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By D. L. Martin

The study of cobalt-platinum alloys has been of interest since they represent a class of permanent-magnet material in which the disorder-to-order transformation plays a controlling role. The magnetic properties of alloys in the range 40 to 60 at. pct have been found to be greatly influenced by composition and heat-treatment. The peak properties of 4700 coercive force and 9,000,000 gauss-oersteds energy product were obtained by controlled cooling and aging. These high values combined with ductility and machin-ability give the alloys useful characteristics although their high cost limits their application. THE cobalt-platinum alloys have been of interest in the study of permanent-magnet materials ever since the discovery by Jellinghaus that they had unusually high coerceive-force values.' The high coercive force was associated by Jellinghaus with the disorder-order reaction which occurred in these alloys. This was later verified by Gebhardt and Koster in a detailed study.2 An investigation of the structure, mechanism, and kinetics of the disorder-order transformation and resulting property changes in cobalt-platinum alloys has been in progress for some years. Certain phases of this study related to equilibrium rela- tions, and to the mechanism and kinetics of the ordering reaction have been published previously.3-5 In this paper, the results of the processing and heat-treatment studies on 40 to 60 at. pct CO alloys are presented. The magnetic properties have been found to be influenced greatly by the composition, by the cooling rate from the disordering treatment, and the final ordering time and temperature. Coercive force values, Hc, of 4700 oersteds and energy values, (BH)m, approaching 9,000,000 gauss-oersteds have been obtained by controlled cooling and ordering. PROCESSING OF THE ALLOYS The composition range of interest for permanent-magnet properties centers around the equiatomic composition Copt. In this region the alloys are dis-

Jan 1, 1959

By J. M. Baker

It seems appropriate here to open with a quotation from the great pre-Confucian philosopher Lao-tze: "The softest thing in the world dashes against and overcomes the hardest. There is nothing in the world softer or weaker than water, and yet for attacking things that are firm and strong there is nothing that can take precedence of it." I am happy to report that our system of mining has worked out, with minor modifications, as well or better than was predicted. This, in a period of rising labor and material costs, has been most gratifying. Gilsonite is a solid hydrocarbon which occurs in vertical fissures cutting the sandstone and shale beds of the Uintah formation in south¬eastern Utah. It is found in other parts of the world under similar occurrence but nowhere else is it now being mined commercially. The Gilsonite veins on entering the shale members of the Green¬river formation break into small veinlets separated by shale, These veinlets are not now economical to mine.

Jan 1, 1959

By L. H. Schwartz, M. V. Nevitt

THE phase Ti2Ni has been described by Laves and Wallbaum,1 who found the phase to be face-centered cubic with 96 atoms per cell, by Duwez and Taylor,2 who confirmed these observations and reported a lattice parameter of 11.333A, and by Rostoker,' who reported the structure to be isomorphous with the double carbide Fe,W,C, type E93, and to have a lattice parameter of 11.29A. In this study a group of isostructural phases has been found among alloys of certain second and third long-period transition elements. The systems investigated included all the combinations of zirconium and hafnium with the Group VIII elements rhodium, palladium, iridium, and platinum. There is evidence that many of these new Ti2Ni-type phases require oxygen for their stability in the temperature ranges in which they were studied. EXPERIMENTAL PROCEDURE Alloy samples weighing 5 g were prepared by arc-melting metals whose purity is indicated in Table I in a helium-argon atmosphere. Samples of the as-cast buttons, wrapped in molybdenum foil and sealed in evacuated quartz tubes, were

Jan 1, 1959

By J. Howard Bird

The purpose of this publication is to describe the power-distribution system of the mine and refinery of the Duval Sulphur & Potash Company at Carlsbad, N. Mex. This distribution system has been excellently predesigned to meet requirements and fit special conditions encountered at the property. In presenting the material, the authors point out various features that would be desirable for incorporation in other systems under similar conditions. Central location of switchgear in pressurized vaults and ventilation of such equipment with filtered air prevent salt accumulations and contribute to trouble-free operation. The simplification of power-distribution circuits and overload protection, as a result of centralization of switchgear, the use of individual control circuits enclosed in conduit (which aids troubleshooting), and central location of control panels, are factors which contribute to efficient, safe operation. Those features are applicable to many operations where fire or explosion hazards are encountered, or where dusty conditions may exist, as well as in operations where numerous individual drives are involved.

