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By Harold E. Rowen

Sintering is accomplished at a temperature of more than 2000°F. For the purpose of this discussion it will be defined as the art of burning a solid fuel with 90 to 95 pct ash content. Think of the problems of combustion involved in keeping a home furnace burning properly with 12 to 20 pct ash in the fuel and remember that the amount of fuel involved in the 5 to 10 pct combustion loss represented by the definition has to be just about right or nothing is going to happen. Our forefathers discovered that many ores containing metals csscntial to the steadily rising standards of living were associated with other minerals, sulfur and arsenic, for example, which had to be removed before ultimate refining. They did this by utilizing the solid fuels they had available-the sulfur or other readily combustible components- to create roasting heat.

Apr 1, 1956

By D. C. DERINGER

METALLURGISTS and mill operators appreciate, in a general way, .the economic or commercial relationship between recovery and grade of product but few have correlated in detail fluctuating metal prices with the metallurgy. They know that many factors such as metal price, dedusiions for returning charge, transportation, percentage of metal in head ore, etc.; all affect the commercial relationship between recovery and grade of product. In practically every mill some one at some ' time has calculated the amount of recovery that can be sacrificed for each percentage increase in grade of concentrate and from this calculated ratio the commercial or ., economic tail has been established. Such a ratio finally becomes a well-entrenched rule by which the progress of the metallurgy is judged.. When once established, these-, ratios are but seldom corrected to changes of metal prices for each possible grade of concentrate that may be produced. The calculation is tedious when often repeated. Other methods have been suggested and used to correlate the commercial with the metallurgical phase. A factor .derived ,by multiplying the grade of concentrate by recovery is often used, but is of little importance because it does not possess a single commercial quantity. The percentage monetary recovery calculated by dividing the gross value of the ore into the net smelter return gives a good economic index and, is to be commended, but it is difficult to correlate exactly and quickly the work of each day on a commercial basis.

Jan 1, 1931

By Leland Wemple

PREVIOUS to 1915, zinc refining had not become a general practice among the zinc smelters in the United States. Such refining as had been carried on was confined chiefly to remelting very high-leaded zinc, such as third-draw metal from the retort furnaces, and slab dross, and hard spelter from galvanizing pots. In this remelting operation, the lead and iron were settled out and the refined spelter obtained graded fifth class, i.e., Prime Western. Owing to the presence of lead in most zinc ores, the bulk of the spelter produced by direct smelting is of this Prime Western grade. Careful selection of ores of low lead content gave purer grades of spelter, i.e., Brass Special and Intermediate; and smelters which could secure ores carrying practically no lead produced high-grade spelter. Thus, in general, the grade of spelter produced by any smelter was pre-determined by the purity of the ore it could obtain. The needs of the warring nations of Europe for enormous quantities of cartridge and other high-grade brass resulted in such a demand for the purer grades of spelter that the available supply of lead-free and low-lead ores could not produce the quantity required. Prime Western grades went begging, so to speak, while high grades sold at times from 5 to 15 c. per pound over the Prime Western market. The great demand, coupled with the wide market margin, which permitted the inherent costs and losses, resulted in the conversion of the lower grades into higher grades by processes of refining. These conditions also accentuated the development and size of the electrolytic plants, which were being worked out at the time this increased demand for pure grade of metal occurred. The electrolytic process, where available, produces a higher grade of spelter from impure ores than does the fire process; a large portion of those impurities in the ore, which by the distillation process would be carried into the spelter, are removed in the leaching of the ores and the purification of the solutions. The refining process, adopted at a number of smelters for the purpose of converting low-grade spelter into "grades suitable for brash was that of redistillation.

