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By P. A. Larssen, P. R. Gage, R. W. Bartlett

The kinetics of formation of intermediate sili-cide compounds from MoSi2/Mo and WSi2/W couples were studied using a cylindrical sample configuration. Concentration profiles of the constituent metals were deter mined from electron-microprobe analysis of cross-sectioned samples after isotlzernzal diffusion annealing. These data also yielded hand widths of phases. Growth of intermediate phases depends on diffusionin them and obeys a parabolic rate law. The rates of formation of the intermediate phases decrease in the order Mo5Si3 > W5Si3 > Mo3Si. Crowth rates. for the isomorphous phases Mo5Si3 and W5Si3 had the same activation energy. 43 kcal per mole. SILICIDE coatings employed to protect refractory metals from high-temperature oxidation are usually formed by a diffusion process requiring concurrent transfer of silicon to the refractory metal surface. For a simple binary system and a coating thickness of one or two mils, the coatings on molybdenum and tungsten are primarily the disilicides WSi2 and MoSi2, respectively. During use of the coated re- fractory-metal system at high temperatures, in the absence of the silicon source, further diffusion causes growth of lower silicide compounds and depletion of the disilicides. Recent investigations have shown that the lower silicides are less effective than the disilicides in forming a glassy oxide film which impedes oxidation.' Consequently, failure of coatings at high temperatures may coincide with complete conversion of the disilicide phase. The purpose of this part of the study is to investigate the growth kinetics of the intermediate compounds in the W-Si and Mo-Si systems. There are three intermetallic compounds in the Mo-Si system: MoSi2 with a tetragonal structure

Jan 1, 1964

By A. M. Gaudin

In a recent paper we have reviewed principles and applications of measurement methods for contact angles and their hysteresis (22). In this paper we apply these methods to a system consisting of rutile, an organic liquid (benzene, decane, or dodecane) and water. Surfactant (dodecylamine hydrochloride) was used at various concentrations and various pH values.

Jan 1, 1964

The widely accepted kinetic model for the gaseous reduction of hematite is critically examined. The formation of the wustite layer during internal reduction cannot be explained in terms of solid-state diffusion. Present evidence indicates the existence of a micropore system in the wustite adjacent to the magnetite with the gas/solid type of reaction occurring not only at the iron/wustite interface but also at the wustite/magnetite interface. During the partial reduction of dense hematite pellets, in a controlled atmosphere, porous magnetite and wustite are formed as products. The mean pore size, as measured by mercury injection, increases with time at constant temperature and with temperature increase over the range 6500C to 950°C. The sizes of the pores indicate that Knudsen diffusion is the principal gaseous transport mechanism across thick layers of magnetite or wustite.The kinetics of the gaseous reduction to iron are consistent with a mixed control mechanism involving the interaction of gaseous diffusion effects with a first order reversible chemical reaction at the iron/wustite interface. Because of the larger pore sizes in the iron layers, ordinary molecular gaseous diffusion must be the principal transport mechanism. The usual experimental methods used for establishing the validity of chemical rate ~ontrol are incapable of differentiating between the mixed control- mechanism and exclusive chemical control.Some implications of mixed control kinetics are developed, including a predicted independence of rate on reducing gas pressure at higher pressures.INTRODUCTIONAn extensive literature review of the reduction of iron oxides has been compiled recently by Themelis and Gauvin (1962). From the large number of papers published and the widely divergent opinions of workers in this field, it appears that a simple unified quantitative analysis of reduction kinetics is not possible. The aim of the present paper is to show that a major cause of confusion is due to the attempts of many workers to interpret experimentally observed reaction rates in terms of a single rate controlling mechanism without due regard to other rate processes which must occur simultaneously.Some of the differences in behaviour reported for particles...