Jan 1, 1959

By Shiou-Chuan Sun

Most previous work on sedimentation of coal1 and mineral2,3 suspensions has been conducted in graduated 1-liter glass cylinders of 6-cm diam. With this type of large container it is often difficult to see through the suspension and tedious to perform a large number of tests. Furthermore, the heavy glass walls and the graduation lines of glass cylinders cause internal and stray reflections, respectively. To obviate these difficulties, an Atlab Emulsion Viewer from Arthur H. Thomas Co. was adopted as an alternative apparatus. Equipment: The viewer,4 shown in Fig. 1, consists of: 1) a stainless steel frame rack holding 21 flat-bottom Nessler tubes or an ungraduated replica 1.64 cm ID and 1.80 cm OD, 2) a movable masked 150-w lumaline lamp behind the tubes, and 3) a scaled glass panel with 100 vertical divisions in front of the tubes. The tubes are snugly held by springs in slots formed by spacer bars, which also serve as shields to eliminate stray light. The lumaline lamp is mounted behind a slit in a movable housing so that it can be positioned behind the suspension to be examined. The lowest or 100-division line on the front glass plate is leveled with the upper side of the bottom of all tubes. The scaled portion of each tube, roughly 19 cm high and 40 ml in volume, is used to study coal and mineral suspensions.

Jan 1, 1959

By M. Metzger, T. A. Read

The strengthening effects of hydroxide and synthetic plastic films in the creep of cadmium crystals were studied. The results were broadly consistent with the naive mechanical model. The dislocation-film reactions and the significance of the macroscopic stresses associated with certain films are discussed in the paper. ALTHOUGH a number of studies have been made of the strengthening of metal single crystals produced by surface films usually less than Ir in thickness, the mechanisms underlying this phenomenon are still not well established. Roscoe' first noted the critical shear stress and the stress-strain curve of cadmium-crystal wires to be raised markedly by the presence of oxide films. Subsequent investigators2-' have confirmed the effect for several metals and films including a number of plated poly-crystalline metal films. Harper and Cottrel1" with a thin film on zinc presumed to have formed as a result of etching and washing treatments) did not detect a strengthening at a rate of extension of 10 ' sec-' although at lo-' sec-' the film raised the flow stress by 7 pct at 0.0005 extension and by 22 pct at 0.01. The marked strengthening at moderate strains thus appeared to be the result of a dynamical effect dependent on the rate and amount of plastic flow. Other observations'. " are consistent with this view. The large effects of films on the tensile creep rate of single crystals were demonstrated when the observation of Andrade and Randall," that the creep rate of cadmium crystals increased on immersion in aaueous solutions of certain cadmium salts. was shown' * to hold only when a film was present initially and was explained by the attack of the solution on the film and the removal of its strengthening effect. Changes in the creep rate interpretable in terms of the removal or formation of various films have been observed by other investigators.3,8,10,31 Certain other experiments have been reported in which surface films or liquid environments have affected the plastic behavior of metals, but these are not within the scope of the present work which deals with the effect of solid films on single-crystal slip. Possible Mechanisms—The film does not significantly reduce the load on the crystal in the elastic range (the elastic moduli of film and crystal are not too greatly different and the area of the film is so small that its share of the load is negligible) so that the initial operation of internal Frank-Read sources is not affected. However, as Fisher" has pointed out, a source terminating on the crystal surface requires only half the critical stress for activation as an internal source of the same length and a relatively strong film (even a very thin one) would pin the free ends of the surface sources so that, if surface sources are responsible for plastic flow in a clean crystal. such a film would increase by roughly a factor of 2 the stress necessary for generation of dislocation loops at a given rate. The other general possibility is that the film resists the passage to the crystal surface of internally generated dislocations. If the film is adherent and if the specimen is to exhibit slip of the same general character as a film-free specimen, the film must deform or fail in shear at the active slip planes. The naive mechanical model, where shear-stress relaxation across the active slip plane in the metal transfers load to the film until it deforms and slip can