Jan 11, 1917

By Stanislaus Skowronski

OVERPOLED copper, as commonly defined, is copper which has been excessively reduced during the poling period of the refining process. Owing to its porosity, such copper is unfit for commercial purposes. The cause of this phenomenon is undoubtedly the lack of oxides in the copper, yet this does not completely explain it. Refined copper of the same "pitch" and "set" varies considerably in oxygen contents, and analyses of overpoled bars also show similar wide differences; moreover, it is possible to melt copper in crucibles so as to obtain bars that are practically free from oxygen although they show a "tough pitch" and "level set" surface. Frederick Johnson advances the following theory: The regulation of the quantity of oxygen in copper is the keynote of all copper refining. It is the presence of a Well defined proportion of oxygen in the form of cuprous oxide, forming a copper-cuprous oxide eutectic, Which enables copper to be cast free from blowholes. It seems that When oxygen is present, other gases are less soluble in molten copper; When oxygen is absent, or is present in insufficient quantity, the copper dissolves other gases, such as hydrogen and carbon monoxide, Which are insoluble in the copper when solid, and, being rejected during the process of solidification, causes internal porosity and external ridges and excrescences.1 The "level set" of Wire bars, etc., is entirely the result of a compromise between the occluded gases and cuprous oxide. With excess of the former the metal would be "overpitch" and spongy, While an excess of the latter would result in the metal being "underpitch" and brittle.2 The result of the absorption and subsequent expulsion of reducing gases, carbon monoxide and hydrogen, and the effect of this action. on the overpoling of copper are in dispute; the literature on the subject is full of contradictory statements and will continue to be so until better analytical methods have been developed. Sulphur, however, is tangible. The refiner can see it in his button sample and consequently attributes to it any trouble that may happen during the melting of the copper.

Jan 3, 1918

By Robert B. Kistler, Ward C. Smith

The borate industry is one of the few sectors of the mining and mineral-processing industry which the United States still dominates. Since about 1927, the United States has supplied over half of the world's total boron and borate raw materials, and many of the chemical derivatives as well. Chiefly responsible for this record are companies producing sodium borates from two large deposits in southern California, at Boron (Kramer) and Searles Lake. The sodium borates, or products derived from borax and borax-containing brines, are the preferred borates for industry because they are soluble in water and combine readily with most other chemicals. Calcium borates (or sodium-free compounds) are required for certain end uses, but in general, nonsodium borates are used only where borax is not avail- able. During the past hundred years, the use of boron compounds throughout the world has risen from a few tons per year to the equivalent of about a million tons of B2O3. Leadership in supplying borates has shifted from country to country and from region to region during this period, generally as the result of the development of newly discovered deposits that were better in quality, more accessible, or more economically exploitable than previous sources (Table 1). Primary Products and End Uses The principal borate products offered by primary producers in the United States are listed in Table 2. In general, these products are utilized worldwide by almost all consumers, regardless of the original source of the primary borates. In the United States, the primary borates all originate in southern California. Colemanite is produced as crude or processed crude ore from the Death Valley area and is utilized by the fiber glass and ceramic industries without further treatment. Production from Searles Lake, Calif., is from brines that are processed in chemical plants where borax and other compounds are recovered and the principal borate products are produced. At Boron, Calif., the world's leading producer is mining a deposit of mineral borax and operating a chemical refinery. The mineral borax is mined together with included clay, and refined borax or "lo-mol" is one of the refinery products. The mineral and the chemical compound are identical, Na2B4O7- lOH2O. In addition to ship- ping all major refined borate products from Boron, the company ships semiprocessed ore concentrates to treatment plants elsewhere.

Jan 1, 1975

By Gieskieng, D. H.