Jan 1, 1964

By Alan Jessop

A small group has been set up at the Dominion Observatory, Ottawa, to make a survey of terrestrial heat flow throughout Canada. Terrestrial heat flow is the heat rising from the interior of the earth and escaping at the surface, and is calculated from a knowledge of under-ground temperature distribution and the thermal conductivity of rocks. A small number of diamond drill holes are being sunk for the purpose of measuring temperatures below the surface, but the program is inadequate for a thorough survey. Mines and holes drilled for other purposes are being sought by the Dominion Observatory group to supplement their own drilling program. F ROM January, 1.962, to December, 1964, geo-physicists of many nations will be cooperating in the "International Upper Mantle Project." Unlike tl1e International Geophysical Year, which was mainly concerned with the fluid layers surrounding the earth, the Upper Mantle Project is an intensive study of the solid earth. Canada, with its large land area and extensive Precambrian Shield, is an active participant in the project.

Jan 1, 1964

By V. G. Leak, R. A. Swalin

The dilhsion of silver and trace concentrations of tin in liquid silver has been rrzeasured in the temperature range from about 975° to 1350°C. The difBsion dala. fil lhe following equations: fov self-diffusion of silver The ratio of DSn to DAg is found to be about 1.34. The higher diffusivity of tin is interpreted in terms of the coullombic repulsion which results from the fact that tin dissolved in silver has a valence of +3 relative to silver. THE phenomenon of diffusion has been well-described theoretically for hard-sphere gases and solids and found to be in good agreement with experimental data for certain gases and solids. Liquid-diffusion phenomena have not been well described theoretically and there is generally a lack of good experimental data. In this investigation self-diffusion and solute diffusion in liquid silver were studied. Silver was chosen as a solvent for two main reasons. First, silver is a noble metal and the atoms are considered to have a spherically symmetric charge field; hence the liquid may be considered to be a random array of approximate hard spheres. Mercury, gallium, and other lower-melting metals were eliminated from consideration since it appears possible that in their liquid states there is some residual long-range order and directional bonding. Second, silver behaves as a monovalent solvent and, while cadmium, indium, tin, and antimony all have nearly the same atomic size, they have chemical valences relative to that of silver of +1, +2, + 3, and +4, respectively. Slifkin, Lazarus, and coworkers1-5 investigated the diffusion of these solutes in solid silver and found that their diffusion rates increased with an increase of the excess valence of the solute. In the solid state the diffusion-rate increase was calculated to be due to a change in local modulus of the solvent caused by the excess valence of the solute.1"3 For the present investigation it was planned to determine the effect of valence upon solute diffusion in liquid silver. It was deduced that a coulombic repulsion between solute and solvent might be responsible for larger volume fluctuations in the vicinity of the solute thereby enhancing the diffusion of the solute atoms. Tin was the first solute investigated and was chosen for experimental convenience. If an excess-valence diffusion effect exists in the liquid state, the solute tin with its excess valence of + 3 might show a large enough effect to distinguish it from the self-diffusion of silver in silver. The silver self-diffusion data were obviously required as a base line for comparison. In addition silver self-diffusion was investigated with a view toward examining the data in connection with the Sutherland- Einstein: Coheen-Turnbull,7 and swalin8 theories of diffusion in liquids. I) EXPERIMENTAL TECHNIQUES The diffusion coefficients for tin and silver in liquid silver were determined in separate experiments using the capillary-reservoir method of Anderson and saddingtono but following closely the experimental techniques outlined by Ma and Swa1in. The radioactive alloy bath was prepared by plating either tin-113 or silver-110 m isotope* onto 99.999 *Isotopes obtained from Oak Ridge National Laboratory. pct Ag rods.* The silver and isotope were melted *Silver obtained from Cominco Co. and mixed in a graphite crucible under a purified argon atmosphere, then outgassed for capillary filling. Some of the fused-silica capillaries were filled individually as reported by Ma and Swalin, but most were filled in a different manner. A long piece of capillary tubing was sealed off on one end and held in the system so that the open end was just above the surface of the molten alloy. The system was evacuated, the open end submerged into the alloy, and argon was admitted into the system up to atmospheric pressure. The molten alloy was forced up the capillary several inches where it solidified and was subsequently cut into segments of the proper length for diffusion annealing. The apparatus for diffusion annealing was the same as that used for capillary filling except that a Pt—Pt, 10 pct Rh therinocouple was placed in the solvent bath in order to accurately measure the temperature during the run. A diagram of the dif-