Jan 1, 1959

By J. J. Gilman

WHEN a zinc crystal is immersed in liquid N, and then plastically bent, it is observed that it bends a certain amount and then fractures. This fracture occurs at a fairly reproducible radius of curvature, and the radius varies systematically with the crystal orientation. Because this phenomenon provides an unusually well-defined set of fracture conditions, it is possible to examine various possible fracture criteria and select the best one. Zinc crystals of various orientations were bent about axes lying in their glide planes (0001) and perpendicular to their glide directions [1210]. The crystals were 0.150 in. diam and had chemically polished surfaces. They were immersed in liquid N, while they were being loaded on an Instron testing machine. A three-point bending jig was used to load them. Table I lists the beam radius at which fracture occurred for each orientation. Each value is the average of at least six measurements. The normal stresses on the cleavage planes, at the time of fracture, were calculated as follows: First, from the fracture radius, R,, the orientation angle, x,, of the (0001) plane at the outer fiber was calculated. If x, = angle between the (0001) and the rod axis prior to bending, d = rod diameter, and X, = angle between the (0001) plane and a tangent to the bent crystal, then1 sinX, _ 2R, sin xn 2R, + d Since the glide shear strain is given by' y ' cot X, — Xo the glide strain at fracture, x,, can be calculated. Next, it is necessary to know the tangential stress in the outer fiber at fracture. This depends on the plastic flow curve, so a series of tensile tests were performed at —196°C on another set of zinc crystals. A curve of the average resolved shear stress versus glide strain was prepared. From this curve, shear stresses, r,, corresponding to the glide strains in the bend tests were taken. These values are listed in Table I. Then the normal stresses in the outer fibres, u,, were calculated from the relation U, = r, tan X, This analysis assumes that the fiber stresses in a bent beam are the same as the stresses in simple

Jan 1, 1959

By E. L. Litchfield

Spark ignition of combustible-gas mixtures is a relatively old subject of investigation and has been treated both experimentally and analytically by many people. Elements of static and current electricity are almost always present in mining and industrial operations, and the spark can be an extremely efficient source of ignition. Thus the practical interest of such problems as the "intrinsic safety" of electrical apparatus is obvious. Ignition and quenching phenomena are the primary laboratory representatives of combustion phenomena that are dynamically nonsteady, and such nonsteady phenomena playa considerable part both in industrial processes and in safety matters, although they are of less immediate practical interest. Considerable effort has been expended by the Federal Bureau of Mines in investigations of spark ignition.5 6 7 8/ Primarily, this work has established the significance of several of the parameters involved. Although the

Jan 1, 1959

By K. K. Kelly

METALLURGICAL thermochemistry of titanium is a broad subject and (if data were available) could include a wide variety of topics. The present report is restricted to extractive metallurgy and to substances and reactions that bear upon the magnesium, sodium, and hydrogen-reduction processes employing titanium tetrachloride. The aim has been to present enough data so that the reader not only can check: the calculations for the reactions discussed but also can conduct related calculations if he so desires, without recourse to other compilations of data. The subject matter divides naturally into two parts-the selection of the data to be adopted and the application of these data to pertinent metallurgical reactions.

