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By R. W. Heckel

The densification of molybdenum powder by hot pressing has been studied as a function of time (up to about 3 x 104 sec) at pressures of 5000, 15,000, and 30,000 psi in the temperature range from 3700o to 1200°C. Excluding results below 2 to 5 x 10 sec, the density (D) - pressure (P) - time (t) data followed the general form:

Jan 1, 1965

The volumes of Transactions, which are published annually, contain the list of officers, rules, etc., the Proceedings, and the papers revised for final publication. (In this revision, after the preliminary publication, authors are permitted to use the largest liberty; and the changes and additions made in papers are sometimes important. It should be borne in mind by those who study or quote a paper in the preliminary edition, that they may not have in that form the ultimate and deliberate expression of the author's views. It should be added, however, that in the majority of cases there are no important changes.) These volumes are for sale as follows, in paper covers:

Jan 1, 1917

By William Kent

DURING the discussions at the Philadelphia meeting in February last, † several speakers expressed their doubts of the general accuracy of chemical analyses of steel made by "iron works chemists," and especially of determinations of manganese. Since the meeting,. the discussion of the "practical value of chemical analyses" has been continued at some length in the columns of the Iron Age. †Transactions, vol. ix, p. 529.

Jan 1, 1882

By E. G. Schempp, W. A. Morgan

The influence of modifications in the molybdenum, vanadium and, to a limited degree, carbon and boron content to a basic composition of 5 pct Cr, 0.75 pct Mo, 1 pct V hot-work tool steel composition, was studied in respect to hardenability, grpain- coarsening temperature, and tempering charactevistics. Tensile, impact, and fatigue pvoperties were studied for the most promising compositions. An alloy with a typical composition of 0.43 pct C, 4.97 pct CI-, 0.33 pct Si, 2.25 pct Mo, and 1.00 pct V uas found to offer the most favorable combination of properties in respect to high-strength applicntions when tempered at 1100°F. MANY 5 pct Cr high-strength steels are at present being manufactured in North America which fit well into the classification of the AISI-SAE system. Much interest has been shown in these materials as ultra-high-strength steels for use at elevated temperatures. The limiting temperature of use lies at the point where the steels begin to soften rapidly. Although a great deal of information has been made available in the past two years on the properties of selected alloys in this series, little information exists on the effect of systematically varying the ccntent of one or more elements in the 5 pct Cr-base alloy. This paper presents the results of an investigation of the effect of variations of the carbon, molybdenum, vanadium, and, to a limited extent, the silicon, manganese, boron, and niobium content of a 5 pct Cr steel to the AISI H-13 base analysis. EXPERIMENTAL PROCEDURE All experimental heats were melted in a 50-lb. induction furnace. The melting stock consisted of

Jan 1, 1962

[EDMUND M. WISE, Chairman ROBERT H. LEACH, Past-Chairman D. K. CRAMPTON, Vice-Chairman CARL E. SWARTZ, Vice-Chairman W. M. CORSE, Treasurer LOUIS JORDAN, Secretary 29 West 39th St., New York, N. Y. Executive Committee 1941 1942 E. A. ANDERSON FRANCES H. CLARK D. L. COLWELL W. L. FINK W. P. SYKES J. T. NORTON 1943ERIC R. JETTE LOUIS W. KEMPF GEORGE SACHS]