Published tables of jaw crusher capacities are compiled for the most part from field performance data, interspersed with interpolations, extrapolations, various safety factors, and other modifications. Such a table attempts to balance and equalize field data from widely different materials, with differences of crushability, efficiency of feeding, sizing of the feed, and so on. The tests described in this paper were undertaken with the objectives of checking previously reported capacities; of studying the effects of various factors upon the capacity, including jaw plate curvature; and, if possible, of deriving a general capacity equation. Such an equation has been derived from the data obtained in these tests. It is given together with factors for its use. While more accuracy than is usually required may be obtained by careful application of the equation, it is of simple form and provides a convenient reference plane upon which the potential capacity of various crushers may be compared, and with which operating adjustments may be made on existing installations. The principal deviation in these tests from the usual approach consists of a laboratory technique which has been developed for the production of selected

Jan 1, 1949

Jan 1, 1967

By AIME AIME

THE fall meeting of the Petroleum Division, held at Tulsa, Okla., on Oct. 11 to 14, devoted two days to technical sessions and two to field excursions. A representative attendance of 250 to 300 engineers and operating officials engaged in oil production marked the sessions and paid close attention throughout to a notable series of highly technical papers. Restricted as the program was to consideration of production problems only, the time proved too short for discussion or even the presentation of the 20 papers submitted. Much informing and pertinent discussion none the less took place, and the sentiment was general to the effect that the meeting was one of the best ever held by the Division. The meetings were held in the auditorium of the Municipal building and local arrangements were well looked after by the Mid-Continent Section of the Institute and the Oil and Gas Association. The combination of the three organizations served to bring together engineers and operators most usefully. F. Julius Fohs, chairman of the Division, presided at the sessions on Monday. Tuesday morning John M. Lovejoy of the local section took over this responsibility in the absence of T. E. Swigart, who was detained in California. The afternoon session was presided over by A. G. Heggam of the Oil and Gas Association and the Tuesday evening banquet by W. C. Franklin of the same organization.

Jan 1, 1926

By Geoffrey Purcell

For anyone contemplating flotation research with only a very limited amount of mineral available for testing, the choice of suitable experimental equipment is by no means obvious. Hallimond's original and delightfully simple cell1 has been modified by subsequent investigators2to give quantitative and reproducible results on small samples. However, the modifications have necessarily compromised its simplicity, and the services of a skilled glass blower are required to duplicate the cell. Vacuum flotation tests3 at best qualitative and may, under certain conditions4, be quite impracticable. A hundred years ago, Thoreau observed that "our life is frittered away by detail," and his advice was to "simplify, simplify," The success of the simple cell described below, which was developed by the author and differs somewhat from Hallimond's original, suggests that Thoreau's advice still has merit a century later. CELL CONSTRUCTION The cell [Fig. 1 (a) and 1 (b)] consists essentially of a 25-ml pipet from which has been cut the con- stricted top. The length cut off is not critical since this merely determines the final volume of the cell. Cell volume may be varied in this way from 20 to 50 cc. A pyrex extension tube, equal in diameter and approximately half the length of the cut pipet, is attached to the top of the pipet by means of 2 ½ in. of close-fitting tygon tubing. When assembled, the two pyrex tubes should be spaced about ½ in. apart. Another length of tygon tubing is added to the extension piece for sealing purposes. A ¾ -in. disc of porous material (teflon cloth is ideal), secured in place over the pipet tip with another piece of shaped tygon tubing, completes the cell assembly. Tygon tubing may be shaped by pushing it over the pipet tip or some similar form and heating carefully over a low flame. For flotation [Fig. 1 (c) 1, the pyrex extension tube is rotated approximately 70º from the vertical and held in position by a wire hook and eye. Floated material, after reaching the free surface, falls and rests on this inclined plane. The barrier formed by the bent tygon tubing ensures that floated material does not slide back and return to the vertical portion of the cell.

