-silicate crucibles were equilibrated with molten iron and liquid slags containing iron oxide and small amounts of sulfur. The oxygen content of metal, iron oxide activities, and desulfurization values of the slags were determined in the temperature range 1530 to 1700°C. The influence of magnesia in the slag and the temperature dependence of the solubility of lime in liquid iron oxide and the ferric oxide content were established. The temperature contour of the liquidus surface of iron-silicate slags saturated with lime and dicalcium silicate was also established at 1600°C. THE importance of the role that slag composition plays in the refining of steel has been known for many years. Numerous studies have been made using actual plant data in order to establish the relationship between the composition of the slag and metal during the refining of a heat of liquid steel. These results rarely represent equilibrium conditions since completion of the various chemical reactions involved in steelmaking is seldom realized. In order to establish quantitatively the equilibrium conditions existing between the slag and metal, several laboratory studies have been conducted in the past 20 years to determine the reactions important in slag control. These investigations have included studies of simple liquid basic and acid slags as well as more complex slag systems which approach those commonly found during the refining of a heat of steel. Since most of the previous studies of simple basic iron-oxide slags equilibriated with molten iron were made in magnesia crucibles, it was not possible to establish the distribution of sulfur and oxygen between molten iron and slags consisting only of the three essential components, lime, silica, and iron oxide. This investigation was undertaken to establish the equilibrium conditions for simple lime-iron oxide and lime-silica-iron oxide slags. Accordingly, it was expedient to prepare crucibles both of lime and dicalcium silicate to establish the equilibrium conditions between molten iron and iron-oxide slags saturated with the refractory materials and free from other components. The only other studies of the equilibrium between molten iron and lime-saturated slags are those of Fischer and vom Ende, 1, 2 in which the solubility of oxygen was determined in an air atmosphere. The

Jan 1, 1959

By F. C. Langenberg, J. Chipman

Jan 1, 1959

By C. Crussard, R. Tamhankar

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

Jan 1, 1959

By N. A. Gokcen

The construction and operation of a simple and accurate vacuum-fusion apparatus are described in detail. Absolute accuracy of the oxygen analysis has been determined by the reduction of oxides weighed to 20.01 mg. The Bureau of Standards steel samples have been analyzed repeatedly, and their inadequacy for the acceptable range of oxygen is presented. The limits of interference of manganese, aluminum, and titanium, and the effects of tin and water-cooling of the furnace tube have been investigated in detail. ANALYSIS by the vacuum-fusion method consists of melting a sample in a degassed graphite crucible under high vacuum and extracting oxygen as carbon monoxide, and nitrogen and hydrogen as gaseous elements. The resulting gas mixture is analyzed for its constituents, from which oxygen, nitrogen, and frequently hydrogen may be determined within 1/2 hr or less. The history and summary of methods1-4 and extensive reviews of literature'.' for the determination of gases in metals have been published in detail. The foundation of the modern vacuum-fusion method of analysis was laid by Jordan and Eckman,11 and Oberhoffer and his associates.1, 10 Diergarten,11, 12 Meyer,13 Thanheiser et al.,14, 15 Ericson and Benedicks,16 Ziegler,17, 18 Sloman,16-23 Thompson et al.,24 and later many others contributed to the improvement, accuracy, and limitations of the method. In some investigations, however, the limitations of the procedure and the errors involved in the analysis require further critical examination and evaluation. In many apparatuses, lunnecessarily complicated and cumbersome features and elaborate precautionary measures do not have conclusive advantages. The purpose of this invest:igation was, therefore, a) to construct a very simple and accurate apparatus, b) to determine the absolute accuracy of results, c) to establish the limits of interference of manganese. aluminum, and titanium, d) to reexamine critically the reduction and recovery of oxygen from oxide powders of various sizes, and e) to evaluate critically the eight steels of the Bureau of Standards."' Apparatus The apparatus used in this investigation is shown in Fig. 1. It has been used for over three years, during which several modifications were made. A brief description of the apparatus is as follows. The transparent silica or Vycor tube, E, is joined to the Pyrex head, B, by mean of a face to face ground joint sealed with mercury. A similarly sealed ball and socket joint would also have been satisfactory. A standard tapered ground joint, successfully used by some investigators, was tried, but in the absence of grease or vacuum cement it was very difficult to disassemble the joint. The graphite crucible, G, 15/16 or l 1/8 in. OD, 2 1/2 or 3 in. high, 1/10 in. wall, shown enlarged in Fig. 3a, is made from the rods containing less than 0.08 pet ash. Two baffles, overlapping sufficiently to prevent spattering, are inserted in two opposite slots cut on a band saw. Two small holes in the baffles permit the temperature measurement of the melt. A second type of crucible, Fig. 2, G, shown enlarged in Fig. 3b, is also satisfactory, though not as convenient as the crucible shown in Fig. 3a. Somewhat similar but more elaborate crucibles with baffles were first tried by Ericson and Benedicks,'" but were abandoned in favor of a crucible with a stopper and a peripheral graphite powder filter. Various versions of their crucible with a stopper have later been used by other analysts, 10-27, 27-30 The crucible is packed directly in E, Figs. 1 and 2, with —35 + 48 graphite powder for shielding and insulation. A minimum layer of 7 mm of powder is necessary for keeping E cool and minimizing the blank. The first use of graphite powder was made by Sloman,10-23 Who found that —200 mesh was the most satisfactory. The author tried various size powders from +20 to —100 mesh and found that a) particles of 28 mesh or larger were not sufficiently insulating and were heated by the induction current, b) the powder finer than 60 mesh packed too much and did not readily permit the escape of gases even when the crucible was heated very slowly; hence, the powder was occasionally blown out of the side in the crucible and in the mercury pump. The optimum size powder is, therefore, 35 to 48 mesh size or 0.4 mm in average diameter. The furnace is designed to eliminate excessive amounts of