Jan 1, 1940

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who called at Institute headquarters during the period August 1, 1916 to September 10, 1916: C. L. Cantley, New Glasgow, N. S. H. M. La Follette, La Follette, Tenn. D. A. Cowell, Columbus, Ohio. Montrose L. Lee, Montevideo, Uruguay. Alexander Deussen, Houston, Texas. V. H. McNutt, Billings, Mont. Chas. E. Dutton, Goldfield, Nev. J. W. Maller, New York, N. Y. H. S. Emlaw, Grand Haven, Mich. Edwin W. Mills, Tul. Mi Chung, Chosen, J. M. Gillette, Swatsburg, N. Y. Korea. E. Gorilla, San Antonio, Texas. Francis R. Pine, Elizabeth N. J. Bertram Grant, Kingman, Arizona. Frank A. Ray, Columbus, Ohio. Ruger W. Hay, Bisbee, Arizona. John A. Rice, El Paso, Texas. C. F. Hendricks, Cobalt, Ontario. W. E. Rice, Ringwood Manor, N. J. Stanley C. Herold, San Jose, Cal. W. H. Staver, Lynchburg, Va. Lloyd Hoffman, Pottersville, N. J. Ralph H. Sweetser, Easton, Pa. Charles Hunter, London, England. Kirby Thomas, New York, N. Y. G. Jansen, Benkoelen, Sumatra. Henry Traphagen, Union Hill. T. H. Jenks, Oatman, Arizona. M. M. Valerius, Tulsa, Okla. Warren jenny, Chanaral, Chile. Wilfrid B. Wainewright, London, Eng. Walter A. Barrows, Jr., of Brainerd, Minn., has been elected president and general manager of the Thomas Iron Co., Easton, Pa., to succeed Ralph H. Sweetser, whose resignation of several months ago becomes

Jan 10, 1916

By G. A. Vissac

The only fine coal washer with proved automatic controls, the feldspar jig is capable of good efficiencies even at low separating gravities, handles a variety of products, and treats 150 tph and over. IN continental Europe the feldspar jig is used almost exclusively for cleaning the fine sizes of coal; it operates with an artificial bed, made up generally of pieces of feldspar or of any other hard and heavy rock with good cleavages. A primitive form of this machine requiring close supervision was used in this country years ago, but output was small. The modern machines are generally air-pulsated Baum-type jigs, with capacities up to 150 tph, and treat sizes from % in. to 0, usually previously dedusted or deslimed. These jigs are equipped with very accurate and sensitive automatic controls insuring satisfactory operation even at low separating gravity and with feeds irregular in quality and quantity. This paper will deal more particularly with coal cleaning separation, but the technical studies apply equally to all minerals. Theory of the Feldspar Jig To understand fully the operation of the feldspar jig and to appreciate its potential value, it is necessary to measure and analyze the motion of small particles of various specific gravities, falling in various media, under various conditions. As no practical formulas were available for that purpose, the writer has developed new theories and established new sets of formulas, which cannot be demonstrated here. They are applicable to all minerals and to many problems of coal or mineral concentration. These formulas do not pretend to absolute accuracy, but results, tested by comparison with experimentally recorded data, are sufficient for practical purposes, as they give definite indications of trends, relative values, and order of magnitude of the many factors involved. For pulsating motions no earlier formulas are available. In the case of continuous currents or motions, such formulas as Rittinger's, Allen's, or Stokes', over a hundred years old, apply only to special shapes and sizes of particles, involve factors and coefficients difficult to measure or appreciate, and deal only with free motions. They are of little use in solving practical problems. Units used with the formulas presented here are in the CGS system. Lateral friction and suction have been taken into account according- to methods currently used in aerodynamics, and only hindered motion is dealt with. As the feldspar jig is primarily intended to create a fluid bed condition, the mixture of fluids and solids obtained is homogeneous, and the apparent specific gravity of the separating medium is calculated accordingly. For instance, if 20 pct of the volume is coal and shale, with an average of 1.60 sp gr, in a liquid of 1.10 sp gr, the actual specific gravity of the separating fluid is 0.80 x 1.1 + 0.20 X 1.6 = 1.20. The fundamental equations are as follows: The general motion of a particle falling in a medium of specific gravity equal to u, hindered motion. is dv/dt = g/Ls [ L (s-u) - u/g v2 [1] g = 981 cm per sec, acceleration of gravity, and L = thickness of the particle of specific gravity (s) and velocity (v). The initial acceleration dv/dt = g (1-u/s ) [2] is a function of the specific gravity of the particle, only for a given medium, and independent of its dimensions—an ideal separating condition. The terminal velocity Vt = gxL- (s-u)/u, [3] for a given value of u, is a function of s and L. Two particles, L, s, and L2 s2, are said to be equivalent if they have the same terminal velocity, and accordingly L1/L2=s2-u/s1-u. [4] Two such particles cannot be separated by continuous currents, in any concentrating device. Because the initial accelerated motion, which provides for efficient separation, is followed by a constant velocity, which has a limiting effect, it is essen-