Jan 1, 1959

By J. B. Gayle

Since the turn of this century, there has been increasing interest in the application of flotation processes to the beneficiation of finely divided minerals of various types, This is reflected by the large numbers of papers dealing with various aspects of this problem published annually both in this country and abroad. For the most part, such papers fall into one of three categories: 1. Those concerned with achieving, by various chemical and/or physical means, a set of conditions under which certain particles become potentially floatable while others do not. 2. Descriptive studies of plants and pilot plants effecting separations between such particles. 3. Studies of the effects of certain design and operating variables on the rates and efficiencies with which such separations can be effected.

Jan 1, 1959

Factors leading to the necessity for some individual testwork in solving most specific hydraulic transportation problems are listed and a description is given of a method used in determining critical flow conditions. An outline is given of the basic theory of the purpose of the testwork, and a means of applying test results for varied pipeline diamet.er and material conditions follows. Engineering and economic factors are applied to the solution of a specific hydraulic transportation problem and the use of the test results in plant practice is illustrated. The advantages of connecting pumps in series in centralised pumping stations rather than individually along the pipeline are stressed. Some notes are added on the future possibilities and economies of post pump injection of solids into high pressure pipelines.THE HYDRAULIC TRANSPORTATION OF SANDSAs well as all the classical variables involved in a pipeline installation, one must consider, when solids are to be transported, the effects of such variables as:(i) Proportion of solids in the pulp.(ii) The average specific gravity of the pulp.(iii) Specific gravity of the solid material.(iv) Solid particle average sizing and possibly shape.(v) Solids particle grading.(vi) Pipeline diameter for effects other than classically hydraulic.(vii) Pipeline material.(viii) Fluid viscosity.(ix) Pump characteristics.(x) Abrasive or corrosive properties of the pulp.Not surprisingly, the application of published data to the hydraulic transportation of a specific material is difficult if not well nigh impossible. Most hydraulic transportation investigations also involve economic and site factors vary...

Jan 1, 1959

By T. M. Nasiatka

This report sterns from a study undertaken by the Federal Bureau of Mines to determine the possibility of reducing filter-cake moisture by applying radiant heat. Suitable laboratory equipment was set up to study the effect of heat, heating time, proximity of the heater to the filter cake, cake thickness, and other variables related to the final filter-cake moisture. A minus-48-mesh coal slurry and application of heat for 60 seconds resulted in filter-cake moistures 5.6 to 13.2 percentage points lower than could be accomplished by filtration alone at 24 inches of Hg for 1-1/4-and 1 1/2-inch cake thickness, respectively. The moisture reduction can be attributed to the combined effect of lower fluid viscosity and evaporation.

Jan 1, 1959

By M. J. Ferrante

A process was investigated for preparing Specification-grade nickel (containing less than 1 percent cobalt) by stripping it electrolytically from a nickel sulfate-boric acid solution and using the stripped electrolyte for the preferential dissolution of nickel from basic carbonates of nickel and cobalt. The basic carbonates were produced at the plant at Nicaro, Cuba, owned by the U.S. Government. Determination of the optimum conditions for deposition of Specification-grade nickel indicated that the upper limit of cobalt concentration was 0.1 gram per liter. The pH, temperature, and concentrations of nickel and boric acid in the electrolyte were not critical. An aluminum cathode and two lead anodes were used at a cathode current density of 1.2 amperes per square decimeter.