Jan 11, 1965

Jan 1, 1969

CONTENTS PAGE MERRISS, M. H.-Direct Electrolysis of Black-copper Anodes of High Nickel-lead Content. Discussed by C. S. Witherell, C. P. Linville, G. E. Dalbey, M. H. Merriss 1 GRISWOLD, GEORGE G.-Calculating the Zinc for Desilverizing Lead Bullion by the Parkes Process. Discussed by C. S. Witherell, George G. Griswold, Milo W. Krejci, Lawrence Addicks, W. F. Gross, H. H. Alexander, A. F. Beasley, C. P. Linville 3 ALEXANDER, H. H. and STACK, J. R.-The Reduction and Refining of Tin in the United States. Discussed by Edward F. Kern, J. R.' Stack, R. L. Hallett, C. R. Hayward, William H. Bassett, R. C. Canby, H. G. S. Anderson 20 GREENAWALT, WILLIAM E.-Greenawalt Electrolytic Copper Extraction Process. Discussed by Stuart Croasdale, Colin G. Fink, Arthur L. Walker, Edward F. Kern, Henry A. Tobelmann, Oliver C. Ralston 26 BENEDICT, C. H. and KENNY, H. C.-Ammonia Leaching of Calumet and Hecla Tailings. Discussed by G. E. Dalbey, C. H. Benedict 34 RALSTON, OLIVER C.-Hydrometallurgy of Lead. Discussed by F. L. Bosqui, Jr., George D. Van Arsdale 34 TAINTON, U. C. and LEYSON, L. T.-Electrolytic Zinc from Complex Ores. Dis¬cussed by W. G. Woolf, C. A. Hansen 39 Direct Electrolysis of Black-copper Anodes of High Nickel-lead Content Discussion of the paper of M. H. MERRISS, presented; at the New York Meeting; February, 1924, and, issued, as Paper No. 1273-M, with MINING AND METALLURGY, September, 1923. C. S. WITHERELL, New- York, N. Y. (written discussion).-This paper is particularly valuable in that it gives the results of operations -carried out under conditions differing from standard practice. In the electrolytic refining of copper, as in other kinds of metal refining, it is occasionally necessary to treat extraordinary foul or complex material, in which cases 'it is valuable to know what other metallurgists have accomplished under similar conditions. As tapping the slimes-covered anodes brought the tank-voltage down to 0.45 to 0.50 volt, the counter electromotive force was, probably not more than 0.1 or 0.2 volt; hence the so-called polarization was, mainly,

Jan 6, 1924

By Kefton H. Teague

Attempts to locate domestic supplies of sillimanite have been unsuccessful until recently. This paper describes recent discoveries of sillimanite-bearing schists in the Southeastern States, with emphasis on geology of the deposits, mineral composition, origin, and reserves. Statements concerning possible methods of mining, milling, and utilization of sillimanite are given. Results from refractory tests on a laboratory scale are summarized.