Jan 1, 1959

By R. N. Edmondson, L. Mair, M. Tenenbaum

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Dr. Gerhord Derge; Editorial Assistant, M. A. Redmyrski; Staff Coordinator, James J. Burke. THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chipmon, Vice President; T. D. Jones, Treosurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. w. Thornton, Chairman; Dennis Carney, John Chipman, J. C. Fulton I. H. Hollomon H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supenision of the following Publications Committees: Extractive Metallurgy Division: T. 0. King Chairman; S. J. Dickenson, R. P. Hermsdorf R. Schuhmann. Jr.. and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman F. Lincoln Vogel Jr., Vice-chairman, W. A. Baikofen, R. W. Boliuffi J. H. Bechtold M. B. Beyer. R S. Busk, C. G. Gaetzel, Paul Gordon C. D. Groham, Jr., Robert F. Hehe-mann,' R. I. Joffee, F. c. Joumot Jr lrving R. Kramer A. J. Lena Harold Morglin, C. J. McHargue, Russell A: Meussner, J. B. Newkirk H. W. Paxton, G. E. Pellissier, I. S, Servi, Alon U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B King, F. C. Langenberg, W. 0.. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining Metallurgical and Petroleum Engineers Inc., 29 West 39th Street, New York 18, N. Y. Telephon: pEnnsvlvanio 6-9220. Subscription 522 Per year for non-AIME members in United States and North South and Central America; $25 foreign;, $5 for AIME members. Single copies, 54.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed In its publications . . . Copyright 1958 by the American lnstltute of Mining Metallurgical and Petroleum Engineers Inc. . . . Registered cable address AIME New York , . . lndexed in Engineering Index Industrial Arts Index and Chemical Abstrats . . . Application for second class mail privileges ii pending at New York, N. Y. Volume 212, Number 4.

Jan 1, 1959

By W. Rostoker, A. Siede

THE venerable problem of hydrogen embrittlement of ferritic iron lacks as yet a complete explanation. Possibly part of the difficulty has been the exclusive preoccupation with the total ductility prior to fracture. In the past few years it has been noted at least twice1,2 that hydrogen charged into iron has the ability to depress the upper yield point and, at room temperature, to eliminate completely the discontinuous yield phenomenon. Cracknell and Petchl rationalize that the depression of the yield stress is an example of the behavior of inhomogeneous stresses. Their explanation requires that microcracks exist in the annealed metal, and that hydrogen collect in these cavities under high hydrostatic pressure. The hydrostatic pressure of hydrogen generates localized tensile stresses in the iron which, with external loading, reach the critical stress for yield prematurely. The local plastic zones will spread across the specimen before the Lüders bands can be generated, and the yield-point elongation phenomenon is eliminated. This viewpoint will be discussed in succeeding paragraphs. Rogers,2 on the other hand, represents the depression of the initial flow stress as a result of the interaction of hydrogen with dislocations. He submits two alternative modes of interaction. In the