Jan 1, 1964

By William G. Fischer

Basic laboratory tests initiated the. Rock Mechanics program. The stress-strain curve, modulus of elasticity, Poisson's ratio, the uniaxial rock strengths, Mohr's envelope, the stress at failure, and creep were investigated. A series of underground problems were then approached using this information; and various field measuring devices, most of which were developed by the Bureau of Mines. Initially, stress concentrations near mine openings were evaluated using the stress relief technique. This required an accurate determination of the pre-mining stress field. Later, stress concentrations associated with the cave line .sere studied. After about thirty stress reliefs over an appropriate time interval the effects of one type of mining could be compared against another. The microseismic technique was used to investigate a possible application of warning devices near the cave line. A study of mane reorientation was made Problems related to the shape and size of pillars and barriers were studied. Partial extraction mining systems were evaluated. The effectiveness of roof bolting patterns were examined. Control of roof stresses was attempted. A new system of mining in heavy ground has been developed using the information secured in the Rock Mechanics program without this system, mining in more than one instance would Nave been next to impossible. Indeed; from this one discovery alone, the Rock Mechanics program has paid off in improved safety as well as in dollars.

Jan 1, 1964

By Kendrick C. Hardcastle

Although the basic techniques employed in hydraulic pumping in open pit mining have been practiced throughout the better part of this century, only relatively recently have studies of' sufficient depth and scope been conducted to improve these techniques. This paper will point out the basic techniques involved and some of the more recently discovered data concerning hydraulic pumping, Inherent in all hydraulic transportation systems apart from the consideration of transportation cast, is the outstanding advantage of slurrying the matrix at the mining pit so as to provide a lengthy and thorough soaking and washing of the material while in the pipe line and thereby reduce the necessity for washing, scrubbing and other treatment in the beneficiation plant. This is quite important in view of the constant increase in demand for a cleaner product.

Jan 1, 1964

By N. A. Tiner, Saara Asunmaa

The early stages of nucleation of vacuunz-deposited gold coatings on electropolished surfaces of pure nickel and binary alloys of Ni-A1 and Ni-Ti have been studied, employing carefully controlled temperature and vacuum conditions. The preferential nucleation of gold on slip-plane edges on the crystal surfaces gave rise to a very pronounced decoration effect which was used in studying the morphology of the pain boundaries, etch pits, and slip planes on crystal faces. Characteristic surface patterns were observed with local dimensional variations. Most pronounced geometric patterns were ohserved in the pain boundaries of nickel and on the crystal faces of Ni-A1 alloy. The nucleation behauior of gold indicates contamination on the Ni-T1 alloy and the getter properties of titanium are presented as a tentative interpretation for the detected contamination. The markings and imperfections on cleavage surfaces of crystals have long been observed by optical microscopy.1,2 Surface-replica techniques are also used to detect the smallest steps and structural details on crystal surfaces by electron microscopy. Recently, Bassett3-5 and Sella, Conjeaud, and Trillat 6 have shown that, when gold is deposited onto a rocksalt cleavage surface, there is preferential nucleation at steps and slip-plane edges on the crystal surface. This gives rise to a very pronounced decoration effect which is invaluable for revealing the lattice steps on a cleavage surface. According to Bassett,3 gold atoms arriving during vacuum evaporation at the crystal surface have a certain mobility on the surface after arrival, particularly at elevated temperature. If a significant

Jan 1, 1964

By J. R. Slotemaker

As successfully pilot-tested at a quarry producing limestone for a large cement plant, swiftly flowing streams of rock enter the Gromax Selector. They are electronically scanned while in motion and light reflection data flashed to logic circuits. The logic circuits compute the total light deviations in each rock as it passes the scanner. Thus, a rock with striated or spotted impurities can be rejected or accepted on the basis of its proportional content. The actual case history of this equipment's development at a limestone quarry in the Southeast serves to illustrate its general area of usefulness.