Jan 1, 1950

Jan 1, 1968

By T. C. M. Pillay, John Chipman

The Si-0 equilibrium in liquid iron was investigated in some detail by Gokcen and Chipman1 who reported equilibrium constants of the following reactions: In each case the thermodynamic equilibrium constant K was obtained by extrapolating K' to infinite dilution. Their results on reaction [I] were consistent with those of earlier observers, and there seems to be little doubt as to the approximate validity of the equilibrium product determined. On the other hand, the results on reactions [2] and [3] indicated unusual curvilinear relationships between the activity coefficients of silicon and of oxygen and the silicon concentration. Since a linear relation is observed in all other similar instances, it was concluded that some source of error had affected the gas-metal equilibrium relationships. Recently the authors undertook a restudy of these equilibria with the view especially to establishing the equilibrium constant of reaction [2]. Their experiments, however, were discontinued before a tbroughly satisfactory answer had been obtained and consequently have remained unpublished until the present time. Quite recently Matoba, Gunji, and Kuwana2 published the results of a very thorough study of these equilibria. It is the purpose of the present note to Compare these three sets of experimental data, a comparison which leads to Confirmation of the results of Matoba and coworkers. The experimental arrangements described by Dutilloy and Chipman were employed. A controlled mixture of Hz, H,0, and argon was led into the induction furnace over the surface of the Fe-Si melt contained in a silica crucible. On account of the slow approach to equilibrium, runs were continued for at least 8 hr and, in some cases, as much as 12 hr. Samples were taken by means of silica tubes at the start and during the final 4-hr period of each run. Out of twelve runs only seven appeared to have approached equilibrium with sufficient certainty to be reported here. The results of these experiments, all at 1600°c, are shown by the triangles in Fig. 1. Equilibrium was approached from both oxidizing and reducing conditions and the direction of approach is indicated by the shape of the triangle. Attempts to extend the study to higher silicon concentrations were unsuccessful on account of the transfer of silica from the metal bath to the upper portions of the crucible by means of a silicon-monoxide mechanism. Matoba, Gunji, and Kuwana used similar methods and approached equilibrium from both sides. Their results at three temperatures are shown by the solid lines of Fig. 1. A line corresponding to 1600 deg is interpolated from their equations and is shown by the dotted line. The results of Gokcen and Chipman at 1600 deg in the range 0.02 to 2.0 pct Si are also shown. At concentrations up to about 0.6 pct Si, these investigators approached equilibrium from both directions, and their results in this range appear to be trustworthy. Above 1 pct Si, however, all of their experiments involved oxidation only, as shown by a decrease in the silicon content of the bath. It now seems certain that they failed to reach equilibrium at these higher silicon concentrations and that the curvilinear relation shown by their results is incorrect. It is evident that their results in the lower silicon range are in good agreement with those of Matoba and coworkers. In fact, a straight line drawn through their results would parallel the dotted line and would differ from it by only 0.05 in log K. The new data also lie close to that line. It may thus be concluded that the three sets of data are in good agreement and that the equations proposed by Matoba and coworkers for reaction [2] are satisfactory . They take the limiting value of log K', at 0 pct Si as log K ,. The slope of each line gives the value

Jan 1, 1962

By Edward B. Cook

INTRODUCTION. THE installation of the Gayley Dry-Air process appealed specially to the management of the Warwick Iron & Steel Co., for the. reason that for fifteen years records had been kept at the works of the company, showing the amount of water entering the furnace in the form of aqueous vapor, and careful observations had been made of its effect upon the working of the furnace. Some years had proved much worse in their effect than others, on account, not only of excessive moisture, but also of great variation in the moisture from day to day, and sometimes within a few hours. It had been found impossible to. make a satisfactory percentage of high-silicon foundry-iron in summer, even on high fuel; and for some years the endeavor had been made so to arrange the sales that, during July and August, only a small percentage of the iron produced would be required to carry more than 2 per cent. of silicon. Our larger furnace, running on basic iron, year after year, produced in February a tonnage 20 per cent. higher than in August, on a much lower fuel-consumption, while, at the same time, the summer months were marked by ? messes," tuyeres closed by slips, and other irregularities, constituting serious additional business losses. It will be easily understood, therefore, that the records made at the Isabella furnace after the installation of the dry blast in 1904 possessed special interest, and were closely watched by us. On the basis of our own experience, we argued that if the moisture could be kept low, and also uniform, the cost of installation would be more than justified. The subject was brought before our Board of Directors in the fall of 1905; and in the spring of 1906 it was decided to install a plant of sufficient capacity to treat 70,000 cu. ft. of air per min., an amount