Jan 1, 1959

By S. R. Seagle, R. Schuhmann, N. A. Parlee

Rates of CO evolution and CO absorption were measured for liquid-iron alloys containing from 0.15 to 4.4 pet C, using a modified Sieverts apparatus. The alloys were held in alumina crucibles, so that both crucible-metal and gas-metal reactions occurred simultaneously. The data are interpreted on the hypothesis that the C-O reaction rate is controlled by oxygen diffusion across the boundary layers at the gas-metal and crucible-metal surfaces. CARBON-monoxide evolution from liquid Fe-C-0 alloys is a key reaction in steelmaking processes, both in the steelmaking furnace and in the ingot mold. Also, this reaction probably is an essential step in the desulfurization of iron under blast-furnace conditions, for which carbon is the principal reducing agent or deoxidizer present in the iron. The thermodynamic properties of the solutions of C and 0 in Fe and the equilibria of these solutions with gaseous CO and CO, have been investigated in some detail and are reasonably well understood. However, while these equilibrium data have accumulated in the laboratory, other data have accumulated to show that equilibrium conditions are often not achieved under plant operating conditions. Thus, an understanding of the rate and mechanism of the carbon-oxygen reaction not only has theoretical interest, but ultimately may assume considerable practical importance. Reaction Mechanisms and Rate Equations The over-all reaction under consideration is C (in liquid Fe) + 0 (in liquid Fe) + CO (gas) [I] Although this appears to be a straightforward heterogeneous reaction, involving just two phases (liquid metal and gas), a wide variety of reaction mechanisms has been proposed. Different authors have expressed divergent views as to the nature of the rate-controlling steps. Accordingly, a brief discussion of the possible reaction steps will be given. 1) Homogeneous Reaction Within Liquid Iron— Feild' and Jette2 have applied chemical reaction-rate theory as if the C-0 reaction were a homogeneous, second-order reaction occurring within the liquid-metal phase. This mechanism necessarily produces CO "molecules" dissolved in liquid iron. In order to yield CO gas, the dissolved CO must nucleate CO gas bubbles, and the dissolved CO also must be transported to the bubble surface where it enters the gas phase. However, this mechanism is inconsistent with present concepts of the structure of liquid-metal solutions. 2) Reaction at Gas-Metal Interface—At the surface of contact between gas and metal, a second-order reaction between dissolved C and 0 may occur to produce a CO molecule which enters the gas phase. This reaction presumably involves an "activated complex" structure in the interface. Some such surface mechanism appears essential because the carbon and oxygen do not occur in the same species in the two phases and therefore must react in some way at the surface. At liquid-iron temperatures, calculations based on reaction-rate theory indicate that the surface reaction must proceed extremely rapidly and thus cannot be a rate-determining step in the C-O reaction under ordinary conditions.3 ccordingly when the over-all reaction is measurably slow, the surface reaction may be considered at equilibrium; that is Cc* Co* = m'Pco [2] in which Co* and Co* are the concentrations of carbon and oxygen (weight per unit volume of metal), respectively, in the liquid-metal phase at the interface, Poo* is partial pressure of CO in the gas phase at the surface (atmospheres), and m' is the mass-action constant for Reaction [I]. Since activities of C and 0 are not strictly proportional to concentrations, m' is not a true thermodynamic equilibrium constant but varies with carbon content.' 3) Mass Transport—If the reaction is to proceed at the gas-metal surface, as described above, dissolved carbon and oxygen in the liquid iron must come to the surface and gaseous carbon monoxide must move away from the surface. Details of the mass-transport mechanisms depend on the kind of system under consideration. For a stirred metal bath in contact with a CO gas phase, the transport of C and 0 to the surface can be described by 1 Do Mols CO evolved per sec = — 1/16— Do/do Agm (CO-Co*) = 1/12 Do/do Agm *(Co-Co*) [3] In this equation, Do and D, are the diffusion constants for oxygen and carbon in liquid iron, 6, and 6,. are the boundary-layer thicknesses, A,,,, is the