Jan 1, 1956

By D. W. Loucks

There is plenty of evidence to indicate that at least one of man's chief interests in life is to make himself as comfortable as possible. If you doubt this, just watch the fellow next to you for the next half hour trying to find the most comfortable position that a hard chair has to offer. Comfort, however, does not always mean an easy chair. To some, it may mean a wealth of money: to another, freedom from worry. But to most of us, it means first of all a comfortable atmosphere in which to live, and to a great many of us it probably also means freedom from that annoying task of firing the furnace. Today more than ever before, automatic heat is one improvement that is placed high on everyone's list. Perhaps this is because automatic heating is becoming relatively cheaper. Perhaps it is because of a good publicity campaign on the part of the oil and gas men or maybe it is just that we are getting lazier day by day. At any rate, almost every issue of Better Homes and Gardens, House Beautiful, or your other favorite home magazine carries an article extolling the virtues of this or that automatic heating system.

Jan 1, 1949

By Paul M. Tyler

THE farmer pays the phosphate miner! Phosphorus is used in fireworks; goes to battle in military smoke screens, incendiary shells, and tracer bullets; and, in vermin destroying pastes, does its part in the war against insects. A lemon phosphate can be had for a nickel at most soda fountains, and tens of thousands of tons of phosphate rock are mined annually for use in the food industries, chiefly for making monocaleium phosphate baking powder. Sodium phosphate cleaning, washing, and scouring compounds consume substantial quantities: the iron and steel industries buy a few thousand tons yearly to make ferrophosphorus and to balance foundry-iron furnace charges; and even nonferrous metallurgists use a little for phosphor bronze and other alloys. Phosphoric acid, its salts, and diverse other derivatives of this versatile element have countless applications, and industrial outlets are increasing rapidly, especially in the United States. Nevertheless, in this country nearly 90 per cent and in the whole world fully 95 per cent of the phosphate rock consumed is absorbed ultimately in agriculture.

Jan 1, 1938

By M. J. Humenick, K. Garwacka

A laboratory experimental research project was conducted to evaluate the use of chlorine for the oxidative destruction of residual ammonia that may remain in ground water after in-situ uranium solution mining operations. The work tested the idea of injecting high strength calcium hypochlorite solution into the mining zone to convert ammonia to nitrogen gas as a final cleanup process for ammonia removal from the ground water system. This paper details ammonia removal efficiency as a function of chlorine dose, reactant, and product material balances, and how the concept may be used as a final ground water restoration process.

Jan 1, 1985

By J. D. Hunt, R. J. McDonald

It is proposed that extensive fluid motion occurs between the dendrites of a Partially solid casting and it is suggested the A segregates in steel castings are a direct result of this motion. The fluid flow arises because of density differences between liquid ahead of the dendrites and the interdendritic liquid. Experiments are described on a model system investigating this fluid motion. The importance of interdendritic fluid flow is discussed with reference to longitudinal segregation. SERIOUS macro segregation is often found in large killed steel ingots. Among the most common segregates are those known as A and V, Fig. 1. The A segregates are arranged over the surface of cones, the wide parts being at the base of the ingot. The A segregates are pencil like in shape and extend from the columnar into the equiaxed region. The V segregates are distributed over inverted cones but have a less well defined shape. They occur at the center of the ingot. Because of the commercial importance of macro inhomogenities these segregates have attracted wide-scale attention. The segregates contain alloying elements and impurities which depress the freezing temperature and are thus the last liquid to freeze. A number of explanations have been proposed to explain their presence. It has been suggested1'' that the segregates are the result of the equiaxed zone growing towards the columnar region together with the interaction of convection within the bulk liquid. It has also been proposed that the segregates are the result of nucleation and rapid growth ahead of the dendritic front.3 Neither of these explanations is completely satisfactory because A segregates are pencil shaped and are not found as continuous cones. In this paper an alternative mechanism is proposed, and experiments are described on a model system to determine whether the mechanism occurs in practice. It is thought that A and V segregates are not peculiar to steels but should occur in many other large castings. Fluid motion within the bulk liquid region of a casting has been extensively discussed. Little attention has been paid to fluid motion within the partially solid regions. The work415 that has been done has been mainly concerned with the fluid motion which results from the volume contraction on freezing. The volume contraction is used to explain various types of macro segregation. The present authors suggest that in many cases the fluid flow resulting from volume contraction will be small compared with that due to other causes. When the columnar region is growing, the liquid still remaining between the dendrites has a much lower temperature near the ingot walls than at the dendrite tips. The composition of the liquid in contact with solid will vary with temperature. The density of the liquid will thus vary both because of changes in temperature and composition. The layers of different density liquid will give rise to a slow but steady liquid flow through the interdendritic regions. If there is no density change with composition, the temperature gradient within the dendritic region should give rise to a downward flow between the dendrites, shown schematically in Fig. 2. When the liquid density changes appreciably with alloy concentration this motion could either be en-