Nov 1, 1908

By I. Cadoff, E. Miller, K. Komarek

Jan 1, 1960

By Warren E. Wilson

THE transportation of solids in pipe lines is a matter of deep concern in many fields of engineering. Much experimental and theoretical work has been done in an effort to devise means of designing pipe lines that will satisfactorily transport given solid loads, but there remain many unanswered questions in this field. The present discussion will be confined to a rather narrow portion of this field and will endeavor to point out certain factors that may well be considered when comparing the relative economy of various installations. The data have been presented previously but a new interpretation was prompted by a suggestion in a paper by Professor O'Brien,1 of the University of California, that the friction work per pound of dry material should be considered in determining the relative efficiency of various installations. This method of considering relative economy in various pipe lines leads to some rather unexpected conclusions, especially with reference to the economy of large pipe sizes. A previous suggestion by the writer3 concerning the economy of a rather peculiar type of installation is strengthened. It is not believed that the considerations set forth herein apply directly in the case of dredge lines, where economy is largely a matter of a high rate of pumping in order to reduce the unit overhead charge. However, it is believed that some value may be gained from these considerations in cases involving the disposal of a fixed amount of solids per unit time with a minimum expenditure of energy and at a low cost for replacement of worn pipes. Such situations are not uncommon in the disposal of mill tailings and the disposal of solids deposited from irrigation waters. It was found that data leading to general conclusions for various pipe sizes were not available but certain definite trends are indicated and methods of analyzing available data are presented in the hope that they may be of assistance in preparing engineering estimates on designs of pipe lines of the type described above. ENERGY. REQUIREMENTS Carrying out the idea contained in Professor O'Brien's paper concerning the method of computing energy required to transport solids, the following analysis leads to some rather interesting conclusions. Let us represent: [Solids load in terms of mass per unit time by W Ratio of mass of suspended solids to total mass of mixture flowing by p Volume rate of flow of mixture by Q Length of pipe by L Slope of energy grade line by s Mass per unit volume of solids by m, Mass per unit volume of liquid by ml Mass per unit volume of mixture by m,,, We then have as an expression for the solids load: W = pQm¬] The work done per unit mass, P, on the mixture to move it along the pipe the

Jan 1, 1945

By G. Thodos, D. E. Matschke

Cansiderable time and effort frequently are expended to establish, with a degree of confidence, the PVT behavior of pure substances. In particular, a great deal of experimental information contributed by a number of investigators is available in the literature. The data of each investigator, although significant in themselves, cannot be used with a high degree of confidence until they are compared with the continuum of information presented by others. Current interest in thermodynamic and transport properties, for not only the gaseous state but the con-densed state as well, requires that PVT infarmation be presented for both regions. The density dependence on temperature and pressure, when presented as a continuum, is of considerable value in itself, especially since the available equations of state fail to properly account for the PVT behavior in the condensed state. For this reason and to incorporate PVT data recently presented in the literature, this investigation was carried out. In their studies concerned with the thermodynamic properties of methane, Matthews and Hurd in 1946 utilized the data of Kvalnes and Gaddy and Olds, Reamer, Sage and Lacey to establish the PVT behavim of methane in the superheated region and the saturated liquid densities of Keyes, Taylor and Smithl in conjunction with the Clapeyron equation to develop the densities for the saturated envelope. Current activity sponsored by API Project No. 44 under the direction of F. D. Rossini has led to a tabular presentation of compressibility factors for gaseous methane in the superheated region.la These values were obtained by using smoothed residuals, developed from experimental data and the Ben edict-Webb-Rubin equation,' to establish internally consistent compressibility factors for the real gas. This approach offers probably the most precise presentation of PVT information for gaseous methane to date. The PVT behavior of methane also can be represented accurately by equations of state such as the Benedict-Webb-Rubin equation or the Martin-Hoa equation.' These equations, although valuable for analytically representing the PVT behavior, lack precision in the compressed-liquid region. The PVT data available in the literature for methane were utilized to obtain reduced densities that are presented in Figs. 1 and 2 as functions of reduced temperature with parameters of reduced pressure. The critical constants utilized for methane are those reported by Kobe and Lynn." These critical values, T, = 191.1°K, PC = 45.8 atm and p, = 0.162 gm/cc, produce a critical compressibility factor, z, = 0.289. The PVT information, as obtained from the literature, in many instances was not presented in an immediately