Jan 1, 1959

By R. W. Fountain, J. Chipman

THE solubility of nitrogen in iron and steel has been of considerable interest due to the role of nitrogen in strain-aging and in quench-aging. It is generally considered that quench-aging is the result of precipitation of carbide and nitride particles from supersaturated solid solution, while strain-aging results from the segregation of carbon and nitrogen atoms to dislocations.1-9 The rate of strain-aging is controlled primarily by the amount of carbon and nitrogen in solution and the temperature. In experiments on strain-aging of pure iron with only carbon or nitrogen as impurities, Fast" has shown that even after 40 hr at 50°C carbon did not give any strain-aging while

Jan 1, 1959

By N. Parlee, V. C. Kashyap

The solubilities of nitrogen in liquid iron and liquid Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys were measured by the Sieverts method. Measurements were made at 1600° to 1800°C on binary alloys up to 20 pet Ni, 10 pet V, 10 pet Mo; and on ternary alloys containing 0 to 3 pet V with 0 to 5 pet Mo. The results on liquid iron confirm that Sieverts' law is obeyed in the range 50 to 750 mm pressure. The measured solubilities and their temperature coefficients are in general agreement with other modern authors. The logarithms of the activity coefficients of nitrogen in the binaries are approximately linear functions of the pet of alloying element. A method suggested by Wagner, Chipman, and others for predicting gas solubilities in complex alloys from solubility data on binaries was applied to the Fe-Mo-V alloys. Reasonably good agreement was obtained between calculated and experimental solubilities. NITROGEN'S solubility in liquid iron has been studied by a number of investigators. It is reasonably well established that the solubility of nitrogen follows Sieverts' law at least up to 1 atm partial pressure and that the solubility increases gradually with temperature. The solubility of nitrogen in Fe-X binary liquid systems has been investigated in only a few cases. Only the systems Fe-Cr,3-5, 7 Fe-V,3 Fe-Mn,3, 5 Fe-Ni,3, 5 Fe-Si,B, H Fe-C, L, H and Fe-P4 appear to have received any study. The only work on liquid Fe-V was done by Brick and Creevy.3 This was limited to 13.5 pet and 26.5 pet V, but no exact temperatures were recorded. No work whatsoever appears to have been done on liquid Fe-Mo alloys and even work on Fe-Ni alloys is rather scant. The work on liquid ternary systems is still more limited, and the only publication available appears to be that of Wentrup and Reif,7 who studied the Fe-Cr-Mn and Fe-Cr-Ni alloys. Rassbach, Saunders, and Harbrecht17 have reported work on the solubility of nitrogen in stainless steel but this was not a systematic study of any particular system. Commercial alloys usually contain several alloying elements. Thus, it often becomes important to be able to predict the nitrogen solubility in systems containing two or more added elements without the necessity of making measurements. Wagner,14 Chipman," Darken and Gurry," and Morris and Buehl 14 have suggested means by which this may be accomplished, and Langenberg14 has recently applied one of these methods to nitrogen solubility in complex liquid alloys. This paper reports the results of nitrogen solubility determinations on Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys and compares calculated and experimental solubilities in the ternary alloy. Attempted measurements on Fe-Cr alloys were not successful by the experimental method employed. Experimental Method The general method of solubility measurement was that of Sieverts.' The apparatus and procedure were essentially the same as used by Liang, Bever, and Floe."' The equipment consisted of a small vacuum furnace heated by a 6 kw induction unit, gas measuring apparatus, and a gas purification train. The crucibles used were Norton Alundum with alumina sand around them for insulation. The crucibles were charged with 100 to 200 g of material, about 180 g or nearly filling the crucible being found most satisfactory. Hot volumes were determined with argon and ranged from 95 to 130 cu cm (stp). Temperature measurements were made with a Leeds and Northrup optical pyrometer which was calibrated periodically against the melting point of iron in the same apparatus."-'* Good quality nitrogen, hydrogen, and argon gases were further purified and dried in standard purification trains. The sources of the high purity iron and other alloying elements used were as follows:

Jan 1, 1959

By J. Chipman, N. J. Grant, H. L. Bishop

In a recent review1 of the iron-oxide activity of simple open-hearth type slags containing lime, magnesia, silica, and iron oxide, it was established that activity values were lacking in the range of slag composition most interesting to open-hearth operators. That is, laboratory experimental results were not available for simple slag compositions having basicity ratios ranging from about 1.5 to 4.0 and iron-oxide concentrations ranging from about 10 to 30 pct. However, in order to estimate iron-oxide activities for the range of slag compositions of interest to open-hearth operators, activity values were calculated using ionic concepts of slags by following the treatment of Flood and Grjotheim.2 A study of these data indicated that the desired slag compositions were probably not obtained due to the limited solubility of the basic constituents lime and magnesia. Thus, it was decided to make additional heats equilibrating molten carbon-free iron with slags containing MnO, P2O5, and A12O3 in percentages commonly found in open-hearth refining slags, and to examine the liquid slag field over a greater composition range than that of the simple slags studied previously. The ranges of the constituents used in the present study are summarized as follows: Metal Pct 0 0.070-0.201 PctMn 0.005-0.142 Slag Pet CaO 24.45-41.90 Pct MgO 3.23- 9.21 Pct MnO 1.13- 9.62 Pct FeO 20.08-48.7 Pet Fe2o3 2.23-10.14 Pct SiO, 3.51-28.50 Pct P2O5 0.23- 3.65 Pct A12O3 0.43- 3.38 The experimental procedure consisted of equilibrating the slag and metal in an induction furnace provided with a carbon-arc slag heater as described previously by Winkler and chipman.3 The data obtained were used to establish both the iron-oxide activity values and the activity coefficients for FeO and MnO in the open-hearth type slags. RESULTS AND DISCUSSION I) Iron-Oxide Activity of Open-Hearth Type Slags—The iron-oxide activities of various iron-oxide contents of the open-hearth type slags, as calculated from the oxygen content of the metal by the method of Taylor and Chipman, 4 are plotted against the molar ratio of bases to acids in Fig. 1. The data represent slag-metal studies carried out in the temperature range 1530" to 1700°C. For the purpose of this study, the constituents CaO, MgO, and MnO are assumed equal on a molar basis in their effect on the iron-oxide activity; and, PO2,5 is calculated as an equivalent to SiO2 and A12O3 on a molar basis. The total iron content of the slag is calculated to FeO and is represented by the symbol (FeO) The points presented in Fig. 1 represent the results of this investigation for iron-oxide slags containing between 1 and 8 mol pct MnO and less than about 2 mol pct each of A12o3 and PO2,5 The curved lines shown in Fig. 1 represent the results of the summary1 of the iron-oxide activities of simple slags of the system (CaO + MgO) - SiOz - (FeO),. The solid portions of the curved lines represent experimental data, and the broken portions represent iron-oxide activities calculated from ionic concepts of slags. The iron-oxide values of the open-hearth type slags of this study are in good agreement with the values of the simple iron-oxide slag system. Only a slight modification is indicated. The results of this study suggest that the line for 20 mol pct (FeO), should be lowered slightly in the basicity range 1.5 to about 3.