Jan 1, 1970

By T. P. Harrington, P. G. Doctor, K. A. Prisbrey

Crushing and grinding ore consumes so much energy that it represents a major component of total processing costs. While it has been estimated that only about 0.6% of the total energy expended in grinding is actually used to create new surfaces, accurate measurement of this quantity is difficult. If energy expended in crushing and grinding could be more directly measured, alternatives for increasing efficiency of the processes could be evaluated more effectively. Since the energy intensity associated with rock fracture is related to fracture sonority, it should be possible to use this sound (acoustic emission) to measure the actual energy expended. However, it is difficult to apply this approach because the mill environment is so noisy. To make the approach practical, a method for differentiating acoustic emissions caused by rock fracture from those caused by extraneous noises must be found. Pattern recognition analysis may provide such a method. This paper presents the results of pattern recognition analysis to make two types of differentiations: acoustic emissions caused by crushing two types of minerals (quartz and chrysocolla) and those caused by two extraneous noise sources, and acoustic emissions produced by each mineral.

Jan 1, 1982

By Chester O. Ensign

Many publications to date have advocated under- seas mining operations, optimistically overlooking the paucity of information on mineral distribution and the ocean environments in which minerals occur. Such articles (smattered with opinion, as is this article) are herein tempered by my more conservative views on the economics of mining under the seas. For purposes of this paper, underseas mining refers only to the deeper surficial deposits of the continental shelf and the deep sea floor, i.e., the deposits of phosphorite and manganese nodules.

Jan 9, 1966

By W. D. Forgeng, B. F. Decker

IT has been known for almost a century' that silicon and nitrogen combine when heated to a high temperature. Three nitrides have been reported, SiN, Si3N,, and Si,N, containing 33.3, 40.0 and 42.9 pct nitrogen by weight, respectively. The existence of SisN, is well established but that of Si,N, and SiN is doubtful. The first systematic study of the reaction between silicon and nitrogen was made in 1910 by Weiss and Engelhart" who determined the rate at which silicon absorbed nitrogen at temperatures from 1250°C to

Jan 1, 1959

By R. W., Ludt

THE use of froth flotation for the separation of minerals has become one of the most important of ore dressing processes. Its particular adaptability to the enrichment of low grade ores has made the process an important factor in the national economy. The methods have been extended to the recovery of a great number of minerals. Among the few minerals which have resisted efforts toward industrial flotation is chrysocolla, a hydrated partly colloidal copper silicate. Chrysocolla, being a product of natural oxidation, has been found to occur in small quantities with many ores which are recovered by flotation methods. In present practice, these small quantities of copper silicate pass off with the tailings and are lost. The advantages to be gained by a satisfactory process for the recovery of chrysocolla is apparent. Any application of principles which points a way toward the satisfactory industrial flotation process for copper silicate would be of advantage. This paper presents an attack on this problem.

Jan 1, 1949

By E. M. MacKevett

The only source of uranium ore in Alaska that has been mined commercially is the Ross-Adams de- posit, a gently inclined, fusiform orebody in alkali granite in which uranothorite and uranoan thorianlte are the chief ore minerals. In mode of occurrence, apparent genetic association with the granite, and to a lesser extent in mineralogy, this type of deposit is uncommon. The mine is in the southern part of Prince of Wales Island (Fig. 1) at an altitude of about 950 ft on the southeast flank of Bokan Mountain. A steep unpaved road 1 ¾ miles long leads to the dock on the West Arm of Kendrick Bay, which can be reached by boat or seaplane from Ketchikan, some 35 miles to the northeast.