By N. O. Gray, John Henderson

Hydrogen-reduction data for naturally occurring single crystals and Prepared polycrystals of dense hematite have been presented. Results cover the temperature range 400o to 1000oC, for particles from ten sources, ranging in size from 0.07 to 10 mm and in shape from spheres to cylinders, cubes, and thin slabs. A consistent pattern of behavior has been demonstrated for single crystals and the reduction mechanism shown to be temperature-dependent. Below 579oC reduction is a simple topochemical process but at higher temperatuves it is complex and occurs in two distinct stages. Prepared particles from these laboratories behave in a similar manner to the single crystals. Data from two investigators showing topochernical reduction of Prepared particles above 575°C are inconsistent with that for other dense hematites. It is concluded that topochenzical reaction should not be used as a model for generalized rate expressions for dense hematites. SINCE 1958, McKewan1-6 has brought to prominence a simple concept of dense hematite reduction. This model is that oxygen is lost from a hematite particle undergoing reduction only from an oxide-iron interface that recedes in such a way that the oxide remaining retains the original shape of the particle, i.e., reduction occurs topochemically. An adjunct to this concept is that any intermediate oxides in the transition from hematite to iron only form thin layers so that oxygen cannot be lost from the particle without movement of the oxide-iron interface. Further, the rate of oxygen loss from the particle is said to be proportional to the area of the receding interface so that the iron layer grows linearly with time and the over-all reduction process can be described by the equation where ro and do are the initial particle radius and density, respectively, R is the fraction of the original oxygen lost, i.e., the fractional reduction, at time t, and K is the rate constant. The idea of an underlying simplicity in hematite reduction is attractive because it gives a tractable basis from which general theories of hematite reduction can be developed and it has received wide support,7-14 based mainly on the large amount of data13 that can be fitted to Eq. [I]. However, despite the fact that this equation has been derived for dense materials, the bulk of the data that have been used to test it13 have been for materials of only about 90 pct of theoretical density (5.26 g cm-3) or less, so that its generality for dense hematites has not been demonstrated. In any case, as will be seen, adherence of reduction data to Eq. [1] does not necessarily imply that reaction occurs topochemically. In this work only data for hematites approaching theoretical density are considered and it will be shown that in only one study besides McKewan's is topochemical behavior observed over the whole range of temperature investigated. For the majority of materials a linear rate of interface advance is observed to complete reduction only when wustite is not a stable intermediate phase in the transition of hematite to iron, i.e., at temperatures below about 575°C. Above this temperature, reduction is an exceedingly complex series of reactions that takes place in two distinct stages and it is only in the first stage that reaction in any way resembles a topochemical process. This means then that, far from representing general behavior as has commonly been supposed, topochemical reaction for dense hematites is only a particular behavior that may be observed under some circumstances. EXPERIMENTAL Hydrogen-reduction data have been collected and cross-checked in these laboratories by three techniques, weight loss, collection of water evolved in the reduction reactions, and direct metallographic examination. Details of these techniques are discussed elsewhere," where it is shown that results obtained by the three methods are in close agreement. The weight-loss method, by which most of the results were obtained, consisted of hanging the sample in a platinum mesh basket from an Ainsworth Model AV-AU-1 vacuum recording balance inside a vertical l 1/4-in.-ID alumina tube furnace. Dry deoxidized hydrogen was flowed downwards through the tube at 2 to 4 liters min-1 (stp). Single crystals from two sources and artificial oxides from three sources have been examined. The single crystals were from hematite deposits at Yampi Sound, Western Australia, and Brazil, the latter being obtained from Gregory, Bottley and Co., London, U.K. The "Yampi Blue" crystals were hand-picked from washed, magnetically concentrated, sized fractions, -200 mesh BSS (mean diameter ca 0.07 mm) and —36 + 44 mesh BSS (mean diameter ca 0.4 mm) while 10-mm cubes were cut from the Brazilian crystals with a diamond saw. The starting materials for the prepared particles were hematites designated, respectively, "Specpure Iron Oxide", Laboratory No. S639 from Johnson Matthey & Co. Ltd., London, U.K., "Calcined Ferric Oxide" from B.D.H. Laboratory Chemicals Division, Poole, U.K., and "Pigment Grade Oxide", EPR-50, from C. K. Williams & Co., Easton, Pa., U.S.A. Approximately spherical particles were prepared from the artificial oxides by rolling the material, moistened if necessary, in a glass jar, and cylindrical compacts approximately 10 mm in diam and of approximately equal height were pressed in a steel die at 200 psi. These spheres and cylinders were subsequently fired in oxygen for 20 to 100 hr at 1370°C. The