Jan 1, 1959

By V. F. Zackay, W. A. Goering

ALLOYS of iron and aluminum up to 35 wt pct aluminum are single-phase solid solutions, and are of potentially wide applicability.1-3 In spite of early and continued interest1-4 little progress has been made until recently in the preparation and evaluation of sound alloys containing more than 6 wt pct aluminum. Vacuum-melting techniques for the production of ductile Fe-A1 alloys have been described recently.1-7 A. procedure for air melting these alloys is presented here. Low-carbon iron is induction melted without a slag in a rammed magnesia crucible. At the beginning of melt-down, aluminum pig (99.95 pct Al), charged in a clay-graphite bottom-pouring crucible is placed in a pot furnace at 1800°F. The primary deoxidation of the molten iron after melt-down is effected by the addition of 0.1 pct aluminum and 0.5 pct manganese. (Hilty and Crafts" have reported a significant increase in the deoxidation efficiency of the aluminum and manganese combination over that of the aluminum alone.) A more drastic deoxidation designed to reduce the oxyen content to the lowest possible level is accomplished by plunging metallic calcium to the bottom of the melt. This is done by wiring small cubes of the metal to a steel rod. A circular shield larger than the diameter of the crucible opening is attached to the rod so that any spa'ttering of the molten metal will not endanger the operator. Since the temperature of the molten metal is above the boiling point of calcium, the bath is vigclrously purged by calcium vapor. It is believed that the calcium-vapor treatment permits a homogeneous distribution of calcium in the melt. Owing to the vigor of the reaction the temperature of the molten metal should be kept below 2900°F prior to the calcium addition. A total of 0.05 pct calcium is added in two stages in this manner. The second calcium deoxidation is made just before charging the molten aluminum into the iron, in order that an excess of calcium be present for the remainder of the melt. The aluminum, which has been removed from the holding furnace, is then hydrogen degassed by bubbling chlorine through a quartz tube immersed in the molten aluminum. The hydrogen-chlorine reaction is an exothermic one preventing the solidification of the aluminum during the 5-min chlorination. Approximately 0.1 pct calcium, based on the amount of aluminum, is then added to the aluminum. A further excess of calcium is introduced into the melt in this manner. The oxide dross is removed, fluorspar is added to the molten iron, and the molten aluminum is poured through the fluorspar slag. The fluorspar should be dried thoroughly prior to its use, as any water present will react with the aluminum. Aluminum oxide formed during the pouring operation reacts with the fluorspar slag to form gaseous aluminum fluoride and calcium oxide. A forced-draft ventilating system is required for this operation as aluminum fluoride is toxic. As soon as the molten aluminum has been added, vigorous manual stirring of the melt is required because the slag-aluminum oxide reaction is highly exothermic and tends to take place near the top of the melt. The combination of high temperature and the slagging action of the fluorspar quickly erodes the crucible at the slag line if the aluminum is not stirred uniformly into the melt. It has been found that at least 4 min of manual stirring combined with induction stirring are necessary to ensure homogeneity. The power is shut off 1 min prior to pouring to allow metal and slag to separate. As much slag as possible is removed from the melt, which is then poured directly into cast-iron molds. A mold wash of aluminum oxide is used to prevent ingot sticking. For slab ingots which are to be rolled into sheet, a carbon-tetrachloride vapor atmosphere or a chlorinated-pitch mold wash is desirable, as the aluminum oxide formed in the pouring operation is subsequently removed by the chlorine in the presence of carbon." As in vacuum melting, a pouring temperature of about 2900°F is recommended. Adequate hot-topping is important as iron-aluminum ingots are subject to very deep piping. Ingots are removed from the molds and buried in vermiculite, where they are allowed to cool slowly to room temperature. The ingots are radiographed,

Jan 1, 1959

By E. F. Steeb, P. C. Rosenthal

BlANKS 8 in. long were cut from the as-received bar stock and austenitized at 1560° F for 1 hr, oil quenched, tempered at 1140°F for 1 hr, and water quenched. The heat-treated blanks were machined into tensile specimens which were subsequently used for the straining operation. Some of the tensile specimens were temper embrittled at 900°F for 24 hr and air cooled prior to or following the straining operation. The specimens were strained in tension up to 5 pct total strain (elastic plus plastic) either at room temperature or at 900°F. The reduced sec- tion of the tensile specimen employed was 5 in. long and 0.600 in. in diam. This size specimen was sufficiently large to permit two standard Charpy impact bars to be machined from it. One group of specimens was temper embrittled at 900°F for 24 hr under stress of about 20,000 psi applied with a hydraulic tensile testing machine. Approximately 0.34 pct plastic strain occurred during this treatment. A comparison of series "A" and "B" data in Table I at 0 pct strain, reveals that the steel was rather highly susceptible to temper embrittlement, the embrittling treatment causing the transition temperature to rise 165°F. The 28 ft-lb level, which was near the center of the sharp-rising portion of the transition curve, was selected as the

Jan 1, 1959

By F. D. Delve

RECENT studies by the author on the reduction of titanium from TiO2-bearing slags have been accompanied by difficulties that are attributed to