Jan 1, 1959

By John R. McWilliams

This report is one of a series published by the Bureau of Mines describing methods and practices at various mines throughout the United States. A previous program, conducted from 1928 to 1939, was well received by the mining industry and technical institutions and provided much source material for engineering textbooks and technical handbooks. The stringent wartime demands on the mining industry, the rapidly changing postwar economic situation, and greatly accelerated technologic growth have combined to render many of the previous data obsolete. The objective of the present program is to assemble reliable technical information on mining methods and practices throughout the country and present it for the use of the mining industry, technical schools, textbook authors, and other interested persons. This report deals with the design and development of the Berkeley open- pit mine at Butte, Mont., owned and operated by The Anaconda Company. The Berkeley pit is but one facet of a well-organized and integrated copper-mining operation involving the entire Butte district. Vein-type mining, important for 75 years, is still in progress at depths from 600 feet to nearly 1 mile; on intermediate levels, low-grade ore left untouched by earlier vein-type mines is being extracted by block caving entire ore zones,3/ and secondarily enriched but lower grade near-surface portions of the same ore zones are being mined by open-pit operations (fig. 1). The Berkeley pit itself is named for the Berkeley mine, one of the old mines that extracted copper ore from high-grade veins in the area that now will be mined by open-pit methods.

Jan 1, 1959

By C. P. Blair

In discussing so-called "volume rates" for the movement of coal, I start from one basic premise: That it is the job of the railroads to devise rates which will move the traffic, while at the same time assuring a fair return on their investment. No matter how reasonable and nondiscriminatory freight rates may be, if they fail to attract and hold traffic to the rails, they are utterly useless - both to the carriers and the shipping public. And it will be my purpose here to show that under certain circumstances the use of volume rates by the railroads enables them. to hold traffic which would otherwise be lost, and to avoid needless dissipation of revenues, Properly employed, volume rates should benefit both the coal industry and the railroads, I do not, however, advocate the discarding of the carload as the basic rate-making unit. Far from it. Sound operating reasons dictate the making of rates based on car- loads, and the tradition of carload rates has a firm foundation in railroad operating costs, many of which vary directly with cars handled. In short, the carload was, Is and, in my opinion, will continue to be the basis for most rail rates on coal, as well as on other commodities. But change is an inevitable result of progress, and we should not be so bound by tradition that we are unwilling to try novel methods of ate making, should the circumstances require, The modern rate maker must, now and then, run the risk of being called an iconoclast if he is to keep up with the times. As T will point out, volume rates were for many years rejected by both the Interstate Commerce Commission and the railroads, But now both the Commission and the carriers have come to recognize that under proper circumstances and conditions volume rates are a powerful and effective tool.

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 H. G. Wolfhard

The propagation of explosions through short cylindrical channels has been investigated by the Bureau of Mines. In the experimental apparatus set up by the Bureau, a single such channel formed a connection between a small explosion vessel in which a gaseous explosion was initiated and a larger, partly enclosing, explosion vessel filled with suitable gaseous mixtures; the larger vessel permitted observation to determine if an explosion was induced therein by mass, energy, and species transfer through the channel, as a result of tie initial explosion, It has been found that transmission of flame through to channel is not an essential to induce the second explosion, for hot gases from an extinguished explosion are able to ignite cold combustible mixtures in the larger vessel. The schlieren patterns of flames or hot burned gases emerging from a channel into the explosion chamber were photographed. These show, in most instances, that vortexes of hot gas ejected from the jet into the cold explosive mixture are responsible for ignition. The study has practical significance in problems of rendering electrical equipment safe for use in potentially flammable atmospheres, INTRODUCTION The propagation of flames through cylindrical or annular channels has practical importance in flameproofing electrical equipment and for flame traps. Much practical work has been done to determine the minimum safe breadth of flanges and the maximum safe gap between the flanges that will permit venting an electric motor without allowing flames to pass.

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 Sidney Katell

An estimated capital investment of $76,499,800 will be required for a plant designed and built to produce 90 million standard cubic feet per day (std.c.f.d.) of synthetic pipeline gas through Lurgi gasification of bituminous char. This investment figure does not include the pretreatment plant, the cost of which is assumed to be reflected in the cost of the char fed to the gasification system. Shift conversion, C02 removal, and methanation are required after gasification in the Lurgi unit to make a gas suitable for pipeline transmission. Capital investment data are based upon equipment costs, January 1959. Based on a 90-percent or 330-day operating year, the operating cost before profit and Federal taxes with the char price as a variable will amount to the following: [ ]

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