Jan 9, 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 Fred E. Carter

AT first sight, the platinum group of metals seem of little import to we, the people," although actually the life of the common man is much influenced by them; this influence is usually indirect, hence his lack of knowledge and interest. He generally associates platinum with high-class jewelry and lets it go at that. Were 11e to go deeper, he would find that platinum metals play their part in his food supply, his clothing. his health, his transportation, his home. And the technical man is in general only slightly better informed, for he usually does not realize how necessary platinum metals are in the manufacture of the many construction materials and chemical products with which he is acquainted. Certainly, our daily lives would be profoundly affected if platinum were suddenly to become unavailable.

Jan 1, 1944

By K. G. Wikle, J. G. Klein, W. W. Beaver

Consolidation of hydride process, electrolytic, calcium reduced, and comminuted thorium powder, as well as saw chips and lathe turnings, by vacuum hot pressing and by cold pressing-vacuum sintering was studied. The mechanical properties of the consolidated material in the extruded form are compared with those of wrought castings. AT present there little little industrial use for thorium metal, although it has some important though small scale applications in electronic equipment. Despite its high inelting point—about 1750°C —a low modulus of elasticity, 11.4xl0 si at 20°C;' relatively low mechanical properties coupled with a high density, 11.7 g per cu cm; and an unusually high chemical activity with normal atmospheres limit any structural applications. The metal is utilized as an alloying element principally in magnesium. Pure thorium finds utility as electrodes in gaseous discharge lamps such as the high intensity mercury lamp' because its low work function and high electron emissivity provide lower starting potentials and more uniform operating characteristics than other available materials. The metal is also found in photoelectric tubes used for the measurement of the ultraviolet spectrum." Thorium metal has been used in germicidal lamps of the cold cathode type as sputtered coatings on nickel in order to provide a low work function surface and a low starting voltage. Other applications have involved the radioactive properties of thorium for the production of ionized particles." The potential value of thorium is much greater than its present use pattern because of possible utility in the field of nuclear power. Th may be converted through nuclear reaction to a fissionable element U which should be capable of acting similarly to U in the g'eneration of atomic power. Thorium has been reported to be about three times as plentiful as uranium in the earth's crust, placing it in the order of abundance of lead and molybdenum." Thus, it is of interest in augmenting the potential supply of fissionable material for nuclear power. Because of its high melting point, thorium is usually produced as a powder through the calcium reduction of its oxide or thermal reduction of halides by sodium, magnesium, and calcium. It may also be produced in flake form by electrolysis of fused alkali or alkaline earth chloricles and fluorides. Therefore, powder metallurgy assumes importance in the fab- rication of thorium metal shapes. Furthermore, it is rather difficult to obtain pure thorium by melting, as the molten metal reacts readily with graphite as well as oxide, carbide, and nitride refractories. These contaminate the melt with oxides, carbides, and metallic impurities." The current investigation was undertaken to examine the fabrication of thorium by powder metallurgy methods which have been used for the commercial production of beryllium and other metals.' A sparcity of data concerning the comparative cold and hot compaction of thorium powders of different derivation existed. Therefore, all commercially available types were examined along with other experimentally produced thorium powders in order to round out the comparison of consolidated thorium powders with melted reguline metal. Review of the Literature By heating a mixture of ThC1, with potassium, Berzelius made the first thorium metal as an impure powder in 1828. Improvements in the basic process, increasing thorium assay to 99 pct, were made by several investigators including Arsem," Lely and Hamberger10 and Von Bolton." Calcium reduction of Tho, to make powders was investigated by Berger," Huppertz,'" Kroll," and Kuzel and Wedekind.'" A thorium powder produced by this method using a CaC1, fluxing agent assayed 99.7 pct, as reported by Marden and Rentschler.'" Compacted and sintered, this product was found to be ductile, and could be fabricated into wire and sheet. Improvements of the calcium reduction process were made later" wherein CaCl, was eliminated from the reaction, producing metal assaying 99.8 pct Th. Further work by Lilliendah118 howed that a coarser metal could be obtained by the substitution of ThC1, or ThOC1, for oxide with consequent advantage of stability to atmospheric reaction. Reports on the technology of thorium developed in Germany during World War II have been made by Espe."' Thorium powder of 99.5 pct Th was obtained by reduction of the oxide by calcium. Screening to —200 mesh, compacting with about 20 tsi, and sintering in vacuo at 1320" to 1360°C for 3 hr resulted in a porous sinter cake. The sinter cake was sufficiently ductile to be worked into bar, wire, and sheet which could be employed as electrode materials.