Jan 1, 1964

By Robert Rother

El presente texto señala el proceso de exploración y preparación que anteceden la etapa de la producción de mina. Para ello, es necesario ubicar un depósito mineral donde se clasifican en vetas, zonas de cizallamiento, contactos, substituciones y diseminaciones, que se distinguen por la forma de la zona débil en la costra terrestre. Asimismo, es necesario anotar datos como: ubicación, acceso, altura sobre el mar, características de la región, labores, posición del cuerpo mineralizado, sobrecarga, caja y ganga, tectónica y todo lo que se puede ver efectivamente. Posteriormente se evalúa el título de las propiedades, mapeo topográrico y geológico del yacimiento, sistema y costo del muestreo planeado, estudio de las vías de acceso y transportes, reservas de mineral, así como considerar el programa de producción (abastecimiento de agua, mano de obra, escala de operación, tratamiento metalúrgico, valor de la producción, costos de operación, utilidad de operación).

Jan 1, 1964

Jan 1, 1964

By M. C. Fuerstenau

A number of interesting and. important phenomena were revealed during a study of the response of beryl to sulfonate flotation (1). Perhaps the most important observation is the effect of various cations on flotation response. Experiments showed that in the vicinity of pH = 3. 0, about three ppm Fe.+++ increased recovery of leached beryl from about 60 to 100 per cent, whereas about four ppm Ca++ reduced the recovery from 60 to 2 per cent. With the exception of ferric iron, all of the other cations investigated reduced flotation recoveries drastically at this pH. As postulated in the paper "Sulfonate Flotation of Beryl", (1) even with low concentrations of polyvalent cations and sulfonate (on the order of one ppm), cation¬ sulfonates are precipitated immediately in solution. That is, blueish-white clouds .were noted to form after given additions of salts to. known solutions of sulfonate. Furthermore, it was also shown that one-hundred-fold more ferric iron than necessary to form the precipitated cloud had to be added to effect complete flotation. In other words, some form of solid ferric sulfonate was found to function as the collector in these systems. The form of the compound was suggested to be Fe (RSC3)2OH and that bonding to the surface occurs through the hydrogen of the hydroxyl. As the form of this compound was shown to be dependent on the extent of hydrolysis of ferric iron, it is to be expected that ferric iron will be unique in some pH region. Further, if the presence of hydroxyl in the neutral precipitated compound is of primary importance, then other cations should function similarly but at different values of pH, since they will hydrolyze at different concentrations of hydroxyl ion. To determine whether the premise of hydrolysis is correct, the study was extended to quartz systems lit the presence of various cations at various values of pH.

Jan 1, 1964

By N. A. Gokcen, E. S. Tankins, G. R. Belton

Equilibrium in the reaction H2(g) + O[in liquid iron, cobalt, or nickel] = H2O(g) has been investigated over wide temperature and composition ranges. Oxygen has been found to obey Henry's Law in each of the three metals at 1550°C. The standard free-energy changes for the above reaction are given by: (1550° to 1700°C) ?Foco = -45,360(±290) + 16.16(±0.16)T (1490° to 1700°C) ?Fo Ni = -48,170(±220) + 16.12(±0.12)T (1465° to 1700°C) where the standard state for dissolved oxygen is the I wt pet solution. ThE thermodynamic behavior of dilute solutions of oxygen in molten iron has been the subject of many investigations over the last thirty years,'-'4 the majority of the investigators having utilized the reaction:

Jan 1, 1964

By T. G. Digges, M. R. Achter

ALTHOUGH zone melting has found favor in recent years because of its convenience and its faster rate of production of single crystals, the older technique of strain annealing still has a number of advantages. It has been reported1 that the lattice of a crystal prepared in this manner has fewer defects than one grown from the melt and, of course, the control of the external geometry is easier. Also, the diameter of the crystal which can be grown by zone melting has a theoretical limit determined by the surface tension, thermal conductivity, and specific gravity of the material, while the size of that which can be grown in the solid state is limited only by practical considerations. In a program for the study of the structure-sensitive properties of niobium and its alloys it was desirable, for ease of handling, to have available single crystals of large diameter. This requirement dictated the choice of the strain-anneal technique. Induction heating was chosen in the present work in preference to other methods because of its deep penetration of large-diameter sections. A five-turn coil, powered by a motor generator operating at 10,000 cps, is contained in a vacuum chamber. The work is lowered through the coil for both the recrystallization and the crystal-growth steps. Starting with electron-beam melted material, the bars are cold-swaged, recrystallized, strained in a tensile machine, and then subjected to the growth step. Single crystals have been grown under the following conditions: Reduction in area during swaging— 79 to 99 pct, recrystallization temperature—1500o to 1667°C at the rate of 1.25 in. per hr, strain—1.0 to 2.5 pct, growth temperature—1600o to 2400°C at rates from 0.15 to 1.25 in. per hr. Starting grain sizes achieved after the recrystallization step varied from 0.6 to 1.55 mm. The starting grain size was found to be critical; if it is too fine and has any residual cold work, as shown by the presence of a fiberlike texture, a single crystal cannot be grown. Using this technique niobium single crystals have been grown from 0.250 in. diameter and 12 in. long to 1.00 in. diameter and 5 in. long as shown in Fig. 1. The 1-in. crystal is the largest to be reported for a refractory metal as compared to 0.500 in. for molybdenum grown by zone melting.2 As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and Smallman,3 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point ahead of the interface between the single and polycrystalline portions. Finally, it is returned to the chamber and growth is continued "around the corner". The amount of bending which can be imparted to the rod is limited by coil geometry which up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. The perfection of these single-crystal specimens as a function of process variables is being measured by X-ray and metallographic techniques and the results will be reported in a forthcoming paper. This work was partially supported by the Advanced Research Projects Agency.

Jan 1, 1964

By R. C. Woodhead

During past years the most difficult problem presented to the coal preparation engineer has been the cleaning of fine coal, The problem of handling fine coals is more involved than the coarser sizes, because the higher surface moisture contents complicate screening, and the larger percentages of fine near size material complicate separating problems. Low gravity high capacity specific gravity separations were not possible with equipment available at that time. Coal preparation engineers did develop machines that would effect a separation of the fines, however, to maintain a high efficiency, the point of separation had to be a relatively easy one. The more difficult separations were made in the coarse coal sections of the washeries, and the fines were generally cleaned at higher specific gravities in equipment such as tables, feldspar jigs, rheolaveurs, etc. Clean products from both processes were mixed, resulting in overall lower ash contents, During the last several years, however, we have been confronted with increasing demands ZGP more precise separations of finer coals to still further reduce ash contents. A study was begun and a program instigated to improve the cleaning of fine coal, The result of this endeavor was the development of the new cycloidal heavy medium cyclone.

Jan 1, 1964

By Harry Perry

The decline in coal production has been slowed somewhat in recent years, mostly because of the industry's own remarkable success in holding the line on costs, and partly as a result of advances achieved through industry and government research. Nevertheless, the decline has continued. This downward trend combined with the increased productivity of labor through mechanization that has been necessary for coal to retain even its present competitive position, has resulted in a serious reduction in the number of miners required and large scale economic dislocations in mining communities. For coal to regain a more favorable position it must either expand existing markets by reducing the cost of the delivered product and thereby compete more effectively with other fuels or develop new uses that will require large tonnages of coal. New markets involving several million tons, which would look extremely attractive to most other United States industries--including the organic chemical industry--would do little to alleviate the coal industry?s depressed economic conditions, While such small new markets would be welcome, an industry producing over 400 million tons per year must look to large tonnage outlets for solutions to its long range economic problems.

Jan 1, 1964

By Fred P. Giese

Southeastern reserves of titanium ores are large, widespread, and ample for anticipated demand. The leading titanium industries are mining and beneficiating sand deposits, principally in Florida, and manufacturing titanium pigments. Most of the mineral output is consumed by the producers themselves. In 1962, 20 percent of the national pigment capacity was in the Southeast.