Jan 1, 1959

"Chairman: Professor J. de V. Lambrechts Rapporteur: Mr R. HempPapers:Computer-aided design of a flash smelting installation by M. A. T. Cocquerel, R. T. Gates and L. A. GreenPlanning of mine ventilation by E. U. Reuther and A. DohrnenCoal mine ventilation systems in the U.S.A. by R. Stefanko and R. V. Ramani Heat flow models in ventilation planning by A. J. Dickson and A. M. StarfieldThe first of the papers in the session dealt with a flash smelter installation, while the remaining three papers dealt with mine ventilation. In view of this the Chairman proposed that the paper on flash smelting be introduced and discussed first, after which the remaining three papers would be introduced followed by discussion on all three.Dr Cocquerel, who presented the first paper, used some typical flow diagrams to illustrate the process and stated that the program considered only steady-state operations and did not take into account the dynamical changes. Subjective judgment was necessary for the preparation of input data and some degree of user appreciation was required.Dr Cocquerel said that no work bad yet been done on an optimization program, but that this was being considered. Such a program would require a large amount of physical and chemical data which were not yet available. The variables to be optimized were the energy and material consumptions and the loss of metal in the slag.The Chairman opened the discussion by asking Dr Cocquerel if he could give a brief description of the flash smelting process for the benefit of those not familiar with the subject. Dr Coquerel replied that in the Outokumpu process con¬centrates were injected directly into the furnace, and that the process was somewhat analogous to flash distillation or evaporation processes, but was perhaps closer to the burning of pulverized fuel.The process had two distinct advantages. First, the heat evolved in the smelting reaction was used to heat the furnace, which resulted in less fuel consumption, and, second, the effluent gases were cheaper to treat than the effluent gases from other pyrometallurgical processes. This was important particularly in view of the current interest in pollution problems.Mr P. Marais thought that the authors had done themselves an injustice by not including details of the very complex processes taking place in the furnace."

Jan 1, 2014

The 1996 Arizona Conference was held in Tucson on Dec. 8 and 9. Attendance was 648, a 12% increase from the 1995 conference. The annual conference is organized by the Arizona Conference Board of Directors, representing SME sections from throughout Arizona and adjacent areas. In addition to those representing mining and processing operations in the Arizona region, the meeting was well attended by interested parties from throughout North America. These included vendors, consultants, academia, research organizations and corporate management. The technical program highlighted the meeting. It consisted of a keynote address and morning and afternoon technical sessions. In the technical sessions, 23 papers were presented by the mining, hydrometallurgical, smelting, geology and mineral-processing divisions. The conference was then capped by a banquet that included a talk by a noted economist. Keynote address The program was kicked off by a keynote address titled "Forecasting for the 105th Congress," by Rep. John Shadegg (R-AZ). He was elected to Arizona's Fourth Congressional District in 1994. Shadegg serves on the House Budget Committee, the Resources Committee and the watchdog Government Reform Committee. He stressed the familiar conservative positions of reducing government spending, balancing the budget and states rights. As a member of the House Resources Committee, Shadegg stated his support for the mining industry. Technical sessions Mining division. Two of the five presentations described developments at two Arizona mining operations. T.J. Swendseid of Phelps Dodge presented a paper titled "New developments at Morenci" and P. Garretson of BHP presented a paper titled "Startup of the Robinson Project." Morenci continues to expand its operation and recently broke records for production. Other developments at Morenci included the completion of a 600-m (2,000-ft) drainage tunnel and stockpile rehandling. In addition, Phelps Dodge moved Morenci's crusher plant. It was completely disassembled and reassembled in just eight days. Another interesting presentation was "Predictive maintenance techniques for large electric shovels at Cyprus Sierrita," presented by T. Ritzel of Cyprus Amax. The presentation described high-technology methods for predicting maintenance problems. These methods included vibration analysis, ultrasonic detection, infrared thermography, electrical measurements and tribology (the science of lubricant evaluation). The benefits of these techniques are reduced downtime of the equipment, as was demonstrated in case studies at the mine. The other presentations were "Introduction to NOSA 5-star safety program," by R. McKinnon, BHP Copper North America, and "A new design guideline for mine sealing," by K. Fuenkajorn, Rock Engineering International. Hydrometallurgical division. The hydrometallurgical session consisted of five papers. These included a presentation titled "Recovery of gold and silver using guanidine-based extractants," by M. Vining of Henkel Corp., Tucson, AZ. In this presentation, guanidine-based extractants LIX-79 and AURIX resin were introduced. LIX-79 was shown to have applications in copper-gold and high silver ores. In ammonia-cyanide leaching, AURIX was shown to be more selective in CIL vs. RIL comparisons. Other papers in the hydrometallurgical division included "Application of cobalt in the copper industry," by J. Hawke, OMG Apex Inc.; "Series parallel conversions and production gains at Cyprus Miami Mining's dump leach and solvent extraction operation," by E. Bilson of Cyprus Amax; "Lead alloy anode corrosion at the San Manuel SXEW tankhouse," by W .M. Gort of BHP Copper and "Hydrometallurgical treatment of copper refinery slimes," by B.C. Wesstrom of Phelps Dodge. Smelting division. Three papers were presented in the smelting division session. These included updates and reports on improvements at the Hayden, Hidalgo and BHP San Manuel smelters. For example, W.A. Dutton of Phelps Dodge presented "Recent improvements at the Hidalgo Smelter." These changes were aimed at reducing environmental emissions and increasing production. They included modifications to the fugitive-gas collection system to reduce particulate emissions, rubber lining the acid plant scrubbers to reduce corrosion and the installation of a cold lime softening system for water treatment. Equally interesting papers were presented by D. Norton of Asarco, Hayden, AZ, in a paper titled "Update of the Hayden smelter process," and by D. Jones of BHP Copper, San Manuel, AZ, in a paper titled "Update on first campaign of the BHP San Manuel Copper." Geology division. The session began with a paper that outlined the progress of an exploration project in South America. "The Pierina exploration project, Ancash Province, Peru" was presented by J.D. Lowell, Lowell Mineral Exploration, Rio Rico, AZ. Another paper was then presented on a copper deposit in Grant County, New Mexico. "Zonation of supergene copper minerals at Hanover Mountain, Grant