Jan 1, 1957

By A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20'- (in silicate melt) = O,(g) + 4e- at a platinum anode in lithium silicate melts have been studied al 1350°C by galvanostatic methods. Plots of the sleady-state overpotential, q, as a function of the logarithm of the current density, i, showed injlections and were linear only at high current densities. The value of the overpotential was influenced by bubbling gas through the electrolyte. The ocer potential was also studied as a function of time. The rise and decay of overpotential were very slow processes. At low current densities transport is the likely rate-controlling process but at high current densities passivation of the electrode, Presumably by an oxide film on the surface, seems to be a contributory functor. IT is well-established that molten silicates behave as electrolytes'5 and, except in a few cases,6 conduction is entirely ionic. Moreover, it is supposed that a possible, and perhaps predominant, mechanism for phase boundary reactions between metals and slags is similar to that in corrosion whereby anodic and cathodic processes occur at unrelated sites, the metal serving to conduct electrons.1'8 Thus electrochemical studies of some slag-metal reactions would seem to be a useful way to diagnose the rate-controlling steps in the overall reaction. The electrochemical method is, in principle, a better diagnostic tool than the direct chemical method for the following reasons: 1) The partial electrochemical reactions, which are simpler than the overall reaction, may be studied individually. 2) The rate of reaction can be controlled at will and independently of the concentrations of reactants. 3) Fast reactions can be studied by relaxation methods.' Esin and his coworkers5'10"12 have pioneered such studies in silicates and have deviloped some ingenious techniques. Not all of their findings, however. can be accepted without a good deal of further work. In this investigation, the kinetics of the oxygen discharge reaction: 202- (in silicate melt) = Oz(g) + 4e- [I] at a platinum electrode were studied by both steady-state and transient galvanostatic techniques. Interest in this reaction was first developed as a result of the findings of Fulton and chipman13 that the reduction of silica, in a silicate slag, by carbon, dissolved in liquid iron, is a very slow reaction. Subsequent work, for example, by Rawling and ~lliott,'~ has demonstrated that the reaction under these conditions must be slow, because the rate is limited by diffusion of oxygen in the iron to the metal-crucible phase boundary at which a CO bubble may be nucleated. Further work by Tarassof,'~ in which the reduction of silica by aluminum dissolved in copper was studied, has shown that under these conditions, where carbon monoxide evolution is not involved, control of the reaction rate resides in diffusion of silica in the slag phase. However, there is no practical way of inducing sufficient convection in the system to make it clear that the phase boundary reaction is indeed fast. The overall reaction of silica reduction involves the discharge of silicon ions at cathodic sites and oxygen ions at anodic sites. In the examples cited, the discharged ions are dissolved in a liquid metal. In the present study of oxygen ion discharge, gaseous oxygen may be evolved at high current densities or oxygen may simply dissolve, possibly as oxygen molecules, in the silicate at very low current densities. The discharge of an oxygen ion at an anode must, in silicates less basic than the orthosilicate composition, be preceded by a reaction in the vicinity of the electrode, such as: which makes oxygen ions available. Platinum was chosen as the working electrode since it is comparatively inert to oxygen and is, therefore, expected to come rapidly into equilibrium with the electrolyte and with gaseous oxygen. Minenko, Petrov, and Ivanova16 have measured the electromotive force at a platinum electrode in molten silicates as a function of the partial pressure of oxygen in the atmosphere, the concentration of oxide ions in the melt, and the temperature. They found platinum to behave as a reversible oxygen electrode. At two different oxygen pressures, Po2 (I) and Pq (11). the electromotive force is given by: where F is the Faraday constant, equal to 23,060 cal per v equivalent, indicating that the electrode reaction is as written in Eq. [I.]. Platinum has been similarly used in molten silicates by other inve~ti~ators. "'~~ In this investigation platinum was used only as an anode, since a current deposits other elements on its surface and changes its characteristics.

Jan 1, 1970