Jan 1, 1964

By C R. Crook

A brief outline of production methods and processes is given to show how maintenance fits into the picture at this plant. The work force, and the tools needed to carry out this function, are then described. Preventive maintenance practices, scheduled annual shutdowns and routine check-downs are explained, especially as related to planning and to the materials and labour involved for a mini-mum downtime. A brief explanation of the materials, sup-plies and spare parts program, as well as the part played by the Stores Department in conjunction with the Maintenance Department, is given. Cost control and equipment expenditure indicators are explained. Some specific examples of maintenance jobs are described in order to show the flexibility of the program. S HERRITT GORDON Mines Limited has been in continuous production, except for the planned downtimes needed for expansion tie-ins, or the annual shutdown check-over periods, since the first shipment of nickel on a commercial basis in July of 1954.

Jan 1, 1964

By M. S. Burton, G. V. Smith, A. Rosen

The kinetics of re crystallization and the effect of recovery on recrystallization of pure iron were investigated within the temperature range of 517" to 632 OC. Grain growth and activation energies were also studied. Two stages can be distinguished during recrystallization; the first is gvowth-controlled and the second is nucleation-controlled. The extent to which the first stage succeeds before the second stage begins depends on both temperature of recrystallization and temperature of recovery. The softening of cold-worked metals and alloys due to transformation of the deformed crystals to strain-free equiaxed grains during annealing is well-known, and early inestiators established that recrystallization kinetics is strongly influenced by minute quantities of impurities. Generally, it is believed that impurities decrease the rate of recrystallization and the rate of grain growth. To understand the basic phenomena of recrystallization, investigations should be on pure materials. Most of the research on high-purity materials has been on metals having the fee Bcc materials, and especially high-purity iron, have been studied only in recent years. It is known that recovery may influence recrystalliation;" however, no general description of the influence, applicable to all materials, has been presented. This paper presents results of a study of the recrystallization kinetics of high-purity iron, after 60 pct cold deformation by drawing, with particular reference to the influence of recovery on the rates of recrystallization and grain growth. From observations of these rates, conclusions are drawn concerning nucleation. MATERIAL AND EXPERIMENTAL PROCEDURE Preparation of Material. High-purity iron, prepared by zone refining of vacuum-melted electroiytic iron at Battelle Memorial Institute under sponsorship of the American Iron and Steel Institute, was used in this study. Table I gives the reported chemical analysis of the material, taken at a point near the last molten zone and thereby rep- resenting the maximum impurity level for the entire bar. Prismatic specimens, approximately 10 x 10 X 50 mm, were sawed from the 50-mm-diam bar, perpendicular to the zone-refining direction, and turned to cylindrical shape. These specimens were sealed in quartz capsules under vacuum, approximately 10"e mm Hg, austenitized at 930° C for 15 min, slowly cooled, removed from the capsules, and cold-worked in air by swaging to approximately 20-pct reduction of area. The encapsulating, austenitizing, and swaging operations were repeated two additional times, after which the samples were encapsulated, austenitized, and cold-drawn to 60-pct reduction of area. A further vacuum anneal at 630°C for 120 min and cold drawing to 60-pct reduction of area produced wire 2.8 mm in diameter. The drawn wire was electropolished to remove deformed material on the surface, after which it was sawed into 4-mm-long specimens for the recrystallization study. Microscopical examination before the final cold reduction revealed equiaxed grain structure with very fine grains in a thin layer near the surfaces of the specimen and nearly uniform ASTM 3-4 grain size in the center. Recrystallization Heat Treatment. a) Direct Recrystallization of Cold-Worked The 60 pct cold drawn iron specimens were recrystallized at five temperatures, 517, 556, 590°, 612, and 632C, in a lead bath covered with graphite (the temperature was controlled to 1°C). Specimens were treated for twelve different times at each temperature, and all were water-quenched after heat &eatment. b) Recrystallization Following Preliminary Recovery Heat Treatment. After cold working, specimens were sealed into quartz capsules under vacuum, 105 mm Hg, and recovery-annealed at 362", 400", and 440°C for 20 hr prior to recrystallization. No evidence of recrystallization was found

Jan 1, 1964

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964