Jan 1, 1997

By Robert Stefanko

The importance of underground stress instrumentation cannot be minimized. It was Lord Kelvin who said that unless you can assign a number to a quantity,, you know very little about it. Most engineers will agree although this kind of statement is resented by our friends in non-technical fields. Mining is undergoing a revolution from art to science. But how can mining methods be optimized if there is no way of measuring the effectiveness of a given mining method? Do we know how effective a' support is unless we can determine its reaction to the mine structure? How do we assess the need for modifications to existing systems and supports, and how do we measure the effectiveness of such changes? Cut and try techniques are too wasteful of time and energy, and rarely provide solutions to a given problem. The purpose of underground stress instrumentation is to provide answers to some of the above questions -- answers that cannot be obtained otherwise This does not mean that laboratory studies are not valuable -on the contrary. Laboratory and underground studies supplement one another. Rock mechanics had its conception with the study of stresses in homogeneous, isotropic, and elastic models subjected to various force systems. These analyses were valuable inasmuch as they pinpointed possible sources of trouble due to stress concentrations. If the results observed underground did not always agree with the experimental analysis, it was not an indictment of the latter. More probably, the discrepancy could be attributed to the lack of similitude between model and prototype. The more nearly one can simulate underground conditions in a model, the more apt one is to produce results which correlate well-with underground observations. It is impossible to completely simulate underground conditions because all of the significant design parameters have not been recognized and evaluated. What better way can one evaluate these parameters than by underground stress instrumentation?

Jan 1, 1963

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1934 are available at Institute headquarters, unless otherwise noted They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS Copies of the TECHNICAL PUBLICATIONS have been mailed to those members of the Institute who are registered in the different classes A-Metal Mining, B-Milling and Concentration; C-Iron and Steel Division; D-Nonferrous Metallurgy; E-Insti¬tute of Metals Division; F-Coal Division; G-Petroleum Division; H-Nonmetallic Minerals; I-Mining Geology; J-Mineral Industry Education Division; K-Mining Administration; L-Geophysical Prospecting Other members may obtain copies by writing to the Secretary Copies of CONTRIBUTIONS may also be obtained from the Secretary's office Additional copies are sold at the rate of 1 cent per page, minimum charge, 25 cents Nonmembers may purchase the papers at the prices mentioned

Jan 1, 1935