Jan 1, 1967

By D. I. Bardos, A. M. Bardos, Paul A. Beck

The approximate effective silicon radii in ternary Laves phase alloys with transition elements and silicon were found to range between 1.16 and 1.21A, i.e., considerably smaller than the atomic radius calculated for elemental silicon. The atomic radii were found to increase with the size of the transition element atoms in the structure. It has been noted by Aronsson1 that silicon in solid solution in iron, cobalt, and nickel has an effective CN 12 atomic radius of approximately 1.20Å, a value very much smaller than the CN 12 radius of 1.34Å derived from the interatomic distances in elemental silicon.7 The unusually short metal-silicon interatomic distances in transition element monosilicides and disilicides have been also pointed out by various investigators.1 A similar tendency was observed by Nevitt in Cr3O type silicides.2 Recent work on Laves phases in ternary systems of silicon with transition elements4"8 suggested that extensive Laves phase fields may occur in such systems.8 It has been pointed out by Laves7 that the MgCu2 and MgZn2 type structures lend themselves particularly well for the determination of the effective radii of the component atoms. In these AB2 phases the B atoms are arranged in close packed straight lines, and their distances are related in a simple manner to the lattice parameters.8 The present work was undertaken in order to find out whether or not the B transition element in such AB2 Laves phases can be replaced to an appreciable extent by silicon. In cases where extensive substitution proves to be possible, the "average atomic radius for the B site" at various silicon contents was to be determined, and the effective atomic radius of silicon calculated by extrapolation to complete replacement of the B component by silicon. The following ternary systems were studied: Ti-Mn-Si, Ti-Fe-Si, V-Co-Si, V-Ni-Si, Nb-Fe-Si, Nb-Co-Si, Ta-Fe-Si, Ta-Co-Si, and Mo-Fe-Si. In all of these alloy systems, the Laves phase solid solutions were found to extend over a considerable range of silicon content. As previously reported,4"8 in the V-Co-Si, V-Ni-Si, and Mo-Fe-Si ternary systems Laves phases do occur, even though there are no corresponding binary Laves phases. In stabilizing the Laves phase, silicon acts as if it were decreasing the effective electron concentration of the alloy.8 A more detailed study of the boundaries of the Laves phases in the V-Co-Si and V-Ni-Si systems has been made and will be published elsewhere. In both cases, the elongated Laves phase fields extend parallel to the B-Si side of the composition triangle, clearly showing that silicon is substituting for cobalt, respectively, nickel over a wide range of compositions. The binary Laves phases NbCo2 and TaCo2 have the cubic MgCu2-type structure. It was found that, in both ternary systems with silicon, again the MgZn2-type hexagonal Laves phase is stabilized and that this phase extends to high-silicon contents. In each ternary system at least three Laves phase alloys of the composition A(B1_xSix)2 were used, x here denoting the fractional substitution of the B-transition element atoms by silicon. The alloys, listed in Table I, were prepared by arc melting in argon. Each specimen was water quenched after a homogenizing anneal of 3 days at 110(FC, except for the Mo-Fe-Si alloys, which were annealed at 1200°C. Metallographic examination showed that most of the homogenized alloys consisted of a single phase, although some had minor amounts of a second phase, as shown in Table I. X-ray diffraction patterns were prepared using an asymmetrical focusing camera of large resolution and Fe Ka radiation. The patterns were indexed, and the lattice parameters of the hexagonal Laves phases were determined from the available diffraction lines of highest indices: (213), (205), and (313). The lat-

Jan 1, 1963